Note: Descriptions are shown in the official language in which they were submitted.
Express Mail No. MB179884056
August 10, 1989
~3~
RIGID POLYURETHANE FOAMS PREPARED FROM POLYVINYL
ACETATE/ALLYL ALCOHOL POLYOLS, AND PROCESS FOR MAKING SAME
Background of the Invention
1. Field of the Invention
The present invention relates to rigid poly-
urethane foams, and more particularly, to rigid polyurethane
foams prepared from polyvinyl acetate/allyl alcohol polyols
and the process for making the ~ame.
2. Description of Related Art
It is well known that a polyurethane foam having
insulating utility can be prepared by reacting an organic
polyfunctional isocyanate with a suitable hydroxyl component
in the presence of a blowing agent such as a fluorinated
hydrocarbon. The fluorinated hydrocarbons produce a desir-
able rise in the foamed product, but also play an i~portant
role in producing a foam having a low thermal conductivity
or K factor. However, the use of fluorinated hydrocarbons
adversely impacts the environment. Regulatory agencies have
mandated a reduction in fluorinated hydrocarbon use and have
called for the eventual elimination of the use of fluorin-
ated hydrocarbons. Attempts have been made to substitute
various blowing agents, such as water, in an effort to find
a replacement for fluorinated hydrocarbons. Most of these
~, ~ ?J c~
attempts have produced unsati6factory results. For io-
6tance, while water may be ~ubctituted for fluorinated
hydrocarbons as a blowing agent, the CO2 produced by the
water decreases the insulating properties of rigid foams.
Reretofore, it has been known that use of copolymer~ in
urethane systems could produce improved physical and chemi-
cal properties such as increased load upporting capacity,
increased tensile strength, increased modulus of tensile
elasticity, and increased ~olvent resistance. ~owever, the
use of a copolymer, particularly the copolymer used in the
instant invention, to improve the resistance to thermal
conductivity of the foam has not been recognized.
SummarY of the Invention
Rigid polyurethane foams are prepared from poly-
vinyl acetate/allyl alcohol polyols. The urethane foam is
formulated ~rom a polysl component containing from about 2
to about 100 weight percent of a polyvinyl acetate/allyl
alcohol polyol. The polyvinyl acetate/allyl alcohol has at
least 2 hydroxyl units.
Objects, features and advantages of this invention
are to provide a polyurethane rigid foam cuitable for insul-
ating, from a polyurethane system including a polyvinyl
acetate/allyl alcohol copolymer, which iB characterized by a
,................... ... ... .
s r ~ ~1 r
reduction in the amount of fluorinated hydrocarbons used as
a blowing agent, has improved K factors, may be produced by
utilizing increased amounts of water as a blowing agent
without sacrificing insulation properties, which maintains
improved K factors of the foam with aging, produces foams of
suitable density, maintains low porosity of foam cells,
maintains a suitable gel time and provides an economic co-
polymer for urethane systems not heretofore known.
These and other objects, features and advantages
will be apparent form the detailed description and appended
claims which follow.
Detailed Description of the Present Invention
The present invention is directed to rigid poly-
urethane foams prepared from a polyvinyl acetate/allyl alco-
hol polyol. The urethane foam is formulated from a polyol
component containing from about 2 to about 100 weight per-
cent of the polyvinyl acetate/allyl alcohol polyol. The
copolymers may be hydroxy, isopropoxy, or isopropyl initi-
ated. However, the copolymers are believed not to be
hydroxy or isopropoxy terminated. The polyvinyl allyl
alcohol has at least 2 hydroxyl groups. The polyvinyl
acetate/allyl aleohol polyol may contain from about 2 to
about 95 weight percent vinyl acetate and from about 5 to
-3-
.. . . . . __ _ . . . . , ._ .. .. . . . ... . . . ... . .. . .. ... . .
JJ ~ V 3 ~
about 98 weight percent allyl alcohol. Preferably, the
copolymer includes form about 10 to about to about 25 weight
percent allyl alcohol. The molecular weight of the
polyvinyl acetate/ allyl alcohol polyol may range from about
500 to about 2000.
Preferably, the polyvinyl acetate/allyl alcohol
random copolymer is prepared by a free radical process using
a continuous process tubular reactor system. U.S. Patent
No. 3,673,16B discloses a tubular reactor and continuous
process for producing polymeric materials which are suitable
for use in producing the polyvinyl acetate/allyl alcohol
random copolymer. U.S. Patent No. 3,673,168 is hereby
incorporated by reference. Ratioed amounts of vinyl acetate
monomer and allyl alcohol monomer are continuously fed into
a tubular reactor in the presence of a solvent and an initi-
ator. The vinyl acetate monomer is randomly polymerized
with the allyl alcohol monomer to yield a polyol in the
tubular reactor. The polyol crude product 50 produced is
continuously withdrawn from the tubular reactor reaction
mixture.
The polyurethane foam is prepared by reacting an
isocyanate with an active hydroyen containing compound, and
the polyvinyl acetate/allyl alkyl random copolymer in the
presence of ~lowing agent.
-4-
~3~ ~ ~t~'~
It has been unexpectedly discovered that the ufie
of a polyvinyl acetate/allyl alcohol random copolymer in a
urethane foam results in a foam having improved K factors
requiring a reduced amount of chlorofluorocarbon as a blow-
ing agent, is tolerable to an increased amount of water as a
blowing agent without sacrificing insulation properties and
maintains a suitable density and porosity. Such advantages
can be achieved by utilizing from about 2 percent to about
100 percent, preferably from about 2 percent to about 20
percent, and most preferably from about 5 percent to about
10 percent by weight of the polyvinyl acetate/allyl alcohol
random copolymer in the active hydrogen containing component
of the urethane system. The amount of polyvinyl
acetate/allyl alcohol copolymer utilized in the formulation
will vary with the overall polyol system chosen and i~ an
amount effective in producing a foam having lower K-factors
than foams produced without the copolymer. In most cases,
an amount of the copolymer in the range of about 2 to 20
percent weight of the component will be effective.
Polyurethane foams having the above cited desir-
able characteristics can be produced utilizing a polyvinyl
acetate/allyl alcohol random c~polymer with a variety of
isocyanates, polyols, and additional ingredients which are
more fully described below.
-5-
~ ~'t r ~
In the more than fifty years since Professor Otto
Bayer discovered the addition polymerization reaction
leading to polyurethanes (1937), the field of polyurethane
polymers has become a well established, mature technology.
While the first uses of polyurethanes were in the field of
fibers, rigid foams were developed in 1947 and flexible
foams in 1952. In the year 1981, world production of poly-
urethanes exceeded 3 million metric tons.
By the term "polyurethane" is meant a polymer
whose structure contains predominately urethane
-[-NH-C-O-l-
linkages between repeating units. Such linkages are formed
by the addition reaction between an organic isocyanate group
R-[-NCO] and an organic hydroxyl group [~O-l-R. In order to
form a polymer, the organic isocyanate and hydroxyl group-
containing compounds must be at least difunctional. ~ow-
ever, as modernly understood, the term Npolyurethane" is not
limited to those polymers containîng only urethane linkages,
but includes polymers containing allophanate, biuret,
--6--
_,, _ _ . , , _. .. . . ... .. . .
~ ~ f ,~ r~ ~ r ) l ~
carbodiimide, oxazolinyl, isocyanurate, uretidinedione, and
urea linkages in addition to urethane. The reactions of
isocyanates which lead to these types of linkages are
summarized in the Polyurethane Handbook, Gunter Vertel, Ed.,
~anser Publishers, Munich, 1985t in Chapter 2, pages 7-41;
and in Polvurethanes: Chemistry and Technolo~y, J.~.
Saunder~ and K.C. Frisch, Interscience Publishers, New York,
1963, Chapter III, pages 63-118. In addition to polyols
(polyhydroxyl-containing monomers), the most common iso-
cyanate-reactive monomers are amines and alkanolamines. In
these cases, reaction of the amino group leads to urea link-
ages interspersed within the polyurethane structure.
The urethane forming reaction is generally catal-
yzed. Catalysts useful are well known to those ~killed in
the art, and many examples may be found for example, in the
Polyurethane ~andbook, Chapter 3, S3.4.1 on pages 90-95; and
in Polvurethanes: Chemistry and Technolo~y in Chapter IV,
pages 129-217. Most commonly utilized catalysts are ter-
tiary amines and organotin compounds, particularly dibutyl-
tin diacetate and dibutyltin dilaurate. Combinations of
catalysts are often useful also.
In the preparation of polyurethanes, the isocyan-
ate is reacted with the active hydrogen-containing com-
--7--
pound(s) in an isocyanate to active hydrogen ratio o from0.5 to 1 to 10 to 1. The "index" of the composition is
defined as the -NCO/active hydrogen ratio multiplied by
100. While the extremely large range described previously
may be utilized, most polyurethane processes have indices of
from 90 to about 120 or 130, and more preferably from 95 to
about 110. In the case of polyurethanes which also contain
significant quantities of isocyanurate groups, indices of
greater then 200 and preferably greater tAen 300 may be used
in conjunction with a trimerization catalyst in addition to
the usual polyurethane catalysts. In calculating the quan-
tity of active hydrogens present, in general all active
hydrogen containing compounds other then non-dissolving
solids are taken into account. Thus the total i~ inclusive
of polyols, chain extenders, functional plasticizers, etc.
Hydroxyl group-containing compounds ~polyols)
useful in the preparation of polyurethanes are described in
the Polyurethane Handbook in chapter 3, S3.1 pages 42-61;
and in Polvurethanes: Chemistrv and Technology in Chapter
II, SSIII and IV, pages 32-47. Many hydroxyl-group contain-
ing compounds may be used, including simple aliphatic gly-
cols, dihydroxy aromatics, bisphenol~, and hydroxyl-termin-
ated polyethers, polyester~, and polyacetals, among
:~ .
S,
others. Extensive lists of suitable polyols may be found in
the above references and in many patents, for example in
columns 2 and 3 of U.S. Patent 3,652,639; columns 2-6 of
U.S. Patent 4,421,872; and column 4-6 of U.S. Patent
4,310,632; these three patents being hereby incorporated by
reference.
Preferably used, in addition to the polyvinyl
acetate/allyl alcohol polyol, are hydroxyl-terminated poly-
oxyalkylene and polyester polyols. ~he former are generally
prepared by well known methods, for example by the base
catalyzed addition of an alkylene oxide, preferably ethylene
oxide (oxirane), propylene oxide (methyloxirane) or butylene
oxide (ethyloxirane) to an initiator molecule containing on
the average two or more active hydrogens. Examples of pre-
ferred initiator molecules are dihydric initiators such as
ethylene glycol, propylene glycol, butylene glycol, neo-
pentyl glycol, 1,6-hexanediol, hydroquinone, resorcinol, the
bisphenols, aniline and other aromatic monoamines, aliphatic
monoamines, and monoesters of glycerine; trihydric initi-
ators such as glycerine, trimethylolpropane, trimethylol-
ethane, N-alkylphenylenediamines, mono-, di-, and
trialkanolamines; tetrahydric initiators such as ethylene
diamine, propylenediamine, 2,4'-, 2,2~-, and 4,4'-methylene-
_~_
~;.3d ~ .4 f_~ ' f 'V ~
dianiline, toluenediamine, and pentaerythritol; pentahydricinitiators such as diethylenetriamine; and hexahydric and
octahydric initiators such as sorbitol and sucrose.
Addition of alkylene oxide to the initiator mole-
cules may take place simultaneously or sequentially when
more than one alkylene oxide is used, resulting in block,
heteric, and block-heteric polyoxyalkylene polyethers. The
number of hydroxyl groups will generally equal the number of
active hydrogens in the initiator molecule. Processes for
preparing such polyethers are described both in the PolY-
urethane ~andbook and Polyureti~.anes: ChemistrY and
Technolo~y as well as in many patents, for example U.S.
Patents 1,922,451; 2,674,619; 1,922,459; 3,190,927; and
3,346,557.
Polyester polyols also represent preferred poly-
urethane-forming reactants. Such polyester6 are well known
in the art and are prepared simply by polymerizing poly-
carboxylic acids or their derivatives, for example their
acid chlorides or anhydrides, with a polyol. Numerous poly-
carboxylic acids are suitable, for example malonic acid,
citric acid, succinic acid, glutaric acid, adipic acid,
pimelic acid, azelaic acid, sebacic acid, maleic acid,
fumariG acid, terephthalic acid, and phthalic acid. Numer-
--10--
.. , . ,, . _ . .. _ _ . . . . . . . . .
~ ~ ri ~
ous polyols are ~uitable, for example the various aliphaticglycols, trimethylolpropane and trimethylolethane, ~-methyl-
glucoside, and sorbitol. Also suitable are low molecular
weight polyoxyalkylene glycols such as polyoxyethylene glyc-
ol, polyoxypropylene glycol, and block and heteric polyoxy-
ethylene-polyoxypropylene glycols. These lists of dicar-
boxylic acids and polyols are illustrative only, and not
limiting. An excess of polyol should be used to ensure
hydroxyl termination, although carboxy groups are also re-
active with isocyanates. Methods of preparation of such
polyester polyols are given in the PolYurethane Handbook and
in Polyurethanes: Chemistrv and Technoloqy.
Also suitable as the polyol are polymer modified
polyols, in particular the so-called graft polyols. Graft
polyols are well known to the art, and are prepared by the
in situ polymerization of one or more vinyl ~onomers, pre-
ferably acrylonitrile and styrene, in the presence of a
polyether or polyester polyol, particularly polyols contain-
ing a minor amount of natural or induced unsaturation.
Methods of preparing such graft polyols may be found in
columns 1-5 and in the Examples of U.S. Patent 3,652,639; in
columns 1-6 and the Examples o~ U~S. Patent 3 t 823,201: par-
ticularly in columns 2-B and the Examples of U.S. Patent
.. . . .. . . .. . . . . . .
~ '`3
4,690,956; and in U.S. Patent 4,524,157; all of which pat-
ents are herein incorporated by reference.
Non-graft polymer modified polyols are also pre-
ferred, for example those prepared by the reaction of a
polyisocyanate with an alkanolamine in the presence of a
polyol as taught by U.S. Patents 4,293,470; 4,296,213; and
4,374,209; dispersions of polyisocyanurates containing pend-
ant urea yroups as taught by U.S. patent 4,386,167; and
polyisocyanurate disper~ions also containing biuret linkages
as taught by U.S. patent 4,359,541. Other polymer modified
polyols may be prepared by the in situ size reduction of
polymers until the particle size i5 less than 20~m, prefer-
ably less than 10~m.
Also useful in preparing polyurethanes are mono-
mers containing other functional groups which are reactive
with isocyanates. Examples of these are preferably the
amines, for example the substituted and unsubstituted
toluenediamines and methylenedianilines; the alkanolamines;
the amino-terminated polyoxyalkylene polyethers; and sulf-
hydryl terminated polymers, to name but a few. The alkanol-
amines and amines, particularly diamines, are particularly
u~eful, as the amino group reacts faster than the hydroxyl
group and thus these molecule~ can act as isocyanate chain
-12-
.
2 J~ ~ r 3 J .J lj';
extenders in situ without the need to prepare prepolymers.
Examples of hindered, alkyl substituted aromatic diamines
which are particularly u6eful are disclosed in U.S. Patent
4,218,543.
Many i~ocyanates are u~eful in the preparation of
urethanes. Examples of such isocyanates may be found in
columns 8 and 9 of U.S. Patent 4,690,956, herein incorpor-
ated by reference. The i~ocyanates preferred are the
commercial isocyanates toluenediisocyanate (TDI) methylene-
diphenylenedii~ocyanate (~DI), and crude or polymeric MDI.
Other isocyanates which may be u~eful include isophorone-
diisocyanate and tetramethylxylylidenediisocyanate. Other
isocyanates may be found in the Polvurethane handbook,
Chapter 3, S3.2 pages 62-73 and Polvurethanes: Chemistry
and Technology Chapter II, ~ pages 17-31.
Modified isocyanates are also useful. Such iso-
cyanates are generally prepared through the reaction of a
commercial isocyanate, ~or example TDI or MDI, with a low
molecular weight diol or amine, or alkanolamine, or by the
reaction of the iEocyanates with themselves. In the former
case, isocyanates containing urethane, biuret, or urea link-
ages are prepared, while in the latter case isocyanates
containing allophanate, carbodiimide, or isocyanurate link-
ages are formed.
-13-
.. .
Chain extenders may also be useful in the prepara-
tion of polyurethanes. Chain extenders are generally con-
sidered ~o be low molecular weight polyfunctional compounds
or oligomers reactive with the isocyanate group. Aliphatic
glycol chain extenders commonly used include ethylene gly-
col, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.
Amine chain extenders include aliphatic monoamines but espe-
cially diamines such as ethylenediamine and in particular
the aromatic diamines such as the toluenediamine6 and the
alkylsubstituted (hindered) toluenediamines.
Other additives and auxiliaries are commonly used
in polyurethanes. These additives include plasticizers,
flow control agents, fillers, antioxidants, flame retard-
ants, pigment6, dyes, mold release agents, and the like.
Many ~uch additives and auxiliary materials are discussed in
the Polyurethane ~andbook in Chapter 3, ~ 3.4, pages 90-109;
and in Polyurethanes: Chemistry and Technoloqy, Part II,
Technology.
Polyurethanes may be prepared in the form of films
and coatings, fibers, extruded forms, castings and foams.
Non-cellular or microcellular polyurethanes are prepared in
substantial absence of blowing agents, while polyurethane
foams contain an amount of blowing agent which i8 ~ nver~ely
proportional to the desired foam density. ~lowing agents
may be physical (inert~ or reactive (chemical) blowing
agents. Physical blowing agents are well known to those in
the art and include a variety of saturated and unsaturated
hydrocarbons having relatively lo~ molecular weights and
bo;ling points. Examples are butane~ isobutane, pentane,
isopentane, hexane, and heptane. Generally the boiling
point is chosen such that the heat of the polyurethane-form-
ing reaction will promote volatilization.
The most commonly u~ed physical blowing agents,
however, are currently the halocarbons, particularly the
chlorofluorocarbons. Examples are methyl chloride, methyl-
ene chloride, trichlorofluoromethane, dichlorodifluoro-
methane, chlorotrifluoromethane, chlorodifluoromethane, the
chlorinated and fluorinated ethanes, and the like. Bromin-
ated hydrocarbons may ~lso be useful. Blowing agents are
listed in the Polvurethane ~andbook on page 101. Current
research is directed to lowering or eliminating the use of
chlorofluorocarbon~ in polyurethane foams.
Chemical blowing agents are generally low molec-
ular weight species which react with isocyanates to generate
carbon dioxide. ~ater is the only practical chemical blow-
ing agent, producing carbon dioxide in a one to one mole
-15-
?,~, "; ;
ratio based on water added to the foam formulation. Unfor-
tun~tely, completely water-blown foams have not proven
~uccessful in many applications, and thus it is common to
use water in conjunction with a physical blowing agent.
Blowing agents which are ~olids or liquids which
decompose to produce gaseous byproducts at elevated tempera-
tures can in theory be useful, but have not achieved commer-
cial success. Air, nitrogen, argon, and carbon dioxide
under pressure can also be used in theory, but have not
proven commercially viable. Research in such areas con-
tinues, particularly in view of the trend away from chloro-
fluorocarbons.
Polyurethane foams generally require a surfactant
to promote uniform cell sizes and prevent foam collapse.
Such 6urfactants are well known to tho~e skilled in the art,
and are generally polysiloxanes or polyoxyalkylene poly-
siloxanes. Such surfactants are described, for example, in
the Polyurethane ~andbook on pages 98-101. Commercial sur-
factants for these purposes are available from a number of
sources, for example from Wacker Chemie, the Union Carbide
corporation, and the Dow-Corning Corporation.
Processes for the preparation of polyurethane
foams and the equipment used therefore are well known to
-16-
.. .. . .... . . ..
G`J ' '~ : ~
i ! J !.~ }
those in the art, and are described, for example, in the
Polvurethane Handbook in Chapter 4, pages 117-160 and in
Polyurethanes: Chemistry and Technoloqv, Part II, Tech-
nology, in Chapter VII, SIII and IV on pages 7-116 and
Chapter VIII, SIII and IV on pages 201-23B.
The following Examples illustrate the nature of
the invention. All parts are by weight unless otherwise
designated. The following abbreviations were employed in
the Examples below~
Polyol A is a polyester derived from a phthalic
acid and diethylene glycol, having a hydroxyl number of
approximately 240, and a functionality of 2.
Polyol B is a polyester derived from phthalic acid
and ethylene glycol, having a hydroxyl number o approx-
imately 200, and a functionality of 2.
Polyol C is a polyester derived from diethylene
glycol and phthalic acid, having a hydroxyl number of
approximately 250, and a functionality of 2.
Polyol D is a polyethylene terephthalate ester
derived from PET scrap, having a hydroxyl number of approx-
imately 350, and a functionality of 2.
Polyol E is a mixture of dimethyl and diethylene
glycol esters of terephthalic acid, having a hydroxyl number
of approximately ~10, and a functionality of 2.
-17-
.
PVAc/AA i a random copolymer of polyvin,yl acetate
and allyl alcohol as prepared by Example 1.
DC 1~3 is a fiurfactant avail~le from Dow Corning,
Midland, Michigan as DC193.
"POLYCAT 8" is ~ diethylcyclo-hexylamine.
"FREON 11~ OR ~REON" is a fluorocarbon, preferably
~richlorofluoromethane.
Index is the -NCO/active hydrogen ratio multiplied
by 100.
"LUPRANATE" ~20S is a polymeric methylene di-
phenyldiisocyanate (MDI), containing about 40 percent 2-ring
MDI sold by BASF Corporation.
Mixing time is the period in seconds from the
start of mixing of the isocyanate and polyol components
until a homogeneous solution is achieved.
Gel time i~ the period in seconds from the start
of mixing of the isocyanate and polyol components until that
state is reached whereby the polyaddition product is no
longer flowable.
Ri6e time i8 the period in seconds from the start
of mixing of the isocyanate and polyol components until the
foam no longer rises.
-18-
r j ~
Tack free time is the period in seconds from the
start of mixing of the isocyanate and polyol components
until the 6urface of the foam is totally tack free.
The physical properties were determined using the
following ASTM standards: density - ASTM D1622; compression
strength - ASTM D1621; K-factor measured at 75P - ASTM
C177-85; porosity - ASTM D2856; Friability - ASTM C421-83.
-19-
Example 1
A polyvinyl acetate/allyl alcohol random copolymer
useful in the present invention was prepared by a free rad-
ical process utilizing a continuous process tubular reactor
system. The following reactants were utilized:
Vinyl acetate, 450 grams
Allyl alcohol, lS0 grams
Isopropyl alcohol, 340 grams
50 percent hydrogen peroxide, 70 grams.
The reactants were added in no special order to a 2,900 ml.
flask and then transferred to a water-cooled feeder vessel
and ~tirred. Nitrogen was bubbled through the reaction
mixture continuously. The mixture was gravity fed into a
diaphragm pump and transferred at 450 psi and at a rate of
300 ml per hour into a tubular reactor heated to 155C. The
resction mixture contact time elapsed from entry to e~it in
the tubular reactor was approximately 2 hours. A ~lightly
viscous yellow liquid was collected at the end of the tube
in a colle~tor ves6el. Volatiles were stripped off usiny a
rotary evaporator. The resulting viscous oil was dissolved
in ethyl acetate and neutralized to a p~ of 8 with aqueous
~odium bicarbonate. The organic layer was extracted, then
wa6hed with brine. The organic layer was collected and
-20-
. , , . . _ . .
G ~ ! S ~ e '
dried over sodium sulfate to give a 40-50 percent yield
after stripping off ethylene acetate. The resulting poly-
vinyl acetate/allyl alcohol random cspolymer was analyzed
with the following results:
Polyvinyl/allyl alcohol copolymer analytical
data: GPC WMn - 613 g/mole
OH Number = 217 mg KOH/g polyol
Percent ~2 = 0.19%
Saponification Number = 451 mg KO~/g polyol.
The polyvinyl acetate/allyl alcohol copolymer 50 formed is
hereafter referred to as PVAc/AAD
Exam~le 2
Rigid polyurethane foams were prepared having the
formulations and the physical characteristics indicated
below.
-21-
J ~.J ~1 ,J ~J ~:
,
TABLE A ..
Rigid ~Oam ~OrmU1atiOnS
EXAMPLE 1 2 3 4
POLYOL C 100 95 _- _
POLYOL B -~ 0Q 95
PVAC/AA -- 5 __ 5
DC_1g3 ~ . 5 1 . 5 1 . 5
P0LYCAT 8 ~.1 1.1 1.1 1.1
~IATE~ 2.0 2.0 2.0 2.0
~REON ~ 5 15 15 15
INDEX 105 105 105 105
LUPRANATE H20S 93.5 92.~ 81.1 80.9
MIX ~SEC~ ~ 3 ~ 3
CREAM tSEC~ 18 ~1 20 21
6EL (SEC~ 40 4~ 47 50
RSSE ~5~C) 52 ~;9 63 64
FR2A8SLIT)~ 0 0 0 0
DENSITY IPCF~ ~.98 1.82 1.96 1.93
POROS~ t%CC) 88.4 89.2 85.0 94.6
K-~ACTOR (0 DA'~5 ) .119 .120 ~,122 .121
K-FACTOR 110 D~YS) * .133 .117 .166 .134
* ~t 140F
.
' Z~ . ' ',
. . .
., . . . _ .. = , .. . , _. _ _ _ . _ . ... ... , ... .. . _ .... .
~ Jc
This Example ~hows that when 5 percent by weight
of polyvinyl acetate/allyl alcohol random copolymer was
added to a polyurethane 6ystems containing Polyol ~ or
Polyol C the resultin~ foam had a lower K-factor than corre-
sponding polyols containing solely Polyol B or Polyol C
respectively. The addition of the polyvinyl acetate/allyl
alcohol did not adver~ely affect the reaction parameters or
other physical properties such as density or porosity. K
factors were measured at 0 days and at 75~F.
-23-
.. . . . .. .
Example 3
In this Example, varying weight percents o~
PVAc~AA were added to a urethane system containing Polyol C.
The weight percent of water and Freon were also varied.
~ABLE E
Foam 5 6 7 8
Polyol C 100 95 90 80
PYAc/AA 0 5 10 20
DC-193 1.5 1.5 1.5 1.5
POLYCAT 8 0.8 0.8 0.B 0.B
Water 3 3 3 3
FRE~N F-llA 10 10 10 10
Total 115O3 115.3 115.3 115.3
Index 105 1~5 105 105
LUPRANATE M20S 109.1 109~00 10B.B3 108.66
Mix ~sec.] 7 7 7
Gel " 49 56 64 69
Rise " 68 74 78 88
Tack Free " 75 71 75 B0
Resin 149.9 149.9 149.9 149.9
Iso. 141.8 lql.7 141.6 141.3
Density, Core ~pcf) 1.98 1.42 1.62 1.62
Comp Str 10~ Par 50.3 25.3 25.8 26.0
Comp Str 10% Perp 6.2 4.4 4.9 4.3
K~factor, Orig 0.137 0.124 0~126 0.126
10 days* 0.138 0.125 0.126 0.125
30 days* 0.156 0.134 0.127 0.150
~t 140~
As can be seen from the above data, a urethane
system containing from 5 percent to 20 percent PVAc/ M , 3
percent water and 10 percent Freon consistently produced
lower ~-factors, at 0 days and after aging for 10 and 30
days at 140~, in comparison to urethane systems containing
solely Polyol C at 140F.
-25-
i;J'~
xample 4
In this Example, varying amounts of PVAc/AA were
added to a urethane system containing Polyol D.
TABLE C
Foam 9 10 11 12 13
Polyol D 100 98 95 90 80
PVAc/AA 0 2 5 10 20
D C 193 1.5 1.5 1.5 1.5 1.5
POLYCAT 8 0.8 0.8 0.8 0~8 0.8
Water 2 2 2 2 2
FREON F-llA 15 15 15 15 15
total 119.0 119.3 119.3 119.3 119.3
Index 105 105 105 105 105
LUPRANATE N20S 118.5 117.80 116.73 114.94 111.37
~ix [s~c.l 8 8 8 8 8
Gel " 48 30 34 34 34
Rise ~ 63 45 51 51 54
Tack Free " 72 39 42 40 44
Resin 154.7 155.1 155.1 155.1 155.1
Iso. 154.05 153.1 151.7 149.4 144.8
Density,Core~pcf) 2.09 2.04 2.12 2.05 2.02
Comp Str 10% Par 56.4 47.2 55.0 51.6 50.4
Comp Str 10% Perp 9.1 9.9 7.8 7.8 8.5
K-factor, Orig. 0.139 0.126 0.125 0.131 0.129
10 days* 0.1~9 0.124 0.116 0.126 0.127
30 days~ 0.148 0.131 0.131 0.133 0.138
at 140F
-26-
As can be seen from this example, the additi~n of
~ to 20 percent by weight PVAc/AA to a urethane systeM
containing Polyol D consi~tently produced lower K-factors at
0 days and after aging at 10 and 30 days compared to ure-
thane systems containing no PVAc/AA.
-27-
. .. . .. . . . , . _ .. , . , . . ~ . . _, . _ _ _ _ _ .. ~ , . .. . . _ . . . . . .. . . .
xample 5
In this example, varying amounts of PVAc/AA were
added to urethane systems containing Polyol E.
TABLE D
Foam 14 15 16 17 18
Polyol E 100 98 95 90 B0
PVAc/AA 0 2 5 10 20
D C 193 1.5 1.5 1.5 1.5 1.5
POLYCAT 8 0.32 0.8
Water 2 2 2 2 2
FREON F-llA 15 15 15 15 lS
total 120.4 119.3 119.5 119.5 119.5
Index 105 105 105 105 105
LUPR~NATE M20S 109.8 109.24 108.43 107.08 104.35
Mix lsec.l 5 8 8 8 8
Gel " 54 73 43 40 41
Rise " 70 95 58 58 63
Tack Free " 77 95 80 50 49
Resin 156.5 155.1 155.4 155.4 155.4
Iso. 142.7 142.0 141.0 139.2 135.7
Density 2.09 2.02 1.92 1.92 1.~7
Comp Str 10% Par 52.2 42.3 48.9 41.2 42.1
Comp Str 10% Perp 8.9 6.9 5.1 408 7.0
K-factor, Orig. 0.129 0.130 0.128 0.131 0.127
10 days* 0.133 0.128 0.126 0.126 0.125
30 days* 0.152 0.141 0.136 0.137 0.142
* at 140F
-28-
.. . . .
This example 6hows that the addition of 2, 5, 10,
or 20 percent PVAc/AA produces lower K-factors for aged
foams at 10 days and 30 days in comparison to urethane sy5-
tems containing Polyol E and no PVAc/AA. Lower K-factors
were observed in systems containing 5 percent or 20 percent
PVAc/AA and Polyol E compared to 6ystems containing no
PVAc/AA at 0 days. Slightly higher K-factors at 0 days were
observed in urethane systems c~ntaining 2 percent or 10
percent PVAc/AA and Polyol E in comparison t~ systems con-
taining no PVAc/AA.
2~-
.. , . . . . . . .. . . _ _ ., _ . ... ... _ ... . . , . ~ . . ..
Exam~le 6
In this example, varying amount~ of PVAc/AA were
added to urethane systems containing Polyol A.
TABLE E
Foam 19 20 21 22 23
Polyol A 100 98 95 ~0 80
PVAc~AA 0 2 5 10 20
D C 193 1~5 1.5 1.5 1.5 1.5
POLYCAT 8 0.8 0.8 0~8 0.8 0.8
Water 2 2 2 2 2
FREON F-llA 15 15 15 15 15
total 119.3 119.3 119.3 119.3 119.3
Index 105 105 105 105 105
LUPRANATE M20S 91 90.86 90.64 90.23 ~g.40
Mix lsec-l 5 8 8 8 8
Gel " 20 - 50 50 50
Rise " 52 - 73 72 74
Tack Free " 75 - 64 - 65
Resin 155.1 155.1 lS5.1 155.1 155.1
IBO . 118 . 3 11B .1 117 . 8 117 ~ 3 116 . 2
DenSitY 2.11 2-14 2-14 2-14 2-09
Comp Str 10% Par 41.0 35~4 34.6 37.7 38.9
Comp Str 10% Perp 3.1 6.7 7.2 6~7 8.0
K-factor, Ori~. 0.122 0.123 0.121 0.122 0.125
10 days* 0.137 0.145 0.123 0.125 0.136
30 days* 0.165 0.175 0.136 0.141 0.163
* at 140~F
-3~-
. .
As can be seenr the addition of 5 to 10 weight
percent PVAc/AA to a urethane system containing Po].yol A
produced lower K-factors and after aging 10 and 30 days as
compared to the urethane system containing no PVAc/AA.
-
_x~ l 7
In this example, a urethane foam was made using
solely PVAc/AA as the polyol component.
TABLE_F
Foam 24 25
PVAc/AA 100 100
D C 193 1.5 1.5
POLYCA~ 8 0.8 0.8
Water 2 3
Freon 11 A 17 12
Total 121.3 117.3
Index 105 105
LUPRANATE M20 84.31 99.87
Mix lsec.] 12 15
Gel n 116 B5
Tack Free " 182 147
Rise " 191 155
Density, Core (pcf) 1.61 1.79
Compression Strength
10% PAR 16.~ 21.1
10~ PERP 3.1 11.3
K-factor, original 0.147 0.153
10 days* 0.175 0.182
30 days* 0.190 0.203
* at 140~F
As can be seen, a rigid urethane foam can be pro-
duced using sole PVAc/AA a~ the polyol component. 5uch a
foam has useful thermal properties.
-32-
