Note: Descriptions are shown in the official language in which they were submitted.
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POLYMER POLYOL AND PREFORMED STABILIZER SYSTEMS
The present invention relates to a polymer polyols and a
process for the preparation thereof, and preformed stabilizer used for
the preparation of polymer polyols.
Polymer polyols suitable for the preparation of polyurethane
foams and elastomers are well known and are widely used on commercial
scale. Polyurethane foams made from polymer polyols have a wide
variety of uses. The two major types of polyurethane foams are slabstock
and moulded foam . Polyurethane slabstock foams are used in carpet,
furniture and bedding applications. Moulded polyurethane foams are
used in the automotive industry for variety of applications.
Polymer polyols are produced by polymerizing one or more
ethylenically unsaturated monomers dissolved or dispersed in a polyol in
the presence of a free radical catalyst to form a stable dispersion of a
polymer particles in the polyol. Initially, polymer polyols producing
polyurethane foams having higher load-bearing properties than those
produced from unmodified polyols were prepared using acrylonitrile
monomer; however, many of these polymer polyols had undesirably high
viscosity.
Presently, polyurethane foams having high load-bearing
properties are predominantly produced using polymer polyols which are
prepared using a high styrene content monomer mixture (e.g., 65 to 75
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percent styrene). However, polymer polyols produced from such high
styrene monomer mixture often do not satisfy the ever-increasing
industry needs, including acceptable viscosity, strict stability
requirements and increased load-bearing properties.
Stability and low viscosity of polymer polyols is of increasing
importance to polyurethane foam manufacturers due development of
sophisticated, high speed and large volume equipment and systems for
handling, mixing and reacting polyurethane-forming ingredients.
Polymer polyols must meet certain minimum polymer particles size
requirements to avoid filters, pumps and other parts of such foam
processing equipment becoming plugged or fouled in relatively short
periods of time,
Numerous attempts have been made to produce polymer
polyols which will meet foam processing and load-bearing properties
required by polyurethane foam industry.
U.S. Patent No. 4,242,249 (Van Cleve et al) describes polymer
polyols prepared by using certain preformed dispersants or stabilizers.
These polymer polyols provide stability satisfactory for commercial
production, and use of at least one of (i) high amounts of styrene or other
comonomer with acrylonitrile, (ii) higher solids contents or (iii) the use of
lower molecular weight polyols. The particular stabilizer used and the
concel ,tl dtion used vary with respect to the monomer system used in the
preparation of polymer polyols.
U.S. Patent No. 4,652,589 (Simroth et al) describes stabilizer
precursors for po!ymer polyols. Stabilizer A is made by reacting a 34
hydroxyl number, 15 weight percent ethylene oxide capped
polyoxypropylene triol with maleic anhydride and subsequently with
ethylene oxide. Stabilizer A has a hydroxyl number of 32, an
unsaturation of 0.1 meq/g, with the unsaturation being 30/70
maleate/fumarate. Stabilizer B is made by reacting a 28 hydroxyl number
sorbitol started polyol, containing 10 percent internal ethylene oxide,
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with maleic anhydride, and subsequently with propylene oxide.
Stabilizer B has a hydroxyl number of 28 and an unsaturation of
approximately 0.07 meq/g, with the unsaturation being of the fumarate
type.
U.S. Patent No 5,196,476 (Simroth) describes: (a) a high
potency preformed stabilizer; (b) the use of same in the manufacture of
polymer polyols having high solids content, lower viscosity and excellent
product stability; and (c) a polyurethane made using such polymer polyol.
The preformed stabilizer is the free radical polymerization product of at
least one free radically polimerizable ethylenically unsaturated monomer
and at least one polyhydric alcohol adduct comprising a polyhydric
alcohol residue and a residue of a compound having fumaric or maleic
type unsaturation.
U.S. Patent No. 5,364,906 (Critchfield et al) describes a method
for producing a stable, low viscosity polymer polyol via a modified seed
method bythe steps of (1) producing a first reaction product by
polymerizing a first feed in a first continuous reactor in the presence of
20 an initiator, the first feed comprising less than 50 weight percent of a
total monomer proportion in at least 50 weight percent of a total base
polyol proportion, optionally in the presence of a precursor stabilizer
which is prepared by reacting a polyol with maleic anhydride; and (2)
producing a second reaction product by polymerizing a second feed in a
25 continuous reactor in the presence of an initiator, the second feed
comprising (a) the first reaction product, (b) at least 50 weight percent of
the total monomer proportion, and (c) any balance of the base polyol
proportion.
European Patent No. 0 1 6Z 589 B1 (Cloetens et al) describes a
nonaqueous dispersion stabilizer which is the reaction product of a
polyether polyol having an average molecular weight greater than 400
and a hydroxyl number in the range of 20 to 280 with silicon atom
containing compound having at least least one olefinically unsaturated
functional group and at least one functional group attached to the
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silicon atom which is reactable with the hydroxyl groups on the polyether
polyol.
Additional prior art of interest include U.S. Patent No. Re.
32,733 (Simroth et al); U.S. Patent No.3,931,092 (Ramlow et al); U.S.
Patent No.4,014,846 (Ramlow et al); U.S. Patent No.4,093,~73 (Ramlow
et al); U.S. Patent No.4,148.840 (Shah); U.S. Patent No.4,172,825 (Shook
et al); U.S. Patent No.4,342,840 (Kozawa et al); U.S. Patent No.4,390,645
(Hoffman et al); U.S. Patent No. 5,394,491 (Hoffman); U.S. Patent No.
4,454,255 (Ramlow et al); U.S Patent No.4,458,038 (Ramlow et al); and
U.S. Patent No.4,745,153 (Hoffman).
Although there has been progress in reduction of viscosity and
increased in solids content of polymer polyols, there is still a need for
polymer polyols having improved processing and load-bearing properties
and for alternate method for making same.
The present invention is directed to a preformed stabilizer
composition and to the manufacture of polymer polyols therewith which
polymer polyols possess a combination of (a) high polymer content, from
30 weight percent to 60 weight percent, (b) lower viscosities, typically less
than 9,000 centipose, (c) product stability such that 100% passes through
a 150 mesh screen, and (d) up to 100% of the polymer solids content
passes through a 700 mesh screen.
In one aspect, the present invention concerns a preformed
stabilizer composition for use in the preparation of polymer polyols
comprising the reaction product of
(i) a polyol;
(ii) a precursor stabilizer obtainable by reacting a silicon atom
containing compound of formula
RnSiX4 n or RnSi((-OSi(R1)2)pX)4 n
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wherein the R groups are independently saturated or
unsaturated hydrocarbyl groups, at least one R group being an
olefinically unsaturated hydrocarbyl group; R1 is a hydrocarbyl
group, X is a C1 to C10 alkoxy group, n is an integer from 1 to 3
and p is an integer greaterthan zero, with a polyether polyol
having an average moiecular weight in excess of 400 and a
hydroxyl number in the range 20 to 280;
(iii) at least one ethylenically unsaturated monomer which is
copolymerizable with the precursor stabilizer; and
(iv) a free radical polymerization initiator.
In another aspect, the present invention concerns a process for
the preparation of the preformed stabilizer composition which process
lS comprises providing above mentioned composition components (i), (ii),
(iii) and (iv) in a reaction zone maintained at a temperature sufficient to
initiate a free radical polymerization, and under sufficient pressure to
maintain only liquid phases in the reaction zone, for a period of time
20 sufficient to react essentially all the precursor stabilizer and recovering a heterogenous mixture containing the preformed stabilizer composition.
In another aspect, the present invention concerns a polymer
polyol composition which has a polymer content of 30 to 60 weight
25 percent, based on total weight, a viscosity in centipose of not more than
8,000 and product stability such that essentially 1 Oû~/0 passes through a
150 mesh screen and up to 100% passes through a 700 mesh screen
produced by a free radical polymerization of the composition
comprising:~0
(a) a polyol;
(b) the above preformed stabilizer composition;
(c) at least one ethylenically unsaturated monomer;
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(d) a free radical polymerization initiator; and, optionally,
(e) a chain transfer agent.
In another aspect, the present invention concerns a process
5 for the preparatiPn of a polymer polyol composition which process
comprises providing above mentioned polymer polyol forming
composition components (a), (b), (c) and (d) in a reaction zone
maintained at a temperature sufficient to initiate a free radical
polymerization, and under sufficient pressure to maintain only liquid
10 phases in the reaction zone, for a period of time sufficient to react a
major portion of the ethylenically unsaturated monomer to for a
heterogenous mixture containing the polymer polyol and recovering
recovering same from this heterogenous mixture.
Yet in another aspect, the present invention concerns a
polymer polyol composition which possesses a polymer content of 30 to
60 weight percent, based on total weight, a viscosity in centipose of no
more than 8,000 and product stability such that essentially 100% passes
20 through a 150 mesh screen produced by a free radical polymerization of
the above polymer polyol forming composition.
Yet in another aspect, the present invention concerns a
polyurethane foam forming composition comprising the above polymer
25 polyol composition, a polyurethane catalyst, an organic polyisocyanate, a
silicone surfactant, and a blowing agent
Yet in another aspect, the present invention concerns a
polyurethane foam made from the above polyurethane foam forming
30 Composition~
Precursor stabilizers useful in the present invention are
obtained by reacting a silicon atom containing compound of formula
RnSiX4 n or RnSi((-OSi(Rl)2)pX)4 n
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wherein the R groups are independently saturated or unsaturated
hydrocarbyl groups, at least one R group being an olefinically
unsaturated hydrocarbyl group; R1 is a hydrocarbyl group, X is a C1 to C10
alkoxy group, n is an integer from 1 to 3 and p is an integer greater than
5 zero, with a polyether polyol having an average molecular weight in
excess of 400 and a hydroxyl number in the range 20 to 280. The
particularly preferred precursor stabilizers are the reaction products of
vinyltrimethoxy silane, vinyltriethoxy silane or vinyltripropoxy silane with
a polyetherpolyol having an average molecular weight in excess of 400
lO and a hydroxyl number in the range 20 to 280. These precursor stabilizers
and their preparation are described in European Patent No. 0 162 589 B1
(Cloetens et al).
The polyols used in the composition for preparing the
15 preformed stabilizer composition of this invention may be for example
polyether polyols, polyhydroxyl containing polyesters, polyhydroxyl
terminated polyurethane polymers, polyhydric polythioethers, and
polytetrahydrofurans. These polyols are well known and are
commercially available. The preferred polyols are the polyether polyols.
20 The polyether polyol used should have a number average molecular
weight in excess of 400, preferably from 3,000, more preferably from
5,000 and a hydroxyl number in the range 20 to 280. Most preferably, the
polyether polyol should be a poly (oxyethylene) (oxypropylene) adduct of
25 an alcohol selected from glycerol, trimethylolpropane, diethylene glycol,
the isomers of butanetriol, pentanetriol and hexanetriol and
pentaerythritol, sucrose and sorbitol. A mixture of polyols can be used, if
desired. The polyol concentration in the preformed stabilizer forming
composition is not critical and can be varied within wide limits. Typically,
30 the concentration can vary from 50 to 90 weight percent or even more,
preferably 60 to 70 weight percent, based on the total feed to the
reactor. A mixture of various useful polyols can be used, if desired.
Any ethylenically unsaturated monomer which is free radically
polymerizable can be used as component (iii) in the preformed stabilizer
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forming cornposition of this invention. It is preferred to use vinyl
monomers. Styrene, acrylonitrile, methacrylonitrile and methyl
methacrylate are preferred vinyl monomers. Most preferred vinyl
monomers are styrene, acrylonitrile and mixtures thereof. Typically, a
minimum of 2 to 20 percent by weight of an ethylenically unsaturated
5 monomer is used in the preformed stabilizer forming composition. When
a mixture of styrene and acrylonitrile is used, the weight proportion of
styrene can vary from 20 to 80 weight percent and acrylonitrile can
accordingly vary from 80 to 20 weight percent of the mixture. A styrene
10 to acrylonitrile ratio in the monomer mixture of from 80:20 to 20:80 is
preferred, with the ratio of from 70:30 to 50: 50 being most preferred.
The free radical polymerization initiator useful in the
preparation of the preformed stabilizer of this invention can be any
15 compounds which are routinely used to effect grafting of an ethylenically
unsaturated polymerto a polyol including peroxides, perborates,
persulphates, percarbonates and azo compounds. Typical examples of
such free radical initiators include, alkyl and aryl hydroperoxides, dialkyl
and diaryl peroxides, dialkylperoxydicarbonates and azobis(nitriles).
20 Preferred free radical initiators are terrt-butylperoxy diethyl acetate and
tert-butyl peroctoate. The free radical initiator concentration in the
preformed stabilizerforming composition is not critical and can be varied
within wide limits. Typically, the concentration can vary from 0.01 to 2.0
weight percent or even more, preferably 0.05 to 0.2 weight percent,
5 based on the total feed to the reactor. The particular free radical
initiator concer.l,dLion selected will usually be an optimum value
considering all factors, including costs.
Typically, the polyol is used in an amount of from 50 to less 80
30 weight percent, the precursor stabilizer in an amount of from 10 to less
than 50 weight percent, the monomer in an amount of from 5 to 15
weight percent and the free radical polymerization initiate in an amount
of from 0.01 to 2 weight percent in the preformed stabilizer forming
composition of t~is invention.
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The pcocess for preparing the preformed stabilizer is similar to
the process for preparing the polymer polyol. The temperature ran~e is
not critical and may vary from 80 ~C to 150 ~C. The preferred temperature
range is from 110 ~C to 130 ~C. The mixing conditions used are those
5 obtained using a back mixed reactor. The reactors of this type keep the
reaction mixture relatively homogenous and so prevent localized high
monomer to precursor stabilizer ratios such as occur in tubular reactors,
where all of the monomer is added at the beginning of the reactor.
The present invention also concerns the preparation of stable,
high solids polymer polyols compositions which have acceptable
viscosities.
The polymer polyol composition of the present invention
possesses a polymer content of from 30, preferably 40, most preferably 40
weight percent, to 50 weight percent, the remainder being liquid polyol.
Over the range of solids content, it can have a viscosity in centipose less
than 9,000. The polymer polyol compositions of the present invention
also show exceptional stability such that essentially 100 percent passes
through a 150 mesh screen and a significant amounts of high solids
content polymer polyol, essentially 100 percent passes through 700 mesh
screen. As shown in the examples, polymer polyol compositions having a
solids content of 42.2, 45.2, 40.6 and 41.8 percent, with a viscosity of
5550, 6800, 4950 and 3280 centipose, respectively, all passed essentially
100 percent through a 700 mesh screen.
The polymer polyol composition of the present invention is
the reaction product of the composition comprising: (a) a polyol; (b) the
preformed stabilizer composition of the present invention; (c) at least
30 one ethylenically unsaturated monomer; and (d) a free radical
polymerization initiator.
The process for preparing the polymer polyols of the present
invention comprises: (1) providing a heterogenous mixture of the
preformed stabilizer composition of the present invention in
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combination with a polyol, at least one free radically polymerizable
monomer and a free radical polymerization initiator, in a reaction zone
maintained at a temperature sufficient to initiate a free radical
polymerization reaction, and under sufficient pressure to maintain only
liquid phases in the reaction zone, for a period of time sufficient to react
5 a high proportion of the at least one ethylenically unsaturated monomer,
and recovering the resulting polymer polyol.
~ ny known polyol having a functionality of at least tvvo and a
molecular weight in excess of 400, preferably from 1,000 and 15,000,
10 more preferably from 2,00 to 8,000, and a hydroxyl number in the range
20 to 280 can be used for the preparation of polymer polyols of the
present invention. These polyols are well known and are available
commercially. The same or different polyol as the one used for the
15 preparation of the preformed stabilizer may be used for the preparation
of the polymer polyol composition of this invention. Useful polyols may
be for example polyether polyols, polyhydroxyl containing polyesters,
polyhydroxyl terminated polyurethane polymers, polyhydric
polythioethers, and polytetrahydrofurans. The pre~er,ed polyols are the
20 polyether polyols. Most preferably, the polyether polyol should be a poly
(oxyethylene) (oxypropylene) adduct of an alcohol selected from
glycerol, trimethylolpropane, diethylene glycol, the isomers of
butanetriol, pentanetriol and hexanetriol and pentaerythritol. The
polyol concentration in the polymer polyol forming composition is not
Z5 critical and can be varied within wide limits. Typically, the concentration
can vary from 40 to 80, preferably 45 to 70, more preferably from 50 to
60, weight percent, based on the total feed to the reactor. The particular
polyol used will depend on the end use of the polyurethane foam to be
30 produced. A mixture of various useful polyols can be used, if desired.
Any ethylenically unsaturated monomer which is free radically
polymerizable can be used as component (iii) in the preformed stabilizer
forming composition of this invention. It is preferred to use vinyl
monomers. Preferred vinyl monomers are styrene, acrylon;trile,
methacrylonitrile and methyl methacrylate. The most preferred vinyl
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monomers are styrene, acrylonitrile and mixtures thereof. Typically, a
minimum of 30 to 60 percent by weight of an ethylenically unsaturated
monomer is used in the preformed stabilizer forming composition. When
a mixture of styrene and acrylonitrile is used, the weight proportion of
styrene can vary from 80 to 20 weight percent and acrylonitrile can
5 accordingly vary from 80 to 20 weight percent of the mixture. A styrene
to acrylonitrile ratio in the monomer mixture of from 80:20 to 20:80 is
preferred, with the ratio of from 70:30 to 50: 50 being most preferred.
The free radical polymerization initiator useful in the
lO preparation of the preformed stabilizer of this invention can be any
compounds which are routinely used to effect vinyl polymerization
reaction including peroxides, perborates, persulphates, percarbonates
and azo compouflds. Typical examples of such free radical initiators
15 include, alkyl and aryl hydroperoxides, dialkyl and diaryl peroxides,
dialkylperoxydicarbonates and azobis(nitriles). Preferred free radical
initiators are 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(methylbutyro-
nitrile). The free radical initiator concer,tldlion in the polymer polyol
forming composition is not critical and can be varied within wide limits.
20 Typically, the concentration can vary from 0.01 to 5.0 weight percent,
preferably 0.01 to 2.0 weight percent, more preferably 0.05 to 0.2 weight
percent, based on the total feed to the reactor. The particular free
radical initiator concentration selected will usually be an optimum value
considering all factors, including costs.
If desired, any known chain transfer agent can be used in the
prepolymer stabilizer forming composition of the present invention.
Preferred chain transfer agents are monohydroxy alcohols because of
their ease of stripping from the final polymer polyol composition. The
~ most preferred chain transfer agent is isopropanol.
The polymer polyol forming composition is provided into the
reactor, preferably a continuous, stirred, back-mixed reactor. The
internal temperature of the reactor is controlled within a range of from
80 ~C to 150 ~C, preferably 110 ~C to 130 ~C. The contents of the reactor
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are well mixed with the residence time of at least 5 minutes, preferably
preferably from 15 to 45 minutes.
The polymer polyol composition of the present invention is
useful in the preparation of polyurethane foams. Such polyurethane
5 foams have improved load-bearing and tensile strength properties
without impairment of other physical properties of the foam.
The polyurethane foams are prepared by reacting the polymer
polyol composition of the present invention with a polyfunctional
10 organic isocyanate in the presence of a catalyst for the urethane forming
reaction, a blowing agent and a foam stabil;zer.
Polyfunctional organic isocyanates which can be used for the
preparation of the polyurethane foam are well known and are available
15 commercially. Illustrative examples of useful polyfunctional organic
isocyanates include the toluene diisocyanates, especially 2,4-and 2,6-
toluene diisocyanate (TDI) as well as any desired mixture of these
isomers; 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI) as well as any
desired mixture of these isomers; oligomers of MDI (polymeric MDI),
20 polymethylene polyphenyl polyisocyanates (commonly referred to as
"crude MDI"); mixtures of TDI and polymeric MDI and mixtures of the
these polyisocyanates. Prepolymers of the above isocyanate (e.g. with
polyether polyols, glycols or mixtures of these) can also be used in the
present invention. The preferred isocyanate is 80/20 TDI (a mixture of 80
percent 2,4-toluene diisocyanate and 20 percent 2,6-toluene
diisocyanate). Polyfunctional isocyanates are used in amounts well
known to skilled persons.
Any of the known blowing agents conventionally used in the
production of polyurethane foams can be used. Suitable blowing agents
include water and halogenated hydrocarbons of low molecular weight.
The blowing agents are used in amounts well known to skilled persons.
Any of the polyurethane catalysts normally used in the
preparation of polyurethane foams may be used in the process of the
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present invention including tertiary amines and organometallic
compounds. The polyurethane catalyst is used in amounts well known to
skilled persons. Mixtures of polyurethane catalysts may also be employed
in the process of the present invention.
Any of the foam stabilizers or surfactants for cell stability or
other cell size control agents normally used in the preparation of
polyurethane foams can be used in the present invention. The foam
stabilizers, surfactants for cell stability or other cell control agents are
used in amounts well known to skilled persons. Mixtures of one one or
more stabilizers and/or one or more surfactants may also be used.
Suitable surfactants include the diverse silicone surfactants, preferably
those which are block copolymers of a polysiloxane and a
polyoxyalkylene as described in U.S. Patent 3,629,308.
Known crosslinkers may also be used in the process of the
invention to modify polyurethane foam properties. These crosslinkers
are used in amounts well known to skilled persons.
in addition to the above mentioned materials, any number of
20 a variety of additives conventionally used in the production of
polyurethane foams such as, for example, fire retardants, defoamers, anti
oxidants, mold release agents, dyes, pigments and fillers can also be used
in the process of the present invention. These additives are used in
25 amounts well known to skilled persons.
The following designations, symbols, terms and abbreviations
are used in the Examples below:
CP-3040 is a glycerine started polyol having hydroxyl number in
the range of 54 to 59 and Average Molecular Weight of
3,000 and viscosity at 25 ~C of 490 cps, available from The
Dow Chemical Company under the trademark VORANOL
CP-3040.
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14
CP-4702 is a glycerine started polyol having hydroxyi number in
the range of 33-38 and Average Molecular Weight of
4,700 and viscosity at 25 ~C of 820 cps, available from The
Dow Chemical Company under the trademark VORANOL
CP-4702.
DNC-635.04 is a sorbitol started polyol having hydroxyl number of 30
and Average Molecular Weight of 7000.
VTMSP vinyltrimethoxy silane modified precursor stabilizer
prepared according to Example 3 of EP-0 162 589 B1.
Trigonox 27 is a free radical polymerization initiator sold by Akzo
Chemie under the trademark TRIGONOX 27.
Vazo 67 is a 2,2'-Azobis(2-methylbutanenitrile) polymerization
catalyst made by E.J. duPont de Nemours and Co.
Dabco 33LV a 33 percent solution of triethylene diamine in
dipropylene glycol, sold by Air Products and Chernicals
Inc. under the trademark DABCO 33LV.
Niax A-107 is a formic-acid-blocked version of 70% bis(2-
dimethylaminoethyl)etherl30% dipropylene glycol
amine catalyst available from Union Carbide Corp. under
the trademark NIAX A-107.
DEOA is Diethanolamine.
DC-5164 is a silicone surfactant sold by Dow Corning Corporation.
IPA is isopropanol.
TDI-80 is a 80:Z0 mixture of the Z,4- and 2,6-toluene
diisocyanate isomers sold bythe Dow Chemical Company
under the trademark Voranate T80.
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Index is the ratio of the amount of reactive isocyanate groups
in the reaction mixture divided by the amount of active
hydrogen groups in the reaction mixture multiplied by
100.
STN is Styrene.
ACN is Acrylonitrile.
Properties of the polymer polyol composition and
10 polyurethane foams given in the Examples below are determined
according to the following test methods:
Air Flow (cfm) is measured according to the ISO 7231 test method
(on AMSCOR foam porosity instrument).
Density is measured according to the DIN 53420 test
method.
CFD 40% (kPa) is Compression Force Deflection determined
according to DIN 53577.
IFD 25% (N) is lndentation Force Deflection 25% determined
according to ASTM D-3574, Test B1 and B2.
IFD 40% (N) is lndentation Force Deflection 40% determined
according to ASTM D-3574, Test B1 and B2.
IFD 65% (N) is Indentation Force Deflection 65% determined
according to ASTM D-3574, Test B1 and B2.
SAG factor is Indentation Force Deflection 65% divided by
Indentation Force Deflection 25%.
Tensile Strength (kPa) is determined in accordance with ASTM D-
3574.
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16
Elongation (%) is determined in accordance with ASTM D-3574,
Test E.
Tear Strength (N/m) is determined in accordance with ASTM D-3574.
Filterability is Filtration Hindrance determined by diluting one
part by weight sample (e.g. 470 9) of polymer
polyol with two parts by weight anhydruous
isopropanol (e.g. 960 9) to remove any viscosity-
imposed limitations and using a fixed quantity of
material in relation to fixed cros-sectional area of
screen, such that all of the polymer polyol and
isopropanol solution passes by gravitythrough a
1 50-mesh or 700-mesh screen. The 1 ~-mesh screen
has a square mesh with average mesh opening of
105 microns and is a UStandard Tyler" 150 square-
mesh screen. The 700-mesh screen i5 made with a
Dutch twill weave. The actual screen used had a
nominal opening of 30 microns. The amount of
sample which passes through the screen within
3000 seconds is reported as percent, a value of 100
percent indicates that over 99 weight percent
passed through the screen
Viscosity is measured using a Brookfield viscometer, spindle
?~ LVVT3, speed 12, in accordance with ASTM D-
4874.
The following examples are given to illustrate the invention
30 and should not be interpreted as limiting it in any way. Unless stated
otherwise, all parts and percentages are given by weight.
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17
EXAMPLES 1 AND 2
PREPARATION OF PREFORMED STABILIZER
The preformed stabilizer was prepared in a continuous
5 polymerization reactor empolying a tank reactor fitted with baffles and
impeller. The feed components were pumped into the reactor
continuously after going through an in line mixer to assure complete
mixing of the feed components before entering the reactor. The
contents of the reactor were well mixed. The internal temperature of the
10 reactor was controiled to within 1 ~C. The product flowed out the top of
the reactor and into a second unagitated reactor also controlled within
1~C. The product then flowed out the top of the second reactor
continuously through a back pressure regulator that had been adjusted
15 to maintain at least 6~ psig pressure on both reactors. The preformed
stabilizer then flowed through a cooler into a collection container. The
preformed stabilizer feed compositions are shown in Tab!e 1 below.
Table 1
Example 1 2
Formulation:
CP-4702 parts 45.8 0
DNC 63~.04 parts 0 81.8
VTMSP parts 46.0 10.0
Trigonox 27 parts 0.2 0.2
STY parts 5.6 5.6
ACN parts 2.4 2.4
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EXAMPLES 3 TO 9
PREPARATION OF POLYMER POLYOL COMPOSITION
The polymer polyol of the present invention was prepared
using a continuous polymerization system, using a tank reactor fitted
with baffles and impeller. In Examples 3 to 4 and 6 to 9, the polymer
10 polyol composition feed components were pumped into the reactor
continuously after going through an in line mixer to assure complete
mixing of the feed components before entering the reactor. The
contents of the reactor were well mixed. The internal temperature of the
reactor was controlled to within 1~C. The product flowed outthe top of
15 the reactor and into a second unagitated reactor also controlled within
1 ~C. The product then flowed out the top of the second reactor
continuously through a back pressure regulator that had been adjusted
to give about 45 psig pressure on both reactors. The crude polymer
polyol product then flowed through a cooler into a collection vessel.
20 Percent by weight polymer in the polymer polyol was determined from
analysis of the amount of unreacted monomers present in the crude
product. The crude product was vacuum stripped to remove volatiles
before testing. The polymer polyol in Example 5 was prepared by the
25 same procedure as used in Examples 3 to 4 and 6 to 9 except that the
preformed stabilizer was continuouslyfed into the polymer polyol
forming reactor from the reactor it was prepared in while the rest of the
polymer polyol composition feed was pumped into the same reactor. All
the polymer polyols produced were stable compositions. The polymer
30 polyol feed compositions, preparation conditions and polymer polyol
properties are shown in Table 2 below.
S~ S;~ ITE SHEET ~RULE 26)
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Table 2
Example 3 4 5 6 7 8 9
Formulation:
CP-4702 parts50.6 48.3 50.3 0 44.3 49.8 50.6
CP-3040 parts 0 0 0 51.6 0 0 0
Preformed parts 3.8 3.3 3.8 3.8 6.6 4.3 o
Stabilizer of Ex.1
Preformed parts 0 0 0 0 0 0 3.8
Stabilizer of Ex.2
Vazo 67 parts 0.4 0.4 0.4 0.4 0.4 0.41 0.41
STY parts24.3 26.0 24.5 28.9 24.2 24.5 24.3
ACN parts16.2 17.3 16.3 12.4 19.8 16.3 16.2
IPA parts 4.7 4.7 4.7 2.9 4.7 4.7 4.7
Prep. Conditions
React. Temp. ~C 125 125 125 125 115 115 125
Monomer in total wt% 40.5 43.3 40.8 41.3 44 40.8 40.5
feed
Ratio ACN/STY 40t60 40/60 40/60 30/70 45/55 40/60 40/6C
Residual STY parts0.22 0.22 1.3 1.12 0.10 0.3 0.2
Residual ACN parts0.78 0.76 1.64 0.52 0.30 0.9 0.8
Total polymer wt% 42.2 45.2 40.6 41.8 45.9 41.7 41.4
Product
Properties
Viscosity cps 5550 6800 4950 3280 8780 6180 5200
Filterability:
150-mesh % 100 100 100 100 100 100 100
700-mesh % 100 100 100 100 100 100 100
SIJ~ 111 ~JTE SHEET (RULE 26)
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EXAMPLES 1 0 TO 11
PREPARATION OF POLYURETHANE FOAMS
Polyurethane foams were produced by pouring foam
formulations shown in Table 3 below into an aluminum, 16 liter
(40x40x10 cm), 4 vent holes mould heated to a temperature of about 60
l0 oc using Admiral high pressure pouring machine DHF-I and Krauss Maffei
MK12-12/1 6-UL-2K Duplex mixing head and allowing the foam to rise
and curing. The foam demould time was 5 minutes. Kluber 91 8/9K mould
release agent (sold by Kluber A6) was used as the mould release agent.
15 The polyol component/isocyanate component tanks pressure was 3 bars.
Both the polyol component and isocyanate components were dispensed
at about 150 bars pressure. Polymer Polyol A used in the foam
formulation shown in Table 3 below is the polymer polyol produced in
Example 3 herein, diluted with CP-4702 base polyol. Polymer Polyol A has
20 viscosity (at 25 ~C) of 3,000 cps and a solids content of 28 weight percent.
Polymer Polyol B used in the foam formulation shown in Table 3 below is
the polymer polyol produced in Example 3 herein, diluted with CP-4702
base polyol. Polymer Polyol B has viscosity (at 25 ~C) of 3,400 cps and a
solids content of 33 weight percent.Foam formulations and foam
25 properties are shown in Table 3 below. As can be seen from Table 3
below, polyurethane foams prepared in Examples 10 and 11 using a the
polymer polyol of the present invention exhibit high load-bearing
characteristics without any significant loss in other physical
30 characteristics.
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Table 3
Example 10 11
Polyol Component:
Copolymer Polyol A parts 100 0
Copolymer Polyol B 0 100
water parts 3.6 3.6
DEOA (10~%) parts 1.6 1.6
Niax A-107 parts 0.Z 0.2
Dabco 33LV parts 0.2 0.2
lS DC-5164 parts 1.1 1.1
Isocyanate Component
TDI-80 Index 80 80
Foam Properties:
Core Density kg/m335.4 34.8
C.F.D 40% kPa 4.11 4.86
I.F.D.25% N 127 156
I.F.D.40% N 207 251
I.F.D.65% N 449 556
I.F.D.65%/l.F.D.25% 11.61 13.96
Tensile Stréngth kPa 181 166
Elongation % 116 99
Tear Strength Ntm 328 348
SU,.~ 1 l l ~ITE SHEE~ (RULE 26)
