USOO6391935B1

(12) United States Patent (10) Patent No.: US 6,391,935 B1

Hager et al. (45) Date of Patent: May 21, 2002

(54) VISCOELASTIC POLYURETHANE FOAMS 4,950,695 A 8/1990 Stone ......................... 521/174

4,980,386 A 12/1990 Tiao et al. .................. 521/108
(75) Inventors: Stanley L. Hager, Cross Lanes, Veril 4,981,880 A 1/1991 Lehmann et al. ........... 521/174
C. Jividen, Scott Depot, both of WV 4,987,156 A 1/1991 ToZune et al. ................ 521/99
5,420,170 A 5/1995 Lutter et al. ................ 521/159
SEE, C 5,631,319 A 5/1997 Reese et al. ................ 524/590
y, ye, 5,919,395 A 7/1999 Bastin et al. .......... 252/182.24
both of (FR) 6,136.879 A 10/2000 Nishida et al. ............. 521/174
(73) Assignee: Bayer Antwerp, N.V., Antwerp (BE) FOREIGN PATENT DOCUMENTS
-- - CA 2246636 1/1999
(*) Notice: Subject to any disclaimer, the term of this
patent is extended or adjusted under 35 JP O7324161 12/1995
U.S.C. 154(b) by 0 days. * cited by examiner
Primary Examiner John M. Cooney, Jr.
(21) Appl. No.: 09/495,192 (74) Attorney, Agent, or Firm-Joseph C. Gil; Lyndanne M.
(22) Filed: Jan. 31, 2000 Whalen; N. Denise Brown
(51) Int. Cl." ................................................ C08G 18/06 (57) ABSTRACT
(52) U.S. Cl. ....................... 521/170; 521/157; 521/172; Viscoelastic foams and a process for making them are
521/174 disclosed. The foams are produced with a unique isocyanate
(58) Field of Search ................................. 521/170, 172, reactive mixture that includes a low equivalent weight
521/174, 157 polyol and from about 15 to about 70 wt.% of a polyester
or polvoxValkvlene monol having a number average equiva
(56) References Cited Wii R than about F. The monol E. T tO
U.S. PATENT DOCUMENTS formulating excellent Viscoelastic foams over a broad range
of processing conditions and isocyanate indices. A “reac
3,875,086 A 4/1975 Ramey et al. tive' monol gives TDI-based viscoelastic foams with
25. A Real - - - - - - - - - - - - - - - - - 5. improved “hand feel” and reduced levels of residual tolu
3,405.077 A 10/1986 Pastor et al. enediamines.
4,722.946. A 2/1988 Hostettler ................... 521/158
4,839,397 A 6/1989 Lohmar et al. ............. 521/159 29 Claims, No Drawings
 US 6,391,935 B1
1 2
VISCOELASTIC POLYURETHANE FOAMS takes a similar approach with a polyol mixture that contains
a 2500 to 6500 molecular weight polyol having a function
FIELD OF THE INVENTION ality of 2.5 to 6 and a rigid polyol having molecular weight
The invention relates to Viscoelastic polyurethane foams 300 to 1000 and a functionality of 2.5 to 6. None of these
and a process for making them. These Soft foams, which patents teaches to include a monofunctional polyether (a
incorporate a polyoxyalkylene monol, are useful in a wide “monol”) in the formulation.
variety of applications Such as bedding, shoe Soles, ear Monofunctional alcohols have been included in flexible
plugs, and protective Sports equipment. polyurethane foams for various reasons, but they have rarely
appeared in a Viscoelastic foam. Most references that include
BACKGROUND OF THE INVENTION a monol teach foams with high resilience (see, e.g., U.S. Pat.
Flexible, Viscoelastic polyurethane foam (also known as Nos. 4.981,880, 3,875,086, and 3,405.077). Other references
“dead” foam, “slow recovery' foam, or “high damping” teach the use of low molecular weight monofunctional
foam) is characterized by slow, gradual recovery from materials. For example, U.S. Pat. No. 5,631,319 teaches to
compression. While most of the physical properties of use a C-C monoalcohol combined with a hydroxyketone
15 in non-viscoelastic foam. U.S. Pat. No. 4,209,593 teaches to
Viscoelastic foams resemble those of conventional foams,
the resilience of Viscoelastic foams is much lower, generally use a naphthol or other “bulky' monohydroxy compound to
less than about 15%. Suitable applications for viscoelastic make an energy-absorbing foam. Unfortunately, including
foam take advantage of its shape conforming, energy low-molecular-weight (<1000), high hydroxyl number (>60
attenuating, and Sound damping characteristics. For mg KOH/g) monols in Viscoelastic foams can adversely
example, the foam can be used in mattresses to reduce impact important foam properties, particularly compression
preSSure points, in athletic padding or helmets as a shock sets (see Comparative Examples 14 and 15 below). In
absorber, and in automotive interiors for Soundproofing. addition, any monol can remain largely unreacted, especially
Various Synthetic approaches have been used to make in a low-indeX formulation, resulting in a foam that is oily
Viscoelastic foam. Formulators have modified the amount 25
to the touch (i.e., has poor “hand feel”).
and type of polyol(s), polyisocyanate, Surfactants, foaming U.S. Pat. No. 4,950,695 teaches to use a monofunctional
catalysts, fillers (see, e.g., U.S. Pat. No. 4,367,259), or other alcohol or polyether to soften flexible polyurethane foams.
components, to arrive at foams having low resilience, good The formulations also include a 2000 to 6500 molecular
Softness, and the right processing characteristics. Too often, weight triol. Because the inventors did not bother to report
however, the window for processing these formulations is resilience values, a skilled person would infer that the foams
undesirably narrow. lack Viscoelastic character.
Most flexible, Viscoelastic polyurethane foam is produced European Pat. Appl. No. 0 913 414 teaches to make
at low isocyanate index (100 times the mole ratio of -NCO Viscoelastic polyurethane foams that may contain a poly
groups to NCO-reactive groups in the formulation). ether monol. The monol, which has a molecular weight leSS
Usually, the index is less than about 90. See, for example, 35 than 1500, is used with a polyol that has a molecular weight
U.S. Pat. No. 4,722,946 (index: 65–85), U.S. Pat. No. greater than 1800. All of the examples show low-index (less
4,980,386 (index: 65–90), and U.S. Pat. No. 4,839,397 than 90) foams.
(index: <80). Simply raising the index makes it difficult to In Sum, most Viscoelastic foams are made at isocyanate
achieve the required Softness, as evidenced by higher-than indices below 90, but the industry would benefit from a
desirable IFD or CLD numbers (see Comparative Example 40 better way to formulate these low-resilience foams at higher
36 below). index values. In particular, formulations that provide a wider
Unfortunately, low-index foam formulations are processing window are needed. Desirable formulations
extremely Sensitive to Small changes in catalyst and Surfac would give foams with a favorable balance of properties,
tant amounts, So the processing window is undesirably including low resilience, good Softness, low compression
narrow and special (translation: expensive) Silicones are 45 sets, and good “hand feel.” A valuable TDI-based formula
often needed to avoid shrinkage or foam collapse. Foams tion would produce foams having reduced levels of tolu
made at low indeX are prone toward high compression Sets enediamines.
and also tend to discolor upon exposure to heat or ultraViolet SUMMARY OF THE INVENTION
light. Moreover, when toluene diisocyanate (TDI) is used to
make Viscoelastic foams at low index, the foams can contain 50 The invention is a Viscoelastic polyurethane foam and a
undesirably high levels of toluenediamines, particularly process for making it. The foam is produced using a unique
after the normal curing process. (Toluenediamines are now isocyanate-reactive mixture that includes a polyester or
under Severe public and regulatory Scrutiny in Europe polyoxyalkylene polyol and from about 15 to about 70 wt.
because they are highly toxic and possible carcinogens.) In % of a polyester or polyoxyalkylene monol. The monol has
addition, it is often difficult to make low-resilience foams 55 a number average equivalent weight greater than about
having a good balance of physical properties at indices 1000, and the polyol has a number average equivalent
below 90. weight less than about 600. When this isocyanate-reactive
Other approaches to making Viscoelastic foam hinge on mixture is combined with a polyisocyanate, water, a
finding the right mixture of polyether polyols and other Surfactant, and one or more catalysts at an isocyanate index
components. For example, U.S. Pat. No. 4,987,156 arrives at 60 of at least 90, the result is a Viscoelastic polyurethane foam
a Soft, low-resilience foam with a mixture of high and low having a resilience of less than 15% and an excellent overall
molecular weight polyols, each of which has a hydroxyl balance of physical properties.
functionality of at least 2, and a plasticizer having a Solidi We Surprisingly found that using the monol-containing
fication point less than -20° C. U.S. Pat. No. 5,420,170 isocyanate-reactive mixture described above is the key to
teaches to use a mixture that includes one polyol having a 65 formulating Viscoelastic foams over a broad range of pro
hydroxyl functionality of 2.3–2.8, and another polyol having cessing conditions and isocyanate indices. In spite of the
functionality 2–3. Recently issued U.S. Pat. No. 5,919,395 relatively high molecular weight of the monols, the resulting
 US 6,391,935 B1
3 4
foams retain their low resilience and good damping prop epoxide polymerization with a mixture of EO and PO in a
erties. Moreover, the foams have good Softness and low ratio effective to give between 15% and 50% primary
compression Sets. We also unexpectedly discovered that by hydroxyl end groups. The use of EO-tipped monols contrib
using a "reactive' mono (i.e., a monol having a high content utes to excellent processing and foam properties. See
of primary hydroxyl groups) in TDI-based formulations at Example 18, below (Table 3), which includes an EO-tipped
indices higher than 95, we could make foams with improved monol (M8).
“hand feel” and reduced levels of residual toluenediamines.
Yet another preferred class of monols are “EO-capped'
DETAILED DESCRIPTION OF THE monols, which have a primary hydroxyl group content
INVENTION greater than about 50%, more preferably greater than about
Viscoelastic polyurethane foams of the invention include, 80%, and most preferably greater than about 90%. These are
in addition to conventional components, a unique “reactive” monols that have high reactivity with polyisocy
isocyanate-reactive mixture. The mixture includes a poly anates. In spite of the value of all-PO monols for vastly
ester or polyoxyalkylene monol and a polyester or polyoxy improving processing characteristics of Viscoelastic foam,
alkylene triol. Optionally, a chain extender or crosslinker is we found that their low reactivity can at times cause the
included. 15 foams to contain enough unreacted monol to make them oily
The polyester or polyoxyalkylene mono has one hydroxyl to the touch. Reactive monols overcome this problem, as the
group per molecule, and an average equivalent weight “hand feel” results in Table 6 below demonstrate. The added
greater than about 1000. Thus, it also has a number average reactivity permits incorporation of even 50 wt.% monol
molecular weight (Mn) greater than about 1000. Preferably, based on the amount of isocyanate-reactive mixture (see
the monol has an average equivalent weight greater than Examples 32–35), and enables preparation of foams at
about 1500, and most preferably greater than about 2000. indices well over 100. AS Table 6 also shows, the foams
made at 100 index and above with reactive monols have
Preferred monols have a hydroxyl number less than about 56
mg KOH/g. exceptionally low residual toluenediamine contents after a
The monol can be a polyester. Polyesters contain recur Simulated typical curing process (4 h at 140 C.).
25 The polyester or polyoxyalkylene monol is present in an
ring units of a carboxylic acid derivative (e.g., anhydride,
diacid) and a glycol or diol. The polyester contains only one amount within the range of about 15 to about 70 wt.% based
hydroxyl group. The other end groups are ones that do not on the amount of isocyanate-reactive mixture. A more pre
react with isocyanates, Such as alkyl, aryl, or aralkyl ferred range is from about 20 to about 60 wt.%; most
Substituted ethers or esters. preferred is the range from about 25 to about 50 wt.%.
More preferred monols are polyoxyalkylene monols. The isocyanate-reactive mixture includes a polyester or
These are conveniently made by reacting a monoalcohol polyoxyalkylene polyol. These polyols have hydroxyl func
(methanol, ethanol, phenols, allyl alcohol, higher molecular tionalities of 2 or greater, preferably from about 2 to 8, more
weight alcohols, or the like) with multiple equivalents of an preferably from about 3 to 6. Triols are particularly pre
epoxide Such as ethylene oxide, propylene oxide, butylene ferred.
35
oxides, or the like, or mixtures thereof. The epoxide can be The polyols have a number average equivalent weight leSS
polymerized using well-known techniques and a variety of than about 600, preferably less than about 500, and most
catalysts, including alkali metals, alkali metal hydroxides preferably less than about 400. Preferred polyols have
and alkoxides, double metal cyanide complexes, and many hydroxyl numbers greater than about 94 mg. KOH/g, more
others. The monols can also be made by first producing a 40 preferably greater than about 112 mg KOHAg, and most
polyoxyalkylene diol or triol and then converting all but one preferably greater than about 140 mg KOH/g.
of the remaining hydroxyl groups to ether, ester, or other The polyol can be a polyester, prepared as described
non-reactive derivatives using known methods. earlier for the monols, except that two or more hydroxyl
The polyoxyalkylene monols can have any desired groups are present. Preferred polyols are polyoxyalkylene
arrangement of oxyalkylene units. For example, the monols 45 polyols. These are conveniently made by reacting com
can be PO homopolymers, block EO-PO copolymers, pounds having two or more active hydrogens (e.g., glycols,
EO-capped polyoxypropylenes, random EO/PO triols, tetrols, hexols, and polyfunctional amines) with one
copolymers, PO polymers that are “tipped” with a mixture or more equivalents of an epoxide as described earlier. Like
of EO and PO to achieve a desired primary hydroxyl the monols, the polyols can have any desired arrangement of
content, or any other desired configuration. 50 oxyalkylene units. Thus, the polyols can be PO
A preferred class of polyoxyalkylene monols consists of homopolymers, block EO-PO copolymers, EO-capped
polyoxypropylene monols having average equivalent polyoxypropylenes, random EO/PO copolymers, PO poly
weights greater than about 1000, more preferably greater mers that are “tipped' with a mixture of EO and PO to
than about 1500, and most preferably greater than about achieve a desired primary hydroxyl content, or any other
2000. We found that these all-PO monols, which have 55 desired configuration.
hydroxyl numbers less than or equal to 56 mg KOH/g, The polyol is normally present in an amount within the
greatly expand the processability window for making vis range of about 30 to about 85 wt.% based on the total
coelastic foams. See, for example, the wide range of water amount of isocyanate-reactive mixture. A more preferred
levels and indices Suitable for use in making Viscoelastic range is from about 40 to about 70 wt.%.
foams with the all-PO monols (M6 and M7) in Examples 60 The isocyanate-reactive mixture optionally includes a
9-13 (Table 2), Examples 20–22 (Table 4), and Examples minor proportion of a chain extender or crosslinker in
27–29 (Table 5) below. When a lower molecular weight addition to the monol and polyol. Suitable chain extenders
(hydroxyl number=112 mg KOH/g) all-PO monol (M5) is include low molecular weight diols and diamines Such as
used instead, important properties Such as compression Set ethylene glycol, propylene glycol, diethylene glycol, dipro
suffer (see Comparative Examples 14 and 15, Table 2). 65 pylene glycol, 2-methyl-1,3-propanediol, ethylene diamine,
Another preferred class of monols consists of “EO 1,6-hexanediol, and the like, and mixtures thereof. Suitable
tipped' monols, which are usually made by finishing the crosslinkers include triols and alkanolamines Such as
 US 6,391,935 B1
S 6
trimethylolpropane, glycerine, Sorbitol, ethanolamine, herein by reference. Suitable organotin catalysts include tin
diethanolamine, triethanolamine, and the like, and mixtures Salts and dialkyltin Salts of carboxylic acids. Examples
thereof. When a chain extender or crosslinker is included, it include Stannous octoate, dibutyltin dilaurate, dibutyltin
is typically used in an amount within the range of about 0.1 diacetate, Stannous oleate, and the like. Stannous Octoate and
to about 5 wt.%, preferably from about 0.5 to about 3 wt. dibutyltin dilaurate are particularly preferred. Preferred
%, based on the amount of isocyanate-reactive mixture. organoamine catalysts are tertiary amines Such as
Preferred chain extenders and crosslinkers have molecular trimethylamine, triethylamine, triethylenediamine, bis(2,2'-
weights less than about 300 g/mole, more preferably less dimethylamino)ethyl ether, N-ethylmorpholine,
than about 200 g/mole. diethylenetriamine, and the like. The polyurethane catalysts
Polyisocyanates Suitable for use in the invention contain are typically used in an amount within the range of about
two or more free -NCO groups per molecule and are those 0.001 to about 2 parts, more preferably from about 0.05 to
conventionally used to make flexible polyurethane foam. about 1 part, per 100 parts of isocyanate-reactive mixture.
Useful polyisocyanates include aromatic, aliphatic, and The foams optionally include a plasticizer. Suitable plas
cycloaliphatic di- and polyisocyanates. Examples include ticizers are Substances that add further Softness to the foam.
toluene diisocyanates (TDI), diphenylmethane diisocyanates 15 Examples include dioctyl phthalate, distearyl phthalate, di
(MDI), naphthalene diisocyanates, isophorone diisocyanate, Sodecyl phthalate, dioctyl adipate, tricresyl phosphate, triph
hexamethylene diisocyanates (HDI), polymeric MDls, and enyl phosphate, and the like. When a plasticizer is used, it is
polyisocyanates modified with carbodiimide, ester, urea, preferably present in an amount within the range of about
urethane, allophanate, isocyanurate, biuret, or other 0.1 to about 30 wt.%, more preferably from about 5 to about
functionalities, and the like, and mixtures thereof. Preferred 20 wt. 76, based on the amount of isocyanate-reactive
polyisocyanates are TDI (usually a mixture of 2,4- and mixture. Flame retardants, antioxidants, pigments, dyes,
2,6-isomers), MDIs, and mixtures of these. fillers, and many other commercial additives can also be
included in the foams in conventional amounts.
The amount of polyisocyanate used is normally adjusted The foams are prepared using methods that are well
to arrive at a desired isocyanate index. Generally, the amount 25 known in the industry. These methods may include continu
used will be within the range of about 20 to about 50 wt.%, ouS or discontinuous free-rise Slabstock foam processes and
more preferably from about 25 to about 40 wt.%, based on molded foam processes. In a typical slabstock process, the
the combined amounts of isocyanate-reactive mixture and isocyanate is continuously mixed together with the other
polyisocyanate. formulation chemicals by passing through a mixing head
An advantage of the invention is the ability to formulate and then into a trough which overflows onto a moving
Viscoelastic foams over a wide range of water levels and conveyor. Alternatively, the reacting mixture is deposited
isocyanate indices. In particular, exceptionally high indices directly onto the moving conveyor. The foam expands and
(compared with commercial viscoelastic foam) can be used. rises as it moves down the conveyor to form a continuous
In general, the NCO index will be within the range of about foam slab that is cut into blocks or buns of the desired length
90 to about 120. A more preferred index range is from about 35 for curing and Storage. After curing for one or more days,
95 to about 110. As the examples in Table 4 below show, these foam buns can be cut into the desired shapes for the
excellent Viscoelastic foams can be produced throughout the end-use applications. In the discontinuous process, the reac
normal range of indices for ordinary flexible polyurethane tants are quickly mixed together through a head or in a large
foam. In contrast, most Viscoelastic foams are formulated at mixing chamber. The reaction mixture is then deposited into
indices below 90 (see Background). 40 a large box or other Suitable container where foam expansion
Water is used as a reactive blowing agent to make the occurs to form a bun of the lateral dimensions of the
foams of the invention. The amount needed depends on a container.
number of factors, including the desired foam density and A typical molded foam process usually employs a one
Softness, the nature of the polyisocyanate and isocyanate shot approach in which a specific amount of the isocyanate
reactive mixture, the desired processing characteristics, 45 stream (the “A” side) is rapidly combined and mixed with a
whether an auxiliary blowing agent (e.g., dichloromethane Specific amount of the remaining formulation components
or an HCFC) is used, and other factors. Usually, water is (the “B” side). An additional stream may be employed to
used in an amount within the range of about 0.1 to about 10 bring in one or more Specific components not included with
parts per 100 parts of isocyanate-reactive mixture. A more the “B” side stream. The mixture is quickly deposited into a
preferred range is from about 0.5 to about 5 parts; most 50 mold that is then closed. The foam expands to fill the mold
preferred is the range from about 1 to about 3 parts. and produce a part with the shape and dimensions of the
The foam is usually produced in the presence of a mold.
Surfactant, which helps to Stabilize the foam until it cures. Although leSS preferred, a prepolymer approach to mak
Suitable surfactants are those well known in the polyure ing the foams can also be used. In this approach, a significant
thane industry. A wide variety of organosilicone Surfactants 55 portion of the isocyanate-reactive mixture is reacted with the
are commercially available. Examples are Niax L-620 polyisocyanate, and the resulting prepolymer is then reacted
surfactant, a product of CK. Witco, and B8002, a product of with the remaining components.
Goldschmidt. The Surfactant is typically used in an amount Foams of the invention have low resilience, i.e., less than
within the range of about 0.1 to 5, preferably from about 0.2 15% as measured in the standard ball rebound test (ASTM
to 3, parts per 100 parts of isocyanate-reactive mixture. 60
A mixture of polyurethane catalysts is normally used to D3574-95, Test H). Preferably, the foams have resilence less
catalyze the reactions of the monol, polyol, water, and chain than 10%, most preferred are foams having a resilience of
extenders or crosslinkers with the polyisocyanate. It is less than 5%. In addition, the foams preferably have a high
common to use both an organoamine and an organotin degree of softness, as indicated by 25% IFD (indentation
compound for this purpose. Suitable polyurethane catalysts 65 force deflection at 25% compression, ASTM D 3574, Test
are well known in the art, an extensive list appears in U.S. B) values that are preferably less than about 15 lbs., and
Pat. No. 5,011,908, the teachings of which are incorporated more preferably less than about 10 lbs. Alternatively, a
 US 6,391,935 B1
7 8
compression load deflection (CLD) test (ISO 3386-1 with KOH/g (about 500 equivalent weight), the foam compres
measurement at the first compression cycle) may be used to Sion Sets are unacceptable.
indicate the preferred foam Softness. Using this test method,
a 40% CLD value of less than 1.5 kPa is preferred. Preferred Examples 9-13 and Comparative Examples 14 and
foams also have low compression Sets. For example, pre 15 (Table 2)
ferred foams exhibit a 90% compression set value, C.
(ASTM D 3574, Test D), of less than about 15%, more These examples further illustrate the importance of mono
preferably less than about 10%. hydroxyl number. Note the higher-than-acceptable compres
The following examples merely illustrate the invention. Sion Sets of the foams made using the 112 mg KOHAg
Those skilled in the art will recognize many variations that hydroxyl number monol. In contrast, the foams of Examples
are within the Spirit of the invention and Scope of the claims. 9-13 exhibit low compression sets and good overall foam
properties.
EXAMPLES
Preparation of Viscoelastic Foams-General Procedure 15
The following procedure is used for Examples 1-31. A Examples 16-19 and Comparative Example 8
series of nominally 3 pound/ft (pcf free-rise viscoelastic (Table 3)
foams is prepared in the laboratory using conventional A wide range of different polyols, crosslinkers, and chain
bench foaming procedures. The ingredients other than tolu extenders can be used with the monol to make Viscoelastic
ene diisocyanate (TDI) are mixed thoroughly. Next, TDI foams at 100 index. The foams have excellent processing
(commercial 80:20 mixture of 2,4- and 2,6-isomers) is added and properties that rival those of the commercial, low-index
and mixed briefly. The mixture is poured into a standard 14 foam (Comparative Example 8).
inch (35.6 cm)x14 inchx6 inch (15.2 cm) cake box. The
mixture is allowed to rise freely to full height, after which 25
Examples 20-25 and Comparative Example 26
the degree of Settling is measured. The foam is cured in an
oven at 125 C. for 5 min. (or in a few cases, at 150° C. for (Table 4)
30 min.). After a minimum of 16 h at room temperature, The use of the claimed isocyanate-reactive mixture allows
Shrinkage, if any, is noted, and a 12 inch (30 cm)x12 inchx4 formulators great latitude in varying the isocyanate index.
inch (10 cm) Sample is cut for physical testing. The Good foams are easily made at indices from 95 to 110. As
formulations, processing characteristics, and foam proper Comparative Example 26 illustrates, it is not possible to
ties are noted in Tables 1-5.
A slightly different procedure is used for Examples 32-39. merely increase the NCO index in the commercial formu
The foams are nominally 80 kg/m (5 pounds/ft). The TDI 35
lation. Doing So results in poor processing, excessive
used is a commercial blend that contains a 65:35 mixture of Shrinkage, and a product that is not testable.
2,4- and 2,6-isomers. The reacting mixture is allowed to rise
freely to full height, and the resulting foam is cured in an Examples 27-29 and Comparative Examples 30-31
oven at 140 C. for 4 h. After a minimum of 24 h at room (Table 5)
40
temperature, 4 Samples of 1 cmx1 cmx10 cm are cut for
toluenediamine (TDA) analysis, and a 12 inch (30 cm)x12 The effect of water level is shown here. With a 14 mg
inchx4 inch (10 cm) sample is cut for physical testing. The KOH/g hydroxyl number monol present, the water level can
content of residual 2,4-TDA in the foam is measured in range from 1 to 3 parts per hundred parts of isocyanate
accordance with the method approved by the Isocyanate 45
reactive mixture while maintaining good processing and
Producers Association (ISOPA). The method involves good foam properties. In contrast, when the commercial
extraction of TDA from a foam Sample with aqueous acetic formulation is modified from 2 parts water to 1 part water
acid Solution; no derivatization is used. Table 6 Summarizes (Comparative Example 30), processing falters, the foam
the formulations and foam properties. Shrinks, and testing is not possible. Similar problems occur
50 at 100 index (Comparative Example 31).
Examples 1-6 and Comparative Examples 7-8
(Table 1) Examples 32-35 and Comparative Examples 36-39
These examples show how the claimed isocyanate (Table 6)
reactive mixtures enable formulation of low-resilience foam 55
at high NCO index. Comparative Example 8 is a typical A reactive monol is advantageous for making Viscoelastic
commercial Viscoelastic foam formulated at 83 indeX. foams at high indices with good “hand feel” and low residual
levels of toluenediamines. Foams made from an all-PO
Examples 1-6 show that a range of monols prepared using
different catalysts (KOH or double metal cyanide) and monol can be oily to the touch if the monol does not react
having different amounts of oxyethylene contents and dif 60 completely with the polyisocyanate. 2,4-Toluenediamine
ferent hydroxyl numbers can be used to formulate Viscoelas levels in cured (140° C., 4 h) foam of less than 5 ppm can
tic foam at 100 index. The foams process as well or better be achieved by producing the foams at 100 index and above
than the control and have no Shrinkage problems. In using the reactive monol (Examples 32–35). These levels are
addition, they generally have a favorable balance of physical 65 much lower than those found in foams made at lower
properties. Comparative Example 7 shows that the monol isocyanate indices without monol and with all-PO monols
equivalent weight is important: at hydroxyl number 112 mg (see Comparative Examples 36–39).
 US 6,391,935 B1
13 14
TABLE 4-continued
Effect of Index

Example 2O 21 22 23 24 25 C26 C8

Foam Processing
Blowoff, s 157 148 144 2O3 18O 165 Ole 229
Settle, 7% 1.1 1.1 2.9 1.1 1.1 1.6 1.O 6.O
Shrink nil nil nil nil nil slight excessive nil
Foam Properties
Density, pcf 2.71 2.72 2.81 2.62 2.58 2.71 not 3.15
Resilience, 26 8 1O 14 1O 11 13 testable 1O
Air flow, scfm 18 2.O 3.2 4.3 3.7 2.5 O.7
25% IFD, Ibs 11.6 15.2 25.8 6.2 7.5 1O.O 10.6
25% Return, % 65.2 56.3 49.2 81.7 82.2 81.0 87.5
Tensile, psi 11.4 14.4 19.3 5.9 7.6 10.1 9.6
Elongation, % 181 148 97 2OO 215 189 238
Tear, pli O.9 1.1 1.5 O.7 O.7 O.8 O.9
90% CS, (7% 5.7 5.6 6.6 86.9 813 18.5 5.9
75% HACS, (7% 7.5 5.9 6.6 57.0 28.5 18.2 11.4

TABLE 5 TABLE 5-continued

25
Effect of Water Level Effect of Water Level
Example 27 28 29 C30 C31 Example 27 28 29 C30 C31

Formulation Foam Processing

3O Blowoff, s undetected 158 140 Ole Ole
Monol M7 M7 MT Settle, 7% 1.1 1.O 2.1 2.5 O.2
pbw 40 40 40 Shrink nil nil nil excessive excessive
Polyol P1 P1 P1 P2 P2 Foam Properties
pbw 60 60 60 1OO 1OO
DEOA 0.4 Density, pcf 4.87 2.74 1.93 not not
Water 1.O 2.0 3.0 1.O 1.O 35 Resilience, 7% O 8 14 testable testable
C-183 0.15 - A.E.S."
o , Ibs 14. i. 5.
ity 1.40 0.70 - o 50 o 50 25% Return, % 87.O 62.3 50.9
Tensile, psi 8.4 11.5 11.9
T9 O.O1 O.O6 O.13 O.O1 O.O1 Elongation, % 209 235 129
L-62O O.1 O.6 O6 O1 O.1 40 Tear, pli O.6 O.8 O.7
FR 3.0 3.0 3.0 3.0 3.0 90% CS, (7% 2.3 5.3 11.3
TDI (80/20) 26.2 35.8 45.5 27.5 32.1 75% HACS, (7% 2.5 7.2 13.3
Index 1OO 1OO 1OO 83 1OO

TABLE 6
Effect of Reactive Monol

Example 32 33 34 35 C36 C37 C38 C39

Formulation

Monol M12 M12 M12 M12 M11 M11 M11

%. 1 OH >90 >90 >90 >90 <12 <12 <12
pbw 50 50 50 50 35 35 35
Polyol P11 P11 P11 P11 P11 P11 P11 P11
pbw 50 50 50 50 1OO 65 65 65
Water 1.10 1.10 1.25 1.25 1.10 1.10 1.10 1.10
A-1 O.14 O.15 O.14 O.15 O.14 0.17 O.14 O.15
33-LV O.30 O.30 O.30 O.30 O.35 O40 O.32 O.30
T9 O.OS O.OS O.05 O.OS O.OS O.05 O.OS O.OS
B80O2 0.70 O.70 O.70 0.70 0.70 O.70 0.70 O.70
TDI (65/35) Index 1OO 105 103 107 95 85 90 95
Foam Properties
Density, kg/m 83 8O 78 76 77 84 82 79
Resilience, 26 O O O 2 7 O O 4
CLD, kPa, 40% O.90 1.35 1.18 1.62 5.20 O.70 1.73 2.07
Tensile, kPa 28.7 25.9 27.0 29.0 49.1 35.2 35.5 38.8
Elongation, % 147 155 139 132 235 224 223 197
 US 6,391,935 B1
15 16
TABLE 6-continued
Effect of Reactive Monol

Example 32 33 34 35 C36 C37 C38 C39

70% Comp. set 1O 8 8 11 11 9

70% HACS 5 4 3 7 6 6
2,4-TDA, ppm 4.5 1.1 0.4 &O.3 15 23 2O 18
Hand feel Oil- Oil- Oil- Oil- Oil- oily oily slightly
oily oily oily oily oily oily

We claim:
TABLE 7 1. A Viscoelastic polyurethane foam which comprises the
15 reaction product of water, a Surfactant, one or more catalysts,
Description of Monols, Polyols, and Formulation Components a polyisocyanate, and an isocyanate-reactive mixture com
Monols:
prising:
(a) a polyester or polyoxyalkylene monol having a num
MS-1 A blend of monols having an average mol. wt. of about 200 ber average equivalent weight greater than about 1000
used as a starter for making the other monols. 2O and an OH number less than about 56;
M-1 45 OH #, all-PO. (b) a polyester or polyoxyalkylene polyol having a num
M-2 42 OH #, made by double metal cyanide (DMC)-catalyzed
alkoxylation of MS-1 with a 7/93 blend of EO/PO to 1100 ber average equivalent weight leSS than about 600 and
mol. wt., followed by tipping with a 70/30 blend of EO/PO to an OH number greater than about 94; and
M-3
a final mol. wt. of 1335. Total EO content: 20%.
13 OH #, made by DMC-catalyzed alkoxylation of M-6 with 25
(c) optionally, a chain extender or crosslinker;
a 12/88 blend of EO/PO to 3400 mol. wt., followed by wherein the monol comprises from about 15 to about 70 wt.
tipping with 70/30 EO/PO to a final mol wt. of 4315. Total % of the isocyanate-reactive mixture;
EO content: 20%. Primary OH content: 39%. wherein the foam is produced at an isocyanate index of at
M-4 62 OH #, made by propoxylating MS-1. No EO cofeed. least 90, and
M-5 112 OH #, made by alkoxylating allyl alcohol with 3/97 wherein the foam has a resilience less than about 15%.
EO/PO to 210 mol. wt., followed by tipping with 70/30 2. The foam of claim 1 having a 90% compression set less
EO/PO to mol. wt. 501. Total EO content: 45%. 3O than about 15%.
M-6 35 OH #, made by propoxylating MS-1 using DMC catalyst.
No EO cofeed. 3. The foam of claim 1 wherein the monol is a polyox
M-7 4 OH #, made by propoxylating MS-1 using DMC catalyst. ypropylene monol having a number average equivalent
No EO cofeed. weight greater than about 1500.
M-8 20 OH #, made by DMC-catalyzed alkoxylation of M-4 with 4. The foam of claim 1 wherein the monol comprises at
0/90 EO/PO to 2340 mol. wt., followed by tipping with 35 least about 25 wt.% of the isocyanate-reactive mixture.
60/40 EO/PO to mol. wt. 2800. Total EO content: 15%.
Primary OH content: 37%. 5. The foam of claim 1 having a resilience less than about
M-11 6 OH #, made by propoxylation of allyl alcohol, 5%.
<12% primary hydroxyl groups. 6. The foam of claim 1 wherein the monol has a primary
M-12 25 OH #, made by propoxylation of allyl alcohol to mol. wt. hydroxyl end group content within the range of about 15 to
800, followed by capping with EO to a final mol. wt. of 40 about 50%.
2200; >90% primary OH groups.
Polyols 7. The foam of claim 1 wherein the monol has a primary
hydroxyl end group content greater than about 50%.
P-1 68 OH #, made by propoxylating glycerine. 8. The foam of claim 7 wherein the monol has a primary
P-2 Commercial polyol blend used to make viscoelastic foam. It hydroxyl end group content greater than about 90%.
has OH # 145 and a functionality of 3. 45 9. The foam of claim 1 wherein the polyol is a copolymer
P-4 12 OH #, made by propoxylating glycerine. of ethylene oxide and propylene oxide having an oxyethyl
P-5 37 OH # triol made by DMC-catalyzed alkoxylation of a
240 OH # starter triol (propoxylated glycerine) with 8/92 ene content within the range of about 5 to about 50 wt.%.
EO/PO to 1025 mol. wt., followed by tipping with 60/40 10. The foam of claim 1 wherein the chain extender or
EO/PO to mol. wt. 1230. Total EO content: 15%. Primary
OH content: 29%.
crosslinker has a number average molecular weight less than
P-11 240 OH #, made by propoxylating glycerine. 50 about 200 and is used in an amount within the range of about
Other components 0.1 to about 5 wt.% based on the amount of isocyanate
reactive mixture.
DEOA
DEG
diethanolamine
diethylene glycol
11. The foam of claim 1 further comprising from about 0.1
PG propylene glycol to about 30 wt.% of a plasticizer.
DPG dipropylene glycol 55 12. The foam of claim 7 having a non-oily “hand feel.”
MPD 2-methyl-1,3-propanediol 13. The foam of claim 7 having a compression load
C-183
33-LV
Niax C-183 amine catalyst blend
Dabco 33-LV amine catalyst
deflection (40% CLD) value, measured at the first compres
A-1 Niax A-1 amine catalyst sion cycle, within the range of about 0.7 to about 1.5 kPa.
T9 StannOuS Octoate 14. A Viscoelastic polyurethane foam which comprises the
T-12 dibutyltin dilaurate 60 reaction product of water, a Surfactant, one or more catalysts,
L-620 Niax silicone surfactant, product of CK. Witco toluene diisocyanate, and a polyether mixture comprising:
B8002 silicone surfactant, product of Goldschmidt (a) a polyoxyalkylene monol having a number average
FR flame retardant
TDI toluene diisocyanate (standard 80/20 or 6.5/35 blend) equivalent weight greater than about 1000 and an OH
number less than about 56;
65 (b) a polyoxyalkylene polyol having a number average
The preceding examples are meant only as illustrations. equivalent weight less than about 600 and an OH
The following claims define the invention. number greater than about 94,
 US 6,391,935 B1
17 18
(c) optionally, a chain extender or crosslinker; 24. The foam of claim 20 having a non-oily “hand feel.”
wherein the monol comprises from about 20 to about 60 wt. 25. The foam of claim 20 having a compression load
% of the isocyanate-reactive mixture; deflection (40% CLD) value, measured at the first compres
wherein the foam is produced at an isocyanate index of at sion cycle, within the range of about 0.7 to about 1.5 kPa.
least 95; and 26. The foam of claim 14 having a residual toluenedi
wherein the foam has a resilience less than about 15%. amine content following curing of less than 5 ppm.
15. The foam of claim 14 having a 90% compression set 27. The foam of claim 20 having a residual toluenedi
less than about 15%. amine content following curing of less than 5 ppm.
16. The foam of claim 14 wherein the polyoxypropylene 28. The foam of claim 14 further comprising from about
monol has a number average equivalent weight greater than 0.1 to about 30 wt.% of a plasticizer.
about 2000.
17. The foam of claim 14 wherein the monol comprises at 29. In a process for making a Viscoelastic polyurethane
least about 25 wt.% of the polyether mixture. foam by reacting water, a Surfactant, one or more catalysts,
18. The foam of claim 14 having a resilience less than a polyisocyanate, and an isocyanate-reactive mixture, the
about 5%. 15 improvement which comprises using as the isocyanate
19. The foam of claim 14 wherein the monol has a reactive mixture:
primary hydroxyl end group content within the range of (a) a polyester or polyoxyalkylene monol having a num
about 15 to about 50%. ber average equivalent weight greater than about 1000
20. The foam of claim 14 wherein the monol has a and an OH number less than about 56;
primary hydroxyl end group content greater than about 50%. (b) a polyester or polyoxyalkylene polyol having a num
21. The foam of claim 20 wherein the monol has a ber average equivalent weight leSS than about 600 and
primary hydroxyl end group content greater than about 90%. an OH number greater than about 94; and
22. The foam of claim 14 wherein the polyol is a copoly (c) optionally, a chain extender or crosslinker;
mer of ethylene oxide and propylene oxide having an wherein the monol comprises from about 15 to about 70 wt.
oxyethylene content within the range of about 5 to about 50 25
% of the isocyanate-reactive mixture;
wt.%.
23. The foam of claim 14 wherein the chain extender or wherein the foam is produced at an isocyanate index of at
crosslinker has a number average molecular weight less than least 90, and
about 200 and is used in an amount within the range of about wherein the foam has a resilience less than about 15%.
0.1 to about 5 wt.% based on the amount of isocyanate
reactive mixture.