U.S. patent application number 14/735552 was filed with the patent office on 2016-12-15 for novel polymer polyol compositions, a process for preparing these novel polymer polyol compositions, flexible foams prepared from these novel polymer polyols and a process for the preparation of these flexible foams.
This patent application is currently assigned to Bayer MaterialScience LLC. The applicant listed for this patent is Bayer MaterialScience LLC. Invention is credited to Rick L. Adkins, Brian L. Neal.
Application Number | 20160362519 14/735552 |
Document ID | / |
Family ID | 56148733 |
Filed Date | 2016-12-15 |
United States Patent
Application |
20160362519 |
Kind Code |
A1 |
Adkins; Rick L. ; et
al. |
December 15, 2016 |
NOVEL POLYMER POLYOL COMPOSITIONS, A PROCESS FOR PREPARING THESE
NOVEL POLYMER POLYOL COMPOSITIONS, FLEXIBLE FOAMS PREPARED FROM
THESE NOVEL POLYMER POLYOLS AND A PROCESS FOR THE PREPARATION OF
THESE FLEXIBLE FOAMS
Abstract
This invention relates to novel polymer polyols, to a process
for preparing these novel polymer polyols, to flexible polyurethane
foams comprising these novel polymer polyols, and to a process for
the production of these flexible polyurethane foams. These novel
polymer polyols provide unexpected improvements in foams prepared
therefrom.
Inventors: |
Adkins; Rick L.;
(Canonsburg, PA) ; Neal; Brian L.; (Pittsburgh,
PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Bayer MaterialScience LLC |
Pittsburgh |
PA |
US |
|
|
Assignee: |
Bayer MaterialScience LLC
|
Family ID: |
56148733 |
Appl. No.: |
14/735552 |
Filed: |
June 10, 2015 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 2101/0083 20130101;
C08G 2101/005 20130101; C08J 9/125 20130101; C08F 283/06 20130101;
C08G 18/7671 20130101; C08J 2375/08 20130101; C08G 2101/0008
20130101; C08G 18/71 20130101; C08G 18/4072 20130101; C08G 65/34
20130101; C08F 290/067 20130101; C08G 18/4841 20130101; C08J 9/0042
20130101; C08G 18/4837 20130101; C08G 18/632 20130101; C08G 18/7621
20130101 |
International
Class: |
C08G 65/34 20060101
C08G065/34; C08J 9/00 20060101 C08J009/00; C08J 9/12 20060101
C08J009/12 |
Claims
1. A polymer polyol composition having a solids content of from 10
to 72% by weight, and comprising (A) a polymer polyol having a
solids content of from 44 to 75% by weight, a viscosity at
25.degree. C. of less than 50,000 mPas, and which comprises the
reaction product of: (1) at least one base polyol having a
functionality of from 2 to 8 and a hydroxyl number of from 20 to
400; (2) one or more ethylenically unsaturated monomers; (3) a
preformed stabilizer which comprises the reaction product of: (a) a
macromer that contains reactive unsaturation and comprises the
reaction product of: (i) a starter compound having a functionality
of 2 to 8 and a hydroxyl number of from 20 to 50; (ii) 0.1 to 3% by
weight, based on 100% by weight of the sum of components (i), (ii)
and (iii), of a hydroxyl-reactive compound that contains reactive
unsaturation; and (iii) 0.05 to 3% by weight, based on 100% by
weight of the sum of components (i), (ii) and (ill), of
diisocyanate; with (b) one or more ethylenically unsaturated
monomers; and (c) at least one free radical initiator; in the
presence of (d) a polymer control agent; and, optionally, (e) a
liquid diluent; in the presence of (4) at least one free radical
initiator; and, optionally, (5) a chain transfer agent; and (B) at,
least one polyol component having a functionality of from 1 to 8
and a hydroxyl number of from 20 to 400; wherein component (B) is
present in an amount sufficient to reduce the total solids content
in said polymer polyol (A) by at least 5% by weight.
2. The polymer polyol composition of claim 1, wherein (A)(3)(a)
said macromer comprises the reaction product of (i) a starter
compound having a functionality of 3 to 6 and a hydroxyl number of
from 25 to 40; (ii) 0.1 to 3% by weight, based on 100% by weight of
the sum of components (i), (ii) and (iii), of a hydroxyl-reactive
compound that contains reactive unsaturation that is selected from
the group consisting of isopropenyl dimethyl benzyl isocyanate,
methyl methacrylate, maleic anhydride, adducts of isophorone
diisocyanate and 2-hydroxyethyl methacrylate and mixtures thereof;
(iii) 0.1 to 3% by we based on 100% by weight of the sum of
components (i), (ii) and (iii), of one or more isomers of
diphenylmethane diisocyanate.
3. The polymer polyol composition of claim 1, wherein (A)(3)(a)(i)
said starter contains from 1 to 40% by weight, based on 100% by
weight of (A)(3)(a)(i), of ethylene oxide which is added either as
a co-feed or as a cap.
4. The polymer polyol composition of Claim 1, wherein (A)(3)(b)
said one or more ethylenically unsaturated monomers comprises a
mixture of styrene and acrylonitrile.
5. The polymer polyol composition of Claim wherein (A)(3)(b) said
mixtures of styrene and acrylonitrile is present in a weight ratio
of from 20:80 to 80:20.
6. The polymer polyol composition of claim 1, wherein (A)(3)(c)
said free radical initiator is selected from the group consisting
of azo compounds and peroxide compounds.
7. (canceled)
8. The polymer polyol composition of claim 1, wherein (A)(2) said
ethylenically unsaturated monomers comprises styrene and
acrylonitrile in a weight ratio of 80:20 to 20:80.
9. The polymer polyol composition of claim 1, wherein (A)(1) said
base polyol has a functionality of from 3 to 6 and a hydroxyl
number of from 25 to 200.
10. The polymer polyol composition of claim 1, wherein (A)(4) said
free radical initiator is selected from the group consisting of azo
compounds, peroxide compounds and mixtures thereof.
11. The polymer polyol composition of claim 1, wherein (B) said
polyol has a functionality of from 2 to 6 and an OH number of from
25 to 200.
12. The polymer polyol composition of claim 1, wherein component
(B) is present in an amount sufficient to reduce the total solids
content in said polymer polyol (A) by at least 33% by weight.
13. The polymer polyol composition of claim 1, wherein component
(B) is present in an amount sufficient to reduce the total solids
content in said polymer polyol (A) by at least 61% by weight.
14. A polymer polyol composition having a solids content of from 10
to 72% by weight, and comprising (A) a polymer polyol having a
solids content of from 44 to 75% by weight, a viscosity at
25.degree. C. of less than 50,000 mPas, and which comprises the
reaction product of: (1) at least one base polyol having a
functionality of from 2 to 8 and a hydroxyl number of from 20 to
400; (2) one or more ethylenically unsaturated monomers; (3) a
preformed stabilizer which comprises the reaction product of: (a) a
macromer that contains reactive unsaturation and comprises the
reaction product of: (i) a starter compound having a functionality
of 2 to 8 and a hydroxyl number of from 20 to 50; (ii) 0.1 to 3% by
weight, based on 100% by weight of the sum of components (i), (ii)
and (iii), of a hydroxyl-reactive compound that contains reactive
unsaturation; and (iii) 0.05 to 3% by weight, based on 100% by
weight of the sum of components (i), (ii) and (iii), of
diisocyanate comprising one or more isomers of diphenylmethane
diisocyanate or an isomeric mixture of diphenylmethane
diisocyanate; with (b) one or more ethylenically unsaturated
monomers; and (c) at least one free radical initiator; in the
presence of (d) a polymer control agent; and, optionally, (e) a
liquid diluent; in the presence of (4) at least one free radical
initiator; and, optionally, (5) a chain transfer agent; and (B) at
least one polyol component having a functionality of from 1 to 8
and a hydroxyl number of from 20 to 400; wherein component (B) is
present in an amount sufficient to reduce the total solids content
in said polymer polyol (A) by at least 5% by weight.
15. A process for preparing a novel polymer polyol composition
comprising: (I) blending: (A) a polymer polyol having a solids
content of from 44 to 75% by weight, a viscosity at 25.degree. C.
of less than 50,000 mPas, and which comprises the reaction product
of: (1) at least one base polyol having a functionality of from 2
to 8 and a hydroxyl number of from 20 to 400; (2) one or more
ethylenically unsaturated monomers; (3) a preformed stabilizer
which comprises the reaction product of: (a) a macromer that
contains reactive unsaturation and comprises the reaction product
of: (i) a starter compound having a functionality of 2 to 8 and a
hydroxyl number of from 20 to 50; (ii) 0.1 to 3% by weight, based
on 100% by weight of the sum of components (i), (ii) and (iii), of
a hydroxyl-reactive compound that contains reactive unsaturation;
and (iii) 0.05 to 3% by weight, based on 100% by weight of the sum
of components (i), (ii) and (iii), of diisocyanate; with (b) one or
more ethylenically unsaturated monomers; and (c) at least one free
radical initiator; in the presence of (d) a polymer control agent;
and, optionally, (e) a liquid diluent; in the presence of (4) at
least one free radical initiator; and, optionally, (5) a chain
transfer agent; and (B) at least one polyol component having a
functionality of from 1 to 8 and a hydroxyl number of from 20 to
400; wherein component (B) is present in an amount sufficient to
reduce the total solids content in said polymer polyol (A) by at
least 5% by weight.
16. A flexible polyurethane foam comprising the reaction product
of: (I) one or more diisocyanates, polyisocyanates or mixtures
thereof; with (II) an isocyanate-reactive component comprising the
polymer polyol composition of claim 1; in the presence of (III) one
or more catalysts; (IV) one or more blowing agents; and,
optionally, (V) one or more surfactants.
17. A process for the production of a flexible polyurethane foam
comprising reacting: (I) one or more diisocyanates, polyisocyanates
or mixtures thereof; with (II) an isocyanate-reactive component
comprising the polymer polyol composition of claim 1; in the
presence of (III) one or more catalysts; (IV) one or more blowing
agents; and, optionally, one or more surfactants.
18. The flexible polyurethane foam of claim 16, which is
characterized by an increased solids efficiency at X% IFD as
measured in accordance with ASTM D3574, wherein X% IFD equals 25%
IFD, 50% IFD or 65% IFD.
19. The process for the production of a flexible polyurethane foam
of claim 17, wherein the resultant flexible foam is characterized
by an increased solids efficiency at X% IFD as measured in
accordance with ASTM D3674, wherein X% IFD equals 25% IFD, 50% IFD
or 65% IFD.
Description
BACKGROUND OF THE INVENTION
[0001] This invention relates to novel polymer polyol compositions,
to a process of making these novel polymer polyol compositions, to
polyurethane foams prepared from these polymer polyol compositions
and to a process for the preparation of these polyurethane
foams.
[0002] Polymer polyols are known to be useful in preparing
polyurethane foams, including flexible foams. The general trend in
foam properties of polyurethane foams which are prepared from a
high solids content (i.e. at least 30% by weight solids) SAN
polymer polyols is that the solids efficiency (i.e. the foam
hardness per unit of SAN solids) decreases as the % by weight of
solids in the polymer polyol increases.
[0003] It has been surprisingly found that the novel polymer
polyols described herein can be used to prepare flexible
polyurethane foams in which both foam load bearing (firmness) and
foam set properties are improved compared to conventional
polyurethane foams.
SUMMARY OF THE INVENTION
[0004] This invention relates to novel polymer polyol compositions.
These novel polymer polyol compositions have a solids content of
from 10 to 72% by weight, and comprise [0005] (A) a polymer polyol
having a solids content of from 30 to 75% by weight, a viscosity at
25.degree. C. of less than 50,000 mPas, and which comprises the
reaction product of: [0006] (1) at least one base polyol having a
functionality of from 2 to 8 and a hydroxyl number of from 20 to
400; [0007] (2) a mixture of ethylenically unsaturated monomers;
[0008] (3) a preformed stabilizer which comprises the reaction
product of: [0009] (a) a macromer that contains reactive
unsaturation and comprises the reaction product of: [0010] (i) a
starter compound having a functionality of 2 to 8 and a hydroxyl
number of from 20 to 50; [0011] (ii) 0.1 to 3% by weight, based on
100% by weight of the sum of components (i), (ii) and (iii), of a
hydroxyl-reactive compound that contains reactive unsaturation; and
[0012] (iii) 0 to 3% by weight, based on 100% by weight of the sum
of components (i), (ii) and (iii), of a diisocyanate; with [0013]
(b) one or more ethylenically unsaturated monomers; and [0014] (c)
at least one free radical initiator; in the presence of [0015] (d)
a polymer control agent; and, optionally, [0016] (e) a liquid
diluent; in the presence of [0017] (4) at least one free radical
initiator; and, optionally, [0018] (5) a chain transfer agent; and
[0019] (B) at least one isocyanate-reactive component having a
functionality of from 1 to 8 and a hydroxyl number of from 20 to
400; wherein component (B) is present in an amount sufficient to
reduce the total solids content in said polymer polyol (A) by at
least 5% by weight.
[0020] The present invention also relates to a process for
preparing the above novel polymer polyol compositions. This process
comprises: [0021] (I) blending: [0022] (A) a polymer polyol having
a solids content of from 30 to 75% by weight, a viscosity at
25.degree. C. of less than 50,000 mPas, and which comprises the
free radical polymerization product of: [0023] (1) at least one
base polyol having a functionality of from 2 to 8 and a hydroxyl
number of from 20 to 400; [0024] (2) a mixture of ethylenically
unsaturated monomers; [0025] (3) a preformed stabilizer which
comprises the reaction product of: [0026] (a) a macromer that
contains reactive unsaturation and comprises the reaction product
of: (i) a starter compound having a functionality of 2 to 8 and a
hydroxyl number of from 20 to 50; (ii) 0.1 to 3% by weight, based
on 100% by weight of the sum of components (i), (ii) and (iii), of
a hydroxyl-reactive compound that contains reactive unsaturation;
and (iii) 0 to 3% by weight, based on 100% by weight of the sum of
components (i), (ii) and (iii), of a diisocyanate; [0027] with
[0028] (b) one or more ethylenically unsaturated monomers; and
[0029] (c) at least one free radical initiator; in the presence of
[0030] (d) a polymer control agent; and, optionally, [0031] (e) a
liquid diluent; in the presence of [0032] (4) at least one free
radical initiator; and, optionally, [0033] (5) a chain transfer
agent; and [0034] (B) at least one isocyanate-reactive component
having a functionality of from 1 to 8 and a hydroxyl number of from
20 to 400; wherein component (B) is present in an amount sufficient
to reduce the total solids content in said polymer polyol (A) by at
least 5% by weight.
[0035] This invention also relates to a flexible polyurethane foam
comprising the reaction product of: [0036] (I) one or more
diisocyanates, polyisocyanates or mixtures thereof; with [0037]
(II) an isocyanate-reactive component that comprises the novel
polymer polyol compositions described herein; [0038] (III) one or
more catalysts; [0039] (IV) one or more blowing agents; and,
optionally, [0040] (V) one or more surfactants.
[0041] The present invention also relates to a process for
preparing a flexible polyurethane foam by reacting: [0042] (I) one
or more diisocyanates, polyisocyanates or mixtures thereof; with
[0043] (II) an isocyanate-reactive component comprising the polymer
polyol composition of claim 1; in the presence of [0044] (III) one
or more catalysts; [0045] (IV) one or more blowing agents; [0046]
(V) and, optionally, [0047] (VI) one or more surfactants.
[0048] In another embodiment of the invention, the novel polymer
polyol compositions. These novel polymer polyol compositions have a
solids content of from 10 to 72% by weight, and comprise [0049] (A)
a polymer polyol having a solids content of from 44 to 75% by
weight, a viscosity at 25.degree. C. of less than 50,000 mPas, and
which comprises the reaction product of: [0050] (1) at least one
base polyol having a functionality of from 2 to 8 and a hydroxyl
number of from 20 to 400; [0051] (2) a mixture of ethylenically
unsaturated monomers; [0052] (3) a preformed stabilizer which
comprises the reaction product of: [0053] (a) a macromer that
contains reactive unsaturation and comprises the reaction product
of: [0054] (i) a starter compound having a functionality of 2 to 8
and a hydroxyl number of from 20 to 50; [0055] (ii) 0.1 to 3% by
weight, based on 100% by weight of the sum of components (i), (ii)
and (iii), of a hydroxyl-reactive compound that contains reactive
unsaturation; and [0056] (iii) 0 to 3% by weight, based on 100% by
weight of the sum of components (i), (ii) and (iii), of a
diisocyanate; with [0057] (b) one or more ethylenically unsaturated
monomers; and [0058] (c) at least one free radical initiator; in
the presence of [0059] (d) a polymer control agent; and,
optionally, [0060] (e) a liquid diluent; in the presence of [0061]
(4) at least one free radical initiator; and, optionally, [0062]
(5) a chain transfer agent; and [0063] (B) at least one
isocyanate-reactive component having a functionality of from 1 to 8
and a hydroxyl number of from 20 to 400; wherein component (B) is
present in an amount sufficient to reduce the total solids content
in said polymer polyol (A) by at least 5% by weight.
DETAILED DESCRIPTION OF THE INVENTION
[0064] Various embodiments are described and illustrated in this
specification to provide an overall understanding of the structure,
function, properties, and use of the disclosed inventions. It is
understood that the various embodiments described and illustrated
in this specification are non-limiting and non-exhaustive. Thus,
the invention is not limited by the description of the various
non-limiting and non-exhaustive embodiments disclosed in this
specification. The features and characteristics described in
connection with various embodiments may be combined with the
features and characteristics of other embodiments. Such
modifications and variations are intended to be included within the
scope of this specification. As such, the claims may be amended to
recite any features or characteristics expressly or inherently
described in, or otherwise expressly or inherently supported by,
this specification. Further, Applicant(s) reserve the right to
amend the claims to affirmatively disclaim features or
characteristics that may be present in the prior art. Therefore,
any such amendments comply with the requirements of 35 U.S.C.
.sctn.112 and 35 U.S.C. .sctn.132(a). The various embodiments
disclosed and described in this specification can comprise, consist
of, or consist essentially of the features and characteristics as
variously described herein.
[0065] Any patent, publication, or other disclosure material
identified herein is incorporated by reference into this
specification in its entirety unless otherwise indicated, but only
to the extent that the incorporated material does not conflict with
existing definitions, statements, or other disclosure material
expressly set forth in this specification. As such, and to the
extent necessary, the express disclosure as set forth in this
specification supersedes any conflicting material incorporated by
reference herein. Any material, or portion thereof, that is said to
be incorporated by reference into this specification, but which
conflicts with existing definitions, statements, or other
disclosure material set forth herein, is only incorporated to the
extent that no conflict arises between that incorporated material
and the existing disclosure material. Applicant(s) reserves the
right to amend this specification to expressly recite any subject
matter, or portion thereof, incorporated by reference herein.
[0066] In this specification, other than where otherwise indicated,
all numerical parameters are to be understood as being prefaced and
modified in all instances by the term "about", in which the
numerical parameters possess the inherent variability
characteristic of the underlying measurement techniques used to
determine the numerical value of the parameter. At the very least,
and not as an attempt to limit the application of the doctrine of
equivalents to the scope of the claims, each numerical parameter
described in the present description should at least be construed
in light of the number of reported significant digits and by
applying ordinary rounding techniques.
[0067] Also, any numerical range recited in this specification is
intended to include all sub-ranges of the same numerical precision
subsumed within the recited range. For example, a range of "1.0 to
10.0" is intended to include all sub-ranges between (and including)
the recited minimum value of 1.0 and the recited maximum value of
10.0, that is, having a minimum value equal to or greater than 1.0
and a maximum value equal to or less than 10.0, such as, for
example, 2.4 to 7.6. Any maximum numerical limitation recited in
this specification is intended to include all lower numerical
limitations subsumed therein and any minimum numerical limitation
recited in this specification is intended to include all higher
numerical limitations subsumed therein. Accordingly, Applicant(s)
reserves the right to amend this specification, including the
claims, to expressly recite any sub-range subsumed within the
ranges expressly recited herein. All such ranges are intended to be
inherently described in this specification such that amending to
expressly recite any such sub-ranges would comply with the
requirements of 35 U.S.C. .sctn.112 and 35 U.S.C. .sctn.132(a).
[0068] The grammatical articles "one", "a", "an", and "the", as
used in this specification, are intended to include "at least one"
or "one or more", unless otherwise indicated. Thus, the articles
are used in this specification to refer to one or more than one
(i.e., to "at least one") of the grammatical objects of the
article. By way of example, "a component" means one or more
components, and thus, possibly, more than one component is
contemplated and may be employed or used in an implementation of
the described embodiments. Further, the use of a singular noun
includes the plural, and the use of a plural noun includes the
singular, unless the context of the usage requires otherwise.
[0069] As used herein, the following terms shall have the following
meanings.
[0070] The term "monomer" means the simple unpolymerized form of a
chemical compound having relatively low molecular weight, e.g.,
acrylonitrile, styrene, methyl methacrylate, and the like.
[0071] The phrase "polymerizable ethylenically unsaturated monomer"
means a monomer containing ethylenic unsaturation (>C=C<,
i.e. two double bonded carbon atoms) that is capable of undergoing
free radically induced addition polymerization reactions.
[0072] The term pre-formed stabilizer is defined as an intermediate
obtained by reacting a macromer containing reactive unsaturation
(e.g. acrylate, methacrylate, maleate, etc.) with one or more
monomers (i.e. acrylonitrile, styrene, methyl methacrylate, etc.),
with and at least one free radical initiator, in the presence of a
polymer control agent (PCA) and, optionally, in a diluent, to give
a co-polymer (i.e. a dispersion having e.g. a low solids content
(e.g. <30%), or soluble grafts, etc.).
[0073] The term "stability" means the ability of a material to
maintain a stable form such as the ability to stay in solution or
in suspension. Polymer polyols having good stability generally also
have good filterability.
[0074] The phrase "polymer polyol" refers to such compositions
which can be 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
polymer particles in the polyol. These polymer polyols have the
valuable property, for example, that polyurethane foams and
elastomers produced therefrom exhibit higher load-bearing
properties than are provided by the corresponding unmodified
polyols.
[0075] The term "solids efficiency" as used herein refers to the
ratio of a selected % IFD value for a foam relative to the polymer
solids content in the polyol portion of the foam formulation (i.e.
PS.sub.FOAM) which was used to prepare the foam, while maintaining
other foam variables such as Isocyanate Index, pad weight/density,
pack lever/water content, etc. constant. The IFD (Indentation Force
Deflection) which is a known and accepted means of quantifying foam
firmness is measured in accordance with ASTM D3574. The 25% IFD,
the 50% IFD and the 65% IFD values of foams are traditionally
measured to characterize the firmness of foams at these percent
deflections.
[0076] As used herein, "solids" efficiency" in a polymer polyol is
calculated as follows:
The weight percent polymer solids content of a direct made polymer
polyol is expressed as PS.sub.PMPO, and the blended down polymer
solids content in the polyol portion of the foam formulation is
expressed as PS.sub.FOAM. The following relationship exists for one
hundred parts of polyol in the foam formulation:
PS.sub.FOAM=pphp Polymer Polyol*PS.sub.PMPO
Thus, if (for example) the weight percent polymer solids content of
a polymer polyol (i.e. PS.sub.PMPO) equals 50%, and the pphp
Polymer Polyol in the foam formulation equals 50 pphp, the polymer
solids content of the resultant foam formulation (i.e. PS.sub.FOAM)
is calculated by solving the equation below:
PS.sub.FOAM=50 pphp (Polymer Polyol).times.50% (PS.sub.PMPO)=25%
solids
Once the blended down polymer solids content in the polyol portion
of the foam formulation (PS.sub.FOAM) is determined, the solids
efficiency of the polymer polyol can be determined by calculating
the ratio of a selected % IFD value of a foam to the PS.sub.FOAM
value.
Solids Efficiency (at X% IFD)=Measured IFD (at X%
IFD)/PS.sub.FOAM
As used in the above equation, X% IFD represents the 25% IFD, the
50% IFD or the 65% IFD. As previously stated, the % IFD value is
calculated using the test protocol in ASTM D3574, while other foam
variables such as, for example, isocyanate index, density and/or
pad weight, pack level/water content, etc. are kept constant.
[0077] As used herein "viscosity" is in millipascal-seconds (mPas)
measured at 25.degree. C. on an Anton Paar SVM3000 viscometer.
[0078] In accordance with the present invention, it is understood
that the total solids reduction of the polymer polyol (A) is at
least 5% by weight. It can, however, be greater than 5% by weight.
For example, it is possible to have a 50% reduction in the solids
content of a 30% by weight solids containing polymer polyol; or to
have an 85% reduction in the solids content of a 75% by weight
solids containing polymer polyol. These two examples would result
in the novel polymer polyol compositions herein having a solids
content of 15% by weight; or about 11% by weight, respectively. The
maximum percent of total solids reduction of the polymer polyol (A)
is such that the total solids content of the novel polymer polyol
compositions herein does not go below 10% total solids
[0079] The polymer polyols (A) of the present invention are
characterized by a solids content of 30 to 75% by weight, and a
viscosity at 25.degree. C. of less than 50,000 mPas.
[0080] These polymer polyols (A) may have a minimum solids content
of 30%, of 35%, of 40%, or of 44%, or of 45% by weight. They may
also have a maximum solids content of 75%, of 70%, of 60%, or of
55%. The polyols polyols (A) of the invention may have a solids
content ranging between any combination of these upper and lower
values, inclusive, e.g. from about 30% to about 75%, from about 35%
to about 70%, from about 40% to about 60% or from about 45% to
about 55% by weight.
[0081] In one embodiment, the polymer polyols (A) are characterized
by a solids content of from 44% to 75% by weight, or from 45% to
75% by weight, of from 45% to 65 by weight.
[0082] Polymer polyols (A) of the invention are typically
characterized by a viscosity (at 25.degree. C.) of less than 50,000
mPas. These polymer polyols may also have a viscosity (at
25.degree. C.) of less than 40,000, of less than 30,000, of less
than 20,000 or of less than 10,000 mPas.
[0083] Suitable polyols to be used as (A)(1) the base polyols in
the present invention include, for example, polyether polyols.
Suitable polyether polyols include those having a functionality of
at least about 2, or of at least about 3. The functionality of
suitable polyether polyols is less than or equal to about 8, or
less than or equal to about 6. The suitable polyether polyols may
also have functionalities ranging between any combination of these
upper and lower values, inclusive, such as from about 2 to about 8,
or of from about 2 to about 6, or of from about 3 to about 6. The
OH numbers of suitable polyether polyols is at least about 20, or
at least about 25, or at least about 30. Suitable polyether polyols
typically also have OH numbers of less than or equal to about 400,
or less than or equal to about 200, or less than or equal to about
150. The suitable polyether polyols may also have OH numbers
ranging between any combination of these upper and lower values,
inclusive, such as, for example, from at least about 20 to less
than or equal to about 400, or from at least about 25 to less than
or equal to about 200, or from at least about 30 to less than or
equal to about 150.
[0084] The suitable polyether polyols for component (A)(1) may have
functionalities ranging from about 2 to about 8, or from about 3 to
about 6.
[0085] As used herein, the hydroxyl number is defined as the number
of milligrams of potassium hydroxide required for the complete
hydrolysis of the fully phthalylated derivative prepared from 1
gram of polyol. The hydroxyl number can also be defined by the
equation:
OH=(56.1.times.1000.times.f)/mol. wt.
[0086] wherein:
[0087] OH: represents the hydroxyl number of the polyol,
[0088] f: represents the functionality of the polyol, i.e. the
average number of hydroxyl groups per molecule of polyol,
[0089] and
[0090] mol. wt. represents the molecular weight of the polyol.
[0091] Examples of such compounds for component (A)(1) include
polyoxyethylene glycols, triols, tetrols and higher functionality
polyols, polyoxypropylene glycols, triols, tetrols and higher
functionality polyols, mixtures thereof, etc. When mixtures as
used, the ethylene oxide and propylene oxide may be added
simultaneously or sequentially to provide internal blocks, terminal
blocks or random distribution of the oxyethylene groups and/or
oxypropylene groups in the polyether polyol. Suitable starters or
initiators for these compounds include, for example, ethylene
glycol, propylene glycol, diethylene glycol, dipropylene glycol,
tripropylene glycol, trimethylol-propane, glycerol,
pentaerythritol, sorbitol, sucrose, ethylenediamine, toluene
diamine, etc. By alkoxylation of the starter, a suitable polyether
polyol for the base polyol component can be formed. The
alkoxylation reaction may be catalyzed using any conventional
catalyst including, for example, potassium hydroxide (KOH) or a
double metal cyanide (DMC) catalyst.
[0092] Other suitable polyols for the base polyol of the present
invention include alkylene oxide adducts of non-reducing sugars and
sugar derivatives, alkylene oxide adducts of phosphorus and
polyphosphorus acids, alkylene oxide adducts of polyphenols,
polyols prepared from natural oils such as, for example, castor
oil, etc., and alkylene oxide adducts of polyhydroxyalkanes other
than those described above.
[0093] Illustrative alkylene oxide adducts of polyhydroxyalkanes
include, for example, alkylene oxide adducts of
1,3-dihydroxypropane, 1,3-dihydroxybutane,
1,4-dihydroxybutane,1,4-, 1,5- and 1,6-dihydroxyhexane, 1,2-, 1,3-,
1,4- 1,6- and 1,8-dihydroxyoctant, 1,10-dihydroxydecane, glycerol,
1,2,4-tirhydroxybutane, 1,2,6-trihydroxyhexane,
1,1,1-trimethyl-olethane, 1,1,1-trimethylolpropane,
pentaerythritol, caprolactone, polycaprolactone, xylitol, arabitol,
sorbitol, mannitol, and the like.
[0094] Other polyols which can be employed include the alkylene
oxide adducts of non-reducing sugars, wherein the alkoxides have
from 2 to 4 carbon atoms. Non-reducing sugars and sugar derivatives
include sucrose, alkyl glycosides such as methyl glycoside, ethyl
glucoside, etc. glycol glucosides such as ethylene glycol
glycoside, propylene glycol glucoside, glycerol glucoside,
1,2,6-hexanetriol glucoside, etc. as well as alkylene oxide adducts
of the alkyl glycosides as disclosed in U.S. Pat. No. 3,073,788,
the disclosure of which is herein incorporated by reference.
[0095] Other suitable polyols include the polyphenols and
preferably the alkylene oxide adducts thereof wherein the alkylene
oxides have from 2 to 4 carbon atoms. Among the polyphenols which
are suitable include, for example bisphenol A, bisphenol F,
condensation products of phenol and formaldehyde, the novolac
resins, condensation products of various phenolic compounds and
acrolein, including the 1,1,3-tris(hydroxy-phenyl)propanes,
condensation products of various phenolic compounds and glyoxal,
glutaraldehyde, other dialdehydes, including the 1,1,2,2-tetrakis
(hydroxyphenol)ethanes, etc.
[0096] The alkylene oxide adducts of phosphorus and polyphosphorus
acid are also useful polyols, These include ethylene oxide,
1,2-epoxy-propane, the epoxybutanes, 3-chloro-1,2-epoxypropane,
etc. as preferred alkylene oxides. Phosphoric acid, phosphorus
acid, the polyphosphoric acids such as, tripolyphosphoric acid, the
polymetaphosphoric acids, etc. are desirable for use herein.
[0097] It should also be appreciated that blends or mixtures of
various useful polyols may be used if desired.
[0098] Suitable compounds to be used as the ethylenically
unsaturated monomers, i.e. component (A)(2) the present invention
include, for example, those ethylenically unsaturated monomers
described above with respect to the preformed stabilizer. Suitable
monomers include, for example, aliphatic conjugated dienes such as
butadiene and isoprene; monovinylidene aromatic monomers such as
styrene, a-methyl-styrene, (t-butyl)styrene, chlorostyrene,
cyanostyrene and bromostyrene; .alpha.,.beta.-ethylenically
unsaturated carboxylic acids and esters thereof such as acrylic
acid, methacrylic acid, methyl methacrylate, ethyl acrylate,
2-hydroxyethyl acrylate, butyl actylate, itaconic acid, maleic
anhydride and the like; .alpha.,.beta.-ethylenically unsaturated
nitriles and amides such as acrylonitrile, methacrylonitrile,
acrylamide, methacrylamide, N,N-dimethyl acrylamide,
N-(dimethylaminomethyl)-acrylamide and the like; vinyl esters such
as vinyl acetate; vinyl ethers, vinyl ketones, vinyl and vinylidene
halides as well as a wide variety of other ethylenically
unsaturated materials which are copolymerizable with the
aforementioned monomeric adduct or reactive monomer. It is
understood that mixtures of two or more of the aforementioned
monomers are also suitable employed in making the pre-formed
stabilizer. Of the above monomers, the monovinylidene aromatic
monomers, particularly styrene, and the ethylenically unsaturated
nitriles, particularly acrylonitrile are preferred. In accordance
with this aspect of the present invention, it is preferred that
these ethylenically unsaturated monomers include styrene and its
derivatives, acrylonitrile, methyl acrylate, methyl methacrylate,
vinylidene chloride, with styrene and acrylonitrile being
particularly preferred monomers.
[0099] It is preferred that styrene and acrylonitrile are used in
sufficient amounts such that the weight ratio of styrene to
acrylonitrile (S:AN) is from about 80:20 to 20:80, more preferably
from about 75:25 to 25:75. These ratios are suitable for polymer
polyols and the processes of preparing them, regardless of whether
they comprise the ethylenically unsaturated macromers or the
pre-formed stabilizers of the present invention.
[0100] Overall, the polymer solids content that is present in (A)
the polymer polyols herein is at least about 30% by weight, and
less than or equal to about 75% by weight. These polymer polyols
may have solids contents of at least 30% by weight, or of at least
35% by weight, or of at least 40% by weight, based on 100% by
weight of the polymer polyol. The solids contents present in the
polymer polyols is typically about 75% by weight or less, or about
70% by weight or less, or about 55% by weight or less, based on
100% by weight of the polymer polyol. The polymer polyols of the
present invention typically has a solids content ranging between
any combination of these upper and lower values, inclusive, e.g.
from 30% to 75% by weight, or of from 35% to 70% by weight, or of
from 40% to 55% by weight, based on the total weight of the polymer
polyol.
[0101] Suitable preformed stabilizers to be used as component
(A)(3) in the present invention are preformed stabilizers which
comprise the reaction product of: [0102] (a) a macromer that
contains reactive unsaturation; with [0103] (b) one or more
ethylenically unsaturated monomers; and [0104] (c) at least one
free radical initiator; in the presence of [0105] (d) at least one
polymer control agent; and, optionally, [0106] (e) a chain transfer
agent.
[0107] Suitable macromers herein contain reactive unsaturation.
These macromers comprise the reaction product of: (i) a starter
compound having a functionality of 2 to 8, and a hydroxyl number of
20 to 50; (ii) from 0.1 to 3% by weight, based on 100% by weight of
the sum of components (i), (ii) and (iii), of a hydroxyl-reactive
compound that contains reactive unsaturation; and (iii) from 0 to
30% by weight, based on 100% by weight of the sum of components
(i), (ii) and (iii), of a diisocyanate.
[0108] As described in, for example, U.S. Pat, No. 5,196,476, the
disclosure of which is herein incorporated by reference, suitable
preformed stabilizers can be prepared by reacting a combination of
components (a), (b), (c) and (d), and optionally, (e), as described
above, in a reaction zone maintained at a temperature sufficient to
initiate a free radical reaction, and under sufficient pressure to
maintain only liquid phases in the reaction zone, for a sufficient
period of time to react (a), (b) and (c); and recovering a mixture
containing the preformed stabilizer dispersed in the polymer
control agent.
[0109] Suitable starter compounds to be used as (i) in the macromer
containing reactive unsaturation, include compounds having a
hydroxyl functionality of from 2 to 8, or of from 3 to 6; and have
a hydroxyl number of from 20 to 50 or of from 25 to 40. Examples of
such starter compounds include alkylene oxide adducts of hydroxyl
functional compounds such as ethylene glycol, propylene glycol,
diethylene glycol, dipropylene glycol, tripropylene glycol,
glycerin, trimethylolpropane, pentaerythritol, sorbitol,
ethylenediamine, toluene diamine, etc. These alkylene oxide adducts
may comprise propylene oxide, ethylene oxide, butylene oxide,
styrene oxide, and mixtures thereof. It is possible for these
starter compounds comprise 100% of an alkylene oxide such as, for
example, propylene oxide, or a mixture of propylene oxide and a
second alkylene oxide such as ethylene oxide or butylene oxide.
When a mixture of alkylene oxides are used to form the starter
compounds (i), mixtures of propylene oxide and ethylene oxide may
be advantageous. Such mixtures may be added simultaneously (i.e.
two or more alkylene oxide are added as co-feeds), or sequentially
(one alkylene oxide is added first, and then another alkylene oxide
is added). It is possibly to use a combination of simultaneous and
sequential addition of alkylene oxides. In one embodiment, an
alkylene oxide such as propylene oxide may be added first, and then
a second alkylene oxide such as ethylene oxide added as a cap.
[0110] Other examples of such compounds for starter (i) in the
macromer include polyoxyethylene glycols, triols, tetrols and
higher functionality polyols, and mixtures thereof, etc. When
mixtures are used, the ethylene oxide and propylene oxide may be
added simultaneously or sequentially to provide internal blocks,
terminal blocks or random distribution of the oxyethylene groups
and/or oxypropylene groups in the polyether polyol.
[0111] By alkoxylation of the starter, a suitable compound for the
starter of the macromer can be formed. The alkoxylation reaction
may be catalyzed using any conventional catalyst including, for
example, potassium hydroxide (KOH) or a double metal cyanide (DMC)
catalyst.
[0112] Other suitable polyols for the starter (i) of the macromer
in the present invention include alkylene oxide adducts of
non-reducing sugars and sugar derivatives, alkylene oxide adducts
of phosphorus and polyphosphorus acids, alkylene oxide adducts of
polyphenols, polyols prepared from natural oils such as, for
example, castor oil, etc., and alkylene oxide adducts of
polyhydroxyalkanes other than those described above.
[0113] Illustrative alkylene oxide adducts of polyhydroxyalkanes
include, for example, alkylene oxide adducts of
1,3-dihydroxypropane, 1,3-di-hydroxybutane,
1,4-dihydroxybutane,1,4-, 1,5- and 1,6-dihydroxyhexane, 1,2-, 1,3-,
1,4- 1,6- and 1,8-dihydroxyoctant, 1,10-dihydroxydecane, glycerol,
1,2,4-tirhydroxybutane, 1,2,6-trihydroxyhexane,
1,1,1-trimethyl-olethane, 1,1,1-trimethylolpropane,
pentaerythritol, caprolactone, polycaprolactone, xylitol, arabitol,
sorbitol, mannitol, and the like.
[0114] Other polyols which can be employed include the alkylene
oxide adducts of non-reducing sugars, wherein the alkoxides have
from 2 to 4 carbon atoms. Non-reducing sugars and sugar derivatives
include sucrose, alkyl glycosides such as methyl glycoside, ethyl
glucoside, etc. glycol glucosides such as ethylene glycol
glycoside, propylene glycol glucoside, glycerol glucoside,
1,2,6-hexanetriol glucoside, etc. as well as alkylene oxide adducts
of the alkyl glycosides as disclosed in U.S. Pat. No. 3,073,788,
the disclosure of which is herein incorporated by reference.
[0115] Other suitable polyols include the polyphenols and
preferably the alkylene oxide adducts thereof wherein the alkylene
oxides have from 2 to 4 carbon atoms. Among the polyphenols which
are suitable include, for example bisphenol A, bisphenol F,
condensation products of phenol and formaldehyde, the novolac
resins, condensation products of various phenolic compounds and
acrolein, including the 1,1,3-tris(hydroxy-phenyl)propanes,
condensation products of various phenolic compounds and glyoxal,
glutaraldehyde, other dialdehydes, including the 1,1,2,2-tetrakis
(hydroxyphenol)ethanes, etc.
[0116] In one embodiment, the starter compound has a functionality
of from 3 to 6 and a hydroxyl number of from 25 to 40, and is
prepared by reacting a starter such as glycerin,
trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol,
mannitol, etc., with alkylene oxides comprising at least one
alkylene oxide such as, for example, propylene oxide and/or
ethylene oxide.
[0117] In another embodiment, the ethylene oxide comprises from 1
to 40% by weight, or from 5 to 30%, or from 10 to 25% by weight,
based on the total weight of the starter compound.
[0118] In an alternate embodiment, all or a portion of the ethylene
oxide is added as a cap on the end of the starter compound.
Suitable amounts of ethylene oxide to be added as a cap range from
1 to 40, or 3 to 30 or 5 to 25 (based on 100% by weight of the
starter compound).
[0119] Suitable compounds to be used as component (3)(a)(ii) the
hydroxyl-reactive compound that contains reactive unsaturation
include, for example, methyl methacrylate, ethyl methacrylate,
maleic anhydride, isopropenyl dimethyl benzyl isocyanate,
2-isocyanatoethyl methacrylate , adducts of isophorone diisocyanate
and 2-hydroxyethyl methacrylate, adducts of toluenediisocyanate and
2-hydroxypropyl acrylate, etc.
[0120] The macromer (a) may additionally comprise (iii) 0 to 3% by
weight, or from 0.05 to 2.5% by weight, or 0.1 to 1.5% by weight,
based on 100% by weight of the sum of components (i), (ii) and
(iii), of a diisocyanate component. Suitable diisocyanates include
various isomers of diphenylmethane diisocyanate and isomeric
mixtures of diphenylmethane diisocyanate such as, for example a
mixture of 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane
diisocyanate and/or 2,2'-diphenyl-methane diisocyanate. In one
embodiment, a mixture of 2,4'-diphenylmethane diisocyanate and of
4,4'-diphenylmethane diisocyanate is suitable. Other suitable
isocyanates include toluenediisocyanate, isophoronediisocyanate,
hexamethylenediisocyanate, 4,4'-methylenebis(cyclohexyl
isocyanate), etc.
[0121] Suitable compounds to be used as component (b) above, the
ethylenically unsaturated monomers include, for example, compounds
which contain ethylenic unsaturation. Of particular relevance are
those compounds that are free radically polymerizable. Some
examples of suitable compounds include aliphatic conjugated dienes
such as butadiene and isoprene; monovinylidene aromatic monomers
such as styrene, .alpha.-methylstyrene, (t-butyl)styrene,
chlorostyrene, cyanostyrene and bromostyrene;
.alpha.,.beta.-ethylenically unsaturated carboxylic acids and
esters thereof such as acrylic acid, methacrylic acid, methyl
methacrylate, ethyl acrylate, 2-hydroxyethyl acrylate, butyl
acrylate, itaconic acid, maleic anhydride and the like;
.alpha.,.beta.-ethylenically unsaturated nitriles and amides such
as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide,
N,N-dimethyl acrylamide, N-dimethylaminomethyl)acryl-amide and the
like; vinyl esters such as vinyl acetate; vinyl ethers, vinyl
ketones, vinyl and vinylidene halides as well as a wide variety of
other ethylenically unsaturated materials which are copolymerizable
with the aforementioned macomer. It is understood that mixtures of
two or more of the aforementioned ethylenically unsaturated
monomers are also suitable to be employed in making the pre-formed
stabilizer. Of the above monomers, the monovinylidene aromatic
monomers such as styrene, and the ethylenically unsaturated
nitriles, such as acrylonitrile may be particularly suitable.
[0122] It is preferred that (b) comprises a mixture of
acrylonitrile and at least one other ethylenically unsaturated
comonomer which is copolymerizable with acrylonitrile.
Illustrations of ethylenically unsaturated comonomer
copolymerizable with acrylonitrile include styrene and its
derivatives, acrylates, methacrylates such as methyl methacrylate,
vinylidene chloride, and the like. Mixtures of styrene and
acrylonitrile may be used.
[0123] When using acrylonitrile with a comonomer, it is recommended
that a minimum of about 5 to 15 percent by weight acrylonitrile be
maintained in the system. Styrene will generally be used as the
comonomer, but methyl methacrylate or other monomers may be
employed in place of part or all of the styrene. A specific monomer
mixture for component (b) in making the preformed stabilizer
composition (3) comprises mixtures of acrylonitrile and styrene.
The weight proportion of acrylonitrile can range from about 20 to
80 weight percent of the comonomer mixture, or from about 30 to
about 70 weight percent, and styrene can accordingly vary from
about 80 to about 20 weight percent, or from about 70 to about 30
weight percent of the mixture. An acrylonitrile to styrene ratio in
the monomer mixture of from about 20:80 to 80:20 can be used. A
mixture of acrylonitrile to styrene having a weight ratio of from
about 30:70 to about 70:30 can also be used.
[0124] The free radical polymerization initiators suitable for use
as component (c) in the suitable preformed stabilizers (3) of the
present invention encompass any free radical catalyst suitable for
grafting of an ethylenically unsaturated polymer to a polyether
containing compound, such as polyether polyol. Examples of suitable
free-radical polymerization initiators for the present invention
include initiators such as, for example, peroxides including both
alkyl and aryl hydro-peroxides, persulfates, perborates,
percarbonates, azo compounds, etc. Some specific examples include
catalysts such as hydrogen peroxide, di(t-butyl)-peroxide,
t-butylperoxy diethyl acetate, t-butyl peroctoate, t-butyl peroxy
isobutyrate, t-butyl peroxy 3,5,5-trimethyl hexanoate, t-butyl
perbenzoate, t-butyl peroxy pivalate, t-amyl peroxy pivalate,
t-butyl peroxy-2-ethyl hexanoate, lauroyl peroxide, cumene
hydroperoxide, t-butyl hydroperoxide, azobis(isobutyronitrile),
2,2'-azo bis-(2-methylbutyronitrile), etc.
[0125] Useful catalysts also include, for example, those catalysts
having a satisfactory half-life within the temperature ranges used
to form the preformed stabilizer, i.e. the half-life should be
about 25 percent or less of the residence time in the reactor at a
given temperature. Representative examples of useful catalyst
species include t-butyl peroxy-2-ethyl-hexanoate,
t-butylperpivalate, t-amyl peroctoate,
2,5-dimethyl-hexane-2,5-di-per-2-ethyl hexoate,
t-butylperneodecanoate, and t-butylperbenzoate. Useful also are the
azo catalysts such as azobis-isobutyronitrile, 2,2'-azo
bis-(2-methylbutyro-nitrile), and mixtures thereof. The preferred
free radical catalysts are peroxides such as tertiary butyl
peroctoate.
[0126] Suitable catalysts concentrations range from about 0.01 to
about 2% by weight, preferably from about 0.05 to 1% by weight, and
most preferably 0.05 to 0.3% by weight, based on the total weight
of the components (i.e. 100% by weight of the combined weight of
the macromer, the ethylenically unsaturated monomer, the
free-radical polymerization initiator and, the polymer control
agent, and optionally, the liquid diluent). Up to a certain point,
increases in the catalyst concentration result in increased monomer
conversion and grafting; but further increases do not substantially
increase conversion. Catalyst concentrations which are too high can
cause cross-linking in the preformed stabilizer (3). The particular
catalyst concentration selected will usually be an optimum value
considering all factors, including costs.
[0127] In accordance with the present invention, components (a),
(b), and (c) of the pre-formed stabilizer are soluble in (d) the
polymer control agent. However, the resultant preformed stabilizer
(3) is essentially insoluble in (d) the polymer control agent. This
component may be one polymer control agent or a mixture of polymer
control agents. Suitable compounds to be used as polymer control
agents in accordance with the present invention include various
mono-ols (i.e. monohydroxy alcohols), aromatic hydrocarbons,
ethers, and other liquids, such as those described in, for example,
U.S. Pat. Nos. 3,953,393, 4,119,586, 4,463,107, 5,324,774,
5,814,699 and 6,624,209, the disclosures of which are herein
incorporated by reference. As long as the compound used as the
polymer control agent does not adversely affect the performance of
the preformed stabilizer (3), it is suitable for use in the
practice of the invention. Preferred are the mono-ols because of
their ease of stripping from the final polymer/polyol composition.
Mixtures of one or more mono-ols may be used as polymer control
agents. The choice of mono-ol is not narrowly critical. However, it
should not form two phases under the reaction conditions and it
should be readily stripped from the final polymer/polyol.
[0128] The selection of mono-ol is typically an alcohol containing
at least one carbon atom, such as methanol, ethanol, n-propanol,
isopropanol, n-butanol, sec.-butanol, t-butanol, n-pentanol,
2-pentanol, 3-pentanol, and the like, and mixtures of the same. In
one embodiment, the polymer control agent is isopropanol. Other
known polymer control agents include compounds such as, for
example, ethylbenzene and toluene. In accordance with the present
invention, the most preferred polymer control agents include
isopropanol, ethanol, tert-butanol, toluene, ethylbenzene, etc.
[0129] Polymer control agents (d) can be used in substantially pure
form (i.e. as commercially available) or can be recovered in crude
form from the polymer polyol process and reused as-is. For
instance, if the polymer control agent is isopropanol, it can be
recovered from the polymer polyol process and used at any point in
a subsequent product campaign in which the isopropanol is present
(i.e. such as the production of preformed stabilizer (3)). The
amount of crude polymer control agent in the total polymer control
agent can range anywhere from 0% up to 100% by weight.
[0130] The polyol components suitable as component (e) the diluent
in the present invention include typically the alkylene oxide
adduct of A(OH).sub.>3 described above. Though the polyol used
as component (5) can encompass the variety of polyols described
above, including the broader class of polyols described in U.S.
Pat. No. 4,242,249, at column 7, line 39 through column 9, line 10,
the disclosure of which is herein incorporated by reference. It is
preferred that the polyol component (5) be the same as or
equivalent to the polyol used in the formation of precursor used to
prepare the preformed stabilizer (PFS). Typically, the polyol need
not be stripped off.
[0131] Because of the number of components, the variability of
their concentration in the feed, and the variability of the
operating conditions of temperature, pressure, and residence or
reaction times, a substantial choice of these is possible while
still achieving the benefits of the invention. Therefore, it is
prudent to test particular combinations to confirm the most
suitable operating mode for producing a particular final polymer
polyol product.
[0132] In general, the amount of the components in the formulation,
on a weight percent of the total formulation for forming preformed
stabilizer (3), is as follows:
TABLE-US-00001 Component of Formulation Amount, weight % (a) about
10 to 40, preferably 15 to 35, (b) about 10 to 30, preferably 15 to
25, (c) about 0.01 to 2, preferably 0.1 to 1, (d) about 30 to 80,
preferably 40 to 70, (e) about 0 to 40, preferably 0 to 20, or more
preferably 0 to 10.
[0133] In the formulations proposed above for the preformed
stabilizer (3), the %'s by weight of components (a), (b), (c) and
(d), and optionally (e), totals 100% by weight of component (3),
the preformed stabilizer.
[0134] The process for producing the preformed stabilizer (3) is
similar to the process for making the polymer polyol. The
temperature range is not critical and may vary from about
80.degree. C. to about 150.degree. C. or perhaps greater. Another
suitable range is from 115.degree. C. to 125.degree. C. The
catalyst and temperature should be selected so that the catalyst
has a reasonable rate of decomposition with respect to the hold-up
time in the reactor for a continuous flow reactor or the feed time
for a semi-batch reactor.
[0135] The mixing conditions employed are those obtained using a
back mixed reactor (e.g. -a stirred flask or stirred autoclave).
The reactors of this type keep the reaction mixture relatively
homogeneous and so prevent localized high monomer to macromer
ratios such as occur in tubular reactors, where all of the monomer
is added at the beginning of the reactor. In addition, more
efficient mixing can be obtained by the use of an external pump
around loop on the reactor section. For instance, a stream of
reactor contents may be removed from the reactor bottom via
external piping and returned to the top of the reactor (or vice
versa) in order to enhance internal mixing of the components. This
external loop may contain a heat exchanger if desired.
[0136] Suitable free-radical initiators to be used as component (4)
in the present invention include, for example, those as described
previously for the formation of the preformed stabilizers. Examples
of suitable free-radical polymerization initiators for the present
invention include initiators such as, for example, peroxides
including both alkyl and aryl hydroperoxides, persulfates,
perborates, percarbonates, azo compounds, etc. Some specific
examples include catalysts such as hydrogen peroxide,
di(t-butyl)-peroxide, t-butylperoxy diethyl acetate, t-butyl
peroctoate, t-butyl peroxy isobutyrate, t-butyl peroxy
3,5,5-trimethyl hexanoate, t-butyl perbenzoate, t-butyl peroxy
pivalate, t-amyl peroxy pivalate, t-butyl peroxy-2-ethyl hexanoate,
lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide,
azobis(isobutyronitrile), 2,2'-azo bis-(2-methylbutyronitrile),
etc.
[0137] Useful initiators also include, for example, those catalysts
having a satisfactory half-life within the temperature ranges used
in forming the polymer polyol. Typically, the half-life of the
catalyst should be about 25% or less of the residence time in the
reactor at any given time. Preferred initiators for this portion of
the invention include acyl peroxides such as didecanoyl peroxide
and dilauroyl peroxide, peroxyesters such as t-butyl
peroxy-2-ethylhexanoate, t-butylperpivalate, t-amyl peroxy
pivalate, t-amyl peroctoate, 2,5-dimethyl-hexane-2,5-di-per-2-ethyl
hexoate, t-butyl perneodecanoate, t-butylper-benzoate and
1,1-dimethyl-3-hydroxybutyl peroxy-2-ethylhexanoate, and azo
catalysts such as azobis(isobutyronitrile), 2,2'-azo
bis-(2-methoxyl-butyronitrile), and mixtures thereof. Most
preferred are the peroxyesters described above and the azo
catalysts. A particularly preferred initiator comprises
azobis(isobutyronitrile).
[0138] Particularly preferred in the practice of the invention, are
the use of azo catalysts and the aforementioned peroxyesters of the
above formula. The preferred peroxyesters include those which have
the unique advantage of affecting the desired degree of
polymerization essentially without raising the viscosity of the
polymer polyol over that obtained with the azo catalyst. This
enhances one's ability to achieve higher solids polymer polyols
with good product stability without raising product viscosity. Such
peroxyesters can be used in molar amounts substantially less than
the amounts required when using other free radical catalysts in
forming the polymer polyols.
[0139] The quantity of free-radical initiator used herein is not
critical and can be varied within wide limits. In general, the
amount of initiator ranges from about 0.01 to 2% by weight, based
on 100% by weight of the final polymer polyol. Increases in
catalyst concentration result in increases in monomer conversion up
to a certain point, but past this, further increases do not result
in substantial increases in conversion. The particular catalyst
concentration selected will usually be an optimum value, taking all
factors into consideration including costs.
[0140] In addition, the polymer polyol and the process of preparing
the polymer polyol may optionally comprise (5) a chain transfer
agent. The use of chain transfer agents and their nature is known
in the art. Examples of suitable materials include compounds such
as mercaptans including, e.g. dodecane thiol, ethane thiol, octane
thiol, toluene thiol, etc., halogenated hydrocarbons such as, e.g.
carbon tetrachloride, carbon tetrabromide, chloroform, etc., amines
such as diethylamine, enol-ethers, etc. If used at all in the
present invention, a chain transfer agent is preferably used in an
amount of from about 0.1 to about 2 wt. %, more preferably from
about 0.2 to about 1 wt. %, based on the total weight of the
polymer polyol (prior to stripping).
[0141] The polymer polyols from the present invention can be made
using any process (including continuous and semi-batch) and reactor
configuration that is known to be suitable to prepare polymer
polyols, such as, for example, a two-stage reaction system
comprising a continuously-stirred tank reactor (CSTR) fitted with
impeller(s) and baffles (first-stage) and a plug-flow reactor
(second stage). A typical reaction system may be equipped with any
combination of jacket/half-coil, internal coil/tubes or external
loop/cooler to remove the heat of reaction. Furthermore, the
reaction system can utilize a wide range of mixing conditions. The
reaction system may be characterized by energy inputs of from 0.5
to 350 horsepower per 1000 gallons, with preferred mixing energies
of from 2 to 50 horsepower per 1000 gallons on average for the bulk
phase volume of each reactor as a particularly useful mixing power
input. Mixing can be provided by any combination of impeller(s) and
pump-around loop/jet mixing. It will be appreciated by one of
ordinary skill in the art that the optimum energy input will most
likely vary with the dispersion stability and the molecular weight
of the base polyether polyol, e.g., a greater amount of energy is
preferred for products with higher viscosities. In addition,
polymer polyols of the present invention can be prepared from
various types and combinations of axially and/or
radially/tangentially acting impellers including, but not limited
to, 4-pitched-blade, 6-pitched-blade, 4-flat-blade, 6-flat-blade,
pitched-blade turbine, flat-blade turbine, Rushton, Maxflow,
propeller, etc. For a continuous production process to prepare
polymer polyols including those described in the present invention,
a residence time ranging from about 20 to about 180 minutes for the
first reactor may be particularly useful. It is understood that for
a multistage reactor system, total residence time is additive based
on number of reactors.
[0142] The reactants are pumped from feed tanks through an in-line
static mixer, and then, through a feed tube into the reactor. It
may be particularly useful to prepare a premix of the initiator
with part of the polyol stream, as well as of polyol and
stabilizer. In general, feed stream temperatures are ambient (i.e.
25.degree. C.). However, if desired, feed streams can be heated to
.gtoreq.25.degree. C. prior to mixing and entering the reactor.
Other process conditions, which may be useful, include cooling of
the feed tube in the reactor. Furthermore, the suitable reaction
conditions for polymer polyols in general as well as the specific
products of the present invention mixture are characterized by a
reaction temperature in the range of 80 to 200.degree. C. and a
pressure in the range of 20 to 80 psig. Typically, the product can
then treated in a single or multi staged stripping step to remove
volatiles before entering a stage, which can essentially be any
combination of filtration and/or product cooling. In the present
case, the wt.-% total polymer in the product was calculated from
the concentrations of monomers measured in the crude polymer polyol
before stripping.
[0143] In accordance with the present invention, the polymer
polyols are preferably produced by utilizing a low monomer to
polyol ratio which is maintained throughout the reaction mixture
during the process. This is achieved by employing conditions that
provide rapid conversion of monomer to polymer. In practice, a low
monomer to polyol ratio is maintained, in the case of semi-batch
and continuous operation, by control of the temperature and mixing
conditions and, in the case of semibatch operation, also by slowly
adding the monomers to the polyol.
[0144] The temperature range is not critical and may vary from
about 80.degree. C. to about 200.degree. C. or perhaps greater,
preferably from about 100.degree. C. to about 140.degree. C., with
a more preferred range being from 115.degree. C. to 125.degree. C.
As has been noted herein, the catalyst and temperature should be
selected such that the catalyst has a reasonable rate of
decomposition with respect to the hold-up time in the reactor for a
continuous flow reactor or the feed time for a semi-batch
reactor.
[0145] A suitable continuous process for making polymer polyols
comprises (1) providing a heterogenous mixture of the preformed
stabilizer and, optionally, liquid diluent, in combination with a
polyol, a free radically polymerizable ethylenically unsaturated
monomer, and a free radical polymerization initiator, (2) in a
reaction zone maintained at a temperature sufficient to initiate a
free radical reaction, and under sufficient pressure to maintain
only liquid phases in the reaction zone, for a period of time
sufficient to react at least a major portion of the ethylenically
unsaturated monomer to form a heterogenous mixture containing the
enhanced polymer polyol, unreacted monomers and diluent, and
stripping the unreacted monomers and diluent from the enhanced
polymer polyol to recover the unreacted monomers and diluent. This
continuous process allows the manufacture of high solids, white
polymer polyols with lower viscosities and good stability. This
product has excellent product stability and requires less free
radical catalyst in the production process. Other pertinent details
for the continuous process of preparing polymer polyols can be
found in, for example, U.S. Pat. No. 5,196,476, the disclosure of
which is herein incorporated by reference.
[0146] The mixing conditions employed are those obtained using a
back mixed reactor (e.g.-a stirred flask or stirred autoclave). The
reactors of this type keep the reaction mixture relatively
homogeneous and so prevent localized high monomer to polyol ratios
such as occur in tubular reactors when such reactors are operated
with all the monomer added to the beginning of the reactor.
[0147] The polymer polyols of the present invention comprise
dispersions in which the polymer particles (the same being either
individual particles or agglomerates of individual particles) are
relatively small in size and, in the preferred embodiment, have a
weight average size less than about ten microns. However, when high
contents of styrene are used, the particles will tend to be larger;
but the resulting polymer polyols are highly useful, particularly
where the end use application requires as little scorch as
possible.
[0148] Following polymerization, volatile constituents, in
particular those from the PCA and residues of monomers are
generally stripped from the product by the usual method of vacuum
distillation, optionally in a thin layer of a falling film
evaporator. The monomer-free product may be used as is, or may be
filtered to remove any large particles that may have been
created.
[0149] In one embodiment, all of the product (viz. 100%) will pass
through the filter employed in the 150 mesh filtration hindrance
(i.e. filterability) test that will be described in conjunction
with the Examples. This ensures that the polymer polyol products
can be successfully processed in all types of the relatively
sophisticated machine systems now in use for large volume
production of polyurethane products, including those employing
impingement-type mixing which necessitate the use of filters that
cannot tolerate any significant amount of relatively large
particles.
[0150] In accordance with the present invention, polymer polyol (A)
and at least one isocyanate-reactive component (B) are combined to
form the novel polymer polyol compositions having a solids content
of from 10 to 72% by weight, with component (B) present in an
amount sufficient to reduce the total solids content in the polymer
polyol (A) by at least 5% by weight.
[0151] Suitable compounds to be used as isocyanate-reactive
component (B) include those which have a hydroxyl functionality of
from 1 to 8 and a hydroxyl number of from 20 to 400. These
compounds may also have a functionality of at least about 2, or at
least about 3. In addition, the suitable compounds may have a
hydroxyl functionality of about 7 or less, or of about 6 or less.
Suitable compounds may also be characterized by a hydroxyl number
of at least 20, or of at least 25 or of at least 30. These may also
have a hydroxyl number of about 400 or less, or of about 200 or
less; or of about 150 or less.
[0152] Examples of suitable compounds to be used as the
isocyanate-reactive component (B) include polyether polyols,
polyester polyols, polyether carbonate polyols, etc. Also suitable
are relatively low molecular weight compounds based on a
functionality of 1 and an OH # of 400 (MW=140). Other suitable
compounds include, for example, polyoxyalkylene polyols, polyester
polyols, polythioethers, polyacetals, polycarbonates,
polyethercarbonate polyols, etc. Lower molecular weight
isocyanate-reactive components such as crosslinkers and/or chain
extenders may also be present.
[0153] In accordance with the present invention, flexible
polyurethane foams may be prepared from the novel polymer polyols
described herein. These foams comprise the reaction product of a
polyisocyanate component, with an isocyanate-reactive component
that comprises the novel polymer polyols described herein, in the
presence of one or more catalysts, one or more blowing agents, and
optionally, one or more surfactants. In addition, the
isocyanate-reactive component may additionally comprise one or more
crosslinking agents, one or more chain extenders, and/or one or
more polyether polyols containing a high ethylene oxide content. It
is also possible that the isocyanate-reactive component
additionally comprises one or more polyoxyalkylene polyols,
polyether polyols, polyester polyols, polycarbonate ether polyols,
polythioethers, polycarbonates, polyacetals, etc., and mixtures
thereof. Various additives and/or auxiliary agents which are known
to be useful in preparing foams may also be present.
[0154] The flexible polyurethane foams of present invention which
comprise the reaction product of the novel polymer polyols
described herein have been found to exhibit improved solids
efficiency.
[0155] The process of preparing the flexible polyurethane foams
comprises reacting (I) a polyisocyanate component, with (II) an
isocyanate-reactive component comprising the novel polymer polyols
described herein, in the presence of (III) one or more catalysts,
(IV) one or more blowing agents and, optionally, (V) one or more
surfactants. In addition, crosslinking agents, chain extenders,
other isocyanate-reactive components, etc., as described herein
above, as well as various other additives and auxiliary agents may
also be present.
[0156] Suitable polyisocyanates for the polyisocyanate component
(I) comprise those known in the art, to be suitable for the
preparation of flexible polyurethane foams. The polyisocyanates may
be di- or poly-functional, and include, for example,
(cyclo)aliphatic di- and/or polyisocyanates, aromatic di- and/or
polyisocyanates, and araliphatic di- and/or polyisocyanates. Some
specific examples of suitable aromatic polyisocyanates and aromatic
diisocyanates include compounds such as toluene diisocyanate,
diphenylmethane diisocyanate, polymethylene polyphenyl
polyisocyanate, etc., and mixtures or blends thereof.
[0157] Suitable blends of polyisocyanates for component (I)
include, for example, blends comprising (1) from 10 to 90 wt. % of
one or more isomer of toluene diisocyanate and (2) from 90 to 10
wt. % of polymethylene polyphenylisocyanate and/or one or more
isomers of diphenylmethane diisocyanate, with the sum of the wt.
%'s totaling 100 wt. % of the polyisocyanate component; blends
comprising (1) 70 to 90 wt. % of one or more isomers of
diphenylmethane diisocyanate, and (2) 10 to 30 wt. % of one or more
isomers of toluene diisocyanate, with the sum of the wt. %'s
totaling 100 wt. % of the polyisocyanate component; and blends
comprising (1) 70 to 90 wt. % of one or more isomers of toluene
diisocyanate, and (2) 30 to 10 wt. % of polymethylene
polyphenylisocyanate, with the sum of the wt. %;s totaling 100 wt.
% of the polyisocyanate component.
[0158] Suitable compounds to be used as component (II), the
isocyanate-reactive component, herein for the preparation of
flexible polyurethane foams include the novel polymer polyols
described herein. In accordance with the present invention, the
isocyanate-reactive component (II) may additionally comprise a
conventional (i.e. non-solids containing) isocyanate-reactive
component such as, for example, a polyoxyalkylene polyol, a
polyether polyol, a polyester polyol, a polythioether, a
polyacetal, a polycarbonate, a polycarbonate ether polyol, etc.,
and mixtures thereof. These isocyanate-reactive compounds having a
functionality of from 2 to 8, or from 2 to 6, or from 2 to 4, and a
molecular weight of from 1000 to 12,000, or from 1000 to 8,000, or
from 2000 to 6000. In addition, lower molecular weight
isocyanate-reactive components such as crosslinkers and/or chain
extenders may be used. These lower molecular weight
isocyanate-reactive components include chain extenders which may
have functionalities of 2 and molecular weights ranging from 61 to
500; and cross linking agents which may have functionalities of 3
to 4 and molecular weights ranging from 92 to less than 1000, or
from 92 to less than or equal to 750. Examples of suitable chain
extenders include ethylene glycol, 2-methyl-1,3-propanediol, 1,2-
and 1,3-propanediol, 1,3- and 1,4- and 2,3-butanediol,
1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene
glycol, etc., and mixtures thereof, and alkylene oxide adducts
thereof. Some examples of suitable crosslinking agents include
glycerol, trimethylolpropane, pentaerythritol, diethanolamine,
triethanolamine, etc., mixtures thereof, and alkylene oxide adducts
thereof. It is also possible to use a polyether polyol that
contains a high ethylene oxide content.
[0159] At least one polyurethane catalyst is required to catalyze
the reactions of the monol, polyols and water with the
polyisocyanate. It is common to use both an organoamine and an
organotin compound for this purpose. Suitable polyurethane
catalysts are well known in the art; an extensive list appears in
U.S. Pat. No. 5,011,908, the disclosure of which is herein
incorporated by reference. Suitable organotin catalysts include tin
salts and dialkyltin salts of carboxylic acids. Examples include
stannous octoate, dibutyltin dilaurate, dibutyltin diacetate,
stannous oleate, and the like. Suitable organoamine catalysts are
tertiary amines such as trimethylamine, triethylamine,
triethylenediamine, bis(2,2'-dimethylamino)ethyl ether,
N-ethylmorpholine, diethylenetriamine, and the like. Preferred
catalysts are amine catalysts such as, for example,
bis(dimethylaminoethyl)ether in dipropylene glycol and triethylene
diamine in dipropylene glycol. These are commercially available as
Niax A-1 and Niax A-33, respectively.
[0160] The polyurethane catalysts are typically used in an amount
within the range of about 0.05 to about 3 parts, more preferably
from about 0.1 to about 2 parts, per 100 parts of
isocyanate-reactive mixture.
[0161] Suitable (III) blowing agents for the present invention
include, for example chemical blowing agents and/or physical
blowing agents. Some examples of the suitable blowing agents for
the present invention include water, formic acid, carbon dioxide,
chlorofluorocarbons, highly fluorinated and/or perfluorinated
hydrocarbons, chlorinated hydrocarbons, aliphatic and/or
cycloaliphatic hydrocarbons such as propane, butane, pentane,
hexane, etc., or acetals such as methylal, etc. It is possible to
use a mixture of blowing agent in the present invention. When using
a physical blowing agent, this is typically added to the
isocyanate-reactive component of the system. These can, however,
also be added in the polyisocyanate component or to a combination
of both the isocyanate-reactive component and to the polyisocyanate
component. Blowing agents may also be used in the form of an
emulsion of the isocyanate-reactive component. Combinations of
water and one or more auxiliary blowing agents are also suitable
herein, In addition, water may be used as the sole blowing
agent.
[0162] The amount of blowing agent or blowing agent mixture used is
from 0.5 to 20%, preferably from 0.75 to 10% by weight, based in
each case on the total weight of the component (B). When water is
the blowing agent, it is typically present in an amount of from 0.5
to 10%, and preferably from 0.75 to 7% by weight, based on the
total weight of the component (B). The addition of water can be
effected in combination with the use of the other blowing agents
described.
[0163] Surfactants are preferably used to prepare the foams.
Surfactants are known help to stabilize the foam until it cures.
Suitable surfactants for the invention are those well known in the
polyurethane industry. A wide variety of organosilicone surfactants
are commercially available. Examples of suitable surfactants
include DC-5043, DC-5164 and DC-5169, as well as Niax L-620, a
product of Momentive Performance Materials, and Tegostab B8244, a
product of Evonik-Goldschmidt. Many other silicone surfactants
known to those in the art may be substituted for these suitable
silicones. The surfactant is typically used in an amount within the
range of about 0.1 to 4, preferably from about 0.2 to 3, parts per
100 parts of isocyanate-reactive mixture.
[0164] Other optional components that may be present in the
flexible foam formulations include, for example, flame retardants,
antioxidants, pigments, dyes, liquid and solid fillers, etc. Such
commercial additives are included in the foams in conventional
amounts when used.
[0165] The flexible foams are prepared using methods that are well
known in the industry. These methods may include continuous or
discontinuous free-rise slabstock foam processes and molded foam
processes. In a typical slabstock process, the isocyanate is
continuously mixed together with the other formulation chemicals by
passing through a mixing head and then into a trough which
overflows onto a moving conveyor. Alternatively, the reacting
mixture is deposited directly onto the moving conveyor. In another
embodiment, high pressure liquid carbon dioxide is fed into one or
more of the formulation components, typically the polyol, entering
into the mixing head and the resin blend is passed through a
frothing device where the pressure is let down and the resultant
froth is deposited onto the conveyor. The foam expands and rises as
it moves down the conveyor to form a continuous foam slab that is
cut into blocks or buns of the desired length for curing and
storage. After curing for one or more days, these foam buns can be
cut into the desired shapes for the end-use applications. In the
discontinuous process, the reactants are quickly mixed together
through a head or in a large mixing chamber. The reaction mixture
is then deposited into a large box or other suitable container
where foam expansion occurs to form a bun of the lateral dimensions
of the container.
[0166] A typical molded foam process usually employs a one-shot
approach in which a specific amount of the isocyanate stream (the
"A" side) is rapidly combined and mixed with a specific amount of
the remaining formulation components (the "B" side). An additional
stream may be employed to bring in one or more specific components
not included with the "B" side stream. The mixture is quickly
deposited into a mold that is then closed. The foam expands to fill
the mold and produce a part with the shape and dimensions of the
mold.
[0167] In accordance with the present invention, the flexible foams
are prepared at isocyanate indices ranges from 70 to 130, or from
80 to 120 or from 90 to 110. The term "isocyanate index", which may
also be referred to as the NCO index, is defined herein as the
ratio of reactive isocyanate groups (equivalents) to active
hydrogen groups (equivalents), multiplied by 100%.
[0168] Although less preferred, a prepolymer approach to making the
foams can also be used. In this approach, a significant portion of
the isocyanate-reactive mixture is reacted with the polyisocyanate,
and the resulting prepolymer is then reacted with the remaining
components.
[0169] Certain embodiments of the present invention, therefore, are
directed to a polymer polyol composition having a solids content of
from 10 to 72% by weight, and comprising (A) a polymer polyol
having a solids content of from 30 to 75% by weight, a viscosity at
25.degree. C. of less than 50,000 mPas, and which comprises the
reaction product of: (1) at least one base polyol having a
functionality of from 2 to 8 and a hydroxyl number of from 20 to
400; (2) one or more ethylenically unsaturated monomers; (3) a
preformed stabilizer which comprises the reaction product of: (a) a
macromer that contains reactive unsaturation and comprises the
reaction product of: (i) a starter compound having a functionality
of 2 to 8 and a hydroxyl number of from 20 to 50; (ii) 0.1 to 3% by
weight, based on 100% by weight of the sum of components (i), (ii)
and (iii), of a hydroxyl-reactive compound that contains reactive
unsaturation; and (iii) 0 to 3% by weight, based on 100% by weight
of the sum of components (i), (ii) and (iii), of one or more
diisocyanates; with (b) one or more ethylenically unsaturated
monomers; and (c) at least one free radical initiator; in the
presence of (d) a polymer control agent; and, optionally, (e) a
liquid diluent; in the presence of (2) at least one free radical
initiator; and, optionally, (3) a chain transfer agent; and (B) at
least one polyol component having a functionality of from 1 to 8
and a hydroxyl number of from 20 to 400; wherein component (B) is
present in an amount sufficient to reduce the total solids content
in said polymer polyol (A) by at least 5% by weight.
[0170] Certain embodiments of the present invention are directed to
the polymer polyol compositions of the previous paragraph, wherein
(A)(3)(a) the macromer comprises the reaction product of (i) a
starter compound having a functionality of 3 to 6 and a hydroxyl
number of from 25 to 40; (ii) 0.1 to 3% by weight, based on 100% by
weight of the sum of components (i), (ii) and (iii), of a
hydroxyl-reactive compound that contains reactive unsaturation that
is selected from the group consisting of isopropenyl dimethyl
benzyl isocyanate, methyl methacrylate, maleic anhydride, adducts
of isophorone diisocyanate and 2-hydroxyethyl methacrylate and
mixtures thereof; (iii) 0.1 to 3% by weight, based on 100% by
weight of the sum of components (i), (ii) and (iii), of one or more
isomers of diphenylmethane diisocyanate.
[0171] Certain embodiments of the present invention are directed to
the polymer polyol compositions of either of the previous two
paragraphs, wherein (A)(3)(a)(i) the starter contains from 1 to 40%
by weight, based on 100% by weight of (A)(3)(a)(i), of ethylene
oxide which is added either as a co-feed or as a cap.
[0172] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous three
paragraphs, wherein (A)(3)(b) the one or more ethylenically
unsaturated monomers comprises a mixture of styrene and
acrylonitrile.
[0173] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous four
paragraphs, wherein (A)(3)(b) the mixtures of styrene and
acrylonitrile is present in a weight ratio of from 20:80 to
80:20.
[0174] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous five
paragraphs, wherein (A)(3)(c) the free radical initiator is
selected from the group consisting of azo compounds and peroxide
compounds.
[0175] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous six
paragraphs, wherein (A) the polymer polyol has a solids content of
from 35 to 70% by weight.
[0176] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous seven
paragraphs, wherein (A)(2) the ethylenically unsaturated monomers
comprises styrene and acrylonitrile in a weight ratio of 80:20 to
20:80.
[0177] Certain embodiments of the present invention are directed to
the Polymer polyol compositions of any of the previous eight
paragraphs, wherein (A)(1) the base polyol has a functionality of
from 3 to 6 and a hydroxyl number of from 25 to 200.
[0178] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous nine
paragraphs, wherein (A)(4) the free radical initiator is selected
from the group consisting of azo compounds, peroxide compounds and
mixtures thereof.
[0179] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous ten
paragraphs, wherein (B) the polyol has a functionality of from 2 to
6 and an OH number of from 25 to 200.
[0180] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous eleven
paragraphs, wherein component (B) is present in an amount
sufficient to reduce the total solids content in said polymer
polyol (A) by at least 33% by weight.
[0181] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous twelve
paragraphs, wherein component (B) is present in an amount
sufficient to reduce the total solids content in said polymer
polyol (A) by at least 61% by weight.
[0182] Certain embodiments of the present invention, therefore, are
directed to a polymer polyol composition having a solids content of
from 10 to 72% by weight, and comprising (A) a polymer polyol
having a solids content of from 44 to 75% by weight, a viscosity at
25.degree. C. of less than 50,000 mPas, and which comprises the
reaction product of: (1) at least one base polyol having a
functionality of from 2 to 8 and a hydroxyl number of from 20 to
400; (2) one or more ethylenically unsaturated monomers; (3) a
preformed stabilizer which comprises the reaction product of: (a) a
macromer that contains reactive unsaturation and comprises the
reaction product of: (i) a starter compound having a functionality
of 2 to 8 and a hydroxyl number of from 20 to 50; (ii) 0.1 to 3% by
weight, based on 100% by weight of the sum of components (i), (ii)
and (iii), of a hydroxyl-reactive compound that contains reactive
unsaturation; and (iii) 0 to 3% by weight, based on 100% by weight
of the sum of components (i), (ii) and (iii), of one or more
diisocyanates; with (b) one or more ethylenically unsaturated
monomers; and (c) at least one free radical initiator; in the
presence of (d) a polymer control agent; and, optionally, (e) a
liquid diluent; in the presence of (2) at least one free radical
initiator; and, optionally, (3) a chain transfer agent; and (B) at
least one polyol component having a functionality of from 1 to 8
and a hydroxyl number of from 20 to 400; wherein component (B) is
present in an amount sufficient to reduce the total solids content
in said polymer polyol (A) by at least 5% by weight.
[0183] Certain embodiments of the present invention are directed to
the polymer polyol compositions of the previous paragraph, wherein
(A)(3)(a) the macromer comprises the reaction product of (i) a
starter compound having a functionality of 3 to 6 and a hydroxyl
number of from 25 to 40; (ii) 0.1 to 3% by weight, based on 100% by
weight of the sum of components (i), (ii) and (iii), of a
hydroxyl-reactive compound that contains reactive unsaturation that
is selected from the group consisting of isopropenyl dimethyl
benzyl isocyanate, methyl methacrylate, maleic anhydride, adducts
of isophorone diisocyanate and 2-hydroxyethyl methacrylate and
mixtures thereof; (iii) 0.1 to 3% by weight, based on 100% by
weight of the sum of components (i), (ii) and (iii), of one or more
isomers of diphenylmethane diisocyanate.
[0184] Certain embodiments of the present invention are directed to
the polymer polyol compositions of either of the previous two
paragraphs, wherein (A)(3)(a)(i) the starter contains from 1 to 40%
by weight, based on 100% by weight of (A)(3)(a)(i), of ethylene
oxide which is added either as a co-feed or as a cap.
[0185] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous three
paragraphs, wherein (A)(3)(b) the one or more ethylenically
unsaturated monomers comprises a mixture of styrene and
acrylonitrile.
[0186] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous four
paragraphs, wherein (A)(3)(b) the mixtures of styrene and
acrylonitrile is present in a weight ratio of from 20:80 to
80:20.
[0187] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous five
paragraphs, wherein (A)(3)(c) the free radical initiator is
selected from the group consisting of azo compounds and peroxide
compounds.
[0188] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous six
paragraphs, wherein (A) the polymer polyol has a solids content of
from 35 to 70% by weight.
[0189] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous seven
paragraphs, wherein (A)(2) the ethylenically unsaturated monomers
comprises styrene and acrylonitrile in a weight ratio of 80:20 to
20:80.
[0190] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous eight
paragraphs, wherein (A)(1) the base polyol has a functionality of
from 3 to 6 and a hydroxyl number of from 25 to 200.
[0191] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous nine
paragraphs, wherein (A)(4) the free radical initiator is selected
from the group consisting of azo compounds, peroxide compounds and
mixtures thereof.
[0192] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous ten
paragraphs, wherein (B) the polyol has a functionality of from 2 to
6 and an OH number of from 25 to 200.
[0193] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous eleven
paragraphs, wherein component (B) is present in an amount
sufficient to reduce the total solids content in said polymer
polyol (A) by at least 33% by weight.
[0194] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous twelve
paragraphs, wherein component (B) is present in an amount
sufficient to reduce the total solids content in said polymer
polyol (A) by at least 61% by weight.
[0195] Certain embodiments of the present invention are directed to
the polymer polyol compositions of any of the previous thirteen
paragraphs, wherein component (A) has a solids content of from 45%
to 75% by weight.
[0196] Certain embodiments of the present invention are directed to
the process of preparing the novel polymer polyol compositions
which have a solids content of from 10 to 72% by weight. This
process comprises blending (A) a polymer polyol having a solids
content of from 30 to 75% by weight, a viscosity at 25.degree. C.
of less than 50,000 mPas, and which comprises the free-radical
polymerization product of: (1) at least one base polyol having a
functionality of from 2 to 8 and a hydroxyl number of from 20 to
400; (2) one or more ethylenically unsaturated monomers; (3) a
preformed stabilizer which comprises the reaction product of: (a) a
macromer that contains reactive unsaturation and comprises the
reaction product of: (i) a starter compound having a functionality
of 2 to 8 and a hydroxyl number of from 20 to 50; (ii) 0.1 to 3% by
weight, based on 100% by weight of the sum of components (i), (ii)
and (iii), of a hydroxyl-reactive compound that contains reactive
unsaturation; and (iii) 0 to 3% by weight, based on 100% by weight
of the sum of components (i), (ii) and (iii), of one or more
diisocyanates; with (b) one or more ethylenically unsaturated
monomers; and (c) at least one free radical initiator; in the
presence of (d) a polymer control agent; and, optionally, (e) a
liquid diluent; in the presence of (2) at least one free radical
initiator; and, optionally, (3) a chain transfer agent; with (B) at
least one polyol component having a functionality of from 1 to 8
and a hydroxyl number of from 20 to 400; wherein component (B) is
present in an amount sufficient to reduce the total solids content
in said polymer polyol (A) by at least 5% by weight.
[0197] Certain embodiments of the present invention are directed to
the process of the previous paragraph wherein (A) the polymer
polyol has a solids content of from 44 to 75% by weight.
[0198] Certain embodiments of the present invention are directed to
the processes of the previous two paragraphs, wherein (A)(3)(a) the
macromer comprises the reaction product of (i) a starter compound
having a functionality of 3 to 6 and a hydroxyl number of from 25
to 40; (ii) 0.1 to 3% by weight, based on 100% by weight of the sum
of components (i), (ii) and (iii), of a hydroxyl-reactive compound
that contains reactive unsaturation that is selected from the group
consisting of isopropenyl dimethyl benzyl isocyanate, methyl
methacrylate, maleic anhydride, adducts of isophorone diisocyanate
and 2-hydroxyethyl methacrylate and mixtures thereof; (iii) 0.1 to
3% by weight, based on 100% by weight of the sum of components (i),
(ii) and (iii), of one or more isomers of diphenylmethane
diisocyanate.
[0199] Certain embodiments of the present invention are directed to
the processes of the previous three paragraphs, wherein
(A)(3)(a)(i) the starter contains from 1 to 40% by weight, based on
100% by weight of (A)(3)(a)(i), of ethylene oxide which is added
either as a co-feed or as a cap.
[0200] Certain embodiments of the present invention are directed to
the processes of the previous four paragraphs, wherein (A)(3)(b)
the one or more ethylenically unsaturated monomers comprises a
mixture of styrene and acrylonitrile.
[0201] Certain embodiments of the present invention are directed to
the processes of the previous five paragraphs, wherein (A)(3)(b)
the mixtures of styrene and acrylonitrile is present in a weight
ratio of from 20:80 to 80:20.
[0202] Certain embodiments of the present invention are directed to
the processes of the previous six paragraphs, wherein (A)(3)(c) the
free radical initiator is selected from the group consisting of azo
compounds and peroxide compounds.
[0203] Certain embodiments of the present invention are directed to
the processes of the previous seven paragraphs, wherein (A)(3)(c)
the free radical initiator is selected from the group consisting of
azo compounds and peroxide compounds.
[0204] Certain embodiments of the present invention are directed to
the processes of the previous eight paragraphs, wherein (A) the
polymer polyol has a solids content of from 35 to 70% by
weight.
[0205] Certain embodiments of the present invention are directed to
the processes of the previous nine paragraphs, wherein (A)(2) the
ethylenically unsaturated monomers comprises styrene and
acrylonitrile in a weight ratio of 80:20 to 20:80.
[0206] Certain embodiments of the present invention are directed to
the processes of the previous ten paragraphs, wherein (A)(1) the
base polyol has a functionality of from 3 to 6 and a hydroxyl
number of from 25 to 200.
[0207] Certain embodiments of the present invention are directed to
the processes of the previous eleven paragraphs, wherein (A)(4) the
free radical initiator is selected from the group consisting of azo
compounds, peroxide compounds and mixtures thereof.
[0208] Certain embodiments of the present invention are directed to
the processes of the previous twelve paragraphs, wherein (B) the
polyol has a functionality of from 2 to 6 and an OH number of from
25 to 200.
[0209] Certain embodiments of the present invention are directed to
the processes of the previous thirteen paragraphs, wherein
component (B) is present in an amount sufficient to reduce the
total solids content in said polymer polyol (A) by at least 33% by
weight.
[0210] Certain embodiments of the present invention are directed to
the processes of the previous fourteen paragraphs, wherein
component (B) is present in an amount sufficient to reduce the
total solids content in said polymer polyol (A) by at least 61% by
weight.
[0211] Certain embodiments of the present invention are directed to
flexible polyurethane foams, wherein the foam comprises the
reaction product of: (I) at least one diisocyanate and/or
polyisocyanate component, or a mixture thereof; with (II) an
isocyanate-reactive component comprising the polymer polyol
composition of any of the paragraphs [0104] through [0130]; in the
presence of (III) one or more catalysts; (IV) one or more blowing
agents; and, optionally, (V) one or more surfactants.
[0212] Certain embodiments of the present invention are directed to
the flexible polyurethane foams of the previous paragraph, wherein
(I) the at least one diisocyanate and/or polyisocyanate component
comprises a mixture of one or more isomers of toluene diisocyanate,
and a mixture of one or more isomers of diphenylmethane
diisocyanate and/or polyphenylmethane polyphenylisocyanate.
[0213] Certain embodiments of the present invention are directed to
any of the flexible polyurethane foams of the previous two
paragraphs, wherein (II) the isocyanate-reactive component
additionally comprises one or more of (1) at least one conventional
polyol selected from the group consisting of polyether polyols,
polyoxyalkylene polyols, polyester polyols, polycarbonate ether
polyols, polycarbonate polyols, polyacetals and polythioethers; and
(2) at least one of chain extenders and crosslinking agents.
[0214] Certain embodiments of the present invention are directed to
any of the flexible polyurethane foams of the previous three
paragraphs, wherein the chain extenders and/or crosslinking agents
are selected from ethylene glycol, 2-methyl-1,3-propanediol, 1,2-
and 1,3-propanediol, 1,3- and 1,4- and 2,3-butanediol,
1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene
glycol, glycerol, trimethyloipropane, pentaerythritol,
diethanolamine, triethanolamine and mixtures thereof, and alkylene
oxide adducts thereof.
[0215] Certain embodiments of the present invention are directed to
any of the flexible polyurethane foams of the previous four
paragraphs, wherein the blowing agent comprises water.
[0216] Certain embodiments of the present invention are directed to
a process for the production of flexible polyurethane foams, by
reacting: (I) one or more diisocyanates, polyisocyanates or
mixtures thereof; with (II) an isocyanate-reactive component
comprising the polymer polyol composition of any of the paragraphs
[0104] through [0130]; in the presence of (Ill) one or more
catalysts; (IV) one or more blowing agents; and, optionally, (V)
one or more surfactants.
[0217] Certain embodiments of the present invention are directed to
the process of the previous paragraph, wherein (I) the at least one
diisocyanate and/or polyisocyanate component comprises a mixture of
one or more isomers of toluene diisocyanate, and a mixture of one
or more isomers of.diphenylmethane diisocyanate and/or
polyphenylmethane polyphenylisocyanate.
[0218] Certain embodiments of the present invention are directed to
any of the processes of the previous two paragraphs, wherein (II)
the isocyanate-reactive component additionally comprises one or
more of (1) at least one conventional polyol selected from the
group consisting of polyether polyols, polyoxyalkylene polyols,
polyester polyols, polycarbonate ether polyols, polycarbonate
polyols, polyacetals and polythioethers; and (2) at least one of
chain extenders and crosslinking agents.
[0219] Certain embodiments of the present invention are directed to
any of the processes of the previous three paragraphs, wherein the
chain extenders and/or crosslinking agents are selected from
ethylene glycol, 2-methyl-1,3-propanediol, 1,2- and
1,3-propanediol, 1,3- and 1,4- and 2,3-butanediol, 1,6-hexanediol,
diethylene glycol, triethylene glycol, dipropylene glycol,
glycerol, trimethylolpropane, pentaerythritol, diethanolamine,
triethanolamine and mixtures thereof, and alkylene oxide adducts
thereof.
[0220] Certain embodiments of the present invention are directed to
any of the processes of the previous four paragraphs, wherein the
blowing agent comprises water.
[0221] The following examples further illustrate details for the
preparation and use of the compositions of this invention. The
invention, which is set forth in the foregoing disclosure, is not
to be limited either in spirit or scope by these examples. Those
skilled in the art will readily understand that known variations of
the conditions and processes of the following preparative
procedures can be used to prepare these compositions. Unless
otherwise noted, all temperatures are degrees Celsius and all parts
and percentages are parts by weight and percentages by weight,
respectively.
EXAMPLES
[0222] The following components were used in the examples. [0223]
Polyol A: A propylene oxide adduct of sorbitol containing 16%
ethylene oxide with a hydroxyl number of 28 [0224] Polyol B: A
propylene oxide adduct of sorbitol containing 16% ethylene oxide
with a hydroxyl number of 36 [0225] Polyol C: A propylene oxide
adduct of glycerin containing 15% ethylene oxide with a hydroxyl
number of 28 [0226] Polyol D: A propylene oxide adduct of glycerin
containing 15% ethylene oxide with a hydroxyl number of 36 [0227]
Base Polyol A: A propylene oxide adduct of glycerine containing a
20% ethylene oxide cap with a hydroxyl number of 36 and having a
viscosity of 820 mPas [0228] Base Polyol B: a glycerin/sorbitol
started polyether polyol containing about 81 to 82% of propylene
oxide and about 17 to 18% of ethylene oxide, having a nominal
functionality of about 3.5 and an OH number of about 31.5 [0229]
CTA: Isopropanol, a chain transfer agent [0230] TMI: Isopropenyl
dimethyl benzyl isocyanate (an unsaturated aliphatic isocyanate)
sold as TMI.RTM. by Allnex [0231] Isocyanate A: A monomeric MDI
comprising about 42% by weight of the 4,4'-isomer of MDI, about 57%
by weight of the 2,4'-isomer of MDI and the balance being the
2,2'-isomer of MDI [0232] Isocyanate B: toluene diisocyanate
comprising 80% by weight of the 2,4-isomer and 20% by weight of the
2,6- isomer, and having an NCO group content of 48.3% [0233] TBPEH:
tert-Butylperoxy-2-ethylhexanoate [0234] AIBN:
2,2'-Azobisisobutyronitrile, a free-radical polymerization
initiator commercially available as VAZO 64 from E.I. Du Pont de
Nemours and Co. [0235] DEOA-LF: diethanolamine, a commercially
available foam crosslinker/foam modifier that is commercially
available from Air Products [0236] Catalyst A: 70% by weight
bis[2-dimethylaminoethyl]ether in 30% dipropylene glycol, an amine
catalyst, commercially available from Momentive Performance
Materials as NIAX A-1 [0237] Catalyst B: 33% by weight
diazabicyclooctane in 67% by weight dipropylene glycol, an amine
catalyst, commercially available from Momentive Performance
Materials as NIAX A-33 [0238] Surfactant A: a silicon surfactant
commercially available as DC5043 from Air Products [0239]
Viscosity: Dynamic viscosities reported in mPas at 25.degree. C.
[0240] Filtration: Filterability was determined by diluting one
part by weight sample (e.g. 200 grams) of polymer polyol with two
parts by weight anhydrous isopropanol (e.g. 400 grams) to remove
any viscosity-imposed limitations and using a fixed quantity of
material relative to a fixed cross-sectional area of screen (e.g.
11/8 in. diameter), such that all of the polymer polyol and
isopropanol solutions passes by gravity through a 150-mesh screen.
The 150-mesh screen is made with a Dutch twill weave. The actual
screen used had a nominal opening of 100 microns. The amount of
sample which passes through the screen within 600 seconds is
reported in percent, a value of 100 percent indicates that over 99
weight percent passes through the screen.
Macromer Preparation:
[0241] The Macromers in Table 1 were prepared by heating the
relative amounts (see Table 1) of polyol, TMI, Isocyanate A, and
100 ppm of bismuth(III)neodecanoate catalyst at 75.degree. C. for 4
hours. Wt. % is based on total macromer weight.
TABLE-US-00002 TABLE 1 Macromers A through R Hydroxyl Percent
Percent Viscosity, Number of TMI Iso A mPa s Macromer Starter
Starter (wt. %) (wt. %) (25.degree. C.) A Polyol A 28 0.45 0.4 3112
B Polyol A 28 1 0.1 1975 C Polyol C 28 0.5 0.2 1550 D Polyol A 28
1.5 0.2 2318 E Polyol C 28 0.5 0 1308 F Polyol C 28 1.5 0.2 1699 G
Polyol D 36 1.5 0 982 H Polyol B 36 1.5 0 1319 I Polyol A 28 1 0.1
1978 J Polyol A 28 1.5 0 1860 K Polyol D 36 0.5 0.2 1009 L Polyol A
28 0.5 0 1472 M Polyol C 28 1.5 0 1410 N Polyol B 36 0.6 0.2 1846 O
Polyol B 36 0.5 0 1206 P Polyol D 36 1.5 0.2 1140 Q Polyol B 36 0.5
0.2 1453 R Polyol A 28 1 0.1 1984
Preformed Stabilizer (PFS) Preparation:
[0242] The pre-formed stabilizer was prepared in a two-stage
reaction system comprising a continuously-stirred tank reactor
(CSTR) fitted with an impeller and 4 baffles (first-stage) and a
plug-flow reactor (second stage). The residence time in each
reactor was about 60 minutes. The reactants were pumped
continuously to the reactor from feed tanks through an in-line
static mixer and then through a feed tube into the reactor, which
was well mixed. The temperature of the reaction mixture was
controlled at 120.+-.5.degree. C. The product from the second-stage
reactor overflowed continuously through a pressure regulator
designed to control the pressure in each stage at 65 psig. The
product, i.e. the pre-formed stabilizer, then passed through a
cooler and into a collection vessel. The preformed stabilizer
formulation is disclosed in Table 2.
[0243] Preformed stabilizers A-R in Table 3 were prepared from
Macromers A-R, respectively, using the following formulation:
TABLE-US-00003 TABLE 2 Preformed Stabilizer Composition Component
PFS CTA type Isopropanol CTA, wt. % 60.0% Macromer Macromer A
Macromer, wt. % 24.0% Monomer, wt. % 15.9% Styrene/acrylonitrile
ratio 50:50 TBPEH, wt. % 0.1%
TABLE-US-00004 TABLE 3 Preformed Stabilizers A-R Preformed
Stabilizer Macromer A A B B C C D D E E F F G G H H I I J J K K L L
M M N N O O P P Q Q R R
Polymer Polyol Preparation:
[0244] This series of examples (Table 4) relates to the preparation
of polymer polyols. The polymer polyols were prepared in a
two-stage reaction system comprising a continuously-stirred tank
reactor (CSTR) fitted with an impeller and 4 baffles (first-stage)
and a plug-flow reactor (second stage). The residence time in each
reactor was about 60 minutes. The reactants were pumped
continuously from feed tanks through an in-line static mixer and
then through a feed tube into the reactor, which was well mixed.
The temperature of the reaction mixture was controlled at
115.+-.5.degree. C. The product from the second-stage reactor
overflowed continuously through a pressure regulator designed to
control the pressure in each stage at 45 psig. The product, i.e.
the polymer polyol, then passed through a cooler and into a
collection vessel. The crude product was vacuum stripped to remove
volatiles. The wt. % total polymer in the product was calculated
from the concentrations of residual monomers measured in the crude
polymer polyol before stripping.
TABLE-US-00005 TABLE 4 Formulations for Polymer Polyols PMPO A PMPO
B PMPO C Base Polyol A A A Base Polyol (wt. % in feed) 51.6 46.5
45.7 PFS A A N PFS (wt. % in feed) 7.8 8.3 8.3 Styrene (wt. % in
feed) 25.6 28.4 28.0 Acrylonitrile (wt. % in feed) 14.8 16.4 16.2
AIBN (wt. % in feed) 0.29 0.32 0.32 CTA (wt. % in feed) 4.7 5.0 6.5
Total Polymer (wt. %) 43.0 47.9 48.0 Viscosity mPa s @ 25.degree.
C. 5185 7375 6632 Filterability - 150 mesh (%) 100 100 100 Mean
particle size (microns) 1.05 1.39 1.42
General Procedure for Making Foams:
[0245] The following PMPO blends were used in the foam formulation
in Table 5: [0246] PMPO Blend A: PMPO A (40 wt. %) was added to
Base Polyol B (60 wt. %) to give Blend A containing a total solids
of 17.2% by weight. [0247] PMPO Blend B: PMPO B (35.8 wt. %) was
added to Base Polyol A (4.2 wt. %) and Base Polyol B (60 wt. %) to
give Blend B containing a total solids of 17.2% by weight. [0248]
PMPO Blend C: PMPO B (35.8 wt. %) was added to Base Polyol B (64.2
wt. %) to give Blend C containing a total solids of 17.2% by
weight. [0249] PMPO Blend D: PMPO C (35.8 wt. %) was added to. Base
Polyol A (4.2 wt. %) and Base Polyol B (60 wt. %) to give Blend D
containing a total solids of 17.2% by weight.
[0250] The foams in Table 5 were prepared by mixing, the
surfactant, water, catalysts, and diethanolamine in a flask to
create a master blend. Then, the desired amount of polymer polyol
blend was added to a cup containing the desired amount of master
blend. The contents of the cup were mixed for 55 seconds. The
desired amount of Isocyanate component necessary to give an
isocyanate index of 100 was added to the cup containing the master
blend and polymer polyol mixture. The contents of the cup were
mixed together for 5 seconds, and the reacting mixture was quickly
poured into a 150.degree. F. water-jacketed mold. After 4.5
minutes, the foam was removed from the mold, run through a
cell-opening crushing device, and then placed in a 250.degree. F.
oven for 30 minutes to post cure. After 24 hours of aging in a
controlled temperature and humidity laboratory, the foams were
submitted for physical property testing.
TABLE-US-00006 TABLE 5 Foam Formulations and Physical Properties
Foam 1 Foam 2 Foam 3 Foam 4 PMPO type Blend A Blend B Blend C Blend
D % Total S/AN 17.2 17.2 17.2 17.2 solids PMPO 100 100 100 100
WATER 3 3 3 3 DEOA-LF 1.73 1.73 1.73 1.73 Surfactant A 0.5 0.5 0.5
0.5 Catalyst B 0.24 0.24 0.24 0.24 Catalyst A 0.1 0.1 0.1 0.1
Isocyanate B 39.57 39.56 39.56 39.56 INDEX 100 100 100 100 Physical
Properties Density (lb/ft.sup.3) 2.4 2.5 2.4 2.5 IFD 25% 42.0 48.0
48.7 49.9 IFD 50% 73.9 84.7 85.9 87.7 IFD 65% 113.0 129.8 131.5
133.5 CFD 50% 0.37 0.42 0.50 0.43 Comp. Set. 9.06 8.82 10.2 9.19
50% HA Ld Loss 0.33 0.36 0.35 0.36 50% HACS 50% 14.0 12.8 11.9 10.8
Wet Set 50% 27.2 20.8 19.1 20.7 Solids 4.3 4.9 5.0 5.1 Efficiency
(50% IFD)* *Solids Efficiency = Measured IFD value (@ 50%
IFD)/17.2% solids
[0251] Although the invention has been described in detail in the
foregoing for the purpose of illustration, it is to be understood
that such detail is solely for that purpose and that variations can
be made therein by those skilled in the art without departing from
the spirit and scope of the invention except as it may be limited
by the claims.
* * * * *