U.S. patent application number 12/751643 was filed with the patent office on 2010-07-22 for polyurethane foams comprising oligomeric polyols.
This patent application is currently assigned to CARGILL, INCORPORATED. Invention is credited to Timothy W. Abraham, Jack A. Carter, Dimitri Dounis, Jeff Malsam.
Application Number | 20100184878 12/751643 |
Document ID | / |
Family ID | 36699037 |
Filed Date | 2010-07-22 |
United States Patent
Application |
20100184878 |
Kind Code |
A1 |
Abraham; Timothy W. ; et
al. |
July 22, 2010 |
POLYURETHANE FOAMS COMPRISING OLIGOMERIC POLYOLS
Abstract
The invention relates to polyurethane foams comprising
oligomeric polyols. In embodiments of the invention, the
polyurethane foams comprise the reaction product of: (a) a
polyisocyanate; and (b) an active-hydrogen containing composition
comprising an oligomeric polyol having a hydroxyl number of about
45 to about 65 mg KOH/g, a number average hydroxyl functionality
(Fn) of less than about 2.7, and about 40% weight or greater
oligomers. The polyurethane foams of the invention may be slabstock
foams or molded foams. Also disclosed are low odor polyols and
polyurethane compositions.
Inventors: |
Abraham; Timothy W.;
(Minnetonka, MN) ; Carter; Jack A.; (Greensboro,
NC) ; Dounis; Dimitri; (Denver, CO) ; Malsam;
Jeff; (Minneapolis, MN) |
Correspondence
Address: |
CARGILL, INCORPORATED
P.O. Box 5624
MINNEAPOLIS
MN
55440-5624
US
|
Assignee: |
CARGILL, INCORPORATED
Wayzata
MN
|
Family ID: |
36699037 |
Appl. No.: |
12/751643 |
Filed: |
March 31, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11411357 |
Apr 25, 2006 |
7691914 |
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12751643 |
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60674879 |
Apr 25, 2005 |
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60677272 |
May 2, 2005 |
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60741123 |
Dec 1, 2005 |
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60786594 |
Mar 27, 2006 |
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Current U.S.
Class: |
521/156 ;
521/159 |
Current CPC
Class: |
C08G 2110/0083 20210101;
C08G 18/36 20130101; C08G 2110/005 20210101; C08G 2110/0008
20210101; C08G 18/6696 20130101; C08G 18/4072 20130101 |
Class at
Publication: |
521/156 ;
521/159 |
International
Class: |
C08G 18/32 20060101
C08G018/32 |
Claims
1. A polyurethane foam comprising the reaction product of: (a) a
polyisocyanate; and (b) an active-hydrogen containing composition
comprising an oligomeric polyol having a hydroxyl number of about
45 to about 65 mg KOH/g, a number average hydroxyl functionality of
less than about 2.7, and about 40% weight or greater oligomers.
2. The polyurethane foam of claim 1, wherein the oligomeric polyol
has from about 55% to about 65% weight oligomers.
3. (canceled)
4. The polyurethane foam of claim 1, wherein the oligomeric polyol
has a number average hydroxyl functionality less than about
2.5.
5. The polyurethane foam of claim 1, wherein the oligomeric polyol
has a number average hydroxyl functionality less than about
2.0.
6. The polyurethane foam of claim 1, wherein the oligomeric polyol
has an acid value that is less than about 1.0 mg KOH/gram.
7. The polyurethane foam of claim 1, wherein the oligomeric polyol
has a number average molecular weight (Mn) of about 1000 to 5000
grams/mole.
8. The polyurethane foam of claim 1, wherein the oligomeric polyol
has a weight average molecular weight (Mw) of about 5000 to 50,000
grams/mole.
9. The polyurethane foam of claim 1, wherein the oligomeric polyol
has a viscosity of about 0.5 to about 10 Pas at 25.degree. C.
10. (canceled)
11. The polyurethane foam of claim 1, wherein the oligomeric polyol
has a residual epoxy oxygen content of about 0.01% to about
5.0%.
12. The polyurethane foam of claim 1, wherein the oligomeric polyol
is made from an epoxidized natural oil.
13. The polyurethane foam of claim 12, wherein the natural oil is
selected from soybean oil, safflower oil, linseed oil, corn oil,
sunflower oil, olive oil, canola oil, sesame oil, cottonseed oil,
palm-based oil, rapeseed oil, tung oil, peanut oil, fish oil, lard,
tallow, and combinations thereof.
14. The polyurethane foam of claim 13, wherein the natural oil
comprises soybean oil.
15. The polyurethane foam of claim 13, wherein the palm-based oil
comprises palm-olein.
16. The polyurethane foam of claim 1, wherein the active-hydrogen
containing composition further comprises a petroleum-derived
polyol.
17. The polyurethane foam of claim 16, wherein the
petroleum-derived polyol is a triol.
18. The polyurethane foam of claim 16, wherein the
petroleum-derived triol has a molecular weight of about 3000
grams/mole.
19. The polyurethane foam of claim 16, wherein the active-hydrogen
containing composition comprises about 45% to about 90% weight
petroleum-derived polyol and about 10% to about 60% weight
oligomeric polyol.
20. The polyurethane foam of claim 1, wherein the polyisocyanate is
toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, polymeric
4,4'-diphenylmethane, or a mixture thereof.
21. The polyurethane foam of claim 1, wherein the active-hydrogen
containing composition comprises about 10% to about 50% weight of
the oligomeric polyol.
22. (canceled)
23. The polyurethane foam of claim 1, wherein the polyurethane foam
is flexible slabstock foam.
24. The polyurethane foam of claim 1, wherein the polyurethane foam
is a molded foam.
25. The polyurethane foam of claim 1, wherein the polyurethane foam
has a density of about 0.5 to about 5.0 lbs/ft.sup.3.
26. The polyurethane foam of claim 1, wherein the wherein the
active hydrogen-containing composition comprises at least 10 PPH
oligomeric polyol, and wherein the polyurethane foam exhibits a
percent tensile strength reduction relative to a control
formulation that is less than or equal to formula (I): percent
tensile strength reduction=0.89.times.(PPH oligomeric polyol) (I)
for polyurethane foam having a density of about 1.5 lb/ft.sup.3 and
a 25% IFD of about 23 N/323 cm.sup.3.
27. The polyurethane foam of claim 26, wherein formula (I) equals:
percent tensile strength reduction=1.0.times.(PPH oligomeric
polyol) (I).
28. The polyurethane foam of claim 1, wherein the active
hydrogen-containing composition comprises at least 10 PPH
oligomeric polyol, and wherein the polyurethane foam exhibits a
tear strength reduction relative to a control formulation that is
less than or equal to formula (II): percent tear strength
reduction=1.40.times.(PPH of oligomeric polyol) (II) for
polyurethane foam having a density of about 1.5 lb/ft.sup.3 and a
25% IFD of about 23 N/323 cm.sup.2.
29. The polyurethane foam of claim 1, wherein the active-hydrogen
containing composition comprises at least 10 PPH oligomeric polyol,
and wherein the polyurethane foam exhibits a percent elongation
reduction that is less than or equal to formula (III): percent
elongation reduction=1.36.times.(PPH of oligomeric polyol) (III)
for polyurethane foam having a density of about 1.5 lb/ft.sup.3 and
a 25% IFD of about 23 N/323 cm.sup.2.
30-52. (canceled)
53. A polyurethane foam comprising the reaction product of: a
polyisocyanate; and an active hydrogen containing composition
comprising at least 10 PPH of an oligomeric polyol having a number
average hydroxyl functionality less than about 2.7, wherein a
polyurethane foam having a density of about 1.5 lb/ft.sup.3 foam
has a tensile strength of at least about 85 kPa.
54. The polyurethane foam of claim 53, wherein the foam has an
elongation of at least about 90%.
55. The polyurethane foam of claim 53, wherein the foam has a tear
of at least about 150 N/m.
56. The polyurethane foam of claim 53, wherein the foam has a 90%
compression set of less than about 20%.
57-63. (canceled)
64. The polyurethane foam of claim 53, wherein the oligomeric
polyol has a hydroxyl number from about 45 to about 65 mg
KOH/g.
65-76. (canceled)
77. The polyurethane foam of claim 53, wherein the foam, upon
exposure to light under ambient conditions for a period of 6 weeks
in the absence of an ultraviolet stabilizer, has a reflectance
specular included color characterized by an (L) value of at least
70 units.
78. The polyurethane foam of claim 53, wherein the foam, upon
exposure to light under ambient conditions for a period of 6 weeks
in the absence of an ultraviolet stabilizer, has a reflectance
specular included color characterized by an (L) value of at least
80 units.
79-84. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application Ser. No. 60/674,879, filed Apr. 25, 2005, entitled
"Foams Incorporating Low Functionality Polyols"; U.S. Provisional
Application Ser. No. 60/677,272, filed May 2, 2005, entitled "Foams
Incorporating Low Functionality Polyols"; U.S. Provisional
Application Ser. No. 60/741,123, filed Dec. 1, 2005, entitled
"Polyurethane Foams Comprising Oligomeric Modified Vegetable
Oil-based Polyols; and U.S. Provisional Application Ser. No.
60/786,594, entitled "Oligomeric Polyols from Palm-Based Oils and
Polyurethane Compositions Made Therefrom", filed Mar. 27, 2006; the
disclosures of which are all incorporated herein by reference in
their entirety.
FIELD
[0002] This invention relates to polyurethane foams comprising
oligomeric polyols.
BACKGROUND
[0003] Flexible polyurethane foams are commonly made by reacting
petroleum-derived polyols or polyol compositions with organic
polyisocyanates in the presence of catalysts, blowing agents and
other optional ingredients. Since the 1960's, flexible polyurethane
foams have been used as a cushioning, load-bearing, and
comfort-providing component of automotive, bedding and
transportation.
[0004] In producing flexible polyurethane foams, several properties
of the polyols or polyol compositions used are important for
manufacturing flexible foams that have desirable characteristics.
One important polyol property is the number average hydroxyl
functionality of the polyol. Typically, to form a flexible
polyurethane foam having desirable characteristics, a polyol having
a number average hydroxyl functionality of about 3 is desired. It
is conventionally understood that as the number average hydroxyl
functionality decreases from that desired range, the quality of the
polyurethane polymer network is lost and the foam characteristics
quickly degrade. Once the number average functionality is 3.0 or
less, it is expected that stable open cell foam will not form or if
formed will have such poor physical properties that it will not be
useful.
[0005] Polyurethane foam properties can be measured by various
methods. In general, foams may be measured for tensile strength,
tear, hardness, elongation, compression, and other properties. The
relative importance of the properties varies, depending upon the
expected use of the foam.
[0006] Petroleum-derived polyols have been widely used in the
manufacturing of foams. However, there has been an increased
interest in the use of renewable resources in the manufacturing of
foams. This has led to research into developing vegetable oil-based
polyols for use in the manufacturing of foams.
[0007] Other researchers have tried to make flexible foam from
biobased polyols. WO 2004/096883A1 and WO2004/09882A1 report how to
make TDI-based conventional slabstock foams from biobased polyol
formulations and provide physical properties of the resulting
foams. The reported biobased polyols have a number average hydroxyl
functionality greater than 2.8.
SUMMARY
[0008] The invention relates to polyurethane foams that comprise
oligomeric polyols. In some embodiments, the polyurethane foams are
slabstock foams, for example, flexible slabstock foams. In other
embodiments, the polyurethane foams are molded foams.
[0009] In one aspect, the invention provides polyurethane foams
comprising the reaction product of: (a) a polyisocyanate; and (b)
an active-hydrogen containing composition comprising an oligomeric
polyol having a hydroxyl number of about 45 to about 65 mg KOH/g, a
number average hydroxyl functionality (Fn) of less than about 2.7,
and about 40% weight or greater oligomers.
[0010] In some embodiments, the oligomeric polyol has a degree of
ring-opening and oligomerization of an epoxidized natural oil that
provides the oligomeric polyol with a desired balance of
properties. That is, the degree of ring-opening and oligomerization
are controlled to provide an oligomeric polyol having a desired
hydroxyl (OH) number, number average hydroxyl functionality (Fn),
epoxy oxygen content (EOC), viscosity, molecular weight, distance
between reactive hydroxyl groups, and the like. For example, in
some embodiments, the epoxidized natural oil is partially
ring-opened in order to provide an oligomeric polyol having a
residual epoxy oxygen content (EOC) of about 0.01 to about 5.5%. In
some embodiments, the degree of oligomerization of the polyol is
controlled so that the oligomeric polyol has about 40% weight or
greater oligomers, for example, about 55% to about 65% weight
oligomers, wherein the oligomers include dimers, trimers,
tetramers, and higher order oligomers. For example, the oligomeric
polyol may comprise about 8% to about 12% weight dimers, about 5%
to about 10% weight trimers, and about 35% weight or greater
tetramers and higher order oligomers. In some embodiments, the
oligomeric polyol has a hydroxyl number from about 45 to about 65
mg KOH/g.
[0011] In some embodiments, the oligomeric polyol is used to
replace at least a portion of one or more petroleum-derived polyols
in a polyurethane foam formulation. For example, in flexible
slabstock polyurethane foam formulations, the oligomeric polyol can
replace at least a portion of a petroleum-derived polyol, for
example, a petroleum-derived triol having a molecular weight of
about 3000 grams/mole and a hydroxyl number of about 56 mg KOH/g.
Accordingly, in some embodiments, the active-hydrogen containing
composition comprises an oligomeric polyol and a petroleum-derived
polyol. Typically, the active-hydrogen containing composition
comprises about 10% to about 60% weight oligomeric polyol and about
40% to about 90% petroleum-derived triol, or about 15% to about 40%
weight oligomeric polyol and about 60% to about 85%
petroleum-derived polyol.
[0012] Advantageously, it has been observed that when the
active-hydrogen containing compound comprises an oligomeric polyol
and a petroleum-derived polyol, the support factor of the resulting
flexible slabstock foam can be controlled by varying the amount of
oligomeric polyol and petroleum-derived polyol independent of the
density of the foam. Specifically, as the amount of oligomeric
polyol is increased, the support factor also increases for constant
density foams.
[0013] In many embodiments, the oligomeric polyol has a low number
average hydroxyl functionality, for example, about 2.7 or less.
Although low hydroxyl functionality polyols are known to
deteriorate some physical properties (e.g., tensile strength, tear
strength, etc.) of flexible polyurethane foams due to the fact that
monofunctional species may act as chain terminators, polyurethane
foams of the present invention have physical properties that are
better than that which would be predicted for foams comprising a
low number average hydroxyl functionality polyol.
[0014] In some embodiments, the polyurethane foams of the invention
have an outer skin density that is lower than the outer skin
density of a polyurethane foam comprising a control formulation
based on petroleum-derived triol. In some embodiments, the density
of the outer skin of the polyurethane foam is reduced by about 0.25
lb/ft.sup.3 or greater as compared to a control formulation. In
some embodiments, the density of the outer skin is reduced by about
0.50 lb/ft.sup.3 or greater, or about 0.75 lb/ft.sup.3 or greater,
or about 1.0 lb/ft.sup.3 or greater as compared to the control
formulation.
[0015] In some embodiments, the polyurethane foams of the invention
have improved hand touch as compared to polyurethane foams
comprising a control formulation that does not include the
oligomeric polyol. Hand touch may be measured, for example, by 5%
IFD, surface roughness, and average cell size. In some embodiments,
the 5% IFD is reduced by about 2% or greater as compared to the IFD
of the control formulation.
[0016] In some embodiments, the polyurethane foams of the invention
have improved flame retardancy as compared to polyurethane foams
comprising a control formulation that does not include the
oligomeric polyol. For example, the polyurethane foams may have
improved char length as measured by Technical Bulletin 117
"Requirements, Test Procedure and Apparatus for Testing the Flame
Retardance of Resilient Filling Materials Used in Upholstered
Furniture" (March 2000).
[0017] In some embodiments, the oligomeric polyols are low in
odor-producing compounds resulting in polyurethane foams having low
odor. Odor can be measured, for example, by measuring the amount of
odor-producing compounds, for example, the compounds hexanal,
nonanal, and decanal. Accordingly, in another aspect, the invention
provides low odor oligomeric polyols and low odor polyurethane
foams made therefrom. In some embodiments, the oligomeric polyol or
polyurethane foam has about 30 ppm or less hexanal. In some
embodiments, the oligomeric polyol or polyurethane foam has about
30 ppm or less nonanal. In some embodiments, the oligomeric polyol
or polyurethane foam has about 20 ppm or less decanal. In some
embodiments, the combined amount of hexanal, nonanal, and decanal
in the oligomeric polyol or polyurethane foam is about 80 ppm or
less.
[0018] Other advantages of the polyurethane foams of the invention
are described herein including, for example, improved water
resistance, color-fastness, and IFD gradient.
[0019] As used herein "polyol" refers to a molecule that has an
average of greater than 1.0 hydroxyl groups per molecule. It may
also include other functionalities.
[0020] As used herein "oligomeric polyol" refers to a non-naturally
occurring polyol prepared by ring-opening a fully or partially
epoxidized natural oil (such as a plant-based oil or an animal fat)
in a manner that results in the formation of oligomers.
[0021] As used herein "oligomer" refers to two or more
triglyceride-based monomers that have been chemically bonded to one
another by an epoxide ring-opening reaction. Oligomers include
dimers, trimers, tetramers, and higher order oligomers.
[0022] As used herein "dimer" refers to two triglyceride-based
monomers that have been chemically bonded to one another by an
epoxide ring-opening reaction.
[0023] As used herein "trimer" refers to three triglyceride-based
monomers that have been chemically bonded to one another by an
epoxide ring-opening reaction.
[0024] As used herein "tetramer" refers to four triglyceride-based
monomers that have been chemically bonded to one another by an
epoxide ring-opening reaction.
[0025] As used herein "slabstock" refers to polyurethane foam made
by mixing the reactants and dispensing them onto a carrier where
they free-rise and cure to form a continuous block or bun of
polyurethane foam that typically has a nominal rectangular
cross-section. Included within slabstock polyurethane foams are
flexible slabstock polyurethane foams.
[0026] As used herein "molded" refers to polyurethane foam that is
prepared by mixing the reactants and dispensing them into a mold
where they react to fill the mold and assume the shape of the mold
cavity.
[0027] As used herein "active hydrogen-containing composition"
refers to a composition that includes reactants having hydrogen
atom-containing groups that are capable of reacting with isocyanate
groups. Examples include alcohols (e.g., polyols) and amines (e.g.,
polyamines).
[0028] As used herein "petroleum-derived polyol" refers to a polyol
manufactured from a petroleum feedstock.
[0029] As used herein "control formulation" refers to a
polyurethane formulation where the oligomeric polyol has been
replaced by an equal amount of petroleum-derived triol such as a
3000 gram/mole petroleum-derived triol.
DETAILED DESCRIPTION
[0030] The invention relates to polyurethane foams (e.g., flexible
slabstock polyurethane foams) comprising oligomeric polyols.
Preparation of Oligomeric Polyols
[0031] The oligomeric polyols useful in the polyurethane foams of
the present invention can be prepared by ring-opening an epoxidized
natural oil. In many embodiments, the ring-opening is conducted
using a reaction mixture comprising: (1) an epoxidized natural oil,
(2) a ring-opening acid catalyst, and (3) a ring-opener. These
materials are described in more detail below. Also useful in some
embodiments of the polyurethane foams of the invention are the
modified vegetable oil-based polyols reported in WO 2006/012344A1
(Petrovic et al.).
[0032] Epoxidized Natural Oil
[0033] The first component is an epoxidized natural oil. Epoxidized
natural oils include, for example, epoxidized plant-based oils
(e.g., epoxidized vegetable oils) and epoxidized animal fats. The
epoxidized natural oils may be partially or fully epoxidized.
Partially epoxidized natural oil may include at least about 10%, at
least about 20%, at least about 25%, at least about 30%, at least
about 35%, at least about 40% or more of the original amount of
double bonds present in the oil. The partially epoxidized natural
oil may include up to about 90%, up to about 80%, up to about 75%,
up to about 70%, up to about 65%, up to about 60%, or fewer of the
original amount of double bonds present in the oil. Fully
epoxidized natural oil may include up to about 10%, up to about 5%,
up to about 2%, up to about 1%, or fewer of the original amount of
double bonds present in the oil.
[0034] Examples of natural oils include plant-based oils (e.g.,
vegetable oils) and animal fats. Examples of plant-based oils
include soybean oil, safflower oil, linseed oil, corn oil,
sunflower oil, olive oil, canola oil, sesame oil, cottonseed oil,
palm-based oils, rapeseed oil, tung oil, peanut oil, and
combinations thereof. Animal fats may also be used, for example,
fish oil, lard, and tallow. The plant-based oils may be natural or
genetically modified vegetable oils, for example, high oleic
safflower oil, high oleic soybean oil, high oleic peanut oil, high
oleic sunflower oil, and high erucic rapeseed oil (crambe oil). The
number of double bonds per molecule in a natural oil may be
quantified by the iodine value (IV) of the oil. For example, a
vegetable oil having one double bond per molecule corresponds to an
iodine value of about 28. Soybean oil typically has about 4.6
double bonds/molecule and has an iodine value of about 127-140.
Canola oil typically has about 4.1 double bonds/molecule and has an
iodine value of about 115. Typically, iodine values for the
vegetable oils will range from about 40 to about 240. In some
embodiments, vegetable oils having an iodine value greater than
about 80, greater than about 100, or greater than about 110 are
used. In some embodiments, vegetable oils having an iodine value
less than about 240, less than about 200, or less than about 180
are used.
[0035] Useful natural oils comprise triglycerides of fatty acids.
The fatty acids may be saturated or unsaturated and may contain
chain lengths ranging from about C12 to about C24. Unsaturated
fatty acids include monounsaturated and polyunsaturated fatty
acids. Common saturated fatty acids include lauric acid (dodecanoic
acid), myristic acid (tetradecanoic acid), palmitic acid
(hexadecanoic acid), steric acid (octadecanoic acid), arachidic
acid (eicosanoic acid), and lignoceric acid (tetracosanoic acid).
Common monounsaturated fatty acids include palmitoleic (a C16
unsaturated acid) and oleic (a C18 unsaturated acid). Common
polyunsaturated fatty acids include linoleic acid (a C18
di-unsaturated acid), linolenic acid (a C18 tri-unsaturated acid),
and arachidonic acid (a C20 tetra-unsaturated acid). The
triglyceride oils are made up of esters of fatty acids in random
placement onto the three sites of the trifunctional glycerine
molecule. Different vegetable oils will have different ratios of
these fatty acids. The ratio of fatty acid for a given vegetable
oil will also vary depending upon such factors, for example, as
where the crop is grown, maturity of the crop, weather during the
growing season, etc. Because of this it is difficult to provide a
specific or unique composition for any given vegetable oil, rather
the composition is typically reported as a statistical average. For
example, soybean oil contains a mixture of stearic acid, oleic
acid, linoleic acid, and linolenic acid in the ratio of about
15:24:50:11. This translates into an average molecular weight of
about 800-860 grams/mole, an average number of double bonds of
about 4.4 to about 4.7 per triglyceride, and an iodine value of
about 120 to about 140.
[0036] In an exemplary embodiment, the epoxidized natural oil is
fully epoxidized soybean oil. Although not wishing to be bound by
theory, it is believed that the use of saturated epoxidized
vegetable oils having residual epoxy groups leads to oligomeric
polyols having good oxidative stability. It is also believed that
the use of unsaturated epoxidized vegetable oils leads to
oligomeric polyols having a lower viscosity as compared to products
prepared using saturated epoxidized vegetable oils.
[0037] In another exemplary embodiment, the natural oil is a
palm-based oil. As used herein "palm-based oil" refers to an oil or
oil fraction obtained from the mesocarp and/or kernel of the fruit
of the oil palm tree. Palm-based oils include palm oil, palm olein,
palm stearin, palm kernel oil, palm kernel olein, palm kernel
stearin, and mixtures thereof. Palm-based oils may be crude,
refined, degummed, bleached, deodorized, fractionated, or
crystallized. In many embodiments, the palm-based oils are refined,
bleached, and deodorized (i.e., an "RBD" oil).
[0038] Palm oil refers to the oil derived from the mesocarp of the
oil palm fruit. Palm oil is typically a semi-solid at room
temperature and comprises about 50% saturated fatty acids and about
50% unsaturated fatty acids. Palm oil typically comprises
predominately fatty acid triglycerides, although monoglycerides and
diglycerides may also be present in small amounts. The fatty acids
typically have chain lengths ranging from about C12 to about C20.
Representative saturated fatty acids include, for example, C12:0,
C14:0, C16:0, C18:0, and C20:0 saturated fatty acids.
Representative unsaturated fatty acids include, for example, C16:1,
C18:1, C18:2, and C18:3 unsaturated fatty acids. Representative
compositional ranges for palm oil are listed in TABLE A.
[0039] Palm olein refers to the liquid fraction that is obtained by
fractionation of palm oil after crystallization at a controlled
temperature. Relative to palm oil, palm olein has a higher content
of unsaturated fatty acids, for example, C18:1 and C18:2 fatty
acids, and has a higher iodine value. In some embodiments, the palm
olein is fractionated multiple times to produce palm olein having a
higher content of unsaturated fatty acids (C18:1, C18:2) and a
higher iodine value. Multiple fractionated palm olein may in some
instances be referred to as super palm olein. Representative
compositional ranges for palm olein are listed in TABLE A.
Representative examples of commercially available palm oil and palm
olein include those commercially available under the trade
designations "SANS TRANS 25", "SANS TRANS-39", and "DURKEX NT100"
from IOI Group, Loders Croklaan Company; and "FULLY REFINED PALM
OLEIN IV 62--SUPEROLEIN" (from Cargill, Incorporated).
[0040] Palm stearin refers to the solid fraction that is obtained
by fractionation of palm oil after crystallization at controlled
temperature. Relative to palm oil, palm stearin contains more
saturated fatty acids and has a higher melting point. A
representative composition for palm stearin is provided in TABLE
A.
TABLE-US-00001 TABLE A Palm Oil Palm Olein Palm Stearin Fatty Acid
(% wt.) (% wt.) (% wt.) C12:0 <1% <1% <1% C14:0 <2%
<2% <2% C16:0 40-50% 35-45% 45-75% C16:1 <1% <1% <1%
C18:0 3-6% 3-5% 4-6% C18:1 35-45% 40-47% 10-40% C18:2 8-12% 10-15%
2-10% C18:3 <1% <1% <1% C20:0 <1% <1% <1% Iodine
50 to 65 55 to 62 20 to 50 Value (IV)
[0041] A partially epoxidized or fully epoxidized natural oil may
be prepared by a method that comprises reacting a natural oil with
a peroxyacid under conditions that convert a portion of or all of
the double bonds of the oil to epoxide groups.
[0042] Examples of peroxyacids include peroxyformic acid,
peroxyacetic acid, trifluoroperoxyacetic acid,
benzyloxyperoxyformic acid, 3,5-dinitroperoxybenzoic acid,
m-chloroperoxybenzoic acid, and combinations thereof. In some
embodiments, peroxyformic acid or peroxyacetic acid are used. The
peroxyacids may be added directly to the reaction mixture, or they
may be formed in-situ by reacting a hydroperoxide with a
corresponding acid such as formic acid, benzoic acid, fatty acids
(e.g., oleic acid), or acetic acid. Examples of hydroperoxides that
may be used include hydrogen peroxide, tert-butylhydroperoxide,
triphenylsilylhydroperoxide, cumylhydroperoxide, and combinations
thereof. In an exemplary embodiment, hydrogen peroxide is used.
Typically, the amount of acid used to form the peroxyacid ranges
from about 0.25 to about 1.0 moles of acid per mole of double bonds
in the vegetable oil, more typically ranging from about 0.45 to
about 0.55 moles of acid per mole of double bonds in the vegetable
oil. Typically, the amount of hydroperoxide used to form the peroxy
acid is about 0.5 to about 1.5 moles of hydroperoxide per mole of
double bonds in the vegetable oil, more typically about 0.8 to
about 1.2 moles of hydroperoxide per mole of double bonds in the
vegetable oil.
[0043] Typically, an additional acid component is also present in
the reaction mixture. Examples of such additional acids include
sulfuric acid, toluenesulfonic acid, trifluoroacetic acid,
fluoroboric acid, Lewis acids, acidic clays, or acidic ion exchange
resins.
[0044] Optionally, a solvent may be added to the reaction. Useful
solvents include chemically inert solvents, for example, aprotic
solvents. These solvents do not include a nucleophile and are
non-reactive with acids. Hydrophobic solvents, such as aromatic and
aliphatic hydrocarbons, are particularly desirable. Representative
examples of suitable solvents include benzene, toluene, xylene,
hexane, isohexane, pentane, heptane, and chlorinated solvents
(e.g., carbon tetrachloride). In an exemplary embodiment, toluene
is used as the solvent. Solvents may be used to reduce the speed of
reaction or to reduce the number of side reactions. In general, a
solvent also acts as a viscosity reducer for the resulting
composition.
[0045] Subsequent to the epoxidation reaction, the reaction product
may be neutralized. A neutralizing agent may be added to neutralize
any remaining acidic components in the reaction product. Suitable
neutralizing agents include weak bases, metal bicarbonates, or
ion-exchange resins. Examples of neutralizing agents that may be
used include ammonia, calcium carbonate, sodium bicarbonate,
magnesium carbonate, amines, and resin, as well as aqueous
solutions of neutralizing agents. Typically, the neutralizing agent
will be an anionic ion-exchange resin. One example of a suitable
weakly-basic ion-exchange resin is sold under the trade designation
"LEWATIT MP-64" (from Bayer). If a solid neutralizing agent (e.g.,
ion-exchange resin) is used, the solid neutralizing agent may be
removed from the epoxidized vegetable oil by filtration.
Alternatively, the reaction mixture may be neutralized by passing
the mixture through a neutralization bed containing a resin or
other materials. Alternatively, the reaction product may be
repeatedly washed to separate and remove the acidic components from
the product. In addition, on or more of the processes may be
combined in neutralizing the reaction product. For example, the
product could be washed, neutralized with a resin material, and
then filtered.
[0046] Subsequent to the epoxidation reaction, excess solvents may
be removed from the reaction product (i.e., fully epoxidized
vegetable oil). The excess solvents include products given off by
the reaction, or those added to the reaction. The excess solvents
may be removed by separation, vacuum, or other method. Preferably,
the excess solvent removal will be accomplished by exposure to
vacuum.
[0047] Useful fully-epoxidized soybean oils include those
commercially available under the trade designations EPOXOL 7-4
(from American Chemical Systems) and FLEXOL ESO (from Dow Chemical
Co.).
[0048] Ring-Opening Acid Catalyst
[0049] In many embodiments, the ring-opening reaction is conducted
in the presence of a ring-opening acid catalyst. Representative
examples of ring-opening acid catalysts include Lewis or Bronsted
acids. Examples of Bronsted acids include hydrofluoroboric acid
(HBF.sub.4), triflic acid, sulfuric acid, hydrochloric acid,
phosphoric acid, phosphorous acid, hypophosphorous acid, boronic
acids, sulfonic acids (e.g., para-toluene sulfonic acid,
methanesulfonic acid, and trifluoromethane sulfonic acid), and
carboxylic acids (e.g., formic acid and acetic acid). Examples of
Lewis acids include phosphorous trichloride and boron halides
(e.g., boron trifluoride). Ion exchange resins in the protic form
may also be used. In an exemplary embodiment, the ring-opening
catalyst is hydrofluoroboric acid (HBF.sub.4). The ring-opening
catalyst is typically present in an amount ranging from about 0.01%
wt. to about 0.3% wt., more typically ranging from about 0.05% wt.
to about 0.15% wt. based upon the total weight of the reaction
mixture.
[0050] Ring-Opener
[0051] The third component of the reaction mixture is a
ring-opener. Various ring-openers may be used including alcohols,
water (including residual amounts of water), and other compounds
having one or more nucleophilic groups. Combinations of
ring-openers may be used. In some embodiments, the ring-opener is a
monohydric alcohol. Representative examples include methanol,
ethanol, propanol (including n-propanol and isopropanol), and
butanol (including n-butanol and isobutanol), and monoalkyl ethers
of ethylene glycol (e.g., methyl cellosolve, butyl cellosolve, and
the like). In an exemplary embodiment, the alcohol is methanol. In
some embodiments, the ring-opener is a polyol. For use in flexible
foams, it is generally preferred to use polyols having about 2 or
less hydroxyl groups per molecule. Polyol ring-openers useful in
making oligomeric polyols for use in flexible foams include, for
example, ethylene glycol, propylene glycol, 1,3-propanediol,
butylene-glycol, 1,4-butane diol, 1,5-pentanediol, 1,6-hexanediol,
polyethylene glycol, and polypropylene glycol. Also useful are
vegetable oil-based polyols.
[0052] Ring-Opening Reaction
[0053] The ring-opening reaction is conducted with a ratio of
ring-opener to epoxide that is less than stoichiometric in order to
promote oligomerization of the resulting ring-opened polyol. In an
exemplary embodiment, an oligomeric polyol is prepared by reacting
fully epoxidized soybean oil (ESBO) with methanol in the presence
of a ring-opening catalyst, for example, fluoroboric acid.
Typically, the molar ratio of methanol to fully epoxidized soybean
oil will range from about 0.5 to about 3.0, more typically ranging
from about 1.0 to about 2.0. In an exemplary embodiment, the molar
ratio of the methanol to the epoxidized soybean oil ranges from
about 1.3 to about 1.7.
[0054] Typically, at the start of the reaction, the fully
epoxidized soybean oil has an epoxide oxygen content (EOC) ranging
from about 6.8% to about 7.4%. The ring-opening reaction is
preferably stopped before all of the epoxide rings are ring-opened.
For some ring-opening catalyst, the activity of the catalyst
decreases over time during the ring-opening reaction. Therefore,
the ring-opening catalyst may be added to the reactive mixture at a
controlled rate such that the reaction stops at (or near) the
desired endpoint EOC. The ring-opening reaction may be monitored
using known techniques, for example, hydroxyl number titration
(ASTM E1899-02), EOC titration (AOCS Cd9-57 method) or monitoring
the heat removed from the exothermic reaction.
[0055] Typically, when fully epoxidized soybean oil is used, the
ring-opening reaction is stopped when the residual epoxy oxygen
content (EOC) ranges from about 0.01% to about 6.0%, for example,
about 0.5% to about 5.5%, about 1% to about 5.0%, about 2% to about
4.8%, about 3% to about 4.6%, or about 3.5% to about 4.5%. When
other epoxidized natural oils are used, the residual epoxy oxygen
content (EOC) of the polyol may be different. For example, for palm
oil, the residual EOC may range from about 0.01% to about 3.5%, for
example, about 0.2% to about 3.0%, about 0.5% to about 2.0%, or
about 0.8% to about 1.5%. As used herein "epoxy oxygen content" or
"EOC" refers to the weight of epoxide oxygen in a molecule
expressed as percentage.
[0056] During the ring-opening reaction, some of the hydroxyl
groups of the ring-opened polyol react with epoxide groups that are
present on other molecules in the reactive mixture (e.g., molecules
of unreacted fully epoxidized soybean oil or molecules of polyol
having unreacted epoxide groups) resulting in oligomerization of
the polyol (i.e., the formation of dimers, trimers, tetramers, and
higher order oligomers). The degree of oligomerization contributes
to the desired properties of the oligomeric polyol including, for
example, number average hydroxyl functionality, viscosity, and the
distance between reactive hydroxyl groups. In some embodiments, the
oligomeric polyol comprises about 40% weight or greater oligomers
(including dimers, trimers, and higher order oligomers). In some
embodiments, the oligomeric polyol comprises about 35% to about 45%
weight monomeric polyol and about 55% to about 65% weight oligomers
(e.g., dimers, trimers, tetramers, and higher order oligomers). For
example, in some embodiments, the oligomeric polyol comprises about
35% to about 45% weight monomeric polyol, about 8% to about 12%
weight dimerized polyol, about 5% to about 10% weight trimerized
polyol, and about 35% weight or greater of higher order
oligomers.
[0057] Oligomerization may be controlled, for example, by catalyst
concentration, reactant stoichiometry, and degree of agitation
during ring-opening. Oligomerization tends to occur to a greater
extent, for example, with higher concentrations of catalyst or with
lower concentration of ring-opener (e.g., methanol). Upon
completion of the ring-opening reaction, any unreacted methanol is
typically removed, for example, by vacuum distillation. Unreacted
methanol is not desirable in the oligomeric polyol because it is a
monofunctional species that will end-cap the polyisocyanate. After
removing any excess methanol, the resulting polyol is typically
filtered, for example, using a 50 micron bag filter in order to
remove any solid impurities.
Properties of the Oligomeric Polyol
[0058] In some embodiments, the oligomeric polyols have a low
number average hydroxyl functionality. Number average hydroxyl
functionality refers to the average number of pendant hydroxyl
groups (e.g., primary, secondary, or tertiary hydroxyl groups) that
are present on a molecule of the polyol. In some embodiments, the
oligomeric polyol has a number average hydroxyl functionality (Fn)
about 2.7 or less, for example, about 2.6 or less, about 2.5 or
less, about 2.4 or less, about 2.3 or less, about 2.2 or less,
about 2.1 or less, about 2.0 or less, about 1.9 or less, about 1.8
or less, about 1.7 or less, about 1.6 or less, about 1.5 or less,
or about 1.4 or less. Typically, the number average hydroxyl
functionality ranges from about 1.5 to about 2.4 or from about 1.7
to about 2.2.
[0059] In some embodiments, the oligomeric polyol has a hydroxyl
number (OH number) that ranges from about 45 to about 65 mg KOH/g,
or from about 55 to about 65 mg KOH/g. Hydroxyl number indicates
the number of reactive hydroxyl groups available for reaction. It
is expressed as the number of milligrams of potassium hydroxide
equivalent to the hydroxyl content of one gram of the sample. A
hydroxyl number in the range of about 45 to about 65 mg KOH/g is
desirable because it facilitates the use of the oligomeric polyol
in flexible slabstock polyurethane formulations where the
oligomeric polyol replaces at least a portion of petroleum-derived
triols that are typically used in such formulations. For example,
in some embodiments, the oligomeric polyol replaces at least a
portion of a petroleum-derived triol having a molecular weight of
about 3000 grams/mole and a hydroxyl number of about 56.
[0060] In some embodiments, the oligomeric polyol has a low acid
value. Acid value is equal to the number of milligrams of potassium
hydroxide (KOH) that is required to neutralize the acid that is
present in one gram of a sample of the polyol (i.e., mg KOH/gram).
A high acid value is undesirable because the acid may neutralize
the amine catalyst causing a slowing of the foaming rate. In some
embodiments, the oligomeric polyol has an acid value that is less
than about 5 (mg KOH/gram), for example, less than about 4 (mg
KOH/gram), less than about 3 (mg KOH/gram), less than about 2 (mg
KOH/gram), or less than about 1 (mg KOH/gram). In exemplary
embodiments, the acid value is less than about 1 (mg KOH/gram), for
example, less than about 0.5 (mg KOH/gram), or from about 0.2 to
about 0.5 (mg KOH/gram).
[0061] In some embodiments, the number average molecular weight
(i.e, Mn) of the oligomeric polyol is about 1000 grams/mole or
greater, for example, about 1100 grams/mole or greater, about 1200
grams/mole or greater, about 1300 grams/mole or greater, about 1400
grams/mole or greater, or about 1500 grams/mole or greater. In some
embodiments, the Mn is less than about 5000 grams/mole, for
example, less than about 4000 grams/mole, less than about 3000
grams/mole, or less than about 2000 grams/mole. In some
embodiments, the Mn ranges from about 1000-5000 grams/mole, for
example, about 1200-3000 grams/mole, about 1300-2000 grams/mole,
about 1700-1900 grams/mole, or about 1500-1800 grams/mole. Number
average molecular weight may be measured, for example, using light
scattering, vapor pressure osmometry, end-group titration, and
colligative properties.
[0062] In some embodiments, the weight average molecular weight
(i.e, Mw) of the oligomeric polyol is about 5000 grams/mole or
greater, for example, about 6000 grams/mole or greater, about 7000
grams/mole or greater, or about 8000 grams/mole or greater. In some
embodiments, the Mw is less than about 50,000 grams/mole, for
example, less than about 40,000 grams/mole, less than about 30,000
grams/mole, or less than about 20,000 grams/mole. In some
embodiments, the Mw ranges from about 5000-50,000 grams/mole, for
example, about 5000-20,000 grams/mole, or about 6000-15,000
grams/mole. Weight average molecular weight may be measured, for
example, using light scattering, small angle neutron scattering
(SANS), X-ray scattering, and sedimentation velocity.
[0063] Typically the oligomeric polyol has a polydispersity (Mw/Mn)
of about 3-15, for example, about 4-12, or about 5-10.
[0064] In some embodiments, the oligomeric polyol has a viscosity
at 25.degree. C. of about 0.5 to about 10 Pas. When soybean oil is
used, the viscosity of the oligomeric polyol typically ranges from
about 2 to about 8 Pas, or from about 3 to about 7 Pas. When a
palm-based oil is used, the viscosity of the oligomeric polyol is
typically about 4 Pas or less, for example, about 3 Pas or less,
about 2 Pas or less, about 1 Pas or less, or about 0.7 Pas or less.
In some embodiments, the viscosity of the oligomeric polyol made
from a palm-based oil is about 0.5 Pas to about 2 Pas.
[0065] In some embodiments, the oligomeric polyol has few, if any,
residual double bonds. This is particularly true if the oligomeric
polyol is prepared from fully epoxidized soybean oil. One measure
of the amount of double bonds in a substance is its iodine value
(IV). The iodine value for a compound is the amount of iodine that
reacts with a sample of a substance, expressed in centigrams iodine
(I.sub.2) per gram of substance (cg I.sub.2/gram). In some
embodiments, the oligomeric polyol has an iodine value that is less
than about 50, for example, less than about 40, less than about 30,
less than about 20, less than about 10, or less than about 5.
Polyurethane Foam
[0066] The invention provides polyurethane compositions that are
useful for preparing polyurethane foams, for example, slabstock
polyurethane foams or molded polyurethane foams. In some
embodiments, the polyurethane foam comprises the reaction product
of:
[0067] (a) a polyisocyanate; and
[0068] (b) an active-hydrogen containing composition comprising an
oligomeric polyol having a hydroxyl number of about 45 to about 65
mg KOH/gram, a number average hydroxyl functionality of less than
about 2.7, and about 40% weight or greater oligomers.
[0069] The hydroxyl groups of the oligomeric polyol chemically
react with the isocyanate groups of the polyisocyanate to form the
urethane linkages in the resulting polyurethane foam. Thus, the
oligomeric polyol is chemically incorporated into the polyurethane
polymer.
[0070] The amount of oligomeric polyol included in the active
hydrogen-containing composition may be selected based upon the
desired performance of the foam. For example, in some embodiments,
the active-hydrogen containing composition may comprise from about
10% to about 90% weight of the oligomeric polyol, for example,
about 10% to about 60% weight oligomeric polyol, or about 15% to
about 40% weight oligomeric polyol.
[0071] In some embodiments, the active-hydrogen containing
composition comprises an oligomeric polyol and a petroleum-derived
polyol. For example, in some embodiments, the active-hydrogen
containing composition comprises about 10% to about 90% weight
oligomeric polyol and about 10% to about 90% weight
petroleum-derived polyol. In some embodiments, the active-hydrogen
containing composition comprises about 10% to about 60% weight
oligomeric polyol and about 40% to about 90% weight
petroleum-derived polyol. In other embodiments, the active-hydrogen
containing composition comprises about 15% to about 40% weight
oligomeric polyol and about 60% to about 85% weight
petroleum-derived polyol.
[0072] In some embodiments, the petroleum-derived polyol is a
triol. As used herein, the term "triol" refers to a polyol that has
an average of about 2.7 to about 3.1 hydroxyl groups per molecule.
In a specific embodiment, the triol has a weight average molecular
weight (Mw) of about 3000 grams/mole to about 3500 grams/mole.
Representative examples of commercially available petroleum-derived
triols include those available under the trade designations ARCOL
F3040, ARCOL F3022, and ARCOL 3222 (from Bayer), PLURACOL 1385 and
PLURACOL 1388 (from BASF), VORANOL 3322, VORANOL 3010, VORANOL
3136, and VORANOL 3512A (from Dow).
[0073] Polyisocyanates
[0074] Representative examples of useful polyisocyanates include
those having an average of at least about 2.0 isocyanate groups per
molecule. Both aliphatic and aromatic polyisocyanates can be used.
Examples of suitable aliphatic polyisocyanates include
1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate,
1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate,
cyclohexane-1,3- and 1,4-diisocyanate,
1,5-diisocyanato-3,3,5-trimethylcyclohexane, hydrogenated 2,4-
and/or 4,4'-diphenylmethane diisocyanate (H.sub.12MDI), isophorone
diisocyanate, and the like. Examples of suitable aromatic
polyisocyanates include 2,4-toluene diisocyanate (TDI), 2,6-toluene
diisocyanate (TDI), and blends thereof, 1,3- and 1,4-phenylene
diisocyanate, 4,4'-diphenylmethane diisocyanate (including mixtures
thereof with minor quantities of the 2,4'-isomer) (MDI),
1,5-naphthylene diisocyanate,
triphenylmethane-4,4',4''-triisocyanate, polyphenylpolymethylene
polyisocyanates (PMDI), and the like. Derivatives and prepolymers
of the foregoing polyisocyanates, such as those containing
urethane, carbodiimide, allophanate, isocyanurate, acylated urea,
biuret, ester, and similar groups, may be used as well.
[0075] The amount of polyisocyanate preferably is sufficient to
provide an isocyanate index of about 60 to about 120, preferably
about 70 to about 110, and, in the case of high water formulations
(i.e., formulations containing at least about 5 parts by weight
water per 100 parts by weight of other active hydrogen-containing
materials in the formulation), from about 70 to about 90. As used
herein the term "isocyanate index" refers to a measure of the
stoichiometric balance between the equivalents of isocyanate used
to the total equivalents of water, polyols and other reactants. An
index of 100 means enough isocyanate is provided to react with all
compounds containing active hydrogen atoms.
[0076] Polyurethane Catalysts
[0077] Examples of useful polyurethane catalysts include tertiary
amine compounds and organometallic compounds. Specific examples of
useful tertiary amine compounds include triethylenediamine,
N-methylmorpholine, N-ethylmorpholine, diethyl ethanolamine, N-coco
morpholine, 1-methyl-4-dimethylaminoethyl piperazine,
3-methoxy-N-dimethylpropylamine,
N,N-diethyl-3-diethylaminopropylamine, dimethylbenzyl amine,
bis(2-dimethylaminoethyl)ether, and the like. Tertiary amine
catalysts are advantageously used in an amount from about 0.01 to
about 5, preferably from about 0.05 to about 2 parts per 100 parts
by weight of the active hydrogen-containing materials in the
formulation.
[0078] Specific examples of useful organometallic catalysts include
organic salts of metals such as tin, bismuth, iron, zinc, and the
like, with the organotin catalysts being preferred. Suitable
organotin catalysts include dimethyltindilaurate,
dibutyltindilaurate, stannous octoate, and the like. Other suitable
catalysts are taught, for example, in U.S. Pat. No. 2,846,408,
which is hereby incorporated by reference. Preferably, about 0.001
to about 1.0 parts by weight of an organometallic catalyst is used
per 100 parts by weight of the active hydrogen-containing materials
in the formulation. Blends of catalysts may also be used.
[0079] Blowing Agents
[0080] The blowing agent generates a gas under the conditions of
the reaction between the active hydrogen compound and the
polyisocyanate. Suitable blowing agents include water, liquid
carbon dioxide, acetone, methylene chloride, and pentane, with
water being preferred.
[0081] The blowing agent is used in an amount sufficient to provide
the desired foam density and IFD. For example, when water is used
as the only blowing agent, from about 0.5 to about 10, preferably
from about 1 to about 8, more preferably from about 2 to about 6
parts by weight, are used per 100 parts by weight of other active
hydrogen-containing materials in the formulation.
[0082] Other Additives
[0083] Other additives that may be included in the formulation
include surfactants, catalysts, cell size control agents, cell
opening agents, colorants, antioxidants, preservatives, static
dissipative agents, plasticizers, crosslinking agents, flame
retardants, and the like.
[0084] Examples of useful surfactants include silicone surfactants
and the alkali metal salts of fatty acids. The silicone
surfactants, e.g., block copolymers of an alkylene oxide and a
dimethylsiloxane, are preferred, with "low fog" grades of silicone
surfactants being particularly preferred.
[0085] In some cases, a static dissipative agent may be included in
the formulation during foam preparation, or used to treat the
finished foam. Useful examples include non-volatile, ionizable
metal salts, optionally in conjunction with an enhancer compound,
as described in U.S. Pat. Nos. 4,806,571, 4,618,630, and 4,617,325.
Of particular interest is the use of up to about 3 weight percent
of sodium tetraphenylboron or a sodium salt of a perfluorinated
aliphatic carboxylic acid having up to about 8 carbon atoms.
Manufacturing of Polyurethane Foams
[0086] Polyurethane foams of the invention can be manufactured
using known techniques for producing conventional slabstock (i.e.,
free-rise) and molded foams. In slabstock processes, the
polyurethane reactants are mixed together and are poured onto a
conveyor where the reacting mixture rises against its own weight
and cures to form a slabstock bun having a nominal rectangular
cross-section. The resulting slabstock bun can be cut into the
desired shape to suit the end-use. In a molded foam process the
reactants are mixed and dispensed into a mold where they react to
fill the mold and assume the shape of the mold cavity. After the
molded foam is cured, the mold is opened and the molded
polyurethane article is removed.
[0087] Slabstock polyurethane foams can be manufactured using
conventional slabstock foaming equipment, for example, commercial
box-foamers, high or low pressure continuous foam machines, crowned
block process, rectangular block process (e.g., Draka, Petzetakis,
Hennecke, Planiblock, EconoFoam, and Maxfoam processes), or
verti-foam process. In some embodiments, the slabstock foam is
produced under reduced pressure. For example, in variable pressure
foaming (VPF), the complete conveyor section of the foaming machine
is provided in an airtight enclosure. This technique allows for the
control of foam density and the production of foam grades that may
otherwise be difficult to produce. Details of such slabstock
foaming processes are reported, for example, in Chapter 5 of
Flexible Polyurethane Foams, edited by Herrington and Hock,
(2.sup.nd Edition, 1997, Dow Chemical Company).
[0088] In some instances, it is desirable to post-cure the foam
after initial forming (and demolding in the case of molded foam) to
develop optimal physical properties. Post-curing may take place
under ambient conditions, for example, for a period of about 12
hours to 7 days; or at elevated temperature, for example, for a
period of about 10 minutes to several hours.
[0089] The foams can be used in a variety of applications, for
example, they may be incorporated into seat components (e.g. seat
cushions, seat backs, arm rests, and the like) for use in motor
vehicles or furniture.
Properties of Polyurethane Foams
[0090] Slabstock polyurethane foams of the invention exhibit a
number of desirable properties including, for example, adjustable
support factor, reduced skin thickness, improved color-fastness,
low odor, improved hand touch, reduced density spread, reduced IFD
spread, improved flame resistance, and improved comfort as measured
by pressure mapping.
[0091] Tensile, Tear, and Elongation
[0092] It is known in the slabstock foam industry that in slabstock
foam, the use of polyols with a low number average hydroxyl
functionality or containing a significant amount of mono-functional
species will cause chain termination of the polyurethane polymer
which may degrade the tensile, tear, elongation, and durability of
the resulting slabstock foam. Surprisingly, slabstock polyurethane
foams of the invention exhibit only a moderate degradation from the
low number average hydroxyl functionality species that are
present.
[0093] In some embodiments, the polyurethane foams of the invention
comprise an active hydrogen containing composition comprising at
least 10 PPH of oligomeric polyol, and the polyurethane foam has a
percent tensile strength reduction (i.e., a reduction relative to a
control formulation) that is equal to or less than that calculated
from the following equation:
% Tensile Strength Reduction=m.times.(PPH of oligomeric polyol)
when the tensile strength is measured using ASTM3574 (modified to a
minimum 3 day cure time) on a slabstock foam having a density of
about 1.5 lb/ft.sup.3 and a 25% IFD of about 23 N/323 cm.sup.2. In
some embodiments, m is equal to 0.89. In other embodiments, m is
equal to 1.0 or 1.1.
[0094] In some embodiments, the polyurethane foams of the invention
comprise an active-hydrogen containing composition comprising at
least 10 PPH of oligomeric polyol, and the polyurethane foam has a
percent tear strength reduction (i.e., a reduction relative to a
control formulation) that is equal to or less than that calculated
from the following equation:
% Tear Strength Reduction=1.40.times.(PPH of oligomeric polyol)
when the tear strength is measured using ASTM 3574 (modified to a
minimum of 3 day cure time) on a slabstock foam having a density of
about 1.5 lb/ft.sup.3 and a 25% IFD of about 23 N/323 cm.sup.2.
[0095] In some embodiments, the polyurethane foams of the invention
comprise an active-hydrogen containing composition comprising at
least 10 PPH of an oligomeric polyol and the polyurethane foam has
a percent elongation reduction (i.e., a reduction relative to a
control formulation) that is less than or equal to that calculated
from the following equation:
% Elongation Reduction=1.36.times.(PPH of oligomeric polyol)
when the elongation is measured using ASTM 3574 (modified to a
minimum of 3 day cure time) on a slabstock foam having a density of
about 1.5 lb/ft.sup.3 and a 25% IFD of about 23 N/323 cm.sup.2.
[0096] In some embodiments, the polyurethane foam comprises an
active-hydrogen composition comprising at least 10 PPH of an
oligomeric polyol having a number average hydroxyl functionality
less than about 2.7, wherein a polyurethane foam having a density
of about 1.5 lb/ft.sup.3 has a tensile strength of at least about
85 kPa.
[0097] Support Factor
[0098] In some embodiments, the slabstock polyurethane foams of the
invention exhibit an increased support factor as compared to a
control formulation that does not include the oligomeric polyol. As
used herein the term "support factor" refers to the ratio of the
65% IFD to the 25% IFD for a slabstock foam sample as shown in the
equation below. Support factor is also sometimes referred to as
"sag factor" or "modulus" and gives an indication of the cushioning
quality of the slabstock foam. As the support factor increases, the
slabstock foam becomes more resistant to bottoming out.
Support Factor=(Firmness at 65% IFD)/(Firmness at 25% IFD)
In the equation, "IFD" refers to "indentation force deflection
value" which is a measure of the load bearing quality of a foam.
IFD is typically expressed in Newtons per 323 square centimeters
(N/323 cm.sup.2) at a given percentage deflection of the foam. The
higher the force, the firmer the slabstock foam. To obtain IFD, a
323 square centimeter circular plate is pushed into the top surface
of a foam sample, stopping at a given deflection, and reading a
force on the scale. For example, a 25% IFD of 150 means that a
force of 150 N/323 cm.sup.2 is required to compress a 100 mm thick
sheet of foam to a thickness of 75 mm.
[0099] In some embodiments, the slabstock polyurethane foams of the
invention exhibit a support factor that can be controlled by
varying the amount of oligomeric polyol that is present in the
slabstock foam. Advantageously, the support factor of the slabstock
foam can be controlled independent of the grade of the slabstock
foam. By increasing the amount of oligomeric polyol, the support
factor also increases. This allows the foam manufacturer to control
the support factor by adjusting the amount of oligomeric polyol and
petroleum-derived polyol in the formulation. In embodiments of the
invention, the support factor may be 1.5 or greater, for example,
1.6 or greater, 1.7 or greater, 1.8 or greater, 1.9 or greater, 2.0
or greater, 2.1 or greater, 2.2 or greater, 2.3 or greater. In some
embodiments, the support factors ranges from about 1.7 to 2.2.
[0100] When the active-hydrogen containing composition comprises an
oligomeric polyol and a petroleum-derived polyol, the support
factor of the polyurethane foam can be controlled by controlling
the relative amounts of oligomeric polyol and petroleum-derived
polyol. For example, in some embodiments, the amount of oligomeric
polyol ranges from about 10% to about 90% weight and the amount of
petroleum-derived polyol ranges from about 10% to about 90% weight.
In other embodiments, amount of oligomeric polyol ranges from about
10% to about 60% weight and the amount of petroleum-derived polyol
ranges from about 40% to about 90% weight. In yet other
embodiments, the amount of oligomeric polyol ranges from about 15%
to about 40% weight and the amount of petroleum-derived polyol
ranges from about 60% to about 85% weight.
[0101] Skin Thickness
[0102] In some embodiments, the flexible slabstock polyurethane
foams of the invention have a thin or low density outer skin. As
used herein, the term "skin" refers to the high density outer layer
that forms on a slabstock foam bun. Typically, the skin layer of
the bun is cut off and it is discarded as waste or scrap.
Minimizing the thickness, or density, of the outer skin results in
an improved net yield of foam because less foam has to be cut off
and discarded. Skin density may be measured, for example, by
measuring the density of a section of the outer layer of the foam
bun.
[0103] In some embodiments, the skin density (i.e., density of the
outer one inch (1'') of foam) of a foam bun comprising an
oligomeric polyol is reduced by about 20% or greater as compared to
a control formulation that does not include the oligomeric polyol.
In some embodiments, the skin density of a foam bun comprising the
oligomeric polyol is reduced by about 0.25 lb/ft.sup.3 or greater
as compared to a control formulation that does not include the
oligomeric polyol. In other embodiments, the skin density is
reduced by about 0.50 lb/ft.sup.3 or greater, or about 0.75
lb/ft.sup.3 or greater, or even about 1.0 lb/ft.sup.3 or greater as
compared to a control formulation that does not include the
oligomeric polyol.
[0104] Color Fastness
[0105] Another useful attribute of the foams is their color
fastness, which refers to their ability to retain their
as-manufactured white color over extended periods of time upon
exposure to light under ambient conditions. Preferably, the foams,
upon exposure to light under ambient conditions for a period of 6
weeks in the absence of an ultraviolet stabilizer, have a specular
reflectance characterized by an (L) value of at least 70 units, a
(b) value of no greater than 25 units, and, preferably, an (a)
value of no greater than 4 units. In addition, the foams, upon
manufacture, preferably have (L), (a), and (b) values meeting the
enumerated values, and these values do not change substantially
upon exposure to light under the conditions described above. In
particular, the (L) and (b) values do not change by more than 14
units, and the (a) value does not change by more than 5 units.
[0106] Odor of Polyol and Polyurethane Foam
[0107] In some embodiments, the polyurethane foams of the invention
exhibit mild odor that is at least as good as, or better than,
control foams prepared using petroleum-derived polyols rather than
the oligomeric polyol. The mild odor makes the foams acceptable for
commercial foam production. Odor may be measured, for example, by
using human test panels or by measuring the amount of certain
odor-producing compounds that may be present in the oligomeric
polyol. Examples of odor-producing compounds include lipid
oxidation products, which are typically aldehyde compounds, for
example, hexanal, nonanal, and decanal. In some embodiments, the
oligomeric polyol or polyurethane foam has about 30 ppm or less
hexanal, for example, about 25 ppm or less, about 20 ppm or less,
about 15 ppm or less, about 10 ppm or less, about 5 ppm or less, or
about 1 ppm or less hexanal. In some embodiments, the oligomeric
polyol or polyurethane foam has about 30 ppm or less nonanal, for
example, about 25 ppm or less, about 15 ppm or less, about 10 ppm
or less, about 5 ppm or less, or about 1 ppm or less nonanal. In
some embodiments, the oligomeric polyol or polyurethane foam has
about 20 ppm or less decanal, for example about 15 ppm or less,
about 10 ppm or less, about 5 ppm or less, or about 1 ppm or less
decanal. In some embodiments, the combined amount of hexanal,
nonanal, and decanal in the oligomeric polyol or polyurethane foam
is about 80 ppm or less, for example, about 70 ppm or less, about
60 ppm or less, about 50 ppm or less, about 40 ppm or less, about
30 ppm or less, about 20 ppm or less, about 10 ppm or less, about 5
ppm or less, or about 3 ppm or less.
[0108] Hand Touch
[0109] In some embodiments, the foams of the invention have
improved hand touch as compared to a control formulation that does
not include the oligomeric polyol. As used herein the term "hand
touch" refers to the feel of polyurethane foam as a human hand is
rubbed lightly over its surface. If the foam is harsh or rough to
the touch, it is described as having "poor hand touch." If the foam
has a smooth or velvet-like feeling, it is described as having
"good hand touch". Although hand touch is a qualitative property,
it has been observed that improved hand touch correlates well with
a decrease in the measured 5% IFD for comparative slabstock
polyurethane foam samples. That is, as the 5% IFD for a sample
decreases, the hand touch is improved.
[0110] In embodiments of the invention, the flexible slabstock
polyurethane foams have a reduced 5% IFD as compared to control
formulations that do not include the oligomeric polyol. For
example, the 5% IFD may be reduced by about 2% or greater as
compared to the control formulation. In other embodiments, the 5%
IFD may be reduced by 5% or greater as compared to the control
formulation.
[0111] Hand touch may also be correlated to the surface roughness
of flexible slabstock polyurethane foam. Microscopically, the
surface of a foam sample consists of a series of high and low
points. A perthometer provides a quantitative measurement ("Ra") of
the average height of these high and low points on the surface of
the foam. A high Ra value indicates a rough surface correlating to
poor hand touch. A low Ra value indicates a smooth surface
correlating to improved hand touch. Ra for a slabstock polyurethane
foam can be measured using a perthometer, for example, those
commercially available from Mahr GmbH, Gottingen, Germany.
[0112] Hand touch may also be correlated to the average cell size
(e.g., average cell diameter) of the polyurethane foam. As the
average cell size decreases, the foam exhibits improved hand touch.
Average cell size can be measured, for example, by manually
measuring a microscopic image of the foam or by using computer
software to automatically measure the cell size in a microscopic
image.
[0113] Flame Retardancy
[0114] In some embodiments, the foams of the invention have
improved flame retardancy as compared to a control formulation that
does not include the oligomeric polyol. Flame retardancy may be
tested, for example, in accordance with Technical Bulletin 117,
"Requirements, Test Procedure and Apparatus for Testing the Flame
Retardance of Resilient Filling Materials Used in Upholstered
Furniture" (March 2000). Flame retardancy is typically improved by
the addition of one or more flame retardancy agents, for example,
halogenated phosphate, alumina trihydrate, or melamine. Typically,
such agents are added to the polyurethane composition in an amount
ranging from about 6% to 10% by weight halogenated phosphate or up
to about 50% by weight alumina trihydrate or melamine.
[0115] IFD Gradient in Slabstock Buns
[0116] Production buns of flexible slabstock foam are typically
quite large, for example, about 7 feet wide, about 4' tall, and up
to about 300 feet in length. In order to make furniture cushions
having desirably constant properties, it is preferred to have
minimal variation in hardness (e.g., as measured by 25% IFD) and
density across the bun of slabstock foam. Polyurethane foams of the
invention have been observed to have reduced variation in 25% IFD
as compared to a control formulation that does not include an
oligomeric polyol.
[0117] Water Resistance
[0118] In some embodiments, the slabstock polyurethane foams of the
invention exhibit improved water resistance or increased
hydrophobicity as compared to a control formulation that does not
include the oligomeric polyol. Improved water resistance is
important, for example, in outdoor applications and in marine
applications. The water resistance or hydrophobicity of a slabstock
foam can be measured, for example, by placing a measured amount of
water on a surface of the foam and measuring the period of time it
takes for the water to be absorbed into the cellular structure of
the foam. A higher absorption time is characteristic of a foam that
has increased water resistance or hydrophobicity. In some
embodiments, the water absorption time of foams of the invention
are increased by about 20% or more, for example, about 30% or more,
about 40% or more, or about 50% or more as compared to a control
foam that does not include the oligomeric polyol.
[0119] Soft Feel
[0120] In some embodiments, the polyurethane foams of the invention
have a lower 5% IFD while maintaining about the same 25% IFD when
compared to a control formulation that does not include the
oligomeric polyol. This desirable balance of 5% IFD and 25% IFD may
allow a reduction in the amount of polyester (PET) fiber used in
furniture cushions made from the polyurethane foams of the
invention. Specifically, the low 5% IFD provides the foam with a
softer feel, which has heretofore been provided by wrapping the
polyurethane foam with soft polyester fiber.
[0121] The invention will be further illustrated with reference to
the following examples which are intended to aid in the
understanding of the present invention, but which are not to be
construed as a limitation thereof.
EXAMPLES
Abbreviations
[0122] Acid Value (AV)--also known as acid number, measured in (mg
KOH/gram polyol). Iodine Value (IV)--a measurement of the amount of
double bonds in a substance expressed in terms of the number of
centigrams of iodine (I.sub.2) that reacts with a gram of the
substance. Hydroxyl Number (OH Number)--hydroxyl number, measured
in mg KOH/gram polyol. Fn--number average hydroxyl functionality
expressed in number of hydroxyl groups per molecule. Fn is
calculated using the equation Fn=(OH#/56)*(Mn/1000), where Mn is
measured from vapor pressure osmometry. EOC--epoxide oxygen content
(% oxygen from epoxide). Mn (GPC)--number average molecular weight
in (grams/mole) as measured by GPC. Mn (LS)--number average
molecular weight in (grams/mole) as measured by light scattering.
Mn (VPO)--number average molecular weight in (grams/mole) as
measured by vapor pressure osmometry. EW--hydroxyl equivalent
weight calculated as (Mn/Fn) Mw (LS)--weight average molecular
weight in (grams/mole) as measured by light scattering. Monomer
(Mon)--percent weight of monomer in the polyol. Dimer
(Dim)--percent weight of dimer in the polyol. Trimer
(Trim)--percent weight of trimer in the polyol. Tetramer+
(Tetr+)--percent weight of tetramer and higher order oligomers in
the polyol. % Oligomer--total percent weight of all dimer, trimer,
tetramer, and higher order oligomers. g'M--a GPC measure of the
hydrodynamic diameter of the polyol by GPC that is used to
characterize the extent of oligomerization relative to a styrene
standard. g'M decreases as oligomerization increases.
Viscosity--viscosity of a substance measured in Pas at 25.degree.
C. CS=Compression Set expressed as a percentage. PV=peroxide value
as measured by AOCS method Cd 8b-90 and reported in (meq
peroxide/1000 grams sample). B-Side Masterbatch--The premixture of
polyol(s), surfactant(s), crosslinker(s), catalyst(s), additive(s)
and blowing agent(s) that will be later combined with a desired
polyisocyanate to initiate a foam producing reaction. Foam Odor--In
some cases, immediately after a foam is made, each foam was rated
for its odor characteristics. A normal rating was assigned to foams
exhibiting an odor no different from that normally expected from
freshly prepared foam using conventional technology. In other
examples, the foam sometimes took on a notable odor that could be
traced back to the particular polyol being used. A rating of mild
was assigned to those foams having a notably different but not
objectionable level of odor. A rating of strong indicates that the
odor was different and present at such a level that most observers
would object to it. Foam Tightness--A subjective assessment of how
closed cell or open cell a foam is. Tightness infers that the foam
is more closed cell than open. Loadbearing Characteristics--A
collective term used to refer to the results found in testing the
loadbearing capacity of a flexible foam. The normally reported data
include the 25% and 65% indentation force deflection values.
MDI--methylene bis(phenylisocyanate). Sag Factor--a number
calculated as the ratio of the 65% indentation force deflection
value to the 25% indentation force deflection value. TDI--toluene
diisocyanate.
Materials:
[0123] The following materials were used in Examples 1-14:
[0124] Arcol.RTM. F-3022--a petroleum-derived, nominal 3000
molecular weight polyether triol made by the addition of propylene
oxide and ethylene oxide to a glycerine-based initiator compound.
Typical features of the commercially available product include a
water-white color, terminal hydroxyls that are all secondary in
nature, a hydroxyl number of approximately 56, and a 25.degree. C.
viscosity in the range of 480 mPas. The material reveals a very
mild and characteristic polyether polyol odor. This material is
available from Bayer Corporation.
[0125] Soybean oil--when mentioned in this patent soybean oil
refers to commercially available oil of a refined, bleached and
deodorized (RBD) grade.
[0126] Flexol.RTM.--an epoxidized soybean oil, available from Union
Carbide or other commercially available brands of epoxidized
soybean oil. Commercial epoxidized soybean oil typically has the
following properties:
TABLE-US-00002 Specification Limit Method Oxirane, % 6.8 min. AOCS
Cd 9-57 or ACS PER-OXI Rev. 000 Acid Value 0.3 max. AOCS Cd 3d-63
or (mg KOH/g) Equivalent Iodine Value 1.5 max. AOCS Cd 1-25 Gardner
Color 1.0 max. AOCS Td 1a-64
[0127] Dabco.RTM. BL-11--A commercial catalyst product from Air
Products Corporation consisting of a 70 weight % solution of
bis(dimethylaminoethyl)-ether in dipropylene glycol. Typically used
as a catalyst for the blowing reaction.
[0128] Dabco.RTM. DC-5169--A commercial surfactant product from Air
Products Corporation.
[0129] Dabco.RTM. 33-LV--A commercial catalyst product from Air
Products Corporation consisting of a 33 weight % solution of
triethylene-diamine in dipropylene glycol. Typically used as a
polymerization or gelling catalyst.
[0130] DEOA--commercial grade diethanol-amine used as a foam
stabilizing crosslinker.
[0131] Niax.RTM. D-19--A tin-based gelling catalyst available from
GE Silicones-OSI Specialties, Inc.
[0132] Niax.RTM. Y-10184--A silicone-based surfactant available
from GE Silicones-OSI Specialties, Inc. The product is designed for
use in making flexible molded polyurethane foams.
[0133] Tegostab.RTM. B-2370--A commercial surfactant product from
Degussa AG designed for conventional slabstock foam use.
[0134] Tegostab.RTM. B-4690 LF--A low fogging grade of surfactant
commercially available from Degussa AG.
[0135] Toluene Diisocyanate--an 80/20 blend of the 2,4 and 2,6
isomers of toluene diisocyanate obtained from Bayer Corporation and
identified as Grade A of their Mondur.RTM. TD-80 product.
[0136] Water--distilled water was used as an indirect blowing
agent.
Example 1
Partially Epoxidized Soybean Oil A
[0137] A partially epoxidized soybean oil was prepared as
follows:
[0138] A 5-liter, 3-neck, round bottom flask was equipped with
temperature control, an addition funnel, reflux condenser and
stirring. To this reactor system was added: 1500 grams of soybean
oil (RBD grade having an Iodine Value of 131 and a viscosity of 62
mPas, available from Archer Daniels Midland Company); 225 grams of
glacial acetic acid (available from Fisher); and 19 grams of a 50%
solution of sulfuric acid in water (available from Aldrich). These
ingredients were thoroughly mixed while the reactor system was
brought up to a temperature of 70.degree. C. After attaining the
temperature set point, 729 grams of a 35% solution of hydrogen
peroxide in water (available from Aldrich) was added from a
dropping funnel over a period of 30 minutes while maintaining the
70.degree. C. temperature set point and continuing vigorous
stirring.
[0139] After an additional 60 minutes of reaction time, the
contents of the reactor system were transferred to a 3 liter
separatory funnel and allowed to cool down. During the cool down
period, the water and crude partially epoxidized soybean oil
separated into two layers. Product work-up continued by draining
off this first water layer and then water washing the crude
partially epoxidized soybean oil layer three separate times with 1
liter aliquots of distilled water. The washed partially epoxidized
soybean oil was then isolated again and added to an Erlenmeyer
flask, and 100 grams of a basic ion exchange resin (Lewatite MP-64
from Bayer) was added. This mixture was stirred for 2 hours to
allow neutralization of any remaining acid. The product was then
filtered to remove the ion exchange resin and subjected to a low
vacuum to remove residual water.
[0140] A partially epoxidized soybean oil product was obtained
having an iodine value of 83 an epoxy oxygen content (EOC) of
2.74%. A summary of the process used and values obtained can be
found in TABLE 1.1.
TABLE-US-00003 TABLE 1.1 Partially Epoxidized Vegetable Oils Temp
Soybean Acetic (.degree. C.) H.sub.2O.sub.2 Ion Viscosity Oil Acid
H.sub.2SO.sub.4 (preheat/ 35% Ratio Time Resin EOC Iodine (Pa s at
Sample (g) (g) (g) rxn) (g) DB:AA:H.sub.2O.sub.2 (min) (g) (%)
Value 25.degree. C.) EX 1 1500 225 19 70/70 729 1:0.5:1 60 100 2.74
83 --
Example 2
Partially Epoxidized Soybean Oil B
[0141] A partially epoxidized soybean oil was prepared according to
Example 1, except that the amounts of reactants used and timing was
as listed in TABLE 2.1 for the row "EX2." A final partially
epoxidized soybean oil product was obtained having characteristics
as shown in TABLE 2.1.
TABLE-US-00004 TABLE 2.1 Soybean Acetic Temp .degree. C.
H.sub.2O.sub.2 Ion Viscosity Oil Acid H.sub.2SO.sub.4 (preheat/ 35%
Ratio Time Resin EOC Iodine (Pa s at Sample (g) (g) (g) rxn) (g)
DB:AA:H.sub.2O.sub.2 (min) (g) (%) Value 25.degree. C.) EX 2 500 75
6.3 70/70 147 1:0.5:0.6 60 40 2.65 83 --
Example 3
Partially Epoxidized Soybean Oil C
[0142] A partially epoxidized soybean oil was prepared according to
Example 1, except using the amounts of reactants and time as listed
in TABLE 3.1 for the row "EX3." In addition, the hydrogen peroxide
was added by a peristaltic pump at a rate of 7.5 ml/min, rather
than by a dropping funnel over 30 minutes. A final partially
epoxidized soybean oil product was obtained having characteristics
as shown in TABLE 3.1.
TABLE-US-00005 TABLE 3.1 Soybean Acetic Temp .degree. C.
H.sub.2O.sub.2 Ion Viscosity Oil Acid H.sub.2SO.sub.4 (preheat/ 35%
Ratio Time Resin EOC Iodine (Pa s at Sample (g) (g) (g) rxn) (g)
DB:AA:H.sub.2O.sub.2 (min) (g) (%) Value 25.degree. C.) EX 3 1500
225 9 65/70 600 1:0.5:0.73 3 75 3.56 71 0.16
Example 4
Polyol A
[0143] Polyol preparation began with the experimental setup of a 1
liter, 3-neck, round bottom flask equipped with temperature
control, an addition funnel, reflux condenser and stirring. To this
reactor system was added 80 grams of methanol and 0.7 grams of
fluoroboric acid (as a 48% mixture with water, available from
Aldrich). These ingredients were thoroughly mixed while the reactor
system was brought to boiling. Then 250 grams of the partially
epoxidized soybean oil prepared according to Example 1 was quickly
added to the vigorously stirred reactor.
[0144] After an additional 40 minutes of reaction time, the mixture
was cooled to 50-60.degree. C., and about 15 grams of a basic ion
exchange resin (Lewatite MP-64 from Bayer) was added to neutralize
the acid. This mixture was stirred for 1 hour and then allowed to
cool down. Product recovery continued by filtering off the solid
ion exchange resin and removal of residual water and alcohol by
vacuum distillation. A summary of the process and amounts of
reactants used can be found in TABLE 4.1 for "EX4". A summary of
the properties of the resulting oligomeric polyol may be found in
TABLE 4.2 for "EX4".
TABLE-US-00006 TABLE 4.1 Vegetable Oil-Based Polyols Unsaturated
Catalyst Epoxidized. (48% Ratio Ion Soy Oil Feed HBF.sub.4) AMC
Methanol:Epoxy resin Sample Methanol (g) (g) Oil (g) (g) groups (g)
EX 4 80 250 EX 1 0.7 0 6:1 15 EX 5 -- 250 EX 4 -- 2.5 -- -- EX 6
164 500 EX 2 1.4 0.5 6:1 20 EX 7 454 1500 EX 3 4.1 1.5 6:1 60
TABLE-US-00007 TABLE 4.2 Properties of Vegetable Oil-Based Polyols
OH Number Acid Value Viscosity (mg EOC Iodine (mg at 25.degree. C.
Water Oliomer/Monomer Sample KOH/g) (%) Value KOH/gram) (Pa s) (%)
Color Fn Ratio EX 4 98 0.01 77 2.4 0.4 -- Yellow -- 21:79 EX 5 100
0.01 67 2.5 0.43 0.027 Dark -- 20:80 Yellow EX 6 94 0.013 79 0.334
0.26 -- Yellow 1.93 16:84 EX 7 88 0.005 90 0.714 0.22 0.038 -- 1.8
14:86
Example 5
Polyol B
[0145] A 1 liter Erlenmeyer flask was equipped with temperature
control, an addition funnel, reflux condenser and stirring. 250
grams of a polyol prepared according to Example 4 and 2.5 grams of
ammonium carbonate were added to the flask. The ingredients were
thoroughly mixed while the reactor system was brought to
60-70.degree. C.
[0146] After 15 minutes of stirring, the contents of the reactor
system were transferred to a 1-liter separatory funnel and allowed
to cool down. During the cool down period, the water and crude
polyol separated into two layers. Product work-up continued by
draining off this first water layer and then water washing the
crude polyol layer five separate times with 500 milliliter aliquots
of distilled water. The product was then subjected to a low vacuum
to remove residual water. A summary may be found in TABLE 4.1 for
"EX5". The final recovered oligomeric polyol had the properties as
shown in TABLE 4.2 for "EX5".
Example 6
Polyol C
[0147] A polyol was prepared by following the procedure according
to Examples 4 and 5, except using the amounts of reactants and time
as listed in TABLE 4.1 for the row "EX6." The final recovered
oligomeric polyol had the properties as shown in TABLE 4.2 for
"EX6".
Example 7
Polyol D
[0148] A polyol was prepared by following the procedure according
to Examples 4 and 5, except using the amounts of reactants and time
as listed in TABLE 4.1 for the row "EX7." The final recovered
oligomeric polyol had the properties as shown in TABLE 4.2 for
"EX7".
Example 8
Polyol E
[0149] The preparation of Polyol E began with the experimental
setup of a 2 liter, 3-neck, round bottom flask equipped with
temperature control, an addition funnel, reflux condenser and
stirring. To this reactor system was added 35.5 grams of methanol
(certified A.C.S., available from Fisher) and 1.12 grams of
fluoroboric acid (as a 48% mixture with water, available from
Aldrich). These ingredients were thoroughly mixed while the reactor
system was brought up to a temperature of 50.degree. C. After
attaining the temperature set point, 400 grams of an epoxidized
soybean oil ("Flexol," available from Union Carbide) was added to
the reactor. Vigorous stirring continued and the reactor
temperature was increased to 90.degree. C. After 30 minutes of
reaction at these conditions, an additional 100 grams of epoxidized
soybean oil ("Flexol") was added to the reactor and the reaction
continued for an additional 3 hours.
[0150] After 3 hours, the reactor was cooled down to 60.degree. C.
and 15 grams of a basic ion exchange resin (Lewatite MP-64 from
Bayer) was added. This mixture was allowed to stir for 1 hour to
neutralize any remaining acid. The product was then filtered to
remove the ion exchange resin and subjected to a low vacuum to
remove residual water and solvent. In addition, under GPC analysis,
the polyol showed the following composition: 47% monomer; 12%
dimer; 8% trimer; and 33% tetramer & high oligomers. The
properties of the final polyol obtained are shown in TABLE 8.1 for
"EX8". Several other lots of Polyol E were prepared and were used
in Example 10 (see, TABLE 10.1).
TABLE-US-00008 TABLE 8.1 Polyol Properties OH Mn Number Acid Value
Viscosity (GPC) (mg EOC (mg at 25.degree. C. Water (grams/
Oligomers Sample KOH/g) (%) KOH/gram) (Pa s) (%) mole) EW Fn (%) EX
8 83 3.07 0.49 5.7 -- 1700 -- 2.5 53
Example 9
Polyol F
[0151] A series of polyols were produced according to the
preparation of Example 8, except that 33 grams of methanol and
0.05% catalyst were used. These same conditions were repeated four
times to produce four different samples. The resulting polyols had
a light soy oil odor and the properties reported in TABLE 9.1 for
EX9-1, EX9-2, EX9-3, and EX9-4.
TABLE-US-00009 TABLE 9.1 Polyol Properties OH Mn Number Acid Value
Viscosity (GPC) (mg EOC (mg at 25.degree. C. Water (grams/
Oligomers Sample KOH/g) (%) KOH/gram) (Pa s) (%) mole) EW Fn (%) EX
9-1 53.77 4.23 0.33 4.0 0.06 1668 1044 1.6 54.73 EX 9-2 60.43 4.09
0.29 5.1 0.07 1758 929 1.89 56.9 EX 9-3 57.23 3.95 0.29 5.4 0.066
1777 980.4 1.81 58.67 EX 9-4 57.46 4.17 0.33 4.72 0 1759 976.5 1.8
56.94
Example 10
Foams Made Using Polyol E
Preparation of Flexible Foams
[0152] (a) Preparation of Masterbatches
[0153] As a first step in the making of the molded flexible foams
listed in the examples, formulation B-Side masterbatches were made
by adding the various ingredients of the desired foam formulation
to a 1-gallon wide mouth plastic jug. The polyols were added to the
jug first and then placed on an electric, lab duty mixer equipped
with a Jiffy Mixer brand, Model HS-2, mixing blade. Mixing was
started and all other formulation ingredients were added in turn
while the mixer continued to run. After addition of the last
formulation ingredient, mixing continued for an additional 15
minutes. The masterbatch was then removed from the mixer and a 1000
milliliter wide mouth glass jar sample taken for measurement of
viscosity and observation of color and clarity. The remaining
masterbatch was capped and allowed to sit while other preparations
for foam making were completed.
[0154] After temperature conditioning to 25.degree. C., measurement
of the masterbatch viscosity was done using a traditional
rotational style, Brookfield brand, viscometer.
[0155] (b) Procedure for Mixing Ingredients and Foam Production
[0156] Foam production is begun by adding the desired amount of a
formulation B-Side masterbatch to a 33-ounce poly cup (Model
DMC-33, available from International Paper Company). All of the
molded example foams were prepared at a toluene diisocyanate index
of 105. For each formulation, the calculated amount of toluene
diisocyanate was carefully weighed out into a 400-milliliter
tri-pour style plastic beaker and set aside near the mixing
station.
[0157] To initiate the foam producing reactions, the cup containing
the B-Side masterbatch was placed on a mixing device built from a
Delta ShopMaster brand, Model DP-200, 10-inch size shop drill press
fitted with a 3 inch mixing blade (Conn Mixers Company; ConnBlade
Brand, Model ITC, 3-inch diameter). The mixer was set to run at
1100 RPM for a total time of 30 seconds which was controlled by an
electronic count down timer. Mixing was initiated by a foot switch.
As the timer counted down, the beaker of toluene diisocyanate was
picked up and at 6 seconds mixing time remaining, the toluene
diisocyanate was quickly added to the cup.
[0158] At the end of the mixing cycle, the contents of the mixing
cup were allowed to free rise. During the cure period, the center
of the cup was closely observed so that a rise time for that
particular formulation could be recorded.
[0159] At the end of the cure cycle, the foam was removed from the
cup. The foam samples were trimmed, weighed, labeled and allowed to
sit for several days at 25.degree. C. and 50% relative humidity
before testing for physical properties.
Physical Property Testing
[0160] Physical properties of the flexible foams were measured
following the procedures listed in ASTM D 3574. Note that in some
cases the foams were tested before the full 7 day recommended cure
time.
[0161] The following section shows data from conventional slabstock
foams made with different oligomeric polyol formulations. Each of
the oligomeric polyols has the characteristic of having low number
average hydroxyl functionality. However, the physical properties of
the resulting foams were surprisingly good given previous
expectations about the number average hydroxyl functionality of the
polyol used.
[0162] Samples of foams made using polyol E were prepared according
to the above procedure. The tables below show the foam formulations
(TABLE 10.2) and physical property data (TABLE 10.3) of foams made
with two different surfactants.
TABLE-US-00010 TABLE 10.1 Characteristics of Polyol E OH Number
Acid Value Viscosity at (mg Water (mg 25.degree. C. EOC Polyol
KOH/g) (%) KOH/gram) (Pa s) (%) E-1 74.89 0.051 0.42 7.23 3.41 E-2
71.88 0.045 0.55 5.44 3.53 E-3 73.67 0.041 0.51 5.43 3.46
TABLE-US-00011 TABLE 10.2 Polyurethane Formulations Ingredient 10-1
10-2 10-3 10-4 10-5 10-6 Control 1 Control 2 Polyol F- 60 60 60 60
60 60 100 100 3022 E-1 40 40 0 0 0 0 0 0 E-2 0 0 40 40 0 0 0 0 E-3
0 0 0 0 40 40 0 0 B-8221 1 0 1 0 1 0 1 0 (Silicone Surfactant)
EP-H-140 0 1 0 1 0 1 0 1 (Silicone Surfactant) BL-11 0.23 0.23 0.23
0.23 0.265 0.265 0.265 0.265 (Amine) K-29 0.14 0.14 0.14 0.14 0.14
0.155 0.155 0.155 (Tin Catalyst)
TABLE-US-00012 TABLE 10.3 Polyurethane Physical Properties 90% CS
Pores/ Density Resiliency 25% 65% Support CFD Tensile Elongation
Tear Perm (% Inch Sample (pcf) (%) IFD IFD Factor (kPa) (kPa) (%)
(N/m) (cfm) loss) (PPI) 10-1 1.49 28.67 24.39 39.66 1.63 2.02 56.45
73.58 145.0 1.42 14.90 15.24 10-2 1.57 29.67 25.72 48.52 1.89 2.13
75.53 94.39 170.0 3.56 12.29 50.8 10-3 1.48 28.67 24.26 40.85 1.68
1.93 59.16 79.45 150.0 1.50 12.25 20.32 10-4 1.57 31.33 23.42 48.16
2.06 2.07 72.12 94.14 165.0 2.92 10.28 76.2 10-5 1.49 26.67 27.25
46.52 1.71 2.09 68.04 88.50 152.5 0.91 13.33 27.94 10-6 1.53 31
25.37 48.19 1.9 2.24 86.89 106.74 197.5 2.92 10.03 101.6 Control 1
1.52 38.36 25.84 46.08 1.78 2.85 122.33 232.52 514.7 2.75 47.99 --
Control 2 1.55 40.63 26.51 45.73 1.73 2.55 127.70 208.62 519.44
4.27 15.49 --
Example 11
Foams Made Using Polyol F
[0163] The graphs below show conventional slabstock foam physical
property data with Polyol F used at various levels of
incorporation. Due to the small batch size the versions of Polyol F
were combined prior to using as a foam component. The polyol
characteristics are reported in TABLE 11.1. The polyurethane
formulations are reported in TABLE 11.2 and TABLE 11.3. The
polyurethane physical properties are reported in TABLE 11.4.
TABLE-US-00013 TABLE 11.1 Characteristics of Polyols OH Number Acid
Value Viscosity (mg Water (mg at 25.degree. C. EOC Polyol KOH/g)
(%) KOH/gram) (Pa s) (%) Odor F-1 53.77 0.064 0.33 4 4.23 Light Soy
F-2 57.46 0.001 0.33 4.72 4.17 Light Soy F-3022 55.30 0.02 0.03 --
-- --
TABLE-US-00014 TABLE 11.2 Polyurethane Formulations Ingredient 11-1
11-2 11-3 11-4 11-5 11-6 11-7 11-8 11-9 Control Polyol F- 90 80 70
60 50 40 40 40 40 100 3022 F-1 10 20 30 40 50 60 60 60 60 0
EP-H-140 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 (Silicone
Surfactant) BL-11 0.16 0.16 0.16 0.16 0.16 0.16 0.36 0.38 0.38 0.16
(Amine) K-29 0.217 0.217 0.217 0.217 0.217 0.217 0.21 0.21 0.21
0.22 (Tin Catalyst) Water 3.976 3.971 3.967 3.962 3.958 3.954 3.954
3.954 3.954 3.98 TDI Index 105 105 105 105 105 105 105 105 105 105
TDI (PPH) 49.59 49.56 49.54 49.51 49.49 49.47 49.47 49.47 49.47
49.61 TDI Temp 23.2 23.2 23.2 23.2 23.2 23.2 21.9 21.9 21.9 21.6
(.degree. C.) Batch 17.9 18.4 18.4 18.4 18.4 18.4 17.6 17.3 17.5
19.1 Temp (.degree. C.) Reaction 19.6 19.9 19.9 19.9 19.9 19.9 19.0
18.8 18.9 19.9 (.degree. C.) Mix Time 25 25 25 25 25 25 25 25 25 25
(s) Cream 11 14 15 17 18 20 16 12 12 10 Time (s) Top of 45 47 53 57
65 69 45 41 40 42 Cup Time (s) Rise Time 87 89 96 104 115 123 87 79
81 84 (s)
TABLE-US-00015 TABLE 11.3 Polyurethane Formulation Ingredient 11-10
11-11 11-12 11-13 11-14 Control Polyol F- 90 80 70 60 50 100 3022
F-2 10 20 30 40 50 0 EP-H-140 1.0 1.0 1.0 1.0 1.0 1.0 (Silicone
Surfactant) BL-11 0.16 0.16 0.16 0.16 0.16 0.16 (Amine) K-29 0.217
0.217 0.217 0.217 0.217 0.22 (Tin Catalyst) Water 3.982 3.984 3.986
3.988 3.99 3.98 TDI Index 105 105 105 105 105 105 TDI (PPH) 49.65
49.68 49.72 49.76 49.79 49.61 TDI Temp 22.6 22.6 22.6 22.6 22.6
21.6 (.degree. C.) Batch 17.6 17.5 17.5 17.6 17.6 19.1 Temp
(.degree. C.) Reaction 19.2 19.1 19.1 19.2 19.2 19.9 (.degree. C.)
Mix Time 25 25 25 25 25 25 (s) Cream 11 13 15 17 19 10 Time (s) Top
of 45 46 51 57 61 42 Cup Time (s) Rise Time 84 87 93 101 111 84
(s)
TABLE-US-00016 TABLE 11.4 Polyurethane Physical Properties 25% 65%
Density Resiliency IFD IFD Support CFD Tensile Elongation Tear Perm
Sample (pcf) (%) (N/323 cm.sup.2) (N/323 cm.sup.2) Factor (kPa)
(kPa) (%) (N/m) (cfm) 11-1 1.55 40.33 33.86 58.32 1.72 2.79 113.10
150.12 402.5 3.5 11-2 1.57 38.33 29.19 50.52 1.73 2.42 101.66
138.38 422.5 4.0 11-3 1.56 37.67 31.86 54.39 1.71 2.51 102.13
121.45 297.5 3.58 11-4 1.55 35.00 30.57 53.65 1.75 2.38 89.44
101.73 230.0 2.86 11-5 1.54 32.00 29.51 55.32 1.87 2.65 67.51 66.23
177.5 2.44 11-6 1.57 30.67 25.13 50.32 2.00 2.40 56.26 53.32 150.0
2.25 11-7 1.49 29.67 21.43 48.28 2.25 -- 49.44 66.33 137.5 1.73
11-8 1.48 31.33 21.77 42.64 1.96 -- 65.36 69.05 120.0 1.86 11-9
1.47 30.33 21.48 43.05 2.00 -- 59.08 65.40 117.5 2.06 11-10 1.49
41.00 29.92 50.65 1.69 -- 131.05 152.57 382.5 4.14 11-11 1.50 39.33
30.55 51.92 1.70 -- 113.82 119.65 347.5 4.53 11-12 1.50 36.00 27.71
50.75 1.83 -- 102.50 102.96 247.5 4.39 11-13 1.51 31.33 29.55 53.93
1.83 -- 100.46 87.70 185.0 3.44 11-14 1.52 30.33 26.89 52.91 1.97
-- 79.07 65.05 155.0 2.81 Control 1.54 43.83 29.75 51.04 1.72 2.80
119.00 181.00 519.0 3.96
Example 12
Foams Made Using Polyol C
[0164] The data below shows conventional slabstock foam physical
property data for foams made using a conventional petroleum-derived
polyol (Arcol F-3022) and Polyol C. The polyurethane formulation is
reported in TABLE 12.1. The polyurethane foam properties are shown
in TABLE 12.2.
TABLE-US-00017 TABLE 12.1 Polyurethane Formulations Ingredient 12-1
12-2 12-3 12-4 Polyol F- 80.0 60.0 40.0 20.0 3022 Polyol C 20.0
40.0 60.0 80.0 BF-2370 1.0 1.0 1.0 1.0 BL-11 0.235 0.235 0.235
0.270 K-29 0.230 0.230 0.230 0.180 TDI-80 50.80 52.04 53.28 54.51
Water 4.0 4.0 4.0 4.0 TDI Index 105.0 105.0 105.0 105.0 TDI Temp
21.9 21.9 21.9 22.3 (.degree. C.) Batch 25.0 26.10 26.0 25.2 Temp
(.degree. C.) Cream 11.0 12.0 13.0 14.0 Time (s) Top of 30.0 34.0
39.0 46.0 Cup Time (s) Rise time 64.0 71.0 78.0 80.0 (s) Polyol
Good Good Good Good Odor Tackiness Great Good OK --
TABLE-US-00018 TABLE 12.2 Polyurethane Properties 25% 65% Ave. Air
90% IFD IFD Support Rebound Density Tensile Elongation Tear Flow
CS; % Foam (N/323 cm.sup.2) (N/323 cm.sup.2) Factor (%) (pcf) (kPa)
(%) (N/m) (cfm) loss 12-1 56.35 94.72 1.68 38 1.64 112.25 241.14
420 3.23 62.25 1.08 5.54 12-2 56.21 100 1.78 33 1.65 97.09 196.77
290 2.94 54.19 0.71 7.42 12-3 53.39 99.62 1.87 28.33 1.66 78.68
142.16 220 1.88 77.81 0.37 3.15 12-4 43.30 93.83 2.17 24.67 1.66
53.83 78.93 110 -- --
Example 13
Foams Made Using Polyol D
[0165] The data below shows conventional slabstock foam physical
property data for a foam made using a conventional
petroleum-derived polyol (Arcol F-3022) and Polyol D. The
polyurethane formulation is reported in TABLE 13.1. The
polyurethane foam properties are reported in TABLE 13.2.
TABLE-US-00019 TABLE 13.1 Polyurethane Formulation Ingredient 13-1
Polyol F- 60.0 3022 Polyol D 40.0 BF-2370 1.0 BL-11 0.235 K-29
0.230 TDI-80 52.60 Water 4.0 TDI Index 105.0 TDI Temp 20.8
(.degree. C.) Batch 25.7 Temp (.degree. C.) Cream 12.0 Time (s) Top
of 34.0 Cup Time (s) Rise time 71.0 (s) Polyol Bad Odor Tackiness
Tacky
TABLE-US-00020 TABLE 13.2 Polyurethane Properties 25% 65% Ave. Air
90% IFD IFD Support Rebound Density Tensile Elongation Tear Flow
CS; % Foam (N/323 cm.sup.2) (N/323 cm.sup.2) Factor (%) (pcf) (kPa)
(%) (N/m) (cfm) loss 13-1 29.17 54.39 1.86 -- 1.53 97.85 166.85 330
2.59 35.32 0.15 8.56
Example 14
Foams Made Using Polyol F, Color Fastness
[0166] Color Fastness Test Procedure
[0167] The color fastness testing of the foams produced was
conducted according to following procedure.
[0168] 1. Foam samples were exposed to either 6 weeks of ambient
light or two, 8-hour periods of full sun.
[0169] 2. After exposure, the color of the exposed foam was
compared to control samples.
[0170] 3. Foam samples were stored in black plastic bags before and
after color fastness testing.
[0171] Color measurements were performed using a HunterLab
Ultrascan XE Spectrophotometer equipped with a 6 inch integrating
sphere. Reflectance with specular included and with specular
excluded were performed in accordance with ASTM E308 with a 10
degree observer and illuminant D65. The specimen port was circular
and measured 1 inch in diameter with an 8 degree viewing angle and
a beam diameter of 1 inch. The reduction of data was computed from
spectral data taken every 10 nm over the wavelength range from 375
nm to 750 nm. The CIE color scale was used to measure the L, a, b
values.
[0172] A series of polyurethane foams were produced according the
procedure described earlier, and using the formulation shown in
TABLE 14.1.
TABLE-US-00021 TABLE 14.1 Ingredient Parts by Weight Polyol F-3022
100-X Polyol F X Water 4.0 Silicone Surfactant 1.0 Blowing Catalyst
0.1 Blowing & Gelling 0.2 Catalyst Tin Catalyst 0.25 80/20 TDI
Index 105
[0173] The amount of polyol F present in the formulation was
changed in order to obtain a series of polyols. The control sample
included 100 parts petroleum polyol and 0 parts polyol E.
Additional formulations included 10 parts, 20 parts, 30 parts, 50
parts, and 60 parts polyol E. No ultraviolet light stabilizers were
added to any of the foam formulations.
[0174] The series of foams were then tested for color fastness by
exposure to ambient light for six weeks. The RSEX test results are
for spectrophotometric tests with the reflectance specular
excluded, while the RSIN test results are with the reflectance
specular included. The results are reported in TABLE 14.2
TABLE-US-00022 TABLE 14.2 Parts RSEX RSIN Polyol F (L*) (L*) 0
(Control) 82 82.2 10 84 84 20 86 86 30 88 88 40 89.4 88.9 50 90
90.4 60 90.8 91.4
[0175] The L* value is a measure of the light reflected, and the
scale is from a maximum L* of 100, to a minimum L* of 0, or
completely black. Thus, the higher the L* value, the lighter the
sample. As can be seen, increasing the oligomeric polyol in the
flexible polyurethane foams significantly improves the color
fastness as compared to petroleum-derived flexible polyurethane
foams without the use of UV stabilizers. Flexible polyurethane
foams prepared using Polyol E retained their initial white color
better than the foam prepared from a petroleum-derived polyether
polyol when exposed to light under ambient conditions for 6 weeks.
In addition, flexible polyurethane foams prepared using Polyol E
also retained their initial white color better than the foam
prepared from a petroleum-derived polyether polyol when exposed to
direct sunlight.
Ingredient List for Examples 15-24
[0176] ARCOL F-3020: a petroleum-derived, nominal 3000 molecular
weight triol having a hydroxyl number of 54.5 to 57.5 mg KOH/g and
an acid value of 0.02 mg KOH/gram (from Bayer). B-2130: a petroleum
derived primary hydroxyl terminated graft polyether triol having an
hydroxyl number of 23.0 to 26.0 and containing approximately 31%
solids of copolymerized styrene and acrylonitrile. DABCO BL-11: a
blowing catalyst consisting of 70% bis(dimethylaminoethyl)ether and
30% dipropylene glycol (from Air Products). DABCO BL-13: a blowing
catalyst consisting of 23% bis(dimethylaminoethyl)ether and 77%
dipropylene glycol (from Air Products). CP-2:
tris(1,3-dichloro-2-propyl)-phosphate flame retardant (from
Gulbrandsen Co.). DOP: dioctyl phthalate. EPOXOL 7-4: a fully
epoxidized soybean oil (from American Chemical Systems). FILLER:
calcium carbonate. FR-550: phosphorous-bromine flame retardant
(from Great Lakes Chemical). K-29: stannous octoate catalyst (from
Degussa). L-650: silicone surfactant for flame retardant foams
(from GE Silicones). L-5770: silicone surfactant (from GE
Silicones). MELAMINE: flame retardant (from BASF). P-945: a 4800
molecular weight triol (from BASF). P-4600: a secondary
hydroxyl-terminated graft polyether triol having a hydroxyl number
of 27.1 to 30.1 and containing approximately 42% solids of
copolymerized styrene and acrylonitrile. T-9: stannous octoate
(from Air Products). TD-33: an amine catalyst consisting of 33%
triethylene diamine in 67% dipropylene glycol (from Air Products).
TDI: toluene diisocyanate. RC-6366: amine catalyst comprising 70%
bis(2-dimethylamine ethyl)ether and 30% dipropylene glycol (from
RheinChemie). WATER: distilled water.
Example 15
Preparation of Oligomeric Polyols
12 Liter Apparatus
[0177] A 5 neck, 12 liter flask was equipped with a mechanical
stirrer, thermocouple, heating mantle/controller, cooling coil,
peristaltic pump, and nitrogen feed. To the flask was charged 7000
grams of epoxidized soybean oil (EPOXOL 7-4) and 280 grams of
methanol. In a separate container, a catalyst solution was prepared
by mixing 7.62 grams of HBF.sub.4 (48% in water) with 35.0 grams of
methanol. With water flowing through the condenser, the contents of
the reaction mixture was heated at 55.degree. C. and was stirred at
a high rate. Using the syringe pump, the HBF.sub.4 catalyst
solution was added to the flask at a rate of 0.138 ml/min to
provide a total catalyst addition time of about 6 hours. The
catalyst was added to the reaction mixture through a catalyst
addition tube that was positioned near the lower stirrer blade.
When the temperature began to rise, water was circulated through
the cooling coil to maintain a temperature of 55.degree.
C..+-.2.degree. C. in the reaction mixture. The reaction was
monitored hourly by measuring the EOC. The addition of catalyst was
stopped when the EOC reached 3.35% to 4.40%. The catalyst addition
tube was then flushed with about 2-3 ml methanol and was removed
from the flask. The reaction was monitored at 15-minute intervals
until the catalyst EOC remained constant. The target for the final
product was 4.25% EOC. The resulting product was then distilled at
about 80.degree. C. and 4 Torr to remove any unreacted methanol.
Properties of the oligomeric polyols are reported in TABLE
15.1.
TABLE-US-00023 TABLE 15.1 Mn Mn Mw (grams/ (grams/ (LS) OH Acid
Water mole) Fn mole) (grams/ EOC % Polyol Number Value (%) (VPO)
(VPO) (LS) mole) Mw/Mn g'M Viscosity. PV Mon Dim Trim Tetr+ (%)
Olig 15-1 58.03 0.42 0.09 1763 1.84 -- -- -- -- 3.80 -- 43.4 11.8
7.3 37.5 4.21 56.6 15-2 62.56 0.44 0.09 1844 2.06 3206 32180 10.04
0.53 4.65 3.9 41.7 11.5 7.5 39.3 4.22 58.3 15-3 66.19 0.56 0.07
1687 1.99 -- -- -- -- 4.71 -- 40.6 11.4 7.3 40.8 4.13 59.4 15-4
63.42 0.43 0.08 1771 2.03 -- -- -- -- 4.04 -- 42.9 12.0 7.7 37.4
4.21 57.1 15-5 59.80 0.42 0.05 1686 1.80 4537 54670 12.05 0.33 4.48
-- 41.8 11.5 7.4 39.3 4.29 58.2 15-6 54.16 0.43 0.09 1880 1.81 5396
72420 13.42 0.31 9.78 0.8 36.8 9.3 6.5 47.4 4.29 63.2 15-7 62.88
0.45 0.03 2057 2.31 7247 475400 65.60 0.06 6.85 1.4 39.5 11.4 7.6
41.5 4.04 60.5 15-8 57.75 0.24 0.05 1954 2.01 1546 7883 5.10 1.29
3.84 3.8 42.0 11.1 7.6 38.7 4.25 58.0 15-9 59.53 0.26 0.04 2007
2.13 1519 8338 5.49 1.23 4.11 1.5 41.2 11.8 7.7 39.3 4.23 58.9
15-10 62.17 0.33 0.03 1972 2.18 2089 13340 6.39 1.05 5.87 1.5 37.8
10.6 7.0 44.6 4.07 62.2 15-11 55.63 0.30 0.03 1695 1.68 1611 6928
4.30 1.27 3.28 1.5 43.9 11.7 7.9 36.5 4.38 56.1 15-12 58.81 0.28
0.04 1784 1.87 1567 9294 5.93 1.11 4.73 1.9 39.9 11.2 7.3 41.6 4.21
60.1 15-13 62.56 0.44 0.09 1844 2.06 3206 32180 10.04 0.53 4.65 3.9
41.7 11.5 7.5 39.3 4.22 58.3
Example 16
Preparation of Oligomeric Polyols
[0178] The large-scale reaction set-up consisted of a 6000 gallon
continuous stirred tank reactor equipped with a glycol cooling
jacket and pump-around loop with a heat exchanger. Prior to adding
reactants, the stirred tank reactor was flushed with nitrogen gas
to inert the vapor head space. Then, the epoxidized soybean oil was
added to the reactor in the amount shown in TABLE 16.1. Following
this, the methanol was added to the reactor in the amount shown in
TABLE 16.1. The epoxidized soybean oil and methanol were thoroughly
mixed in the reactor so as to minimize local concentration
gradients and the resulting mixture was heated to a temperature of
about 55.degree. C. Separately, a catalyst solution was prepared by
mixing 1 part of aqueous HBF.sub.4 solution (48% weight in water)
with 4.6 parts methanol. Approximately 218 lbs of catalyst solution
was fed into the stirred tank reactor over a period of about 5.5
hours. The heat of reaction was removed by circulating chilled
glycol through the cooling jacket. At about peak exotherm,
additional heat was removed by pumping the reaction mixture through
the pump-around loop/heat exchanger. After all of the catalyst
solution was added, the reactor was maintained at temperature for
approximately 30 minutes. During the course of the reaction, the
change in EOC was monitored. At the end of the reaction, the
remaining methanol was removed by vacuum stripping. The resulting
oligomeric polyol was then conditioned by sparging with nitrogen
gas. The properties of the oligomeric polyols are reported in TABLE
16.2.
TABLE-US-00024 TABLE 16.1 Epoxidized Polyol Soybean Oil Methanol
16-1 36,332 lbs. 1452 lbs. 16-2 36,332 lbs. 1452 lbs. 16-3 36,332
lbs. 1452 lbs.
TABLE-US-00025 TABLE 16.2 Mn Mn Mw (grams/ (grams/ (grams/ OH Acid
% mole) Fn Mole) mole) EOC % Polyol Number Value Water (VPO) (VPO)
(LS) (LS) Mw/Mn g'M Viscosity. PV Mon Dim Trim Tetr+ (%) Olig 16-1
59.52 0.30 0.07 1864 1.98 1674 8345 4.98 1.17 2.95 2.2 41.4 11.4
7.5 39.7 4.49 58.6 16-2 59.52 0.30 0.07 1864 1.98 1674 8345 4.98
1.17 2.95 2.2 41.4 11.4 7.5 39.7 4.49 58.6 16-3 59.52 0.30 0.07
1864 1.98 1674 8345 4.98 1.17 2.95 2.2 41.4 11.4 7.5 39.7 4.49
58.6
Example 17
Preparation of Flexible Slabstock Foams
Step 1: Procedure for Preparing B-Side
[0179] The polyols listed in TABLE 17.1 were weighed into a 400 ml
plastic beaker that was positioned on an electric scale. Next, the
formulation required amount of silicone surfactant and amine
catalyst were added to the beaker. Next, the formulation required
amount of stannous octoate and water were added to the batch. The
temperature of the B-side was adjusted so that upon mixing with the
polyisocyanate the combined mixture had a temperature of
19.2.degree. C.+0.3.degree. C. The batch was mixed with an
electric, lab duty mixer (Delta ShopMaster brand, Model DP-200, 10
inch shop drill press) equipped with a 2'' diameter mixing blade
(ConnBlade Brand, Model ITC from Conn Mixers Co.) for 19 seconds at
2340 rpm's. Separately, the formulation required amount of TDI was
weighed out into a 50 ml plastic beaker and was set near the mixing
station. The TDI was then added to the polyol mixture and was mixed
for 6 seconds. Following this, the mixture was poured into an 83 oz
cup and was allowed to free rise. During the free rise period, the
Cream Time (i.e., the time from the introduction of the TDI until
start of cream rise in the cup), Top of Cup Rise Time (i.e., the
time from the introduction of the TDI until the dome of the foam
reaches the top of the cup), and the Total Rise Time (i.e., the
time from the introduction of the TDI until there is blow-off or no
more rising of the foam) were each recorded. The foam and cup were
then placed into a temperature-controlled oven at 100.degree. C.
for 15 minutes to cure. At the end of the oven cure, the foam was
permitted to cure overnight. After curing overnight, the foam was
conditioned for 72 hours at 25.degree. C. and 50% relative humidity
before testing for physical properties. The physical property test
results are reported in TABLES 17.2-17.4.
TABLE-US-00026 TABLE 17.1 30% 40% 50% Incorporation Incorporation
Incorporation Ingredient (PPH) (PPH) (PPH) Polyol F-3022 70 60 50
Oligomeric Polyol 30 40 50 (See TABLE 15.1 and TABLE 16.2) Water 4
4 4 TDI 105 Index* 105 Index* 105 Index* L-5770 (silicone 1 1 1
surfactant) BL-11 (amine 0.16 0.16 0.16 catalyst) K-29 (stannous
0.22 0.22 0.22 Octoate) *The amount of TDI used was calculated
based on the total water and the hydroxyl number of the polyol to
provide an index of 105.
TABLE-US-00027 TABLE 17.2 (30% INCORPORATION) Top Total 25% 65% Air
Cream Cup Rise Density Rebound IFD IFD Support Tensile Elong Tear
Flow 90% CS Polyol Odor (sec) (sec) (sec) (pcf) (%) (N/323
cm.sup.2) (N/323 cm.sup.2) Factor (kPa) (%) (N/m) (ft.sup.3/min) (%
loss) 15-1 - 13 53 105 1.5 36 25 48 1.88 90 118 296 4.0 11.8 15-2 -
13 56 110 1.5 36 23 42 1.83 86 135 276 3.8 8.6 15-3 - 12 55 108 1.4
35 21 38 1.81 81 132 261 4.1 7.9 15-4 - 13 50 101 1.5 35 25 46 1.81
96 146 296 4.1 11.3 15-5 + 14 52 94 1.5 35 24 43 1.81 97 140 279
4.0 19.8 15-6 ++ 13 52 93 1.5 35 24 43 1.75 88 133 245 3.9 15.7
15-7 + 14 52 95 1.5 35 25 44 1.74 91 142 283 3.8 38.3 15-8 ++ 14 54
104 1.5 36 24 44 1.84 96 138 281 3.6 11 15-9 ++ 15 51 96 1.5 35 24
45 1.84 93 143 291 3.6 15.2 15-10 ++ 14 49 95 1.5 35 23 41 1.81 100
137 264 3.9 14.2 15-11 ++ 14 51 101 1.5 37 23 42 1.86 101 142 298
3.8 11.9 15-12 ++ 12 47 92 1.5 36 23 42 1.81 94 144 286 4.2 12.5
15-13 - 13 56 110 1.5 36 23 42 1.83 86 135 276 3.8 8.6
TABLE-US-00028 TABLE 17.3 (40% INCORPORATION) Top Total 25% 65% Air
Cream Cup Rise Density Rebound IFD IFD Support Tensile Elong Tear
Flow 90% CS Polyol Odor (sec) (sec) (sec) (pcf) (%) (N/323
cm.sup.2) (N/323 cm.sup.2) Factor (kPa) (%) (N/m) (ft.sup.3/min) (%
loss) 15-1 - 14 58 122 1.5 32 25 52 2.04 77 91 215 2.9 13.9 15-2 -
15 63 124 1.5 33 23 43 1.91 65 91 201 2.8 9.5 15-3 - 12 61 122 1.4
32 21 41 1.95 57 81 189 2.9 9.6 15-4 - 14 57 109 1.5 33 26 48 1.87
87 122 215 3.2 11.3 15-5 + 17 57 102 1.5 33 24 45 1.92 82 108 225
3.0 26.7 15-6 + 16 57 102 1.5 33 25 46 1.81 78 104 200 2.8 20.2
15-7 + 17 57 103 1.5 33 27 48 1.82 86 111 218 2.9 39.1 15-8 + 16 60
119 1.6 33 24 48 1.96 81 104 194 3.0 11.8 15-9 + 15 56 110 1.5 32
25 47 1.91 82 113 223 2.9 13.2 15-10 + 15 53 109 1.5 32 24 46 1.91
76 91 184 3.0 12.3 15-11 + 15 55 104 1.5 33 22 42 1.89 77 100 211
3.1 12.0 15-12 ++ 14 52 100 1.5 33 24 44 1.87 76 101 208 2.6 12.0
15-13 - 15 63 124 1.5 33 23 43 1.91 65 91 201 2.8 9.5
TABLE-US-00029 TABLE 17.4 (50% INCORPORATION) Top Total 25% 65% Air
Cream Cup Rise Density Rebound IFD IFD Support Tensile Elong Tear
Flow 90% CS Polyol Odor (sec) (sec) (sec) (pcf) (%) (N/323
cm.sup.2) (N/323 cm.sup.2) Factor (kPa) (%) (N/m) (ft.sup.3/min) (%
loss) 15-1 - 13 67 140 -- -- -- -- -- -- -- -- -- -- 15-2 - 16 72
136 -- -- -- -- -- -- -- -- -- -- 15-3 Not 16 71 141 -- -- -- -- --
-- -- -- -- -- tested 15-4 - 16 65 125 1.6 30 23 49 2.12 64 83 156
2.4 13.6 15-5 + 18 66 117 1.5 31 23 43 1.90 79 93 163 2.9 18.8 15-6
+ 18 65 131 1.6 30 26 51 1.98 65 81 131 2.4 14.8 15-7 + 17 63 111
1.5 31 28 52 1.88 77 88 169 2.2 56.4 15-8 + 16 68 130 -- -- -- --
-- -- -- -- -- -- 15-9 + 16 58 111 1.5 31 23 46 2.02 64 81 168 2.3
15.3 15-10 Not 16 60 -- -- -- -- -- -- -- -- -- -- -- tested 15-11
Not 16 52 -- -- -- -- -- -- -- -- -- -- -- tested 15-12 ++ 15 58
121 1.4 31 19 41 2.19 52 70 -- 2.1 14.5 15-13 - 16 72 136 -- -- --
-- -- -- -- -- -- -- 16-1 ++ 15 62 117 1.5 31 22 45 2.01 70 84 156
2.2 15.8 16-2 ++ 15 63 119 1.5 32 22 46 2.10 65 82 158 2.4 15.6
16-3 ++ 15 62 116 1.5 31 23 46 2.05 66 79 159 2.3 14.9
Example 18
[0180] Flexible slabstock foam buns were prepared using a
full-scale conventional slabstock foam line from MaxFoam. The foam
buns were prepared using the formulations listed in TABLES
18.1-18.4. Skin density measurements were taken from each of the
foam buns according to the technique described below.
TABLE-US-00030 TABLE 18.1 Formulation 1 Formulation 1 Formulation 1
(Control) (25%) Foam Properties Density (lbs/ft.sup.3) 1.8 1.8
Hardness (lbs) 28 28 Cal 117 Yes Yes Ingredients (PPH) (PPH) F-3022
93.5 68.5 OLIG. POLYOL 0 25.0 FILLER 3.25 3.25 MELAMINE 6.5 6.5
P-945 6.5 6.5 TDI 45.42 45.42 WATER 3.34 3.34 L-650 0.97 0.97 T-9
0.24 0.24 TD-33 0.04 0.04 RC-6366 0.29 0.29 ACETONE 2.45 2.45 CP-2
13.0 13.0
TABLE-US-00031 TABLE 18.2 Formulation 2 Formulation 2 Formulation 2
Formulation 2 (Control) (15%) (25%) Foam Properties Density
(lbs/ft.sup.3) 1.45 1.45 1.45 Hardness (lbs) 31 31 31 Cal 117 Form.
No No No Ingredients (PPH) (PPH) (PPH) F-3020 93.95 78.95 62.45
OLIG POLYOL 0 15.0 25.0 FILLER 6 6 6 MELAMINE 3.25 3.25 3.25 P-945
3.25 3.25 3.25 B-2130 2.80 2.80 2.80 TDI 51.10 51.18 51.27 WATER
3.93 3.93 3.93 L-5770 0.96 0.96 0.96 K-29 0.23 0.23 0.23 RC-6366
0.19 0.19 0.19 ACETONE 2.60 2.60 2.60
TABLE-US-00032 TABLE 18.3 Formulation 3 Formulation 3- Formulation
3 Ingredient Control (25%) Foam Properties Density (lbs/ft.sup.3)
1.8 1.8 Hardness (lbs) 25 25 Cal 117 Formulation Yes Yes
Ingredients (PPH) (PPH) F-3022 94.0 69.0 OLIG. POLYOL 0 25.0 FILLER
4.5 4.5 MELAMINE 6.0 6.0 P-945 6.0 6.0 TDI 40.76 41.93 WATER 3.04
3.04 L-650 1.0 1.0 T-9 0.32 0.32 TD-33 0.06 0.06 RC-6366 0.245
0.265 ACETONE 4.40 4.40 CP-2 11.5 11.5
TABLE-US-00033 TABLE 18.4 Formulation 4 Formulation 4 Formulation 4
(Control) (25%) Foam Properties Density (lbs/ft.sup.3) 1.45 1.45
Hardness (lbs) 46 46 Cal 117 Formulation Yes Yes Ingredients (PPH)
(PPH) F-3020 78.5 53.5 OLIG. POLYOL 0 25.0 P-4600 16 16 MELAMINE
5.5 5.5 P-945 5.5 5.5 TDI 62.25 63.5 WATER 4.79 4.79 L-650 0.9 0.9
T-9 0.185 0.185 TD-33 0.026 0.026 RC-6366 0.175 0.175 FR-550 12
12
Skin Density Measurement:
[0181] Skin densities were measured by cutting a
12''.times.12''.times..about.1'' piece of skin (i.e., foam located
on the outer portion of the bun) from representative slabstock foam
buns prepared using a full-scale conventional slabstock foam line
using the polyurethane formulations are listed in TABLES 18.1-18.4.
The height, width, and weight of each sample was measured and
recorded. The thickness of each sample was measured by taking 5 to
9 measurements with a caliper. The measurement locations were
distributed throughout the sample to ensure a representative
average. Measurements were taken at consistent locations from
sample to sample. The surface area, average thickness, and mass
measurements were used to calculate an average density for each
foam skin sample. A lower average density indicated that the sample
had a lower density skin. This is associated with a thinner skin
which results in a higher yield of prime foam from the slabstock
foam bun. The results are reported in TABLE 18.5.
TABLE-US-00034 TABLE 18.5 Density Skin Example No. Formulation
(lb/ft.sup.3) Location Comp. Ex. 18-A Form 1 (Control) 3.36 Top
Example 18-1 Form 1 (25%) 2.60 Top Comp. Ex. 18-B Form 1 (Control)
3.26 Bottom Example 18-2 Form 1 (25%) 3.14 Bottom Example 18-3 Form
1 (25%) 3.36 Bottom Example 18-4 Form 1 (25%) 3.10 Bottom Example
18-5 Form 1 (25%) 2.93 Bottom Comp. Ex. 18-C Form 2 (Control) 3.94
Bottom Example 18-6 Form 2 (15%) 2.99 Bottom Example 18-7 Form 2
(15%) 2.91 Bottom Example 18-8 Form 2 (25%) 3.04 Bottom Example
18-9 Form 2 (25%) 2.95 Bottom Example 18-10 Form 2 (25%) 3.10
Bottom Example 18-11 Form 2 (25%) 2.93 Bottom Comp. Ex. 18-D Form 3
(Control) 3.43 Top Example 18-12 Form 3 (25%) 3.08 Top Example
18-13 Form 3 (25%) 2.67 Top Example 18-14 Form 3 (25%) 2.80 Top
Example 18-15 Form 3 (25%) 2.34 Top Comp. Ex. 18-E Form 3 (Control)
2.98 Bottom Example 18-16 Form 3 (25%) 2.69 Bottom Comp. Ex. 18-F
Form 4 (Control) 2.69 Top Example 18-17 Form 4 (25%) 2.59 Top
Example 19
IFD and Density Spread
[0182] Buns of a 1.45/31 grade slabstock foam were prepared using
full-scale slabstock foam line. The formulations of the foam are
listed in TABLE 18.2. From each bun, eleven (11) test blocks (each
measuring 15'' by 15'' by 4'') were cut from the cross-section of
the bun. The test blocks were numbered and labeled, with either an
"M" (indicating middle of the bun) or "S" (indicating side of the
bun). Each of the test blocks was tested to determined 25% and 65%
IFD and density. ASTM test procedure D3574 was used, except that
the tests were conducted 24 hours after making the bun. The results
are reported in TABLE 19.1.
TABLE-US-00035 TABLE 19.1 Formulation 2 Control 15% 15% 15% 25% 25%
25% 25% 25% 15% Property Mid Mid Side Side Mid Side Side Mid Side
Side 25% IFD 32.49 30.76 30.65 30.92 29.52 28.75 28.68 29.60 29.08
29.21 65% IFD 59.87 57.78 57.60 57.70 54.70 54.00 54.70 57.10 55.10
57.10 25% RT 22.05 20.90 21.20 21.20 19.30 19.10 19.10 19.50 19.10
19.40 IFD Spread 4.20 2.67 1.96 1.67 3.15 2.08 2.27 2.82 1.45 1.67
S-Avg. Ov-All 2.10 1.82 2.50 2.18 1.98 1.56 Density 1.46 1.43 1.42
1.43 1.39 1.39 1.39 1.40 1.40 1.40 Density Spread 0.09 0.06 0.06
0.05 0.05 0.06 0.03 0.05 0.02 0.05 Modulus 1.84 1.84 1.80 1.81 1.82
1.80 1.82 1.92 1.84 1.90 Air Flow 5.2 4.8 4.8 4.8 5.0 4.9 5.1 4.9
5.1 4.9 Rebound 46 41 40 42 38 39 40 40 39 40 Hysterersis 67.0 66.3
66.5 66.7 64.1 63.6 63.7 65.4 63.7 64.6
Example 20
[0183] Buns of flexible slabstock foam were prepared using a
full-scale slabstock foam line. The formulations of the foam are
listed in TABLE 18.1-18.4. The foam was tested for 5% IFD using
ASTM D3574 (modified for 5% indentation). The results are reported
in TABLES 20.2 to 20.4.
TABLE-US-00036 TABLE 20.2 Frm 2 Frm 2 Frm 2 Frm 2 Frm 2 Frm 2- Frm
2 Frm 2- (15%) (15%) (25%) (25%) (25%) Control (25%) Control 5% IFD
20.09 18.93 18.54 18.08 18.60 20.79 17.82 19.37 (N/323 cm.sup.2)
21.04 20.35 20.05 19.71 19.90 21.40 19.55 21.77 21.13 20.68 20.28
19.84 20.04 22.00 19.87 21.81 21.04 20.93 20.27 20.07 19.90 22.24
19.60 22.13 21.08 20.61 19.97 19.98 19.81 22.09 19.30 22.00 20.71
20.49 20.05 19.99 19.76 22.09 19.30 22.31 20.63 20.50 19.92 20.08
19.68 21.86 19.38 21.90 20.38 20.68 20.13 20.22 19.80 21.67 19.45
22.04 20.52 20.87 20.04 20.03 19.99 21.72 19.78 22.07 19.55 20.05
19.92 19.96 19.77 21.75 19.61 21.87 -- -- 18.61 18.54 18.98 21.02
18.72 20.66 5% IFD 20.62 20.41 19.80 19.68 19.66 21.69 19.31 21.63
Ave 5% IFD 1.58 2.00 1.74 2.14 1.44 1.45 2.05 2.94 Spread Average
5% IFD of Formulation 2 = 19.91 Average 5% IFD of Formulation 2
(Control) = 21.66 % Change = 8.08%
TABLE-US-00037 TABLE 20.3 Frm 4 Frm 4 Frm 4 Frm 4- Frm 3- Frm 3-
Frm 3 Frm 3- (25%) (25%) (25%) Control (25%) (25%) Control Control
5% IFD 27.56 29.13 27.02 28.68 16.33 16.08 16.40 16.18 (N/323
cm.sup.2) 27.68 29.52 27.96 29.46 17.31 16.83 17.15 17.08 29.50
31.03 29.91 31.38 17.39 17.06 17.46 17.42 30.79 31.98 31.06 31.76
17.38 17.16 17.34 17.43 31.34 32.95 31.21 31.54 17.22 16.97 17.28
17.33 30.94 32.36 31.65 31.76 17.01 16.98 17.22 17.27 30.21 32.24
30.82 31.21 16.75 16.60 17.09 17.17 29.81 32.47 30.68 31.69 16.55
16.13 16.68 16.78 29.19 31.82 29.82 31.77 15.79 15.66 16.48 16.27
28.20 30.53 28.88 31.09 15.09 14.87 15.03 15.25 26.80 28.41 27.46
28.80 5% IFD 29.28 31.13 29.68 30.83 16.68 16.44 16.81 16.82 AVE 5%
IFD 4.53 4.54 4.63 3.09 2.30 2.29 2.43 2.18 SPREAD Average 5% IFD
of Formulation 4 = 29.84 Average 5% IFD of Formulation 4 (Control)
= 30.98 % Change = 4.85% Average 5% IFD of Formulation 3 = 16.56
Average 5% IFD of Formulation 3-Control = 16.81 % Change =
1.52%
TABLE-US-00038 TABLE 20.4 Frm 1 Frm 1 Frm 1- Frm 1- (25%) (25%)
Control Control 5% IFD 17.56 17.49 18.65 18.72 (N/323 cm.sup.2)
18.75 18.96 19.76 20.28 19.08 19.19 19.98 20.53 19.16 19.12 19.91
20.69 19.20 19.11 20.07 20.67 19.11 18.79 20.01 20.40 18.99 18.79
20.12 20.19 18.78 18.40 19.85 20.07 18.64 18.29 19.76 19.63 17.93
17.35 18.17 17.78 5% IFD 18.72 18.55 19.63 19.90 AVE 5% IFD 1.65
1.83 1.95 2.91 SPREAD Average 5% IFD Formulation 1 = 18.63 Average
5% IFD Formulation 1-Control = 19.76 % Change = 5.71%
Example 21
Support Factor
[0184] Flexible slabstock polyurethane foams having the
formulations listed in TABLE 21.1 were prepared using the polyols
listed in TABLE 21.2. The resulting foam samples were tested
according to ASTM D3574 to provide 25% IFD and 65% IFD values. The
support factor was calculated from the 25% and 65% IFD and is
reported in TABLE 21.3.
TABLE-US-00039 TABLE 21.1 30% 40% 50% Ingredient (PPH) (PPH) (PPH)
3000 M.sub.W triol 70 60 50 Oligomeric. 30 40 50 Polyol (see, Table
21.2) Water 4 4 4 TDI 105 index* 105 index* 105 index* Surfactant 1
1 1 BL-11 (amine 0.16 0.16 0.16 catalyst) K-29 (stannous 0.22 0.22
0.22 octoate) *The amount of TDI used was calculated based on the
total water and the hydroxyl number of the polyol to provide an
index of 105.
TABLE-US-00040 TABLE 21.2 Mn Mn Mw (VPO) (LS) (LS) OH Acid Water
(grams/ Fn (grams/ (grams/ Polyol Number Value (%) mole) (VPO)
mole) mole) Mw/Mn 21-1 55.63 0.30 0.03 1695 1.68 1611 6928 4.30
21-2 58.81 0.28 0.04 1784 1.87 1567 9294 5.93 21-3 62.56 0.44 0.09
1844 2.06 3206 32180 10.04 21-4 63.23 0.44 0.08 1730 1.95 2887
26530 9.19 21-5 59.61 0.42 0.09 1664 1.77 2663 25570 9.60 21-6
58.97 0.43 0.05 1664 1.75 3300 42710 13.00 21-7 61.18 0.46 0.05
1822 1.99 3916 37820 10.59 21-8 65.85 0.43 0.07 1931 2.27 1864
11100 6.60 21-9 62.07 0.42 0.07 1744 1.93 3662 43920 12.00 21-10
65.12 0.43 0.06 1889 2.19 4502 51880 11.52 21-11 64.76 0.47 0.06
1981 2.29 1739 13110 7.54 21-12 63.51 0.32 0.06 1691 1.91 1760 6649
3.78 21-13 55.81 0.26 0.07 1897 1.89 1501 8251 5.50 21-14 54.50
0.25 0.05 1971 1.91 1433 7763 5.42 21-15 59.52 0.30 0.07 1864 1.98
1674 8345 4.98 21-16 59.28 0.32 0.05 1980 2.09 1670 12130 7.27
21-17 60.94 0.22 0.05 1857 2.02 1623 11440 7.05 21-18 57.99 0.27
0.05 1704 1.76 1615 8055 4.99 21-19 56.91 0.30 0.04 1596 1.62 1442
7412 5.14 21-20 56.43 0.26 0.04 1670 1.68 1512 7799 5.13 21-21
60.18 0.42 0.05 1828 1.96 1405 8373 5.96 21-22 57.45 0.34 0.05 1728
1.77 1710 8626 5.04 Viscosity PV Mon EOC Oligomer Polyol g'M (Pa
s). (%) (GPC) Dim Trim Tetr+ (%) (% wt) 21-1 1.27 3.28 1.5 43.9
11.7 7.9 36.5 4.38 56.1 21-2 1.11 4.73 1.9 39.9 11.2 7.3 41.6 4.21
60.1 21-3 0.53 4.65 3.9 41.7 11.5 7.5 39.3 4.22 58.3 21-4 0.58 5.42
2.5 39.8 11.7 7.7 40.8 4.13 60.2 21-5 0.52 4.03 2.7 43.3 11.9 7.6
37.2 4.31 56.7 21-6 0.37 4.99 2.7 45.1 11.5 7.4 35.4 4.18 54.9 21-7
0.45 6.18 2.2 38.9 11.2 7.3 42.4 3.98 61.1 21-8 1.01 4.03 2.7 39.0
11.5 7.4 42.1 4.20 61.0 21-9 0.39 4.94 2.8 41.8 11.2 7.4 39.6 4.03
58.2 21-10 0.37 7.59 3.5 38.6 10.6 6.8 44.0 4.05 61.4 21-11 0.93
6.56 3.3 37.8 11.3 7.0 43.9 3.96 62.2 21-12 1.37 3.41 2.2 43.8 12.2
8.1 35.9 4.08 56.2 21-13 1.49 3.33 2.3 43.7 10.7 6.7 38.9 4.27 56.4
21-14 1.26 3.13 2.5 43.7 11.1 7.3 37.9 4.46 56.3 21-15 1.17 2.95
2.2 41.4 11.4 7.5 39.7 4.49 58.6 21-16 0.98 5.25 2.3 40.2 10.5 6.8
42.4 4.39 59.8 21-17 1.03 5.22 2.0 40.1 10.9 7.2 41.8 4.14 59.9
21-18 1.24 3.73 1.9 42.3 11.0 7.73 39.0 4.37 57.7 21-19 1.22 3.51
1.7 44.2 11.0 7.44 37.9 4.37 55.8 21-20 1.25 3.46 2.0 43.8 10.8
7.12 38.3 4.40 56.2 21-21 1.25 4.00 2.5 41.2 11.4 7.5 39.8 4.25
58.8 21-22 1.26 3.57 2.0 42.3 11.2 7.5 39.0 4.33 57.7
TABLE-US-00041 TABLE 21.3 Support Factor at 30%, 40%, and 50%
Incorporation Sample Support Factor Support Factor Support Factor
(Polyol No.) @ 30% @ 40% @ 50% 21-1 1.86 1.89 -- 21-2 1.81 1.865
2.19 21-3 1.83 1.91 -- 21-4 1.81 1.98 1.98 21-5 1.83 1.94 -- 21-6
1.82 1.815 -- 21-7 1.76 1.985 1.99 21-8 1.96 2.015 2.02 21-9 1.79
1.865 -- 21-10 1.80 2.15 2.15 21-11 1.80 2.075 2.08 21-12 1.85
1.945 1.95 21-13 1.84 1.86 2.18 21-14 1.77 1.85 -- 21-15 1.82 1.99
1.99 21-16 1.80 1.92 1.95 21-17 1.79 1.9 1.95 21-18 1.80 1.91 2.14
21-19 1.82 1.84 2.06 21-20 1.845 1.93 2.13 21-21 1.82 1.85 2.03
21-22 1.84 1.90 2.19 AVE. 1.818 1.927 2.059
Example 22
Flame Retardance
[0185] Slabstock foam samples prepared in Example 18 were tested
for flame retardance in accordance with Technical Bulletin 117,
"Requirements, Test Procedure and Apparatus for Testing the Flame
Retardance of Resilient Filling Materials Used in Upholstered
Furniture" (March 2000). The results are reported in TABLE
22.1.
TABLE-US-00042 TABLE 22.1 Form. Form. 4- Form. 4 3- Form. 3 Form.
1- Form. 1 Control (25%) Control (25%) Control (25%) Smolder % 99.3
99.3 99.2 98.2 83.6 94.9 (Ave.) Char 1.58 1.58 1.88 1.62 1.44 1.34
Length (Ave.) Aged Char 1.54 1.54 1.82 1.64 1.26 0.96 Length
(Ave.)
Example 23
[0186] An oligomeric polyol was fractionated with multiple GPC
column runs. For each fraction, phenyl isocyanate was used to tag
the OH groups in the fraction. The ultraviolet absorbance of each
fraction was then measured to determine hydroxyl content. By
comparison with a standard, hydroxyl number and number average
hydroxyl functionality (Fn) for each fraction were determined. The
results are present in TABLE 23.1.
TABLE-US-00043 TABLE 23.1 GPC Fraction Ave 1 2 3 4 5 6 Fn 1.34 0.51
1.45 2.00 4.00 4.81 11.68 Mn (grams/mole 1760 974 1944 2916 4860
6818 13608 mole % 100.0 42.0 13.9 9.3 10.0 18.7 5.2
Example 24
[0187] An oligomeric polyol having the characteristic shown in
TABLE 24.1 was analyzed for the presence of odor-producing lipid
oxidation products hexanal, nonanal, and decanal. The analytical
technique used solid phase micro-extraction followed by gas
chromatography and flame ionization detection in order to determine
the level of the oxidation products in the oligomeric polyol in
parts per million (ppm). External standards were used to construct
calibration curves for hexanal, nonanal, and decanal. The results
of the analysis on the oligomeric polyol of TABLE 24.1 are shown in
TABLE 24.2.
TABLE-US-00044 TABLE 24.1 Property Value Hydroxy Number 57.6
Monomer (%) 41.6 Dimer (%) 11.5 Trimer (%) 7.3 Tetra + (%) 39.6
Total Olig (%) 58.4 Viscosity (Pa s) 3.88
TABLE-US-00045 TABLE 24.2 Amount of Compound Compound (ppm) Hexanal
10.40 Nonanal 13.78 Decanal 1.17 Total 25.34
[0188] All publications and patents mentioned herein are hereby
incorporated by reference. The publications and patents disclosed
herein are provided solely for their disclosure. Nothing herein is
to be construed as an admission that the inventors are not entitled
to antedate any publication and/or patent, including any
publication and/or patent cited herein.
[0189] Other embodiments of this invention will be apparent to
those skilled in the art upon consideration of this specification
or from practice of the invention disclosed herein. Various
omissions, modifications, and changes to the principles and
embodiments described herein may be made by one skilled in the art
without departing from the true scope and spirit of the invention
which is indicated by the following claims.
* * * * *