HK1068637B - Agents for reducing the force-to-crush of high support flexible foams - Google Patents

Description

Agent for reducing the force to crush of high support flexible foams

Technical Field

The present invention relates generally to High Support (HS) and high support-high resilience (HS-HR) flexible foams having urethane groups, and more particularly to a process for producing HS and HS-HR polyurethane foams having reduced Force To Crush (FTC). The HS and HS-HR foams of the present invention contain low levels of liquid hydrocarbons containing polymerized butadiene.

Background

Flexible polyurethane foams are well known industrial products. The two most common types of flexible polyurethane foams are the conventional and High Resilience (HR) categories, as set forth in ASTM D3770 (now terminated). Current ASTM D3453-01 specifies three buffer grade flexible polyurethane cellular materials, including Normal Support (NS), High Support (HS), and high support-high resilience (HS-HR). The latter nomenclature includes the former HR categories. Flexible foams can also be differentiated by the method of production, i.e. molded or free-rise. Free-rise foams are generally produced in a continuous slabstock process. Molded foams are typically manufactured in a sealed chamber having the shape of the desired finished product. HS and HS-HR foams can be made by both free-rise and molding processes.

HS and HS-HR foams are widely used in furniture, mattresses, automobiles, and many other applications. HS and HS-HR foams differ from conventional foams by a higher support factor. HS-HR foams are also known for their higher resilience. As set forth in ASTM Standard Specification D3453-01, HS foams have a minimum support factor of 2.3, while HS-HR foams have a minimum support factor of 2.4 and a minimum rebound of 55%. The support factor is the ratio of 65% IFD to 25% IFD, and rebound is the percent rebound on a ball drop. The measurements of 25% IFD, 65% IFD and ball rebound are set forth in ASTM D3574-01.

In such foams, high crosslink density is achieved during foaming by the use of more reactive polyols and often by the use of crosslinking agents such as diethanolamine, triethanolamine, glycerol, sorbitol, and the like. Higher functionality isocyanates such as polymeric MDI may also be used with or in place of the crosslinking agent. The enhanced crosslinking provides stabilization to the initiated foam and avoids the need for strong stability silicone surfactants used to create conventional support (NS) foams. The use of a weak silicone or no silicone surfactant helps to produce a foam with a higher support factor. However, a disadvantage inherent in these foam types is that most cell windows remain intact or partially intact as they are created, thus requiring a crushing process to increase air flow and achieve the cushioning and performance requirements needed for the end application. For very reactive systems, such as those encountered in molded automotive seating, the foam may have a predominantly closed cell structure that requires immediate hot crushing to avoid shrinkage or warping of the part. Free-rise foams produced by the continuous slabstock process generally do not contain a significant percentage of fully closed cells and in most cases do not have to be crushed prior to cooling. Molded and free-rise flexible HS and HS-HR foams made with polyoxyalkylene polyols polymerized using Double Metal Cyanide (DMC) alkoxylation catalysts have been found to have improved tightness (U.S. Pat. No. 5,605,939) and can be particularly difficult to crush open.

Process latitude refers to the tolerance limit within which deviations from the formulation can be made while still maintaining commercially acceptable processing and foam performance requirements. These limitations are generally determined on the one hand by the following elements: such as poor foam cure, long demold times, instability, and voids, while on the other hand being determined by foam shrinkage, warping, and the inability to crush the foam sufficiently open to achieve good cushioning properties.

Current mechanical methods of cell opening and porosity enhancement for molded foams typically involve compression crushing, vacuum rupture, or time pressure release. Compressive crushing may be accomplished by removing the part from the mold and pressing immediately manually or between flat plates, or more commonly by passing through rollers.

Vacuum crushing involves evacuating the finished foam to rupture the cells. An industrially attractive cell opening method is Time Pressure Release (TPR), which requires opening the mold during the curing process to release the internal pressure and reclosing during the curing time. The sudden release of internally generated pressure causes the cell windows to rupture, thereby producing a foam that is sufficiently open to avoid shrinkage or buckling (U.S. Pat. Nos. 6,136,876 and 4,579,700). The TPR may be supplemented by a subsequent mechanical crushing step to more completely open the cell windows and achieve high air flow.

Free-rise HS and HS-HR foams can be crushed hot if necessary, but more typically after cooling because these foams are generally produced without significant closed cell content and therefore do not undergo high shrinkage or warping during cooling. However, the air flow is typically very low before the mechanical crushing process is performed. This typically involves passing large slabstock foam chunks through a multi-stage roll crusher that compresses the foam chunks in progressively larger amounts. Typically at least 75% (25% of the initial height) and preferably 90% compression is performed to obtain a fully crushed air flow. Another method is to cut the foam chunks into smaller chunks or end-use part sizes and then crush them individually. In certain cases where the foam is easily crushed, the use of a separate crushing process may be avoided if the foam is sufficiently opened by bending during the manufacturing process or in the final use.

Foam collapse can cause a number of problems in the molding and free-rise production of HS and HS-HR foams. If the foam is not sufficiently opened or the crushing process permanently deforms the part or tears the foam, then too high a crushing force may render the foam unusable in the intended application. In the TPR process, the time window between the time the foam does not react sufficiently to the open mold and the time it is too tight to crush by the process can be very narrow. Foams that are not well crushed may result in poor cushioning properties, and poor durability due to excessive softening, and increased tendency to set. Therefore, chemical agents that can avoid high crushing forces and improve the crushability of HS and HS-HR foams would be welcomed.

U.S. Pat. No. 6,136,876 discloses polyurethane flexible foams comprising an organic polyisocyanate and a polyol in the presence of a catalyst composition, a blowing agent, optionally a silicone surfactant cell stabilizer and a compound containing active methylene-or methine groups which is used as a cell opening agent. The cell opening agent is characterized as belonging to the weak Br * nsted acid. A disadvantage of the process of the' 876 patent is that the weak acid tends to reduce the reactivity of the isocyanate with the active hydrogen component. To compensate, it is often necessary to increase the catalyst level, thereby increasing cost and potentially resulting in higher crushing forces. In addition, these cell opening agents may not be chemically stable if blended with other "B" side components, as is commonly done in molded foam processing. Many HS and HS-HR grade slabstock and molded foams have very high FTC (force to crush) values and do not open adequately when crushed by standard methods. Thus, conventional cell opening methods, such as the use of less gelling catalyst and less stabilized polysiloxane, have met with only limited success in overcoming this problem. Typically such cell opening methods only reduce the FTC while reducing other foam processing and foam properties.

The use of liquid polybutadiene as a mold release agent in the preparation of molded polyurethane and polyurea articles is disclosed in U.S. Pat. No. 5,079,270. This patent relates to the manufacture of elastic or microporous elastomeric articles free of surface defects, which are produced by means of the RIM process. There is no mention of producing flexible foams with improved crushing properties and no examples are given for producing low density flexible polyurethane foams. Liquid polybutadiene is disclosed as 0.5% to 5% by weight of the total reaction components. Based on the compositions and typical formulations listed therein, the 0.5% of the' 270 patent corresponds to at least 0.7 parts of liquid polybutadiene per hundred parts of polyol.

U.S. Pat. No. 5,614,566 discloses the use of liquid higher molecular weight hydrocarbons, such as polybutadiene and polyoctenylene, in the production of rigid foams having a substantially open cell structure. The rigid foam of the '566 patent differs from the flexible foam of the present invention in the properties of the foam and the components used in its production, particularly the high hydroxyl number polyol component, which in the' 566 patent is between 100 and 800 (hydroxyl equivalent weight between 70 and 561). Flexible foam polyols typically have hydroxyl numbers well below 100.

Japanese Kokai JP 74-57325 and JP 92-57873 also disclose the use of liquid polybutadiene as a shrinkage inhibitor in the production of rigid foams.

Thus, the prior art does not provide a recognition of the effect of liquid polybutadiene on the crushing force of flexible foams, as rigid foams cannot be subjected to the crushing process without permanent deformation.

Accordingly, the present invention relates to chemicals for High Support (HS) and high support-high resilience (HS-HR) flexible foams that can reduce FTC at low usage levels and have minimal impact on foam processing, foam odor, and other foam properties.

Disclosure of Invention

The present invention provides High Support (HS) and high support-high resilience (HS-HR) flexible polyurethane foams prepared by reacting one or more di-or polyisocyanates at an isocyanate index of from about 70 to about 130 with:

a. a polyoxyalkylene polyol or polyoxyalkylene polyol blend having an average hydroxyl equivalent weight of at least about 1000 and an average primary hydroxyl content of at least about 25%;

b. an effective amount of an aqueous blowing agent;

in the presence of from about 0.01 to about 0.5 parts by weight, based on 100 parts by weight of the polyol component, of a liquid hydrocarbon containing greater than 50% polymerized butadiene.

Detailed Description

The High Support (HS) and high support-high resilience (HS-HR) flexible polyurethane foams of the present invention are prepared by reacting an isocyanate component with a polyol component in the presence of water as a reactive blowing agent, in addition to the presence of one or more catalysts, foam stabilizing surfactants, and optionally other conventional additives and auxiliaries, such as chain extenders/crosslinkers, physical blowing agents, colorants, fillers, flame retardants, and the like. Examples of suitable isocyanates, catalysts, additives and auxiliaries can be found in: U.S. patent 5,171,759, which is incorporated herein by reference in its entirety, j.h. saunders and k.c. frisch, polyurethane: chemistry and Technology (Polyurethanes: Chemistry and Technology), Interscience publishers, NY, 1963, and the Polyurethane Handbook (Polyurethane Handbook), eds. Gunter eye, Hanser Publications, Munich, 1985.

The isocyanate component of the present invention may be one or more di-or polyisocyanates, including but not limited to aliphatic, cycloaliphatic and aromatic isocyanates. Preferred isocyanates include commercially available mixtures of 2, 4-and 2, 6-Toluene Diisocyanate (TDI), typically provided as 80/20 or 65/35 isomer blends. Methylene diphenylene diisocyanate (MDI) may also be used in the present invention. Technical mixtures of 2, 2 ', 2, 4' -and 4, 4 '-methylenediphenylene diisocyanate are suitable, preferably containing substantial amounts of the 4, 4' -isomer. Polymethylene polyphenylene polyisocyanates having a functionality greater than 2 (polymeric MDI) are also suitable, as are mixtures of TDI, MDI and/or polymeric MDI. Modified isocyanates, such as urea-, urethane-, biuret, and carbodiimide-modified isocyanates are also suitable as non-limiting examples. The isocyanate is preferably present in an amount sufficient to provide an isocyanate index of from about 70 to about 130, more preferably from about 80 to about 120 and most preferably from about 90 to about 115.

Water is preferably the sole blowing agent. However, additional reactive or non-reactive blowing agents may be used with the water. Examples of such blowing agents include, but are not limited to, methylene chloride, difluoromethylene chloride, 1-dichloro-1-fluoroethane, 1, 2-trichloro-1, 2, 2-trifluoroethane, Hydrofluorocarbons (HFCs), Perfluorocarbons (PFCs), lower alkanes such as butane, isobutane, pentane, cyclopentane, various low molecular weight ethers and ketones, and the like. Blowing agents such as air or other gases under pressure and liquid CO under pressure may also be used₂. Water, as noted above, is preferred and is preferably used in an amount of from about 1 to about 7 parts per hundred parts polyol and more preferably from about 1 to about 5 parts per hundred parts polyol.

The liquid hydrocarbons useful in the present invention preferably comprise greater than 50% polymerized butadiene and optionally may comprise minor amounts of other comonomers. Preferred liquid hydrocarbon polymers contain only polymerized butadiene and contain less than about 65% 1, 2 (vinyl) double bonds, based on the percentage of total double bonds present. Most preferred are butadiene polymers containing less than about 50% 1, 2 (vinyl) double bonds.

In the present invention, butadiene polymers and copolymers prepared by polymerizing butadiene alone or together with other monomers in the presence of an alkali metal or organic alkali metal catalyst are preferred. In order to adjust the molecular weight and thereby produce a liquid polymer not containing gel, the living polymerization is preferably carried out in a tetrahydrofuran medium or in a chain transfer polymerization in which ethers such as dioxane and alcohols such as isopropanol are added, and aromatic hydrocarbons such as toluene and xylene function as a chain transfer agent as well as a solvent. Other polymerization techniques, such as those known in the art, may also be used.

Examples of copolymers useful in the present invention include, but are not limited to, those comprising butadiene polymerized with conjugated dienes other than butadiene as a comonomer, such as isoprene, 2, 3-dimethylbutadiene, and piperylene, or with vinyl-substituted aromatic compounds as a comonomer, such as styrene, alpha-methylstyrene, vinyltoluene, and divinylbenzene. The comonomer may be added throughout the polymerization or may be added centrally at a particular stage of the reaction, for example at the end, to form an end-capped product. Butadiene copolymers containing less than 50 wt% of the comonomer and more preferably containing less than 30 wt% of the comonomer may be used.

Surprisingly, butadiene polymers or copolymers that are substantially modified by partially oxidizing the butadiene polymer are considered ineffective in the present invention. In addition, butadiene polymers and copolymers containing active hydrogens that may react with isocyanate moieties, such as hydroxyl-terminated polybutadiene, are also ineffective. High molecular weight polybutadiene or butadiene copolymers, as typically produced by emulsion polymerization processes, are also ineffective.

As commercially sold, liquid butadiene polymers often contain impurities that impart a "rubbery" chemical odor to products incorporating these polymers. Therefore, to avoid odor generation in flexible foams, it is desirable to maintain the amount of butadiene polymer below about 0.5 parts per hundred parts (php) and more preferably below about 0.3 php.

The polyol component may preferably be a polyoxyalkylene polyol component optionally mixed with other isocyanate reactive polymers such as hydroxy-functional polybutadienes, polyester polyols, amino-terminated polyether polyols and the like. Among the polyoxyalkylene polyols which may be used are alkylene oxide adducts of various suitable initiator molecules. Examples include, but are not limited to, binary initiators such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, hydroquinone bis (2-hydroxy-ethyl) ether, various bisphenols, especially bisphenol A and bisphenol F and bis (hydroxyalkyl) ether derivatives thereof, aniline, various N-N-bis (hydroxyalkyl) anilines, primary alkylamines and various N-N-bis (hydroxyalkyl) amines; ternary initiators such as glycerol, trimethylolpropane, trimethylolethane, various alkanolamines such as ethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine and tripropanolamine; tetrainitiators such as pentaerythritol, ethylenediamine, N '-tetrakis [ 2-hydroxy-alkyl ] ethylenediamine, tolylenediamine and N, N' -tetrakis [ hydroxy-alkyl ] tolylenediamine; five-membered initiators such as various alkyl glucosides, especially alpha-methyl glucoside; hexahydric initiators such as sorbitol, mannitol, hydroxyethyl glucoside, and hydroxypropyl glucoside; an eight-membered initiator such as sucrose; and higher functionality initiators such as various starch and partially hydrolyzed starch-based products, and methylol group containing resins and novolac resins such as those prepared from the reaction of an aldehyde, preferably formaldehyde, with phenol, cresol or other aromatic hydroxyl containing compounds.

Preferred polyoxyalkylene polyols for use in producing the HS and HS-HR foams of the present invention are the propylene oxide-ethylene oxide adducts of glycols, glycerin, pentaerythritol, trimethylolpropane, sorbitol and sucrose, having a number average equivalent weight of at least about 1000 and a primary hydroxyl percentage of at least about 25%.

The most common method for polymerizing such polyols is the base-catalyzed addition of an oxide monomer to the active hydrogen groups of the polyhydric initiator and subsequently to the oligomeric polyol moiety. Potassium hydroxide and sodium hydroxide are the most commonly used basic catalysts. The polyols produced by this process may contain significant amounts of unsaturated monohydric alcohols resulting from the isomerization of propylene oxide monomer to allyl alcohol under the reaction conditions. The monofunctional alcohol may act as an active hydrogen site for further oxide addition.

A highly preferred class of polyoxyalkylene polyols in the present invention are the low unsaturation (low monol) poly (propylene oxide/ethylene oxide) polyols made with Double Metal Cyanide (DMC) catalysts. The poly (propylene oxide/ethylene oxide) low unsaturation polyols useful herein are prepared by alkoxylating a suitable hydrogen-containing initiator compound with propylene oxide and ethylene oxide in the presence of a double metal cyanide catalyst. Double metal cyanide complex catalysts, such as those disclosed in U.S. Pat. Nos. 5,158,922 and 5,470,813, the entire contents of which are incorporated herein by reference, are preferably used to obtain equivalent weights greater than about 1000Da and more preferably to obtain equivalent weights of about 1500Da or higher. Equivalent weights and molecular weights expressed herein in daltons (Da) are number average equivalent weights and molecular weights unless otherwise indicated. Random poly (propylene oxide/ethylene oxide) polyols having low unsaturation, as described in U.S. Pat. No. 5,605,939, are particularly preferred. Preferably, the amount of ethylene oxide in the ethylene oxide/propylene oxide mixture is increased at the end of the polymerization to increase the primary hydroxyl content of the polyol. Alternatively, the low unsaturation polyols may be capped with ethylene oxide using non-DMC catalysts.

If the alkoxylation is carried out in the presence of Double Metal Cyanide (DMC) catalysts, it is preferable to avoid the use of initiator molecules which contain strongly basic groups, such as primary and secondary amines. Furthermore, if a double metal cyanide complex catalyst is used, it is generally desirable to alkoxylate an oligomer containing a previously alkoxylated "monomeric" initiator molecule. It has been found that DMC alkoxylation is initially slow, especially for vicinal hydroxyl groups, and may first be a rather long "induction period", in which essentially no alkoxylation takes place. It has been found that the use of polyoxyalkylene oligomers having an equivalent weight of from about 90Da to about 1000Da, preferably from about 90Da to about 500Da, will mitigate this effect. Polyoxyalkylene oligomeric initiators can be prepared by alkoxylating a "monomeric" initiator in the presence of a conventional basic catalyst such as sodium or potassium hydroxide or other non-DMC catalyst. It is generally necessary to neutralize and/or remove those basic catalysts prior to addition and initiation of the DMC catalyst.

Polyol polymer dispersions represent a particularly preferred class of polyoxyalkylene polyol compositions for the production of HS and HS-HR foams. Polyol polymer dispersions are dispersions of polymer solids in a polyol. Polyol polymer dispersions useful in the present invention include, but are not limited to, PHD and PIPA polymer modified polyols and styrene-acrylonitrile (SAN) polymer polyols. PHD polyols include dispersions of polyureas in polyether polyols formed in situ by polymerization of diamines and isocyanates, while PIPA (polyisocyanate polyaddition) polyols include polymer dispersions formed by reaction of alkanolamines with isocyanates. In theory, any of the base polyols known in the art are suitable for use in producing the polymer polyol dispersion, however the previously described polyoxyalkylene polyols are preferred in the present invention.

SAN polymer polyols are typically prepared by the in situ polymerization of one or more vinyl monomers, preferably acrylonitrile and styrene, in a polyol, preferably a polyoxyalkylene polyol, having a low amount of natural or induced unsaturation. Methods for preparing SAN polymer polyols are described, for example, in U.S. Pat. nos. 3,304,273; 3,383,351; 3,523,093; 3,652,639; 3,823, 201; 4,104,236, respectively; 4,111,865, respectively; 4,119,586; 4,125,505, respectively; 4,148,840 and 4,172,825; 4,524,157; 4,690,956; re-28715 and Re-29118.

The SAN polymer polyols useful in the present invention preferably have a polymer solids content of from about 3 to about 60 wt.%, more preferably from about 5 to about 50 wt.%, based on the total weight of the SAN polymer polyol. As mentioned above, SAN polymer polyols are typically prepared by the in situ polymerization of a mixture of acrylonitrile and styrene in a polyol. When used, the ratio of styrene to acrylonitrile polymerized in situ in the polyol is generally in the range of from about 100: 0 to about 0: 100 parts by weight, based on the total weight of the styrene/acrylonitrile mixture, and preferably from about 80: 20 to about 0: 100 parts by weight.

PHD polymer modified polyols are typically prepared by the in situ polymerization of an isocyanate mixture with a diamine and/or hydrazine in a polyol, preferably a polyether polyol. Methods for preparing PHD polymer polyols are described, for example, in U.S. Pat. nos. 4,089,835 and 4,260,530. PIPA polymer modified polyols are typically prepared by in situ polymerization of an isocyanate mixture with a diol and/or a diol amine in a polyol.

The PHD and PIPA polymer-modified polyols useful in the present invention preferably have a polymer solids content of from about 3 to about 30 wt.%, more preferably from about 5 to about 25 wt.%, based on the total weight of the PHD or PIPA polymer-modified polyol. As mentioned above, the PHD and PIPA polymer-modified polyols of the present invention may be prepared by the in situ polymerization of an isocyanate mixture, for example, a mixture consisting of about 80 parts by weight of 2, 4-toluene diisocyanate based on the total weight of the isocyanate mixture and about 20 parts by weight of 2, 6-toluene diisocyanate based on the total weight of the isocyanate mixture, in a polyol, preferably a polyoxyalkylene polyol.

The PHD and PIPA polymer modified polyols useful in the present invention preferably have a hydroxyl number of from about 15 to about 50, more preferably from about 20 to about 40. The polyols used in the preparation of the PHD and PIPA polymer polyols of the present invention are preferably triols based on propylene oxide, ethylene oxide or mixtures thereof.

The term "polyoxyalkylene polyol or polyoxyalkylene polyol blend" as used herein refers to the combination of all polyoxyalkylene polyether polyols, whether polyoxyalkylene polyether polyols not containing a polymer dispersion or base polyols for one or more polymer dispersions. For example, in an isocyanate-reactive polyol comprising 40 parts by weight of a polymer polyol containing 30 weight percent vinyl polymer solids dispersed in a polyoxyalkylene polyether base polyol and 60 parts by weight of a polyoxyalkylene polymer-free polyol, the polyoxyalkylene polyol component weight would be 88 parts by weight, i.e., [60 parts +40 parts (100-30)% ] — 88 parts.

The High Support (HS) and high support-high resilience (HS-HR) flexible foams of the present invention are prepared by mixing together one or more isocyanates with polyols, polymer polyol dispersions, water, catalysts, surfactants, liquid hydrocarbons including polymerized butadiene, and optionally various other ingredients including glycol or glycol amine modifiers, flame retardants, physical blowing agents, colorants, fillers, and other additives known in the art. After mixing, the foam mixture can be placed in an open container or continuously onto a moving conveyor belt and set free to rise (free-rise process). The open container or the conveyor belt can be enclosed in a chamber in order to let the foam rise under vacuum or increased pressure (pressure swing foaming process). Alternatively, the foaming mixture may be placed in a mold, which is then closed, thereby forcing the foam to take the shape of the mold (molding process).

Thus, one possible HS-HR foaming formulation of the present invention may comprise the following components:

a)80/20 isomer ratio of 2, 4/2, 6 toluene diisocyanate present at a level to yield a stoichiometric index of 103 relative to the isocyanate-reactive components in the formulation;

b)100 parts by weight of a polyol-polymer polyol blend comprising

1) 67% of a 28 hydroxy, low unsaturation polyol comprising propylene oxide-ethylene oxide polymerized onto glycerol to produce a nominal triol with a total ethylene oxide content of 21%, wherein one third of the ethylene oxide is randomly incorporated into the interior of the polyol and two thirds is added at the final stage of polymerization by feeding an 70/30 ratio of EO/PO,

2) 33% of a polymer polyol comprising 25% SAN copolymer dispersed in 75% of a reactive polyol produced by KOH-catalyzed alkoxylation of glycerol with propylene oxide and capping with 17% ethylene oxide; the reactive polyol has a hydroxyl number of 32, a nominal functionality of 2.9, and a primary hydroxyl number of about 85%;

c) water in an amount of 3.3 parts per hundred parts of b);

d) a liquid hydrocarbon comprising polymerized butadiene in an amount between 0.01 and 0.5 php;

e) diethanolamine in an amount of 2.5 php;

f) suitable amounts of blended tertiary amine catalysts, e.g. NIAX^RC-183, and optionally a "gelling" catalyst such as dibutyltin dilaurate,

g) HS or HS-HR foam surfactants, e.g. NIAX^RL-5309 polyether-polysiloxane copolymer in an amount of 1.0 php; and

h) other standard additives as required.

Components B) to h) can be premixed and added as a mixed stream, as is carried out in the A-side, B-side molding process, or added individually or in various combinations, as is usually carried out in the continuous free-rise process. A nucleating gas may be injected or dissolved into one or more components to aid in cell size control and increase cell opening. Physical blowing agents such as methylene chloride, acetone or pentane may be added to reduce the foam density and soften the foam. The preferred physical blowing agent is carbon dioxide, which may be added as a pressurized liquid, as specified by the manufacturers of equipment used in such processes [ NOAVFLEX (Hennecke machinery), Cardio (Cannon Viking Limited), and CO-2(Beamech) ].

The following examples further illustrate details of the invention. The invention disclosed above is not to be limited either in spirit or scope by these examples. Those skilled in the art will readily appreciate that known variations of the conditions of the following processes may be used. Unless otherwise indicated, all temperatures are given in degrees Celsius and all parts and percentages are parts by weight and percentages.

Detailed Description

Examples

The following components were used in the working examples of the present application:

polyol:

polyol A: a DMC-produced poly (ethylene oxide-propylene oxide) polyol having a hydroxyl number of about 28, a nominal functionality of 3 and a total polymerized EO content of 21% with 7% of the ethylene oxide fed early in the reaction and the remaining 14% fed at the final end stage in a 70/30EO/PO weight ratio. The primary hydroxyl content was 44%.

Polyol B: a DMC-produced poly (ethylene oxide-propylene oxide) polyol having a hydroxyl number of about 28, a nominal functionality of 3, and a total polymerized EO content of 20% with 10% of the ethylene oxide fed in the initial stages of the reaction and the remaining 10% fed in the final end stage at 50/50EO/PO weight ratios. The primary hydroxyl content was-25%.

Polyol C: DMC-produces a poly (ethylene oxide-propylene oxide) polyol having a hydroxyl number of about 24, a nominal functionality of 3 and a total polymerized EO content of 18%, wherein all of the ethylene oxide is fed in the final end stage of the polymerization in a 50/50EO/PO weight ratio. The primary hydroxyl content was-30%.

Polyol D: a hybrid DMC-KOH poly (ethylene oxide-propylene oxide) polyol having a hydroxyl number of about 25, a nominal functionality of 2.6, and a total polymerized EO content of 20% with 5% of the ethylene oxide fed during the initial DMC-catalyzed stage of the reaction and the remaining 15% fed as 100% EO during the final KOH capping stage. The primary hydroxyl content was 88%.

Polymer polyol:

PP-1: a 28% dispersion of styrene-acrylonitrile in a reactive feedstock polyol blend. The base polyol was produced by KOH-catalyzed addition of PO to the starting material and capping with 100% EO. The polyol blend has an average hydroxyl number of 36, a nominal functionality of 2.9, a% EO of the polyol of 19%, and a primary hydroxyl content of 85%.

PP-2: a 25% dispersion of styrene-acrylonitrile in a reactive feedstock polyol blend. The base polyol was produced by KOH-catalyzed addition of PO to the starting material and capping with 100% EO. The average hydroxyl number of the polyol blend was 32, the nominal functionality was 2.9, the% EO in the polyol was 17%, and the primary hydroxyl content was 85%.

And (3) PP-3: a 26% dispersion of styrene-acrylonitrile in a reactive feedstock polyol blend. The base polyol was produced by KOH-catalyzed addition of PO to the starting material and capping with 100% EO. The average hydroxyl number of the polyol blend was 32, the nominal functionality was 3.3, the% EO in the polyol was 16%, and the primary hydroxyl content was 85%.

PP-4: a 43% dispersion of styrene-acrylonitrile in a reactive feedstock polyol. The base polyol was produced by KOH-catalyzed addition of PO to the starting material and capping with 100% EO. The polyol blend has an average hydroxyl number of 36, a nominal functionality of 2.9, a% EO of the polyol of 19%, and a primary hydroxyl content of 85%.

PP-5: an 8% dispersion of styrene-acrylonitrile in a reactive feedstock polyol blend. The base polyol was produced by KOH-catalyzed addition of PO to the starting material and capping with 100% EO. The average hydroxyl number of the polyol blend was 34, the nominal functionality was 4.4, the% EO in the polyol was 17%, and the primary hydroxyl content was 85%.

PP-6: a 9% dispersion of styrene-acrylonitrile in a reactive feedstock polyol blend. The base polyol was produced by KOH-catalyzed addition of PO to the starting material and capping with 100% EO. The average hydroxyl number of the polyol blend was 33, the nominal functionality was 3.2, the% EO in the polyol was 17%, and the primary hydroxyl content was 85%.

Additive:

DEOA diethanolamine;

c-183 amine catalyst blends, available from Witco;

c-267 amine catalyst blend, available from Witco;

t-9 stannous octoate catalyst, available from Air Products;

t-120 tin (IV) catalyst, available from Air Products;

b-8707 High Resilience (HR) silicone surfactant, available from Goldschmidt;

l-5309 High Resilience (HR) silicone surfactant, available from Witco;

u-2000 High Resilience (HR) silicone surfactants, available from Witco;

y-10366 High Resilience (HR) polysiloxane surfactant, available from OSispecialties; and

DE-60F-SP contains brominated aromatic compounds and organic based (chlorophosphate) flame retardants, available from Great Lakes Chemical Co.

The following examples demonstrate the effectiveness of liquid hydrocarbons comprising polymerized butadiene in reducing the Force To Crush (FTC) of High Support (HS) and high support-high resilience (HS-HR) polyurethane foams. Laboratory scale free-rise foams were prepared by weighing all ingredients except isocyanate and stannous octoate (if used) together into one-half gallon (1.9L) paper cans with metal insulation inserts and then mixing at 2400rpm for 60 s. The resin mixture is left to stand for 15s during which time stannous octoate (if used) is added. Mixing was continued for 15s, during which stage the isocyanate was added over seven seconds. The complete mixture was quickly poured into a 14 inch by 6 inch (35.6cm by 15.2cm) cake box for priming. Foam rise patterns, "blow off", and sedimentation were recorded for five minutes using a sonar device with computer data acquisition. The foam blocks and boxes were placed in a forced air oven at 125 ℃ for five minutes to cure the skin. After removal from the oven, the foam was cured at ambient conditions for at least 16 hours. An indication of shrinkage was recorded and a 12 inch by 4 inch (30.5cm by 10.2cm) sample of cured foam was cut from the center of the foam bun for Force To Crush (FTC) and physical property measurements.

The Force To Crush (FTC) was measured on an uncrushed 12 inch by 4 inch (30.5cm by 10.2cm) sample using a standard IFD tester and a 50 square inch (322.6 square centimeter) crimp. Foam height was determined by slowly lowering the pin until a resistance of 0.5 pounds (226.8g) was detected. A pin was then pressed into the foam at 20 inches/minute (50.8cm/min) to a measured height of 25% (75% compression) and the force applied was immediately recorded. The stitch was immediately returned to the starting foam height and then a second compression cycle and force measurement were started. This process was repeated a third time to complete the measurement. Thus, the forces were obtained for the first cycle (FTC1), the second cycle (FTC2), and the third cycle (FTC3) on each sample. The first measurement provides an indication of the force required to initially crush the foam, while the difference between the second (FTC2) and third (FTC3) values indicates the effectiveness of the initial crushing cycle in opening the foam.

Prior to physical and mechanical property determination, the test pieces were crushed by passing the whole test piece three times through a laboratory roller crusher (87.5% compression) and aged for at least 16 hours under standard constant temperature (25 ℃) and relative humidity (50%). Density, rebound, IFD, tear strength, 90% dry compression set and 75% wet aged compression set were determined according to the standard test methods set forth in ASTM D3574 (Condition J1). The tensile strength and elongation process is similar to that described in astm d3574 except that the clamp separation method is used instead of bench marking. Air flow was measured on a 2 inch x 1 inch (5.1cm x 2.5cm) sample using an AMSCOR Model 1377 foam porosimeter. The 50% wet set process is similar to the ASTM compression set process except that the samples are compressed and held under humid conditions (50% compression for 22 hours at 50 ℃ and 95% relative humidity). Height loss was determined after 30 minutes removal from the oven and plate.

Molded foam manufacture and test procedures were similar to those used in the free-rise method except that the foam mixture was poured into a standard aluminum test pad mold having dimensions of 15 inches by 4 inches (38.1cm by 10.2cm) and preheated to-55 ℃. The sample was removed from the mold after 5 minutes and the FTC measurements were immediately performed on the sample. The samples were aged for one week before completely crushing the foam and performing the performance test.

Foam examples 1 to 7

The FTC and physical properties of the foams prepared in examples 1-7 were determined and are summarized in Table 1 below.

As can be seen by reference to Table 1, free-rise foam examples 2, 3, 4 illustrate that three different liquid butadiene homopolymers (PB-A, PB-B, PB-C) having viscosities of 3500, 700 and 4000cps at 25 deg.C and 1, 2 vinyl percentages of 18, 24 and 20, respectively, at 0.5php, are effective in reducing FTC1 from 420 lbs (comparative example 1) to 231, 170 and 198 lbs, respectively. Crushing efficiency was also improved as evidenced by the reduction in the difference between the second and third cycle FTC values from 27 to 7, 5 and 5, respectively. The physical properties of the foams of examples 2, 3 and 4 (also listed in table 1) were substantially unchanged relative to comparative example 1. Examples 5,6 and 7 show that 0.5php of a liquid butadiene homopolymer with high 1, 2 vinyl content destabilizes the foam, causing collapse. The polyol composition used in examples 1-7 contained 67% of a DMC-catalyzed triol (polyol A) and 33% of a polymer polyol containing 28% SAN solids in a reactive base polyol produced by KOH catalysis.

TABLE 1

	Example C-1	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7
								Polybutadiene (0.5php)	Is free of	PB-A	PB-B	PB-C	PB-D	PB-E	PB-F
1, 2-vinyl%	-	18	24	20	70	70	90
								MW	-	5500	2600	5000	1300	1800	3200
Viscosity @25 deg.C (cps)	-	3500	700	4000	1600	6000	＞10,000
								Foam processing	Good taste	Good taste	Good taste	Good taste	Collapse and shrinkage	Collapse and shrinkage	Collapse and shrinkage
FTC1	420	231	170	198
								FTC2	143	99	93	88
FTC3	116	92	88	83
								FTC2-FTC3	27	7	5	5
Foam performance
								Density (pcf)	1.80	1.84	1.86	1.80
Rebound (%)	53	46	48	47
								Air flow (scfpm)	1.75	1.19	5.30	2.81
IFD-thickness (in.)	4.02	4.03	4.00	4.01
								25％IFD，lb./50in.2	19.6	19.3	21.4	19.3
65％IFD，lb./50in.2	43.2	42.5	47.1	41.0
								65/25 recovery (%)	79.6	80.4	78.5	79.6
65/25IFD ratio	2.20	2.21	2.20	2.13
								Tensile Strength (psi)	15.3	16.2	16.4	16.6
Elongation (%)	151	154	172	165
								Tear (pli)	1.53	1.55	1.54	1.68
90% compression set (Cd) (%)	12.7	8.7	5.0	22.3
								75％HACS(Cd)(％)	12.1	13.6	12.3	13.6
50% Wet set (%)	33.4	31.7	32.4	31.3

In addition to the polybutadiene homopolymer recorded, the foam formulation described above also included: 67php of polyol P-4; 32php of polymer polyol PP-4; 3.3php of water; 2.5php of DEOA; 0.12php C-267; t-9 at 0.13 php; l-5309 at 1.0 php; and 80/20TDI at 43.6php with an isocyanate index of 103.

Foam examples 8 to 13

The FTC and physical properties of the foams prepared in examples 8-13 were determined and are summarized in Table 2 below.

As can be seen by reference to table 2, free-rise foam example 9 and molded foam example 12 demonstrate that a 1php liquid butadiene homopolymer (PB-C) effectively reduced FTC1 from 384 to 187 pounds (free-rise) and from 299 to 199 pounds (molded). While effective in reducing FTC, it was found that this level of butadiene homopolymer imparts a significant rubbery chemical odor to the foam which is difficult to dissipate. Free-rise foam example 10 and molded foam example 13 demonstrate that high MW solid polybutadiene homopolymer (PB-G), as produced by the emulsion polymerization process, is ineffective in lowering the FTC. Thus, liquid butadiene polymers appear to be necessary to reduce FTC.

TABLE 2

	Example C-8	Example 9	Example 10	Example 11	Example 12	Example 13
							Polybutadiene	Is free of	PB-C(1php)	PB-G(0.6php)	Is free of	PB-C(1php)	PB-G(1php)
1, 2-vinyl%	-	20	＜20	-	20	＜20
							MW	-	5000	＞50,000	-	5000	＞50,000
Viscosity @25 deg.C (cps)	-	4000	Solid body	-	4000	Solid body
							Foam processing	Good taste	Good taste	Good taste	Good taste	Good taste	Good taste
FTC1	384	187	364	299	199	501
							FTC2	147	106	140	119	79	246
FTC3	112	98	111	90	64	147
							FTC2-FTC3	35	8	29	29	15	99
Foam performance
							Density (pcf)	1.58	1.85	1.64	2.02	2.03	1.97
Rebound (%)	47	46	50	57	51	56
							Air flow (scfpm)	0.89	1.23	0.96	0.60	0.47	0.91
IFD-thickness (in.)	3.92	3.98	3.90	4.73	4.77	4.66
							25％IFD，lb./50in.2	16.2	20.4	15.9	44.8	47.3	33.4
65％IFD，lb./50in.2	38.2	46.8	40.2	110.0	111.9	87.7
							65/25 recovery (%)	78.0	79.9	78.3	76.1	75.1	78.3
65/25IFD ratio	2.35	2.30	2.54	2.46	2.37	2.62
							Tensile Strength (psi)	16.1	15.7	15.5	20.1	21.0	18.5
Elongation (%)	190	142	168	123	134	106
							Tear (pli)	1.49	1.36	1.32	1.84	2.02	1.51
90% compression set (Cd) (%)	11.9	6.5	11.4	-	-	-
							75％HACS(Cd)(％)	18.5	15.2	20.7	7.4	7.5	8.8
50% Wet set (%)	42.7	38.3	41.3	22.6	22.5	22.8

The free-rise foams (examples 8-10) further included a polyol P-2 of 64 php; 36php of polymer polyol PP-2; 3.2php of water; 2.6php of DEOA; 0.15php of C-183; t-9 at 0.15 php; 2.0php of B-8707; and 80/20TDI at an isocyanate index of 103 for 42.7 php. The molded foams (examples 11-13) further included 42.5php of polyol P-3; 57.5php of Polymer polyol PP-3; 2.7php of water; DEOA at 0.5 php; 0.5php of glycerol; 0.4php of C-183; t-120 at 0.05 php; y-10366 at 1.0 php; and 80/20TDI with an isocyanate index of 100 at 40.14 php.

Foam examples 14 to 20

The FTC and physical properties of the foams prepared in examples 14-20 were determined and are summarized in Table 3 below.

As can be seen by reference to table 3, free-rise foam examples 14-20, while phenyl-terminated polybutadiene (examples 14 and 15) had some effect in lowering initial FTC and increasing crushing efficiency, hydroxy-terminated polybutadiene (example 16), acrylate-terminated polybutadiene (example 17), and butadiene and acrylonitrile copolymer (example 18) were ineffective in lowering initial FTC and increasing crushing efficiency. The polyisobutylene homopolymer (example 19) caused collapse and the mineral oil (example 20) was ineffective. These results indicate that hydrocarbons based primarily on polymerized butadiene have unique effectiveness in lowering FTC while maintaining other foam properties.

TABLE 3

	Example 14	Example 15	Example 16	Example 17	Example 18	Example 19	Example 20
								Polymer additive (0.5php)	Phenyl-terminated butadiene	Phenyl-terminated butadiene	Hydroxy-terminated butadiene	Acrylate-terminated butadiene	Butadiene-acrylonitrile copolymer	Polyisobutenes	Mineral oil
1, 2-vinyl%	45	35	20	-	-	-	-
								MW	2600	1500	6200	13,000	2800	800	-32
Viscosity @25 deg.C (cps)	＞10,000	3000	-	＞10,000	-	＞10,000
								Foam processing	Good taste	Good taste	Good taste	Good taste	Good taste	Collapse and shrinkage	Good taste
FTC1	310	256	431	345	464	-	556
								FTC2	102	20	226	110	134	-	131
FTC3	90	111	104	97	109	-	112
								FTC2-FTC3	12	9	122	13	25	-	19
Foam performance
								Density (pcf)	1.81	1.77	1.81	1.78	1.80	-	1.92
Rebound (%)	51	44	52	51	52	-	53
								Air flow (scfpm)	3.49	0.79	2.56	2.67	1.70	-	1.50
IFD-thickness (in.)	3.95	4.02	3.99	3.99	4.01	-	3.96
								25％IFD，lb./50in.2	18.0	27.2	18.9	20.9	20.8	-	20.6
65％IFD，lb./50in.2	40.3	52.2	410	44.6	43.4	-	47.3
								65/25 recovery (%)	81.6	76.1	79.2	78.8	78.2	-	80.6
65/25IFD ratio	2.24	1.92	2.17	2.14	2.09	-	2.30
								Tensile Strength (psi)	15.8	15.9	16.0	16.7	15.1	-	16.4
Elongation (%)	157	153	159	158	160	-	157
								Tear (pli)	1.53	1.79	1.57	1.33	1.56	-	1.60
90% compression set (Cd) (%)	7.1	6.0	13.7	6.5	21.3	-	4.6
								75％HACS(Cd)(％)	11.5	8.9	11.9	11.0	10.9	-	13.6
50% Wet set (%)	30.2	24.6	29.5	31.2	28.1	-	31.1

In addition to the 0.5php polymer additive noted in Table 3, the foam formulation included 67php polyol P-1; 32php of polymer polyol PP-1; 3.3php of water; 2.5php of DEOA; 0.12php C-267; t-9 at 0.13 php; l-5309 at 1.0 php; and 80/20TDI with an isocyanate index of 103 at 43.6 php.

Foam examples 21 to 24 and 25 to 28

The FTC and physical properties of the foams prepared in examples 21-28 were determined and are summarized in Table 4 below.

As can be seen by reference to table 4, free-rise foam examples 21-28 show that liquid polybutadiene is effective in lowering FTC and increasing crushing efficiency at dosages of 1php up to about 0.03 php. High amounts are no better than low amounts. With a significant unpleasant smell of rubber chemicals at 1ph p content. The foam physical properties were essentially unchanged. The foams in examples 21-24 were made with a polymer polyol blend containing 70% of a reactive base polyol, the core of which was produced by DMC catalysis and capped with EO using K0H catalysis. This was blended with 30% polymer polyol at 43% SAN solids, which was produced in a K0H-catalyzed reactive polyol. The same polyols were used in examples 25-28, except that the ratio was 80% polyol and 20% polymer polyol.

TABLE 4

	Example 21	Example 22	Example 23	Example 24	Example 25	Example 26	Example 27	Example 28
									Polybutadiene PB-A (php)	0	0.13	0.07	0.03	0	0.17	0.33	1
Polyol P-4(php)	70	70	70	70	80	80	80	80
									Polymer polyol PP-4	30	30	30	30	20	20	20	20
Foam processing	Good taste	Good taste	Good taste	Good taste	Good taste	Good taste	Good taste	Good taste
									FTC1	319	178	189	186	351	222	192	268
FTC2	113	99	100	97	120	95	95	91
									FTC3	105	27	97	94	109	92	92	88
FTC2-FTC3	8	2	3	3	11	3	3	3
									Foam performance
Density (pcf)	1.83	1.91	1.88	1.93	2.03	1.96	1.94	1.887
									Rebound (%)	60	60	60	60	65	64	65	64
Air flow (scfpm)	2.50	2.46	2.11	2.44	2.30	3.36	2.36	2.24
									IFD-thickness (in)	3.96	4.03	3.99	4.02	4.04	4.02	4.01	4.05
25％IFD，lb./50in.2	20.1	20.6	20.5	19.6	21.9	22.8	22.2	22.5
									65％IFD，lb./50in.2	46.7	47.8	47.5	45.9	51.0	51.3	50.6	50.9
65/25 recovery (%)	80.4	81.2	81.1	80.7	83.8	84.3	83.8	82.2
									65/25IFD ratio	2.32	2.32	2.32	2.35	2.33	2.25	2.28	2.26
Tensile Strength (psi)	178	177	18.0	17.5	18.2	16.0	16.9	18.3
									Elongation (%)	156	132	158	153	144	135	156	138
Tear (pli)	1.73	1.74	1.86	2.00	-	1.4	1.48	1.60
									90% compression set (Cd) (%)	10.9	7.9	13.8	9.6	5.5	4.6	5.0	5.7
75％HACS(Cd)(％)	30.1	26.4	24.3	25.0	17.5	13.5	17.3	18.0
									50% Wet set (%)	32.7	34.8	30.8	32.3	14.5	15.6	13.9	18.2

Foam formulations 21-24 included 3.3php of water in addition to the amounts of polybutadiene PB-A, polyol P-4, and polymer polyol PP-4 noted in Table 4; 2.5php of DEOA; 0.12php of C-183; t-9 at 0.13 php; 1.0php U-2000; and 80/20TDI with an isocyanate index of 43.6php of 103, while foam formulations 25-28 also included 3.3php of water, 2.5php of DEOA, 0.15php of C-183, 0.10php of T-9, 1.0php of U-2000, 2.0php of DE-60F, and 43.6php of 80/20TDI with an isocyanate index of 103.

Foam examples 29 to 32

The FTC and physical properties of the foams prepared in examples 21-28 were determined and are summarized in Table 5 below.

TABLE 5

	Example C to 29	Example 30	Example C-31	Example 32
					Polybutadiene PB-A (php)	Is free of	0.13	Is free of	0.05
Polymer polyol PP-5	100	100	-	-
					Polymer polyol PP-6	-	-	100	100
Foam processing	Good taste	Good taste	Good taste	Good taste
					FTC1	219	200	227	197
FTC2	120	110	103	103
					FTC3	116	108	100	101
FTC2-FTC3	4	3	3	2
					Foam performance
Density (pcf)	1.92	1.90	1.87	1.94
					Rebound (%)	58	61	61	61
Air flow (scfpm)	3.21	5.01	3.37	3.70
					IFD-thickness (in.)	4.05	4.03	3.98	3.99
25％IFD，lb./50in.2	23.8	22.9	20.3	21.3
					65％IFD，lb./50in.2	52.7	50.8	46.7	48.8
65/25 recovery (%)	81.8	81.6	81.1	82.0
					65/25IFD ratio	2.21	2.21	2.30	2.29
Tensile Strength (psi)	13.4	13.1	15.8	15.8
					Elongation (%)	103	117	127	123
Tear (pli)	0.98	0.32	1.41	1.45
					90% compression set (Cd) (%)	6.0	5.0	7.7	6.7
75％HACS(Cd)(％)	8.9	8.8	41.8	8.4
					50% Wet set (%)	15.9	15.9	24.8	22.2

In addition to the amounts of polybutadiene PB-A, Polymer polyol PP-5, or Polymer polyol PP-6 noted in Table 5, the foam formulation included 3.3php of water; 2.5php DE 0A; 0.12php of C-183; t-9 at 0.13 php; 1.0php U-2000; and 80/20TDI with an isocyanate index of 103 at 44 php.

As can be seen by reference to table 5, free-rise foam examples 29-32 illustrate that liquid polybutadiene also enhances the FTC of foams produced with polymer polyols containing only polyols produced with KOH catalysis. This effect is relatively low because the comparative foams produced without polybutadiene (examples C-29 and C-31) have a lower FTC.

Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.

Claims (34)

1. A High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam prepared by reacting one or more di-or polyisocyanates having an isocyanate index of 70 to 130 with:

(a) a polyoxyalkylene polyol or polyoxyalkylene polyol blend having an average hydroxyl equivalent weight of at least 1000 and an average primary hydroxyl content of at least 25%;

and

(b) an effective amount of a blowing agent comprising water,

in the presence of from 0.01 to 0.5 parts by weight, based on 100 parts by weight of said polyol component (a), of a liquid hydrocarbon comprising polybutadiene in which less than 65% of the unsaturation is of the 1, 2 vinyl type.

2. The High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam according to claim 1, wherein said liquid hydrocarbon is in the range of 0.01 to 0.3 parts by weight.

3. The High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam according to claim 1, wherein said polyol component (a) comprises a polyoxyalkylene polyol prepared at least in part in the presence of a double metal cyanide complex alkoxylation catalyst.

4. The High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam according to claim 1, wherein said polyol polyoxyalkylene blend comprises at least one polyol comprising a polyoxyalkylene polyol prepared at least in part in the presence of a double metal cyanide complex oxyalkylation catalyst.

5. The High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam according to claim 1, wherein said polyol blend further comprises one or more polyol polymer dispersions effective to provide a solids content of from 3 to 50 weight percent based on the weight of said polyol blend.

6. The High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam according to claim 1, wherein said isocyanate index is between 80 and 120.

7. The High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam according to claim 1, wherein said isocyanate index is between 90 and 115.

8. The High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam according to claim 1, wherein said blowing agent comprises water in an amount of 1 to 7 parts by weight per 100 parts of said polyol component (a).

9. The High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam according to claim 1, wherein said blowing agent comprises water in an amount of 1 to 5 parts by weight per 100 parts of said polyol component (a).

10. The High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam according to claim 1, wherein said liquid hydrocarbon is free of isocyanate reactive groups.

11. The High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam according to claim 1, wherein said blowing agent further comprises at least one selected from the group consisting of: dichloromethane, difluorodichloromethane, 1-dichloro-1-fluoroethane, 1, 2-trichloro-1, 2, 2-trifluoroethane, Hydrofluorocarbons (HFC), Perfluorocarbons (PFC), lower alkanes low molecular weight ethers and ketones, air and liquid CO under pressure₂。

12. The High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam according to claim 1, wherein less than 50% of the unsaturation in said polybutadiene is of the 1, 2 vinyl type.

13. A process for producing a High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam comprising reacting one or more di-or polyisocyanates having an index of from 70 to 130 with:

(a) a polyoxyalkylene polyol or polyoxyalkylene polyol blend having an average hydroxyl equivalent weight of at least 1000 and an average primary hydroxyl content of at least 25%; and

(b) an effective amount of a blowing agent comprising water,

the reaction is carried out in the presence of 0.01 to 0.5 parts by weight, based on 100 parts by weight of said polyol component (a), of a liquid hydrocarbon comprising polybutadiene in which less than 65% of the unsaturation is of the 1, 2 vinyl type.

14. The process of claim 13 wherein said polyol component (a) comprises a polyoxyalkylene polyol prepared at least in part in the presence of a double metal cyanide complex oxyalkylation catalyst.

15. The process of claim 13, wherein said polyol polyoxyalkylene blend comprises at least one polyol comprising a polyoxyalkylene polyol prepared at least in part in the presence of a double metal cyanide complex oxyalkylation catalyst.

16. The process of claim 13, wherein the polyol blend further comprises one or more polyol polymer dispersions effective to provide a solids content of from 3 weight percent to 50 weight percent based on the weight of the polyol blend.

17. The method of claim 13, wherein the isocyanate index is between 80 and 120.

18. The method of claim 13, wherein the isocyanate index is between 90 and 115.

19. The method of claim 13 wherein said blowing agent comprises water in an amount of from 1 to 7 parts by weight per 100 parts of said polyol component (a).

20. The method of claim 13 wherein said blowing agent comprises water in an amount of from 1 to 5 parts by weight per 100 parts of said polyol component (a).

21. The method of claim 13, wherein the liquid hydrocarbon does not contain isocyanate reactive groups.

22. The method of claim 13, wherein the blowing agent further comprises at least one selected from the group consisting of: dichloromethane, difluorodichloromethane, 1-dichloro-1-fluoroethane, 1, 2-trichloro-1, 2, 2-trifluoroethane, Hydrofluorocarbons (HFC), Perfluorocarbons (PFC), lower alkanes low molecular weight ethers and ketones, air and liquid CO under pressure₂。

23. The process according to claim 13, wherein less than 50% of the unsaturation in said polybutadiene is of the 1, 2 vinyl type.

24. A method of reducing the Force To Crush (FTC) of a High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam comprising mixing:

a) a polyoxyalkylene polyol or polyoxyalkylene polyol blend having an average hydroxyl equivalent weight of at least 1000 and an average primary hydroxyl content of at least 25%,

b) an effective amount of a blowing agent comprising water,

c) 0.01 to 0.5 parts by weight, based on 100 parts by weight of the polyol component, of a liquid hydrocarbon comprising polybutadiene in which less than 65% of the unsaturation in the polybutadiene is of the 1, 2 vinyl type, and

reacting a), b) and c) in the presence of a catalyst with one or more di-or polyisocyanates having an index of 70 to 130,

wherein the resulting High Support (HS) or high support-high resilience (HS-HR) flexible polyurethane foam has a reduced Force To Crush (FTC).

25. The process of claim 24 wherein said polyol component (a) comprises a polyoxyalkylene polyol prepared at least in part in the presence of a double metal cyanide complex oxyalkylation catalyst.

26. The process of claim 24, wherein said polyol polyoxyalkylene blend comprises at least one polyol comprising a polyoxyalkylene polyol prepared at least in part in the presence of a double metal cyanide complex oxyalkylation catalyst.

27. The method of claim 24, wherein the polyol blend further comprises one or more polyol polymer dispersions effective to provide a solids content of from 3 weight percent to 50 weight percent based on the weight of the polyol blend.

28. The method of claim 24, wherein the isocyanate index is between 80 and 120.

29. The method of claim 24, wherein the isocyanate index is between 90 and 115.

30. The method of claim 24 wherein said blowing agent comprises water in an amount of from 1 to 7 parts by weight per 100 parts of said polyol component (a).

31. The method of claim 24 wherein said blowing agent comprises water in an amount of from 1 to 5 parts by weight per 100 parts of said polyol component (a).

32. The method of claim 24, wherein the liquid hydrocarbon is free of isocyanate reactive groups.

33. The process according to claim 24, wherein less than 50% of the unsaturation in said polybutadiene is of the 1, 2 vinyl type.

34. The method of claim 24, wherein the blowing agent further comprises at least one selected from the group consisting ofThe substance (c): dichloromethane, difluorodichloromethane, 1-dichloro-1-fluoroethane, 1, 2-trichloro-1, 2, 2-trifluoroethane, Hydrofluorocarbons (HFC), Perfluorocarbons (PFC), lower alkanes low molecular weight ethers and ketones, air and liquid CO under pressure₂。