HK1093998B - Polyurethane foams made with vegetable oil hydroxylate, polymer polyol and aliphatic polyhydroxy alcohol - Google Patents

Description

Polyurethane foams made from vegetable oil hydroxylates, polymer polyols and aliphatic polyols

Technical Field

The present invention relates generally to polyurethanes, and more particularly to polyurethane foams made from a polyol component comprising a vegetable oil hydroxylate, a polymer polyol (PMPO) and an aliphatic polyol.

Background

Polyurethane foams have been widely used in many industrial and consumer products. This popularity is attributed to the broad mechanical properties of polyurethanes and the ability to be relatively easy to manufacture. For example, automobiles include many polyurethane parts, such as seats, dashboards, and other cabin interior parts. Polyurethane foams are traditionally classified as either flexible foams, semi-rigid foams or rigid foams; flexible foams are generally softer, less dense, more flexible, and more capable of structural rebound after being loaded than rigid foams.

Methods for preparing polyurethane foams are well known to those skilled in the art. Polyurethanes are formed by the reaction of NCO groups with hydroxyl groups. The most common method of producing polyurethanes is by reaction of polyols with polyisocyanates, which forms backbone urethane groups. Cross-linking agents, blowing agents, flame retardants, catalysts and other additives may also be included in the polyurethane formulation as desired. The softest polyurethane foam formulations contain water as the isocyanate reactive component to form carbon dioxide as the blowing agent by chemical reaction, and an amine component which can further react with the polyisocyanate to form urea backbone groups. These urethane-urea polymers are also included in the broad scope of polyurethanes.

Polyols used in polyurethane production are typically petrochemical in origin, generally derived from propylene oxide, ethylene oxide, and various starters such as propylene glycol, glycerol, sucrose, and sorbitol. Polyester polyols and polyether polyols are the most commonly used polyols in polyurethane production. For flexible foams, polyester polyols or polyether polyols having a molecular weight of from about 2000 to 10000 are generally used, whereas for rigid and semirigid foams, short-chain polyols having a molecular weight of from about 400 to 2000 are generally used. The polyester polyol and polyether polyol may be selected to design a particular polyurethane foam to have desired final toughness, durability, density, flexibility, compression ratio and modulus, and hardness properties. In general, high molecular weight polyols and low functionality polyols tend to produce softer foams than low molecular weight polyols and high functionality polyols.

"Polymer polyols" are a special class of polyols useful in the preparation of polyurethane foams having improved load bearing capacity. These polyols are stable dispersions of reinforcing solid particles in a polyol liquid. The three most common commercial polymer polyols are the SAN, PHD and PIPA families.

Low molecular weight crosslinkers are often used in the production of polyurethane foams. The most widely used cross-linking agents are alkanolamines, such as diethanolamine.

Petroleum derived components such as polyester polyols and polyether polyols pose several disadvantages. The use of such polyester polyols or polyether polyols requires the consumption of petroleum-derived oils, which are non-renewable resources. Moreover, the production of polyols requires a significant investment of energy, since the oil used to make the polyols must be drilled, refined, and then sent to refineries where the oil is refined, processed into refined hydrocarbons that are then converted to alkoxides, ultimately producing the finished polyol. As the mass consumer becomes more aware of the environmental impact of this manufacturing chain, the consumer demand for "greener" products will continue to grow. To help reduce the consumption of petroleum-derived oils while meeting the ever-increasing demands of consumers, it is desirable to replace, partially or wholly, the petroleum-derived polyester polyols or polyether polyols used in the production of polyurethane elastomeric foams with components that are renewable and more environmentally responsible.

Some attempts have been made by workers in the field to achieve the replacement of petroleum-derived polyols with components derived from renewable resources. Plastics and foams have been developed which are manufactured using triglycerides of fatty acids derived from vegetable oils, including soy derivatives. As a renewable, versatile and environmentally friendly resource, soybean has been and will always be an ideal ingredient for plastic manufacturing.

Kurth in a number of U.S. patents including 6180686, 6465569, and 6624244 describes the use of unmodified (oxidized) soybean oil as a polyol in the production of polyurethane materials. This oil was blown with air to oxidize it, but no description was given of any other modification treatment prior to using this oxidized soybean oil as a petroleum-based polyol substitute.

The use of crosslinking agents in the preparation of foams is well known to those skilled in the art. See, for example, Polyurethane Handbook, Gunter Oertel, Hanser Plublysers, 1985 and Muller et al in U.S. Pat. No. 4288566. However, it is well known that most cross-linking agents result in reduced tear and elongation properties of foams made from standard petroleum-derived polyols and polymer polyols. The use of aliphatic polyol crosslinkers with polyols derived from renewable resources in the presence of polymer polyols has not been discussed in the art.

Most of the crosslinkers used in the preparation of polyurethane foams are also petroleum derived. Many aliphatic polyol crosslinkers can be prepared from renewable resources that are more environmentally friendly.

There is no description in the art regarding the use of polymer polyols and aliphatic polyols in vegetable oil-containing polyurethane formulations. There remains a need in the art for polyurethane foams comprising bio-based polyols and those based on vegetable oil crosslinkers.

Disclosure of Invention

Accordingly, the present invention provides polyurethane foams made from a polyol component containing a polymer polyol (PMPO), at least 25 wt.% of a vegetable oil hydroxylate and from 0 to 3 wt.% of an aliphatic polyol having a functionality of from about 3 to 8 and a molecular weight of less than about 350, based on the weight of the polyol component.

Vegetable oil hydroxylates and optionally aliphatic polyols are environmentally friendly "bio-based" polyols. The inclusion of a polymer polyol (PMPO) in the polyol component of the present invention increases the tear resistance, tensile strength, and achieves unexpected elongation of the resulting foam. It has been found that the aliphatic polyol in the polyol component of the present invention improves the hot tear resistance of the resulting foam immediately after the foaming process.

These and other advantages and benefits of the present invention will be apparent from the detailed description of the invention provided below.

Detailed description of the invention

The present invention will now be described for purposes of illustration and not limitation. Except in the examples, or where otherwise indicated, all numbers expressing quantities, percentages, OH numbers, functionalities and so forth in the specification are to be understood as being modified in all instances by the term "about". Unless otherwise indicated, equivalent weights and molecular weights given herein in daltons (Da) are number average equivalent weights and number average molecular weights, respectively.

The present invention provides a polyurethane foam comprising the reaction product of at least one polyisocyanate and a polyol component comprising a polymer polyol (PMPO), at least 25 wt.%, based on the weight of the polyol component, of a vegetable oil hydroxylate, from 0 to 3 wt.%, based on the weight of the polyol component, of an aliphatic polyol having a functionality of from about 3 to 8 and a molecular weight of less than about 350, and optionally a non-vegetable oil-based polyol, optionally in the presence of at least one of blowing agents, surfactants, other cross-linking agents, extenders, pigments, flame retardants, catalysts and fillers.

The present invention also provides a method of making a polyurethane foam involving reacting at least one polyisocyanate with a polyol component containing a polymer polyol (PMPO), at least 25 wt.%, based on the weight of the polyol component, of a vegetable oil hydroxylate, 0 to 3 wt.%, based on the weight of the polyol component, of an aliphatic polyol having a functionality of about 3 to 8 and a molecular weight of less than about 350, optionally a non-vegetable oil-based polyol, optionally in the presence of at least one of blowing agents, surfactants, other crosslinking agents, extenders, pigments, flame retardants, catalysts and fillers.

Surprisingly, the combination of vegetable oil hydroxylates, polymer polyols (PMPOs) and aliphatic polyols can result in foams that: improved processability due to the improved hot tear strength properties while maintaining good strength in the cured foam.

Suitable polyisocyanates are known to those skilled in the art and include unmodified isocyanates, modified polyisocyanates, and isocyanate prepolymers. These organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic polyisocyanates, and a class of heterocyclic polyisocyanates such as those described by w.siefken in Justus liebig annalenger Chemie, 562, pages 75-136. Examples of such polyisocyanates include those represented by the formula Q (NCO)_nPolyisocyanates of the formula (I) wherein n is a number from 2 to 5, preferably from 2 to 3, and Q is an aliphatic hydrocarbon group; an alicyclic hydrocarbon group; an araliphatic hydrocarbon group; or an aromatic hydrocarbon group.

Examples of suitable isocyanates include ethylene diisocyanate; 1, 4-tetramethylene diisocyanate; 1, 6-hexamethylene diisocyanate; 1, 12-dodecane diisocyanate; cyclobutane-1, 3-diisocyanate; cyclohexane-1, 3-and-1, 4-diisocyanate, and mixtures of these isomers; 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate; German Ausleegeschrift 1202785 and U.S. Pat. No. 3401190); 2, 4-and 2, 6-hexahydrotoluylene diisocyanate and mixtures of these isomers; dicyclohexylmethane-4, 4' -diisocyanate (hydrogenated MDI or HMDI); 1, 3-and 1, 4-phenylene diisocyanates; 2, 4-and 2, 6-toluene diisocyanate and mixtures of these isomers (TDI); diphenylmethane-2, 4 '-and/or-4, 4' -diisocyanate (MDI); polymeric diphenylmethane diisocyanate (PMDI), 1, 5-naphthalene diisocyanate; triphenylmethane-4, 4', 4 "-triisocyanate; polyphenyl-polymethylene-polyisocyanates of the kind obtainable by condensation of aniline with formaldehyde and subsequent phosgenation (crude MDI), as described, for example, in GB 878430 and GB 848671; norbornane diisocyanates such as described in U.S. patent 3492330; meta-and para-isocyanatophenylsulfonyl isocyanate described in U.S. Pat. No. 3454606; perchloroaryl polyisocyanates such as those described in U.S. patent 3227138; modified polyisocyanates containing carbodiimide groups as described in us patent 3152162; modified polyisocyanates containing urethane groups such as described in U.S. Pat. Nos. 3394164 and 3644457; modified polyisocyanates containing allophanate groups such as described in GB 994890, BE761616 and NL 7102524; modified polyisocyanates containing isocyanurate groups such as those described in U.S. Pat. No. 3002973, German Patentschriften 1022789, 1222067 and 1027394 and German Offenlegungsschriften 1919034 and 2004048; modified polyisocyanates containing urea groups as described in German Patentschrift 1230778; biuret group-containing polyisocyanates such as those described in German patent publication 1101394, U.S. Pat. nos. 3124605 and 3201372, and GB 889050; polyisocyanates obtained by telomerization as described, for example, in U.S. Pat. No. 3654106; polyisocyanates containing ester groups such as described in GB 965474 and GB 1072956, us 3567763 and German patent disclosure 1231688; the reaction product of the above isocyanates with acetals described in German Patentschrift 1072385; and polyisocyanates containing polymerized fatty acid groups as described in U.S. patent 3455883. It is also possible to use the isocyanate-containing distillation residues accumulated in the industrial scale production of isocyanates, optionally in the form of one or more of the polyisocyanate solutions described above. Those skilled in the art will recognize that mixtures of these polyisocyanates described above may also be used. Particularly preferred in the polyurethane foams of the present invention is polymeric diphenylmethane diisocyanate (PMDI).

Prepolymers may also be used in the preparation of the foams of the present invention. Prepolymers can be prepared by reacting an excess of organic polyisocyanate or mixtures thereof with a small amount of an active hydrogen-containing compound as determined by the well-known Zerewitinoff test, as described by Kohler in the Journal of the American Chemical Society, 49, 3181 (1927). These compounds and their preparation are well known to those skilled in the art. The use of any one particular active hydrogen compound is not critical; any such compound may be used in the practice of the present invention.

The vegetable oil hydroxylates of the present invention may replace at least a portion of the petroleum-derived polyols typically used in the production of polyurethane foams. The preferred vegetable oil for producing the vegetable oil hydroxylate is soybean oil, although the inventors herein contemplate that virtually any other vegetable oil, such as sunflower, canola, linseed, cottonseed, tung, palm, poppy seed, corn and peanut oil, may be hydroxylated and used in accordance with the present invention.

Hydroxylation, by which the inventors herein mean introducing and/or increasing the number of hydroxyl groups (i.e., OH) in the molecule. In the present invention, the vegetable oil may be hydroxylated by any method known in the art including, but not limited to, air oxidation, use of peroxides, and by hydroformylation. Such hydroxylated vegetable oils are commercially available from a number of suppliers.

The vegetable oil hydroxylates useful in the present invention comprise at least 25 wt.% of the polyol component, and have a nominal average functionality in the range of from 1.5 to 6, more preferably in the range of from 2 to 4, and a molecular weight in the range of from 300 to 10000Da, more preferably in the range of from 500 to 7000 Da. The functionality and molecular weight of the vegetable oil hydroxylates useful in the present invention may range between any combination of these values, inclusive of the recited values.

As will be appreciated by those skilled in the art, a polymer polyol (PMPO) is a dispersion of polymer solids in a polyol. The addition of high levels of polymer polyol particles to foam formulations generally results in a decrease in foam elongation and a slight increase in tensile and tear strength. It is therefore highly unexpected that incorporation of a small amount of a polymer polyol into a foam can increase the hot tear strength of the material, thereby overall improving the processability of the foam, while significantly increasing the tear strength of the cured foam without a significant decrease in the elongation. Any polymer (or dispersion) polyol known in the art may be included in the polyol component of the present invention. Preferred polymer polyols for use in the present invention include "SAN" polymer polyols, as well as "PHD" dispersion polyols and "PIPA" dispersion polyols. Although polymer polyols are conventionally referred to as SAN-type, polymer polyols as used herein refer to all three types of polymer/dispersion polyols.

SAN polymer polyols are often prepared by the in situ (insitu) polymerization of one or more vinyl monomers, preferably acrylonitrile and styrene, in a polyol, preferably a polyether polyol having a small amount of intrinsic or incorporated unsaturation. For example, processes for preparing SAN polymer polyols are described in U.S. Pat. Nos. 3304273, 3383351, 3523093, 3652639, 3823201, 4104236, 4111865, 4119586, 4125505, 4148840, and 4172825, 4524157, 4690956, RE-28715, and RE-29118.

The polymer solids content of the SAN polymer polyols useful in the present invention is preferably in the range of from 1 to 60 wt.%, more preferably in the range of from 4 to 50 wt.%, based on the total weight of the SAN polymer polyol. As noted above, SAN polymer polyols are typically prepared by the in situ polymerization of a mixture of acrylonitrile and styrene in a polyol. If the above-mentioned starting materials are used, the weight part ratio of styrene to acrylonitrile, which is polymerized in situ in the polyol, is in the range of from 0: 100 to 80: 20, based on the total weight of the styrene/acrylonitrile mixture. The hydroxyl number of the SAN polymer polyols useful in the present invention is in the range of 10 to 200, more preferably 20 to 60.

As described herein, the polymer polyols may be prepared with other vinyl monomers other than styrene and/or acrylonitrile in combination with styrene and/or acrylonitrile, or with these other vinyl monomers alone. Preferred such other vinyl monomers include halogenated compounds such as bromostyrene and vinylidene chloride.

The polyols used in the preparation of the SAN polymer polyols useful in the present invention have an average nominal functionality of between 2 and 8 and are based on propylene oxide or a mixture of propylene oxide and ethylene oxide. Alkoxylation of the starting materials can be accomplished by using propylene oxide, ethylene oxide, or a mixture of propylene oxide and ethylene oxide, either alone or in sequence, to form a mixed block copolymer. The preferred polyols are formed by the addition of propylene oxide followed by the addition of ethylene oxide to form an ethylene oxide-capped polyol.

PHD polymer polyols are typically prepared by the in situ polymerization of an isocyanate mixture with a diamine and/or a diamine in a polyol, preferably a polyether polyol. For example, processes for preparing PHD polymer polyols are described in U.S. patents 4089835 and 4260530. PIPA polymer polyols are usually prepared by the in situ polymerization of an isocyanate mixture with a diol and/or diol-amine in a polyol, preferably a polyether polyol. The polymer solids content of the PHD and PIPA polymer polyols useful in the present invention is preferably in the range of from 1 to 30 wt.%, more preferably in the range of from 10 to 25 wt.%, based on the total weight of the PHD or PIPA polymer polyol.

The hydroxyl number of the PHD and PIPA polymer polyols useful in the present invention is preferably in the range of 15 to 80, more preferably in the range of 25 to 60. The polyols used to prepare the preferred PHD and PIPA polymer polyols of the present invention are triols based on propylene oxide, ethylene oxide or mixtures thereof. Alkoxylation of the starting materials is preferably achieved by capping with propylene oxide followed by ethylene oxide.

It is well known to those skilled in the art that the addition of isocyanate-reactive cross-linkers and/or extenders (regulators) to polyurethane formulations can improve processability or affect the physical properties of the resulting articles. Such regulators are typically diols or diol amines with molecular weights of less than 350Da and functionalities between 2 and 8.

Preferred crosslinkers in the present invention are aliphatic polyols having a functionality of between 3 and 8 and a molecular weight of less than 350. Examples of such crosslinking additives include glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, alkyl glucosides, sorbitol, mannitol, fructose, glucose, hydroxyethyl glucoside, sucrose, and hydroxypropyl glucoside. Particularly preferred are aliphatic polyols derived from renewable resources. Glycerol is the most preferred aliphatic polyhydroxy crosslinker. The aliphatic polyhydroxy crosslinking agents may be included in the formulation as a formulation additive, or they may be included in a polyol component which may also optionally include one or more non-vegetable oil based polyols. The aliphatic polyhydroxy crosslinking agent is preferably present in the polyurethane foam-forming formulation of the present invention in an amount of from 0 wt.% to 3 wt.%, more preferably from 0.1 wt.% to 3 wt.%, based on the weight of the polyol component.

Non-vegetable oil-based (i.e., petrochemically derived) polyols include, but are not limited to, polyethers, polyesters, polyacetals, polycarbonates, polyesterethers, polyestercarbonates, polythioethers, polyamides, polyesteramides, polysiloxanes, polybutadienes, and polypropions. The optional non-vegetable oil-based polyol may be prepared by standard base-catalyzed alkoxylation reactions well known in the art or alternatively alkoxylation reactions using Double Metal Cyanide (DMC) catalysts. Preferably, double metal cyanide complex catalysts as disclosed in U.S. Pat. Nos. 5158922 and 5470813 are used.

Suitable additives that may optionally be included in the polyurethane-forming formulations of the present invention include, for example, stabilizers, catalysts, cell regulators, reaction inhibitors, plasticizers, fillers, crosslinking agents or extenders other than aliphatic polyols, blowing agents, and the like.

Stabilizers suitable for use in the foam forming process of the present invention include, for example, polyether siloxanes, preferably those foam stabilizers which are insoluble in water. Such compounds generally have a structure in which a shorter chain copolymer of ethylene oxide and propylene oxide is attached to the residue of polydimethylsiloxane. Such stabilizers are described, for example, in U.S. patents 2834748, 2917480 and 3629308.

Catalysts suitable for use in the foam forming process of the present invention include those known in the art. These catalysts include, for example, tertiary amines such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N' -tetramethylethylenediamine, pentamethyldiethylenetriamine and higher homologues (for example, as described in DE-A2624527 and 2624528), 1, 4-diazabicyclo (2.2.2) octane, N-methyl-N '-dimethylaminoethylpiperazine, bis- (dimethylaminoalkyl) piperazine, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylbenzylamine, bis (N, N-diethylaminoethyl) adipate, N, N, N' N '-tetramethyl-1, 3-butanediamine, N, N-dimethyl-beta-phenylethylamine, N, N' -dimethyl-beta-phenylethylamine, N-ethylmorpholine, N-ethyldiethylenetriamine and higher homologues thereof, 1, 2-dimethylimidazole, 2-methylimidazole, monocyclic and bicyclic amines, and bis (dialkylamino) alkyl ethers such as 2, 2-bis (dimethylaminoethyl) ether.

Other suitable catalysts that may be used in the production of the polyurethane foams of the present invention include, for example, organometallic compounds, particularly organotin compounds. Suitable organotin compounds include organotin compounds containing sulfur. Such catalysts include, for example, di-n-butyltin mercaptide. Other types of suitable organotin catalysts include: preferred are tin (II) carboxylates, such as tin (II) acetate, tin (II) octanoate, tin (II) ethylhexanoate and/or tin (II) laurate; tin (IV) compounds, such as dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and/or dioctyltin diacetate.

Water is preferably used in the present invention as the sole blowing agent, although auxiliary blowing agents, such as carbon dioxide, may be used. Water acts as a blowing agent by reacting with the isocyanate component, chemically reacting to form carbon dioxide gas and an amine component which can further react with the polyisocyanate to form urea backbone groups. The amount of water may be up to 10% by weight. Preferably, water is used in the present invention in an amount of from 1 to 8 wt%, more preferably from 1 to 4 wt%, based on the total weight of the isocyanate-reactive mixture.

Further examples of suitable additives which may optionally be included in the flexible polyurethane foams of the present invention may be found, for example, in Kunststoff-Handbuch, Vol.VII, edited by Vieweg & Hochtlen, Carl Hanser Verlag, Munich 1993, third edition, p.104-127. Details regarding the use and mode of action of these additives are also set forth in this document.

Examples

The invention is further illustrated but is not intended to be limited by the following examples in which all amounts given in "parts" and "percentages" are to be understood as being by weight unless otherwise indicated. The following components were used to prepare the foams:

polyol A polyether polyol having a hydroxyl number of about 28 obtainable by epoxidizing the polyol under KOH catalysis

Propane block (84.5 wt% in total epoxide) followed by epoxy

Ethane block (15.5 wt% in total epoxide) vs. sorbitol

The product is prepared by alkoxylation reaction;

polyol B a biobased diol having a hydroxyl number of 54 available as SOYOYL R2-052

Urethane Soy Systems;

polymer polyol having a polyol C hydroxyl number of about 18.5 and a solids content of 41% by weight, which

The medium solids were styrene (64%) acrylonitrile polymerized in situ in the feed polyol

(36%) a mixture of said base polyol having a hydroxyl number of about 32, by reaction at KOH

Catalyzed by propylene oxide blocks (80.7 wt% in total epoxide)

%), followed by a block of ethylene oxide (19.3% by weight of total epoxide

%) mixture of glycerol (72%) and sorbitol (28%) was alkoxylated

The reaction is carried out to obtain;

the polyether polyol having a polyol D hydroxyl number of about 37.0 can be prepared by reacting a polyol with a ring under KOH catalysis

Oxopropane blocks (4.9% by weight in total epoxide) followed by epoxy

Propane (62.7 wt% in total epoxide) and ethylene oxide (in total epoxide)

22.4% by weight of epoxide, mixed block, last used (in all rings)

10% by weight of the oxide) is prepared by alkoxylating glycerol;

the polyether polyol having a polyol E OH number of about 168 can be prepared by using a ring under KOH catalysis

The glycerol is subjected to alkoxylation reaction by using the ethylene oxide to prepare the glycerol;

the polyol F is a polyether polyol having a hydroxyl number of about 36, obtainable by epoxidizing the polyol F under the catalysis of KOH

A block of propane (80% by weight of the total epoxide) followed by a block of ethylene oxide

Alkane block (20 wt% in total epoxide) alkane to glycerol

Prepared by oxidation reaction;

surfactant A is available as TEGOSTAB B-8715 LF from Goldschmidt AG

A silicone surfactant;

DEOA LF diethanolamine containing 15% water;

catalyst A Pentamethyldipropylene commercially available as POLYCAT 77 from Air Products

A triamine base;

catalyst B is a delayed action amine available as DABCO H-1010 from Air Products

A catalyst;

catalyst C bis (dodecyl Sulfur) available as DABCO 120 from Air Products

Alcohol) dibutyltin;

diphenylmethane diisocyanate (PMDI) polymerized from isocyanate A and having an NCO group content of about

32.4, a functionality of about 2.3 and a viscosity of about 25 mPas at 25 ℃.

These components were mixed in the amounts listed in Table I below (parts by weight per 100 parts by weight polyol, pphp) and reacted at an isocyanate index (100A/B) of 90 to produce a free-foaming foam. The hot tear properties were observed immediately after demolding, and these evaluations were strictly qualitative.

TABLE I

	Comparative example 1	2	3	4
					Polyol A	60.0	53.00	53.00	60.00
Polyol B	40.0	40.00	40.00	40.00
					Polyol C	-	7.00	7.00	-
Polyol D	1.00	1.00	1.00	1.00

Polyol E	-	-	2.00	-
					Polyol F	-	-	-	-
Water (W)	2.20	2.25	2.25	2.25
					Surfactant A	0.30	0.30	0.30	0.30
DEOA LF	0.35	-	-	-
					Mineral oil	-	-	-	-
Glycerol	-	0.30	0.30	0.30
					Catalyst A	1.00	1.00	1.00	1.00
Catalyst B	0.90	0.90	0.90	0.90
					Catalyst C	-	-	-	-
Isocyanate A	44.06	44.04	44.74	44.18
Hot tear observations	Difference (D)	Good taste	Good taste	Good taste

The components listed in Table II below (pphp) were mixed and reacted at an isocyanate index (100A/B) of 90 to produce a molded foam. (examples 10 and 11 correspond to isocyanate indices of 80 and 100, respectively.) the hot tear properties observed immediately after foaming are summarized in Table II.

Referring to Table I, it can be seen that the hot tear properties of the free-rise foams made from the glycerol-containing formulations appear to be improved. As can be seen by reference to Table II below, the hot tear strength of the molded foam can be increased by including a polymer polyol in the formulation and the hot tear strength of the molded foam can be further increased by including glycerol in the formulation.

The effect of using glycerol, sucrose or sorbitol with a polymer polyol was tested in examples 16-22. The components listed in Table III below (pphp) were mixed and reacted at an isocyanate index (100A/B) of 90 to produce a foam. Physical testing of the resulting fully cured foam is shown in Table III along with hot tear observations.

TABLE III

	Comparative example 15	16	17	18	19	20	21	22
									Polyol A	60.00	53.00	53.00	60.00	53.00	53.00	60.00	60.00
Polyol B	40.00	40.00	40.00	40.00	40.00	40.00	40.00	40.00
									Polyol C	-	7.00	7.00	-	7.00	7.00	-	-
Polyol D	1.00	1.00	1.00	1.00	1.00	1.00	1.00	1.00
									Water (W)	2.20	2.20	2.25	2.25	1.95	2.12	2.12	1.95
Surfactant A	0.30	0.30	0.30	0.30	0.30	0.30	0.30	0.30
									DEOA LF	0.35	0.35	-	-	-	-	-	-
Glycerol	-	-	0.30	0.30	-	-	-	-
									Sucrose, water content 50%	-	-	-	-	0.60	-	-	0.60
Sorbitol, water content 70%	-	-	-	-	-	0.43	0.43	-
									Catalyst A	1.00	1.00	1.00	1.00	1.00	1.00	1.00	1.00
Catalyst B	0.90	0.90	0.90	0.90	0.90	0.90	0.90	0.90
									Isocyanate A	44.06	43.92	44.04	44.18	44.53	44.03	44.18	44.71
									Density (lb/ft)3)	4.52	4.44	4.55	4.50	4.70	4.70	4.73	4.65

IFD HT	2.74	2.74	2.74	2.74	2.75	2.76	2.75	2.74
									IFD 25％(lb)	62.77	68.30	68.15	64.82	83.70	79.30	76.13	67.72
IFD 50％(lb)	105.67	116.84	115.28	108.33	133.20	128.50	123.20	108.60
									IFD 65％(lb)	166.38	186.22	183.14	169.75	202.70	195.40	186.70	166.60
IFD 25% recovery (lb)	48.02	50.32	51.00	49.93	62.09	59.07	58.01	52.03
									Recovery value (%)	76.51	73.67	74.83	77.02	74.18	74.50	76.20	76.83
IFD50/25	1.68	1.71	1.69	1.67	1.59	1.62	1.62	1.60
									IFD65/25	2.65	2.73	2.69	2.62	2.42	2.46	2.45	2.46
cFD 50％(psi)	0.67	0.74	0.77	0.70	0.85	0.86	0.88	0.76
									Tensile Strength (psi)	14.16	14.59	18.41	16.47	12.23	12.93	9.85	13.33
Elongation (%)	72.58	75.77	78.92	75.07	60.74	59.39	67.85	75.60
									Tear Strength (pli)	0.70	1.00	0.80	0.70	0.82	0.76	0.59	0.59
50% compression ratio (%)	14.98	17.08	16.13	13.84	14.27	13.69	12.97	14.00
									50% compression ratio after humid aging (%)	13.72	15.89	15.17	13.06	15.13	14.83	13.01	13.83

Wet shape 50 (%)	13.02	15.42	14.51	12.49	12.55	13.75	12.42	14.88
									Hot tear Strength observations	Difference (D)	Is slightly improved	Is slightly improved	Good taste	Good taste	Good taste	Difference (D)	Difference (D)

As can be seen from tables II and III, the combination of polymer polyol and aliphatic polyol crosslinker results in the best processability in terms of hot tear and the best tear resistance of the cured foam. The combination also results in comparable or improved elongation to foams made with crosslinkers that do not incorporate polymer polyols.

The polyurethane foams of the present invention may be used in a number of applications, for example where environmental concerns are at a premium, a percentage renewable resource content is required, and/or an increase in tear strength is beneficial.

The foregoing description of the embodiments of the invention has been presented for purposes of illustration and not of limitation. It will be apparent to those skilled in the art that various changes or modifications may be made in the embodiments described herein without departing from the spirit and scope of the invention. The scope of the invention is defined by the appended claims.

Claims (27)

1. A polyurethane foam comprising

The reaction product of at least one polyisocyanate with a polyol component, optionally in the presence of at least one of blowing agents, surfactants, other crosslinking agents, extenders, pigments, flame retardants, catalysts and fillers, the polyol component comprising:

a polymer polyol (PMPO) in a polyol,

at least 25% by weight, based on the weight of the polyol component, of a vegetable oil hydroxylate,

from 0.1 to 3% by weight, based on the weight of the polyol component, of an aliphatic polyol having a functionality of from 3 to 8 and a molecular weight of less than 350,

optionally a non-vegetable oil based polyol selected from the group consisting of polyethers, polyesters, polyacetals, polyester ethers, polythioethers, polyamides, polyesteramides, polysiloxanes, polybutadienes and polypropiophenones.

2. The polyurethane foam of claim 1, wherein the non-vegetable oil based polyol is selected from the group consisting of polycarbonates and polyester carbonates.

3. The polyurethane foam of claim 1, wherein the at least one polyisocyanate is selected from the group consisting of ethylene diisocyanate, 1, 4-butylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 12-dodecane diisocyanate, cyclobutane-1, 3-diisocyanate, cyclohexane-1, 3-and-1, 4-diisocyanate, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate), 2, 4-and 2, 6-hexahydrotoluylene diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate (hydrogenated MDI or HMDI), 1, 3-and 1, 4-phenylene diisocyanate, 2, 4-and 2, 6-Tolylene Diisocyanate (TDI), diphenylmethane-2, 4 ' -and/or-4, 4 ' -diisocyanate (MDI), polymeric diphenylmethane diisocyanate (PMDI), 1, 5-naphthalene diisocyanate, triphenylmethane-4, 4 ' -triisocyanate, polyphenyl-polymethylene-polyisocyanate (crude MDI), norbornane diisocyanate, m-and p-isocyanatophenylsulfonyl isocyanate, perchloroaryl polyisocyanate, carbodiimide-modified polyisocyanate, urethane-modified polyisocyanate, allophanate-modified polyisocyanate, isocyanurate-modified polyisocyanate, urea-modified polyisocyanate, biuret-containing polyisocyanate, biuret-modified polyisocyanate, and polyisocyanate, Isocyanate-terminated prepolymers and mixtures thereof.

4. The polyurethane foam according to claim 1, wherein the at least one polyisocyanate is polymeric diphenylmethane diisocyanate (PMDI).

5. The polyurethane foam of claim 1, wherein the vegetable oil is selected from the group consisting of sunflower oil, canola oil, linseed oil, cottonseed oil, tung oil, palm oil, poppy seed oil, corn oil, peanut oil, and soybean oil.

6. The polyurethane foam of claim 1, wherein the vegetable oil is soybean oil.

7. The polyurethane foam of claim 1, wherein the polymer polyol is a styrene-acrylonitrile (SAN) polymer polyol.

8. The polyurethane foam of claim 1, wherein the polymer polyol is a PHD or PIPA polymer polyol.

9. The polyurethane foam of claim 1, wherein the aliphatic polyol is derived from a non-petroleum based natural source.

10. The polyurethane foam of claim 1, wherein the aliphatic polyol is selected from the group consisting of glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, alkyl glucosides, sorbitol, mannitol, fructose, glucose, sucrose, hydroxyethyl glucoside, and hydroxypropyl glucoside.

11. The polyurethane foam of claim 1, wherein the aliphatic polyol is glycerol.

12. The polyurethane foam of claim 1, wherein the non-vegetable oil based polyol is a polyether polyol.

13. The polyurethane foam of claim 1 having a density of less than 10lb/ft³。

14. A method of making a polyurethane foam, the method comprising: reacting at least one polyisocyanate with a polyol component, optionally in the presence of at least one of blowing agents, other crosslinking agents, extenders, surfactants, pigments, flame retardants, catalysts and fillers, the polyol component comprising:

a polymer polyol (PMPO) in a polyol,

at least 25% by weight, based on the weight of the polyol component, of a vegetable oil hydroxylate,

from 0.1 to 3% by weight, based on the weight of the polyol component, of an aliphatic polyol having a functionality of from 3 to 8 and a molecular weight of less than 350,

optionally a non-vegetable oil based polyol selected from the group consisting of polyethers, polyesters, polyacetals, polyester ethers, polythioethers, polyamides, polyesteramides, polysiloxanes, polybutadienes and polypropiophenones.

15. The method of claim 14, wherein the non-vegetable oil based polyol is selected from the group consisting of polycarbonates and polyester carbonates.

16. The process of claim 14, wherein the at least one polyisocyanate is selected from the group consisting of ethylene diisocyanate, 1, 4-butylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 12-dodecane diisocyanate, cyclobutane-1, 3-diisocyanate, cyclohexane-1, 3-and-1, 4-diisocyanate, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate), 2, 4-and 2, 6-hexahydrotoluylene diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate (hydrogenated MDI or HMDI), 1, 3-and 1, 4-phenylene diisocyanate, 2, 4-and 2, 6-Tolylene Diisocyanate (TDI), diphenylmethane-2, 4 ' -and/or-4, 4 ' -diisocyanate (MDI), polymeric diphenylmethane diisocyanate (PMDI), 1, 5-naphthalene diisocyanate, triphenylmethane-4, 4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanates (crude MDI), norbornane diisocyanate, m-and p-isocyanatophenylsulfonyl isocyanate, perchloroaryl polyisocyanate, carbodiimide-modified polyisocyanate, urethane-modified polyisocyanate, allophanate-modified polyisocyanate, isocyanurate-modified polyisocyanate, urea-modified polyisocyanate, biuret-containing polyisocyanate, isocyanate-terminated prepolymer, and mixtures thereof.

17. The method of claim 14, wherein the at least one polyisocyanate is polymeric diphenylmethane diisocyanate (PMDI).

18. The method of claim 14, wherein the vegetable oil is selected from the group consisting of sunflower oil, canola oil, linseed oil, cottonseed oil, tung oil, palm oil, poppy seed oil, corn oil, peanut oil, and soybean oil.

19. The method of claim 14, wherein the vegetable oil is soybean oil.

20. The method of claim 14, wherein the polymer polyol is a styrene-acrylonitrile (SAN) polymer polyol.

21. The method of claim 14, wherein the polymer polyol is a PHD or PIPA polymer polyol.

22. The method of claim 14, wherein the aliphatic polyol is derived from a non-petroleum based natural resource.

23. The method of claim 14, wherein the aliphatic polyol is selected from the group consisting of glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, alkyl glucosides, sorbitol, mannitol, fructose, glucose, sucrose, hydroxyethyl glucoside, and hydroxypropyl glucoside.

24. The method of claim 14, wherein the aliphatic polyol is glycerol.

25. The method of claim 14, wherein the non-vegetable oil based polyol is a polyether polyol.

26. A polyurethane foam prepared by the method of claim 14.

27. The polyurethane foam of claim 26 having a density of less than 10lb/ft³。