RU2629020C2 - Sugar-based polyurethanes, methods of their obtaining and application - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: fire-resistant polyurethane foam contains two reaction mixtures. The first reaction mixture comprises a polyisocyanate and optionally a surfactant, and the second mixture comprises a natural polyol in which substantially all of the hydroxyl groups are free, a surfactant, an aqueous foaming agent, a catalyst, a flame retardant, and optional additives. The amounts of the first and second reaction mixtures are such that the obtained isocyanate index is from 20 to 50.

EFFECT: the resulting polyurethane foams show a high degree of resistance to fire and have a high index of biomaterial content, and also have a high "green" index according to ASTM standards.

31 cl, 9 dwg, 8 ex

Description

Link to related applications

This application claims priority based on provisional application for the grant of US patent No. 61/513530, filed July 29, 2011, and provisional US patent No. 61/381343, filed September 9, 2010, both documents are incorporated into this document in their entirety. .

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION

The inventions disclosed and referenced herein relate generally to polyurethanes and their manufacture, and more particularly, to methods for producing polyurethane foams of various densities that use sugars as the source of the polyol component.

Description of the Related Art

Products from polyurethane foams are widely used in a wide range of commercial and industrial applications. The prevalence of polyurethane foam products is due in part to the fact that the physical properties of a polyurethane foam product can be selectively changed based on the composition of the reagents that form the polyurethane foam product. You can develop a composition to obtain a product of polyurethane foam, which is soft, elastic and with open cells, which can be used in applications such as seat cushions. On the other hand, it is possible to develop a composition for a product of polyurethane foam, which is rigid, structural, heat-resistant and with closed cells and which, thus, can be used as a panel for thermal insulation.

The best known method of forming products from polyurethane foam is to mix and then react the polyol (e.g., resin composition) with an isocyanate in the presence of a blowing agent. Usually, when the resin composition is mixed with isocyanate to form a reaction mixture in the presence of a blowing agent, a urethane polymerization reaction occurs. As the urethane polymerization reaction takes place, the reaction mixture is crosslinked to form polyurethane, and gas is simultaneously generated and released. Through the nucleation process, the gas foams the reaction mixture, thereby forming voids or cells in the polyurethane foam article.

The resin composition typically contains one or more polyols, a cell opener, a crosslinker, a catalyst, an adhesion promoter, and various additives. Foaming agent forms cells in a polyurethane foam article as described above. The cell opener helps open the cells in such a way that the cells form a connected network and improves the stability of the polyurethane foam product. A crosslinking agent facilitates crosslinking of the reaction mixture, resulting in a polyurethane foam article. The catalyst adjusts the reaction kinetics to improve the timing of the polymerization reaction by balancing the thickening reaction and the foaming agent to form a polyurethane foam article that is stable. Other additives, such as adhesion promoters (e.g., an aprotic solvent), can be added to the composition to facilitate wetting of the reaction mixture and to facilitate adhesion of the polyurethane foam article to the substrates on which the polyurethane foam article is placed. For example, the substrate may be a thermoplastic body or a thermoplastic layer of a picnic refrigerator. The density and stiffness of a polyurethane foam article can be controlled by changing the chemical composition of the isocyanate, resin composition and / or blowing agent and their amounts. Other additives that are typically included in a polyurethane foam product are flame retardants, usually halogenated (e.g. brominated and chlorinated materials) and phosphorus-containing inhibitor materials.

Foams were used as heat insulating materials, light structural materials and flotation materials and for a wide variety of other applications because of their excellent properties. Until recently, their use was partly limited in environments where there is a danger of fire due to their significant contribution as a combustible component, their participation in the rapid spread of flames and the fact that they form large amounts of toxic smoke when decomposed by heat or combustion. to elevated temperatures. This limited the commercial development of polystyrene foam, and large sums of money and a lot of research time was spent trying to reduce these problems.

With the current interest in preserving heating fuel, many existing buildings install additional insulation, and newly constructed buildings contain more insulation than was previously used.

The previously used well-known type of foam insulation for existing buildings is urea-formaldehyde foam, which forms a foam in the space between the outer wall and the inner wall of the building with or without additional fiberglass insulation. Fiberglass insulation alone can be considered porous in nature, since it is usually a layer of small fiberglass, which can contribute to smaller insulation by providing air circulation inside the walls. Fiberglass insulations, however, form an air barrier between the internal and external walls of the building and thus form, as a rule, an impenetrable barrier to air circulation, thus making them better insulating materials. Unfortunately, the urea-formaldehyde foam that was used spontaneously decomposes, releasing formaldehyde vapors in amounts that can be toxic. The use of urea-formaldehyde foams during construction is prohibited in many building codes for this reason.

Another type of material commonly used for insulation is polyurethane foam. However, polyurethane foam makes a significant contribution as a combustible component, spreads flames quickly and releases toxic gases, including carbon dioxide, carbon monoxide and hydrogen cyanide, when burned. In addition, conventional polyurethane foam products are made from petroleum based polyol. As non-renewable raw materials, oil has both environmental and financial disadvantages. Accordingly, there are environmental, economic and commercial advantages associated with the use of polyols based on renewable raw materials, such as natural oils, for the production of so-called “biomaterial based” polyurethane foam products.

Rigid polyurethane foams are usually prepared by reacting an organic polyisocyanate with a polyol. For most commercial purposes, the reaction is carried out in the presence of a foaming agent, a surfactant, a catalyst, and possibly other ingredients. To reduce the cost of producing such foams, attempts have been made regarding the use of polysaccharides, such as starch or cellulose, as a polyol reagent in their preparation. The use of such alternative polyol as one materials has been unsatisfactory to date due to the poor physical properties of the resulting foams, unless they have been modified in any way or supplemented with conventional industrial polyols. For example, oxyalkylated starch gives good foams, however, direct oxyalkylation of starch leads to uncontrolled decomposition or decomposition of starch. When such products are used in the production of foams, foams do not have uniform chemical or physical properties.

The inventions disclosed and referenced herein are directed to polyurethane foams that use natural plant-based polyols or polyols, such as sucrose, for the polyol as one component in the foam composition, the resulting foams exhibiting a high degree of fire resistance and a high biomaterial content , showing that the product is characterized by a very high "green" rate according to ASTM standards.

SUMMARY OF THE INVENTION

Fire-resistant polyurethane foams are described, as well as products for their production using natural polyols or plant-based polyols as the main polyol component. According to one aspect of the disclosure, polyurethane foams are described which are characterized by a high “green rate” and which exhibit a high degree of resistance to fire, the foams containing a plant-based polyol such as sucrose as a polyol as one component, water as a blowing agent and a flame retardant for giving fire resistance to the resulting foams.

According to a first embodiment of the present disclosure, a substantially hydrocarbon-free flame retardant polyurethane foam is prepared that is produced by reacting a first and second reaction mixture together, wherein the first and second reaction mixtures contain a natural polyol, with substantially all hydroxyl groups on the polyol being free; isocyanate; surface-active substance; aqueous blowing agent; polyurethane formation catalyst; and a flame retardant or plasticizer. According to some aspects of this embodiment, the natural polyol is sucrose, invert solution, molasses, or a combination thereof.

According to a further embodiment of the present disclosure, a method for producing a flame retardant polyurethane foam is described, the method comprising (a) mixing an untreated natural polyol in which substantially all hydroxyl groups are free, a surfactant, a polyurethane formation catalyst and water to form a first aqueous solution; (b) adding to the mixture of the first aqueous solution a second solution containing a polyisocyanate; and (c) foaming the mixture.

According to another embodiment of the present disclosure, a method for producing low density polyurethane foam foamed with water is described, the method comprising contacting at least one polyisocyanate with at least one natural polyol, with an isocyanate index of 10-70, more preferably with an index of 20 up to 50, in the presence of a foaming agent composition containing at least 2 mass. % water, preferably at least about 5 wt. % water, and an effective amount of a catalyst composition containing a thickening catalyst, which is also a foaming catalyst, wherein the foam is characterized by a density of 4.8 kg / m ³ to 80 kg / m ³ . Also, according to aspects of this embodiment, the natural polyol is sucrose, invert solution, molasses, or a combination thereof, and provides open-cell foam with low compressive strength and good tensile strength.

Brief Description of the Drawings

The following drawings form part of the present description and are included to further show some aspects of the present invention. The present invention can be better understood based on one or more of these drawings, together with a detailed description of the specific embodiments presented herein.

In FIG. 1 is a graph of typical thermocouple data based on the ICC-ES AC377 flammability test of 16 kg / m ³ foam obtained according to the present disclosure.

In FIG. 2 shows a graph of smoke emission associated with a flammability test of 16 kg / m ³ foam obtained according to the present disclosure.

In FIG. 3 is a graph of heat generation associated with a flammability test of 16 kg / m ³ foam obtained according to the present disclosure.

In FIG. 4 is a graph of heat of radiation associated with a flammability test of 16 kg / m ³ foam obtained in accordance with the present disclosure.

In FIG. 5 is a graph of typical thermocouple data based on the ICC-ES AC377 flammability test of 8 kg / m ³ foam obtained according to the present disclosure.

In FIG. 6 is a graph of smoke emission associated with a flammability test of 8 kg / m ³ foam obtained according to the present disclosure.

In FIG. 7 is a graph of heat evolution associated with a flammability test of 8 kg / m ³ foam obtained according to the present disclosure.

In FIG. 8 is a graph of the heat of radiation associated with a flammability test of 8 kg / m ³ foam obtained according to the present disclosure.

In FIG. 9 shows a comparative table of foam products according to the present disclosure compared to some commercially available products.

Although the inventions described herein undergo various modifications and alternative forms, only a few specific embodiments have been shown by way of example in the graphic materials and described in more detail below. The drawings and detailed descriptions of these specific embodiments are not intended to limit the breadth or scope of the ideas of the invention or the appended claims in any way. Rather, the drawings and detailed descriptions are provided to illustrate the ideas of the invention to a person skilled in the art and to facilitate such a specialist to obtain and use the ideas of the invention.

Definitions

The following definitions are provided to assist those skilled in the art in understanding the detailed description of the present invention.

The term “invert solution” or “invert syrup” as used herein refers to sucrose-based syrups (eg, concentrated glucose and fructose solution) which are derived from hydrolysis of sucrose into glucose, fructose and residual sucrose, and which are characterized by a sugar content in the range of about 50 ° to about 70 ° brix, of which at least 90% are a mixture of fructose and glucose. These syrups are prepared using the invertase glycoside hydrolase enzyme, or an equivalent enzyme, or a suitable acid that breaks down each sucrose disaccharide molecule into its glucose and fructose monomer molecule components; any. The general reaction that produces “invert syrup” is shown below.

С ₁₂ Н ₂₂ О ₁₁ (sucrose) + Н ₂ О (water) = С ₆ Н ₁₂ О ₆ (glucose) + С ₆ Н ₁₂ О ₆ (fructose)

The term “sucrose” or “sugar” as used herein means that the compound with the general structure shown below is called α-D-glucopyranosyl- (1 → 2) -β-D-fructofuranose (a disaccharide consisting of D- glucosyl and D-fructosyl monosaccharide fragments (sometimes called sucrose) and the molecular formula C ₁₂ H ₂₂ O ₁₁ , as well as its salts, hydrates and stereoisomers (e.g., D, L or L, D).

The expression “brix” or “degrees of brix” as used herein (and as represented by the ° Bx symbol) means the unit used in the food industry to measure the approximate amount of dissolved solids (sugar) as the mass ratio of sugar to water in liquids, usually expressed as the percentage of solids dissolved. It is usually measured with a saccharimeter that measures the relative density of a liquid, or with a refractometer of the type that has a crosshair of sight lines. For example, a 25 ° Bx solution is 25% (w / w), with 25 grams of sugar per 100 grams of solution. Or, in other words, there are 25 grams of sucrose sugar and 75 grams of water in 100 grams of solution.

The term "compressive strength" as used herein means the property of foam products, as defined by the test procedure described in ASTM D-3575-77, expressed in pounds per square inch (psi), or according to DIN 53577. The expression "low compressive strength" when used herein refers to polyurethane foams characterized by a compressive strength of less than about 20 at 60% compression.

The phrases “flame retardant”, “non-combustible”, “flame retardant” and “flame retardant” as used herein mean: (a) the ability to not sustain flame, fire and / or combustion, or when a flame or fire is present, or when a heat source or tanning is removed; and / or (b) be an inhibitor or incapable of burning (being flame retardant - do not undergo virtually any changes when exposed to a flame, fire and / or combustion process). A non-combustible substrate or other material may char and / or melt.

The phrase “flame retardant chemical substance” and “non-combustible substance” as used herein means an element, chemical compound, agent or substance that is characterized by the ability to reduce or eliminate the tendency of the substrate to burn when the substrate is exposed to flame or fire, and which is suitable for use with one or more substrates that may be determined by those skilled in the art.

The phrase "flame propagation" as used herein means the advancement of the flame front as defined by ASTM E-84.

The phrase “flame propagation speed” as used herein means the distance that the flame front has advanced during its advancement per unit of time under certain test or other conditions.

The expression “combustibility” as used herein means the propagation limit to which the substrate or material will sustain combustion under certain test or other conditions.

The expression "polyurethane foam" as used herein generally refers to porous products that are obtained by reacting polyisocyanates with hydrogen-containing compounds capable of reacting with isocyanate using foaming agents and, in particular, includes porous products obtained by using water as a reaction a capable foaming agent (including the reaction of water with isocyanate groups, giving urea groups and carbon dioxide and giving polyurea-urethane foams).

As used herein, all numerical ranges provided are intended to accurately include at least all numbers that fall within the limit ranges.

Typically, ranges are expressed herein from “about” one particular value and / or to “about” another specific value. When such a range is expressed, another embodiment includes from one particular value and / or to another specific value. Similarly, when values are expressed as approximate values by using the preceding “about,” it will be understood that the particular value forms another embodiment. It will also be understood that the limit values of each interval are significant both with respect to another limit value and independently of another limit value.

The expression “optional” or “optional” means that the event or circumstance described below may or may not occur, and that the description includes cases where the event or circumstance occurs and cases where it does not. For example, the phrase “optionally substituted” means that the compound may or may not be substituted and that the description includes both unsubstituted compounds and compounds where there is a substitution.

The expression “open cell” or “open cell foam” as used herein refers to a foam having at least 20 percent open cells, as measured according to ASTM D 2856-A.

As used herein, “MDI” refers to methylene diphenyldiisocyanate, also called diphenylmethanediisocyanate, and its isomers. MDI exists as one of three isomers (4,4'-MDI, 2,4'-MDI and 2,2'-MDI) or as a mixture of two or more of these isomers. As used herein, unless otherwise specifically indicated, “MDI” may also refer to and encompass polymeric MDI (sometimes called PMDI). Polymer MDI is a compound that has a chain of three or more benzene rings joined together by methylene bridges, with an isocyanate group attached to each benzene ring. MDI, as used herein, can have an average functionality of from about 2.1 to about 3 inclusive, with a typical viscosity of about 200 MPa at 25 ° C.

The expression “functionality”, “MDI functionality” or “isocyanate functionality” as used herein refers to the average isocyanate functionality of all isocyanates used in the preparation of isocyanate, and is commonly referred to as Fn.

The expression "isocyanate index" or "NCO-index" refers to the ratio of NCO groups relative to capable of reacting with isocyanate hydrogen atoms in the composition, given in percentage terms:

In other words, the NCO index expresses the amount of isocyanate actually used in the composition, relative to the amount of isocyanate theoretically required for the reaction with the amount of hydrogen capable of reacting with the isocyanate used in the composition.

As used herein, the expression “toluene diisocyanate” encompasses all forms and combinations of isomers of this compound. In fact, the entire toluene diisocyanate reacts in a single-function manner, since the para-isocyanate group is more reactive than the ortho-isocyanate group.

In addition, unless otherwise indicated, a formula with chemical bonds shown only as solid lines, and not as wedge-shaped or dashed lines, implies every possible isomer, for example each enantiomer and diastereomer, and a mixture of isomers such as racemic or scalemic ( mixtures of unequal amounts of enantiomers) mixture.

Detailed disclosure of the present invention

The drawings described above and the description of specific structures and functions set forth below are not presented to limit the scope of what the applicants intended or the scope of the appended claims. Rather, the drawings and the description set forth are intended to teach any person skilled in the art how to make and use inventions that are patent protected. Those skilled in the art will appreciate that not all features of a commercial embodiment of the invention are described or shown for clarity and understanding. Those skilled in the art will also appreciate that the development of an actual commercial embodiment containing aspects of the present inventions will require a number of implementations-specific solutions to achieve the ultimate goal of the developer for the commercial embodiment. Such implementation-specific solutions may include, and probably, among other things, compliance with system-related, business-related, government-supported and other restrictions that may vary by specific implementation, location, and from time to time. Although developer attempts can be complex and time-consuming in absolute terms, such attempts will nevertheless be a common task for those skilled in the art to benefit from this disclosure. It should be understood that the inventions disclosed and referenced herein undergo numerous and various modifications and alternative forms. Finally, the use of the singular expression is not intended to limit the number of elements. Also, the use of relative expressions, such as, but not limited to, “top”, “bottom”, “left”, “right”, “upper”, “lower”, “down”, “up”, “side” and the like, are used in the foregoing description for clarity of a specific reference to the drawings and is not intended to limit the scope of the invention or the appended claims.

Applicants have developed polyurethane foam using natural polyols as the main or sole polyol as one component, with a variety of foam densities (for example, from 8 kg / m ³ to 80 kg / m ³ ), and the foams are characterized by a high green rate, as determined by determining the content of biomaterials , and / or high resistance to fire, as determined by a number of standard tests, including flame propagation and / or smoke emission.

Foams are polyurethane foams, which include the following categories: conventional type foam, highly elastic (HR) foam, filled foams, including foams filled with ground polyurethane foam as a type of filler, high load-bearing foam, spray foams, insulating foams, packaging foams and mesh foam, as described by US Pat. Nos. 3,475,525, 3,061,885 and 5,312,846, the relevant sections of the descriptions of which are incorporated herein by reference.

Without being limited by any theory, the concept is that reactive crosslinker or chain extender groups will more readily bind to a few isocyanate groups in areas where hydroxyl groups on natural polyols are not available, thus forming a foam more reliably. The polyurethane foam of the present disclosure is prepared by combining a natural polyol, a multifunctional isocyanate and a non-halogen blowing agent, preferably water or a combination of water and another halogen-free blowing agent, with one or more of a class of plasticizers and one or more of a class of crosslinkers / extenders and, optionally , in the presence of catalysts, stabilizers, emulsifiers and other auxiliary substances and additives, as required depending on the target density spacers of closed cells of a product made of polyurethane foam. Each of these ingredients will be discussed below.

Polyols

The primary raw material for producing the polyurethane foams disclosed herein is a natural polyol, which may be an aliphatic or aromatic polyhydroxy compound that will react with an isocyanate. This polyol may be a simple polyether polyol, a complex polyester polyol, or combinations thereof. Polyether polyols are preferred. The term “natural polyol” as used herein refers to the use of naturally occurring compounds (polyols from natural sources that are non-synthetic) that are classified as polyols, including but not limited to sucrose, dextrose, xylose, fructose, glucose, sorbitol, maltose, erythritol, hexose, sugar invert solution, extracts of sugar beet polyols, molasses, corn syrup and combinations thereof, as well as sugar-based polyols, including mannitol, glycerin, monosaccharides, disaccharide (E.g., lactose), trisaccharides (e.g., maltotriose), poly (n-alkyl glucosides), and other carbohydrate oligomers. The natural polyols used in the compositions of the present disclosure are typically used in amounts ranging from about 20 pphp (parts per hundred parts or mass%, equivalent) to about 70 pphp, and more preferably from about 25 pphp to about 55 pphp, inclusive, and also in amounts within this range, such as about 49 pphp.

Any natural material having active hydrogens as determined using the Cerevitinov method [as described by Kohlerin, Journal of American Chemical Society, Vol. 49, pp 31-81 (1927)], can be used to a certain extent, and thus be included in the broad definition of natural polyols. To produce the foams of the present disclosure, suitable natural polyol (s) are generally characterized by a weight average molecular weight of from about 50 to about 4000, functionality from about 2 to about 14, and a hydroxyl number, as determined by ASTM designation E-222-67 ( method B), in the range of from about 14 to about 1800, preferably from about 50 to about 500, and more preferably from about 100 to about 200.

Polyols of the present polyurethane compositions may also be a mixture of natural polyols and other polyol materials that are synthetic. Examples of such synthetic polyol materials include, but are not limited to, grafted copolymers of polyols such as styrene acrylonitrile (SAN) polyols, urea polyols, stepwise grown polyol copolymers such as polyisocyanate polyaddition polyols (PIPA polyols), i.e. polyols obtained by the reaction of hydrazine and toluene diisocyanate, polyurea dispersion polyols (PHD polyols) and epoxide dispersion polyols.

Polyols that can be used according to the present invention in combination with one or more natural polyols include, but are not limited to, the following simple polyether polyols: alkylene oxide adducts with polyhydroxyalkanes; alkylene oxide adducts with non-reducing sugars and sugar derivatives; alkylene oxide adducts with polyphenols; and alkylene oxide adducts with polyamines and polyhydroxyamines. Two to four carbon alkylene oxides are commonly used, with propylene oxide, ethylene oxide and mixtures thereof being preferred.

A simple polyether polyol is usually characterized by a hydroxyl functionality of 2 to 3 and a molecular weight of 1000 to 6000. The polyol or polyol blend should have an average hydroxy functionality of at least 2. The equivalent mass is determined from the measured hydroxyl number. The hydroxyl number is defined as the number of milligrams of potassium hydroxide required for complete hydrolysis of the fully acetylated derivative obtained from one gram of polyol. The relationship between the hydroxyl number and the equivalent mass is determined using the equation: OH = 56100 / equivalent mass, where OH is equal to the hydroxyl number of the polyol.

Polyols may contain poly (oxypropylene) and poly (oxyethylene-oxypropylene) triols. Ethylene oxide, if used, can be incorporated in any way along the polymer chain. In other words, ethylene oxide can be included either in the indoor units, in the form of end blocks, or can be arbitrarily distributed along the polyol as one chain.

Part or all of the polyol as one component can be added in the form of a polyol polymer in which the reactive monomers are polymerized in the polyol to form a stable dispersion of solid polymer particles in the polyol.

The amount of polyol used is determined by the amount of product to be obtained. Such amounts can easily be determined by a person skilled in the art.

Simple polyether polyols are most often used to produce polyurethane foams. Polyether polyols can be prepared by coupling alkylene oxides to initiators such as sucrose, glycerol, triethanolamine and the like. Suitable alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, N-hexyl oxide, styrene oxide, trimethylene oxide, tetrahydrofuran, epichlorohydrin and the like. Propylene oxide is preferred relative to ethylene oxide because it gives polyether polyols with secondary hydroxyl groups. Typical examples of polyether polyols are polyether diols, such as polypropylene glycol, polyethylene glycol and polytetramethylene glycol; polyether triols, such as glycerol triols; polyether tetrols and pentols, such as aliphatic amine tetrols and aromatic amine tetrols; polyether octols, such as sucrose octol; and others, such as sorbitol, trimethylolpropane and pentaerythritol.

One preferred class of natural polyols used in these formulations are glycerol-based polyether triols.

The polyol may be suitable hydroxyl group-containing polyesters, including, for example, reaction products of polybasic, preferably dibasic, alcohols with optional addition of tribasic alcohols and polybasic, preferably dibasic, carboxylic acids. Examples of such carboxylic acids and their derivatives include dimerized and trimerized unsaturated fatty acids, optionally mixed with monomeric unsaturated fatty acids such as oleic acid, dimethyl terephthalate, terephthalic acid esters of bis-glycol and polyalkylene terephthalate. Suitable polyols include glycols, for example ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and higher polyethylene glycols and polyalkylene glycols.

Polyurethane foams represent the highest yield for polyester polyols. Typical examples of polyester polyols that can be used to make polyurethane foams according to the present disclosure also include ethylene and diethylene glycol adipates, butanediol adipate, polytetramethylene glycol adipate, hexanediol adipate and polyols derived from terephthalate and its derivatives, including, for example, dimethyl terephthalate polyethylene terephthalate, in reaction with diols and triols.

Similarly, the compounds of natural polyols used in the present invention can be any of the usual compounds, examples of which are aliphatic polyester glycols, such as polyethylene adipate; polybutylene adipate; polypropylene adipate and the like with extended chain lengths obtained by the condensation reaction of aliphatic glycol and dibasic carboxylic acid; polyalkylene ether glycols such as polypropylene ether glycol, tetramethylene ether glycol and the like, obtained by ring-opening polymerization of cyclic ethers such as ethylene oxide, propylene oxide, tetrahydrofuran and the like; polyester glycols obtained by ring opening polymerization of epsilon-caprolactone; diol compounds obtained by converting the final groups in polybutadiene to hydroxy groups; copolymers of two or more types of alkylene oxides; copolymers of two or more kinds of glycols and dibasic carboxylic acid; polyester polyols obtained by co-condensing a dibasic carboxylic acid and a polyol such as aromatic glycols, long chain diols, glycerin, trimethylolpropane and the like; and polyether polyols obtained by ring-opening polymerization of cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran, with a polyol such as glycerol or trimethylolpropane as an initiator.

These compounds are only illustrative examples of polyol sources that can be used in connection with the present invention, and it should be understood that any known polyol source that is suitable in the preparation of polyurethane can be used.

Isocyanates

Another desired ingredient in the compositions disclosed herein is one or more isocyanates, such as monomeric and / or multifunctional isocyanates. Diphenylmethanediisocyanate (MDI) and toluene diisocyanate (TDI) are the main raw material for the production of polyurethane foams, both of which are monomeric and can be used in accordance with the compositions and methods of the present disclosure. Polyurethane foams according to the present disclosure can also be obtained by the reaction of polyols and polymer diphenylmethanediisocyanate, a multifunctional isocyanate.

Preferably, the compositions described herein comprise a monomeric MDI component containing 2,4'-MDI. As previously described herein, according to the nomenclature, monomeric MDI means a component containing MDI isomers, such as 2,4'-MDI, 4,4'-MDI or 2,2'-MDI. Compared to 4.4'-MDI and 2.2'-MDI, 2,4'-MDI is an asymmetric molecule and provides two NCO groups with different reactivities. Thus, without limitation by any theory, 2,4'-MDI is usually found in the polyisocyanate composition to optimize the parameters of the foaming reaction of elastic polyurethane, such as stability and cure time of elastic polyurethane foam. 2,4'-MDI is present in the monomeric MDI component in an amount of more than 10 parts by weight 2,4'-MDI based on 100 parts by weight of the monomeric MDI component. 2,4'-MDI is more typically found in the monomeric MDI component in an amount of greater than 35, most typically greater than 65 parts by weight based on 100 parts by weight of the monomeric MDI component.

The monomeric MDI component may also contain 2.2'-MDI and 4.4'-MDI. Preferably, 2,2'-MDI is either not present at all in the monomeric MDI component, or is present in small amounts, i.e. typically 0 to 2, more typically 0.1 to 1.5 parts by weight based on 100 parts by weight of the monomeric MDI component. 4.4'-MDI is usually present in the monomeric MDI component in an amount of from 0 to 65, more typically from 20 to 55, and most typically from 30 to 35 parts by weight based on 100 parts by weight of the monomeric MDI component.

The monomeric MDI component is usually present in the polyisocyanate composition in an amount of from 80 to 100, more typically from 90 to 98 parts by weight based on 100 parts by weight of the polyisocyanate composition.

As indicated above, the polyisocyanate composition may also optionally contain a polymeric diphenylmethanediisocyanate (MDI) component. An isocyanate, if present as a polymeric MDI component, is usually present in the polyisocyanate composition to provide reactive groups, i.e. NCO groups during the foaming reaction of elastic polyurethane, as described in more detail below. The polymeric MDI component is usually a mixture of oligomeric diphenylmethanediisocyanates, i.e. a mixture of MDI and its dimer and / or trimer. The polymeric MDI component contains crude MDI with three or more benzene rings, including NCO groups. Polymer MDI is usually obtained by condensation of aniline and formaldehyde in the presence of an acid catalyst, followed by phosgenation and distillation of the resulting mixture of polymer amines. The polymeric MDI component is usually present in the polyisocyanate composition in an amount of from 1 to 20, more typically from 2 to 10 parts by weight based on 100 parts by weight of the polyisocyanate composition.

According to the present disclosure, compositions of the present disclosure are preferably prepared with an isocyanate having a functionality in the range of from about 2.0 to about 3.0 (inclusive) and more preferably from about 2.1 to about 2.8 inclusive, including functionalities 2.2, 2 , 3, 2,4, 2,5, 2,6 and 2,7, as well as intermediate ranges (for example, from about 2.3 to about 2.7); and NCO content in the range from about 20.0 to about 40.0 mass. %, preferably from about 28.0 wt. % to about 35.0 mass. % inclusive. Typical suitable isocyanates for use herein include, but are not limited to, Lupranate® M10 and Lupranate® M20, both polymeric MDI (Polymethylene Polyphenyl Polyisocyanate) are available from BASF Corporation (Wyandotte, MI).

Other isocyanates can be used in the present invention, either instead of, or in conjunction with MDI, TDI and / or polymeric MDI. Such isocyanate compounds are well known in the art and are selected from, for example, aliphatic, cycloaliphatic and aromatic polyisocyanates, for example alkylenediisocyanates and aryl diisocyanates and combinations thereof. Those skilled in the art are aware of the properties that various isocyanates can impart to the foam.

A wide range of known isocyanate compounds can be used according to the present invention, including isocyanic acid esters. Any of the conventional polyisocyanates known in the art can be used in the present invention. Examples of sources of isocyanates suitable for use with the compositions and methods of the present invention include polyvalent isocyanates, including diisocyanates, such as m-phenylenediisocyanate; p-phenylenediisocyanate; 2,6-trichlorethylene diisocyanate; naphthalene-1,4-diisocyanate; 2,4-trichlorethylenediisocyanate; diphenylmethane-4,4'-diisocyanate (MDI); 3,3'-dimethoxy-4,4'-biphenyldiisocyanate; propylene-1,2-diisocyanate; 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; trimethylhexamethylene diisocyanate; xylene diisocyanate, including xylylene-1,4-diisocyanate; hexamethylene diisocyanate; 4,4'-diphenylpropanediisocyanate; trimethylenediisocyanate; butylene-1,2-diisocyanate; cyclohexanediisocyanate; cyclohexylene-1,2-diisocyanate; cyclohexylene-1,4-diisocyanate; isophorondiisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate and the like; the above 2,4-tolylene diisocyanate (2,4-TDI); 2,6-tolylene diisocyanate (2,6-TDI); mixtures of 2,4-TDI and 2,6-TDI; 2,4-TDI dimer and trimmer; methaxylene diisocyanate; 4,4'-biphenyldiisocyanate; diphenylether-4,4'-diisocyanate; 3,3'-ditoluene-4,4'-diisocyanate; dianisidinediisocyanate; 4,4'-diphenylmethanediisocyanate; 3,3'-diethyl-4,4'-diphenylmethanediisocyanate; 1,5-naphthalenediisocyanate; diisothiocyanates such as p-phenylenediisothiocyanate; xylene-1,4-diisothiocyanate; ethylidene diisothiocyanate and the like; triisocyanates such as triphenylmethane triisocyanate and the like, including 4,4 ', 4' '- triphenylmethane triisocyanate; toluene 2,4,6-triisocyanate and the like; tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate and the like; isocyanate prepolymers, such as the adduct of trichlorethylenediisocyanate with hexanetriol; hexamethylene diisocyanate adduct with hexanetriol; trichlorethylenediisocyanate adduct with hexanetriol; adduct trichlorethylene diisocyanate with trimethylolpropane and the like. Polyisocyanates can also be used in the form of their derivatives, for example, reaction products with phenols, alcohols, amines, ammonia, bisulfite, HCl, etc., and a polyester-based isocyanate-based prepolymer and IPDI. Some examples thereof are phenol, cresols, xylene, ethanol, methanol, propanol, isopropanol, ammonia, methylamine, ethanolamine, dimethylamine, aniline and diphenylamine. Addition products with a relatively high molecular weight, for example polyisocyanates with polyhydric alcohols, such as ethylene glycol, propylene glycol, trimethylolalkanes, or glycerol, can also be used.

These compounds are only typical examples of sources of isocyanates that can be used in conjunction with the present invention, and it should be understood that any known source of isocyanates that is suitable for producing polyurethane can be used.

Organic isocyanates suitable in the preparation of the polyurethane foam of the present invention are organic compounds which contain an average of about one and a half to about six isocyanate groups and preferably about two isocyanate groups.

The amount of isocyanate to be used depends on the desired isocyanate index of the foam and the final properties of the foam that is obtained. The isocyanate index is the percentage of isocyanate present relative to moles of compounds capable of reacting with the isocyanate, expressed as a percentage. If the isocyanate index is 100, then there is a stoichiometric equivalent of the amount of isocyanate needed to react with the polyol component and other active hydrogen containing components, i.e. water in the system. If 3 molar percent of the excess of isocyanate is introduced into the foam, then the isocyanate index is 103. In general, as soon as the isocyanate index increases, the amount of water and free hydroxyl groups available for the reaction decreases.

Although the present invention can be carried out in a wide range of indices, i.e. from about 15 to about 120, a preferred range of indices is from about 20 to about 60 inclusive, more preferably from about 20 to about 40 inclusive. For example, and without limitation, a foamed product with a density of 8 kg / m ³ can be obtained according to the present disclosure, where the index is about 21.

Foaming Agents

In addition to the isocyanate and natural polyol, the production of polyurethane foam requires the use of a foaming or foaming agent. Fluorocarbon blowing agents, such as trichlorofluoromethane, have been used to make foams in the past; however, the future of fluorocarbon blowing agents depends on government regulations, and thus their use in commercial products has been subject to industrial restrictions. The heat of reaction and sometimes externally supplied heat causes decomposition of the fluorocarbon compound when it is used as a foaming agent. Methylene chloride has replaced most fluorocarbon compounds in the production of elastic foams. However, it is becoming more desirable to remove all halogen-containing compounds from the process in order to comply with health and environmental standards. Thus, halogen-free blowing agents, both in the form of liquids, such as pentane, and gases, such as carbon dioxide, can be used according to the present disclosure. Fourth-generation blowing agents, commonly called the AFA series, which can be in either liquid or gaseous formulations, and contain AFA molecules such as 245FA (1,1,1,3,3-pentafluoropropane available as Honeywell's ENOVATE® 3000 International, Inc.) and 134A (1,1,1,2-tetrafluoroethane, available as FORANE® 134a from Arkema, Inc.) may also optionally be included in the present disclosure if necessary.

A common blowing or blowing agent and a preferred blowing agent for the process of the present disclosure is water. Often, water and an optional auxiliary blowing agent can be used together, although this is not necessary for the practice of the present invention, since water alone can be used as a blowing agent. Without being limited by any particular theory, it is believed that water added to the reaction of an isocyanate and a natural polyol reacts with an isocyanate to form unstable carbamic acid, which decomposes into the corresponding amine and carbon dioxide. The amine then reacts with another isocyanate group to form a symmetrical disubstituted urea. Any hydrogen of disubstituted urea can also react with another isocyanate to form a biuret, which provides additional branching or cross-linking of the polymer. The reactions of isocyanate with water and polyol are exothermic.

As indicated above, water is preferably the only blowing agent used in accordance with the present disclosure to produce carbon dioxide by reaction with an isocyanate. Water can be used in an amount in the range of about 0.1 to about 60 parts per hundred parts (pphp) of the natural polyol by weight (pphp), preferably about 2 to about 50 pphp, more preferably about 3 to about 30 pphp, and also in amounts between these ranges, such as from about 3.5 pphp to about 6 pphp, for example, about 4.5 pphp. At foam indices below 100, a stoichiometric excess of water is purged by evaporation, cools the foam and does not take part in the reaction to produce carbon dioxide.

Other blowing agents that are commonly used in the art can be used herein with an aqueous blowing agent, but due to the use of the present composition, large quantities of such agents are no longer necessary, and in many cases are not required at all. Fluorocarbon compounds, such as trichlorofluoromethane, have been used since they foam easily when heated, and they do not react with the polyol and isocyanate. Fluorocarbon compounds continue to be used in the preparation of certain rigid foams; however, methylene chloride has replaced most fluorocarbon compounds in the preparation of elastic foams. Although it is an object of the present invention to provide soft PU foams using water as the primary blowing agent, inert physical blowing agents such as trichlorofluoromethane, methylene chloride, methyl chloroform or acetone can nevertheless be included. Although the amount of inert blowing material can range from about 0 to about 30 pphp, commercially suitable foams can generally be prepared using from about 0 to about 8 pphp, usually from about 0 to about 5 pphp, more typically from about 1 up to about 3 pphp.

It is desirable to replace as much as possible a halogen-containing foaming agent with a non-halogen foaming agent, for example water, carbon dioxide, formic acid, bicarbonates and the like, and it is preferable to use only a non-halogen foaming agent according to the present disclosure.

When, as is preferable in the present invention, water is provided as a foaming agent, the water / isocyanate reaction gives carbon dioxide, which foams to allow swelling or foaming of the polyurethane that is produced. One of the main problems accompanying the replacement of the ozone-depleting fluorocarbon compound as a foaming agent in elastic polyurethane foams with water is the increased stiffness of the resulting foams. This is likely due to bidentate urea groups introduced as a result of the water-isocyanate reaction. Using MDI or TDI-based elastic foams, this problem can be solved because they are chosen because of their softness and elasticity, and increased rigidity makes foams less desirable. One method, as found according to the present invention, for producing softer foamed water foams is the use of plasticizers, some of which are also flame retardant additives.

Plasticizers

The use of water as a foaming (or foaming) agent in flexible polyurethane foams increases the rigidity of the resulting foams. A soft, flexible, plasticized water-foamed polyurethane foam composition can be prepared by reacting a natural polyol and MDI or equivalent isocyanate by adding a plasticizer selected from the group consisting of benzoates, phenols, phthalates, phosphates or phosphorus compounds or classified as flame retardants, and mixtures thereof or combinations in the reaction mixture. Typical types of plasticizers used in the present invention are described in US Pat. No. 5,624,968, the corresponding disclosure of which is incorporated herein by reference.

The polyurethane foam compositions of the present disclosure may contain one or more plasticizers selected from the group of phthalate plasticizers, phosphate or phosphorus-containing plasticizers and benzoate plasticizers, for reaction compounds. These plasticizers can be added to obtain a softer, more flexible polyurethane foam, which, more importantly, exhibits good load-bearing properties without significant loss of other required strength properties.

The effective level of plasticizers is very wide. Typically, suitable polyurethane foams obtained according to the methods of the present disclosure will include plasticizer and / or flame retardant compounds in an amount in the range of from about 0.1 to about 40 pphp inclusive. Although this range is preferred, it is recognized that less plasticizer and / or flame retardant can be added and that this reduced amount of plasticizer will provide some emollient effect for the composition, and large amounts of plasticizer may be desirable in some compositions. Typically, the amount is from about 0.5 pphp to about 35 pphp, preferably from about 1 pphp to about 30 pphp, more preferably from about 1.5 pphp to about 25 pphp, inclusive, as well as amounts or ranges within these ranges, for example about 24 pphp or from about 6 pphp to about 12 pphp. Such amounts may be pure solid or liquid compounds, or the plasticizer may be dissolved in a suitable solution or liquid in concentrations ranging from about 2 molar to about 40 molar, more preferably from about 5 molar to about 15 molar inclusive, as well as concentrations in within these ranges, such as about 7 molar or about 12 molar.

Plasticizers useful in the present invention include phthalate plasticizers, such as, for example, alkyl aryl phthalates or alkyl benzyl phthalates, including butyl benzyl phthalate, alkyl benzyl phthalate, preferably in which the alkyl group has a carbon chain of seven to nine carbon atoms, Texanol ™ benzyl phthalate (which is 2.2 , 4-trimethyl-1,3-pentanediol monobutyrate benzyl phthalate), alkyl phenyl phthalate, symmetric and asymmetric dialkyl phthalates, including diisononyl phthalate, diisodecyl phthalate, dioctyl phthalate, di-n-butyl phthalate, di octyl phthalate, dihexyl phthalate, diheptyl phthalate, butyl octyl phthalate, linear dialkyl phthalate, in which the alkyl groups independently are carbon chains having from seven to eleven carbon atoms, and butyl cyclohexyl phthalate; phosphate plasticizers such as tris- (2-chloro-1-methylethyl) phosphate, tris- (alpha-chloroethyl) phosphate (TCEP), tris- (2,3-dichloro-1-propyl) phosphate, YOKE-V6 (tetrakis - (2-chloroethyl) dichloroisopentyl diphosphate) and the like; phosphate ester plasticizers, such as, for example, 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, mixed dodecyl and tetradecyl diphenyl phosphate, trioctyl phosphate, tributyl phosphate, butyl phenyl diphenyl phosphate and isopropyl triple; and benzoate plasticizers, such as, for example, Texanol ™ benzoate (which is 2,2,4-trimethyl-1,3-pentanediol monobutyrate benzoate), glycol benzoate, propylene glycol dibenzoate, dipropylene glycol dibenzoate and tripropylene glycol dibenzoates.

Preferred plasticizers according to selected embodiments are phthalate and phosphate or phosphorus-containing plasticizers, such as alkyl, aryl or alkyl substituted aryl phosphates. More preferably, the plasticizers are phosphorus-containing plasticizers, with TMP (Tris (2-chloro-1-methylethyl) phosphate, also known as TCRP), which is also flame retardant, being the most preferred plasticizer. Other phosphates or phosphonates may also be used as flame retardants according to the present disclosure.

Other plasticizers that can be used according to the present disclosure include ethoxylated aliphatic monohydric or polyhydric alcohols, alkyl or alkyl phenol oxyl alkylates and alkyl phenols. Water-soluble esters of ethoxylated C ₈ -C ₃₆ aliphatic monohydric or polyhydric alcohols with aliphatic acids and aliphatic dimeric acids can be used according to the present invention. Such ethoxylated esters have a hydrophilic-lipophilic balance (HLB) in the range of 10 to 20.

Suitable ethoxylated aliphatic acids have from about 5 to about 20 moles of added ethylene oxide per mole of acid. Examples include ethoxylated oleic acids, ethoxylated stearic acid and ethoxylated palmitic acid. Suitable ethoxylated dimeric acids are oleic dimeric acid and stearic dimeric acid. Aliphatic acids may be either branched or unbranched and may contain from about 8 to about 36 carbon atoms. Suitable aliphatic acids include azelaic acid, sebacic acid, dodecandionic acid, caprylic acid, capric acid, lauric acid, oleic acid, stearic acid, palmitic acid and the like. Particularly suitable for the purpose of preparing the water-soluble esters of the present invention are aliphatic, preferably saturated and unbranched monobasic and dibasic carboxylic acids containing from about 8 to 18 carbon atoms.

According to other aspects of the present disclosure, the plasticizer may be an alkyl or alkyl phenol oxylalkylate or the like, which may also be classified as a nonionic surfactant. Such preferred plasticizers include, but are not limited to, alcohol alkylalkylates, alkylphenoloxylalkylates, nonionic esters such as sorbitan esters and sorbitan ester alkoxioates. Examples of suitable compounds include, but are not limited to, castor oil alkoxylates, fatty acid alkoxylates, lauryl alcohol alkoxylates, nonylphenol alkoxylates, tridecyl alcohol alkoxylates such as POE-10-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethylated-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethoxylates. POE-12 tridecyl alcohol ethoxylate, POE-14 nonyl phenol ethoxylate, POE-15 nonyl phenol ethoxylate, POE-18 non-phenol ethoxylate, POE-20 non-phenol ethoxylate, POE-20 oleyl alcohol ethoxylate stearic acid oxylate POE-20, tridecyl alcohol ethoxylate POE-3, nonyl phenol ethoxylate POE-30, non-phenol ethoxylate POE-34, nonyl phenol ethoxylate POE-4, non-phenol ethoxylate 40-ethanolate 40 , nonyl phenol ethoxylate POE-50, ethylene acetate tridecyl alcohol POE-50, nonyl phenol ethoxylate POE-6, ethoxylate tridecyl alcohol POE-6, nonyl phenol ethoxylate POE-8, octyl phenol ethoxylate ROE-9, sorbitan, mono-ethanol, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan oleate, sorbitan palmitate, sorbitan sequioleate, sorbitan stearate, sorbitan trioleate, sorbitan tristearate, sorbitan ethoxylate sorbitan monoisostearate POEOEO-20 ethanol, ethanol POOEO-20 ethanol, ethanol POEO-20 ethanol, ethanol POEO-20 ethanol, ethanol POEO-20, ethanol POE-20 sorbitan monopalmitate ethoxylate, POE-20 monostearate sorbitan ethoxylate, POE-20 trioleate sorbitan ethoxylate, POE-20 sorbitan ethoxylate, POE-30 sorbitan ethoxylate, POE-30 sorbitan ethoxylate, tetraolea sorbitan ethoxylate and POE-40 sorbitan hexastearate ethoxylate, POE-6 ethoxylate, sorbitan monostearate, POE-6 ethoxylate, sorbitan tetraoleate, POE-6 and / or sorbitan tetrastearate ethoxylate, POE-60. Preferred plasticizers of this class include alcohol hydroxyalkylates such as POE-23 lauryl alcohol and alkyl phenol ethoxylates such as POE (20) nonylphenyl ether. Other suitable plasticizers are esters, such as sorbitan monooleate.

An additional type of plasticizer that can be used in the compositions of the present disclosure includes alkyl phenols, preferably non-toxic alkyl phenols, including, but not limited to, nonylphenol, dodecylphenol, divoramylphenol and the like, as well as combinations thereof.

Stapler / extension cord

Applicants have found that, depending on the composition of the foam based on a natural polyol, it was possible to overcome the physical deficiencies of water-foamed PU foams that contain plasticizers such as phthalates, benzoates and phosphate esters, while at the same time helping to avoid dangerously high amounts of released heat by introducing an optional chain extender / crosslinker into the low index foam.

In the present invention, one or more special crosslinkers / chain extenders are incorporated into the foam. As used herein, the term “crosslinker” means including compounds generally known as crosslinkers, as well as compounds commonly known as chain extenders or simply extenders. Crosslinkers are compounds that contain two or more isocyanate-capable groups, such as hydroxyl groups, primary amines and secondary amines.

When crosslinkers are used in the compositions of the present disclosure, the formed PU foams can exhibit improved foam stability and / or tensile strength, usually without discoloration of the foam. Typical crosslinkers / chain extenders suitable for use in the compositions and processes of the present disclosure include, but are not limited to, amines, including polyamines; polyhydric alcohols; polyoxyalkylene polyols and polyhydric aromatic compounds, alone or in combination.

Polyamines, 4,4'-methylene-bis- (3-chloro-2,6-diethylaniline) (MCDEA), at 0.5 pphp and polyalkine oxide with an amine at the end, such as JEFFAMINE ™ T-403 (Huntsman Co.) can be used as optionally introduced crosslinkers / chain extenders according to the present disclosure, as well as alkanolamines such as diethanolamine (DEOA), triethanolamine. Other suitable amines include diethanolamine, triisopropanolamine, diisopropanolamine, tert-butyltolylenediamine, triaminonan, diethyltolylenediamine and chlordiaminobenzene.

Polyols can also be used, including, but not limited to, 1,3-butanediol, 1,4-butanediol, mono-, di- and triethylene glycols, 1,2,4-butanetriol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, 2,5 dimethyl-1,2,6-hexanetriol and glycerol.

Polyoxyalkylene polyols can also be used; suitable examples include VORANOL ™ 800 (Dow), QUADROL ™ (BASF) tetrahydroxypropylethylenediamine, HUNTSMAN WL-440 ™, ethoxylated trimethylolpropane PEL-RIG ™ 9145 and propoxylated methyl glucoside, PEL-RIG ™ 9350. Other suitable compounds include VORANOL ™ 370, VORANOL ™ 230-660, VORANOL ™ 220-530, VORANOL ™ 230-238, VORANOL ™ 520, VORANOL ™ 391 (Dow), ARCOL ™ E-746, ARCOL ™ LG-650, ARCOL ™ LHT-240 (Arco), PEG ™ 200, PEG ™ 400, PEG ™ 1000, PLURACOL ™ POLYOL 735 and PLURACOL ™ PEP450 (BASF), a POP derivative of pentaerythritol, can also be used herein. Preferred polyoxyalkylene polyols are in the group where the hydroxyl number is less than about 200, and the average number of hydroxyl groups is in the range of 3 to 8.

Several polyatomic aromatic compounds, including resorcinol (1,3-dihydroxybenzene), catechin, hydroquinone, phloroglucinol and pyrogallol, can also be used if necessary.

The crosslinking / extension agent should be from about 0.1 to about 10 pphp and preferably from about 0.2 to about 5 pphp. It is recognized that smaller amounts of crosslinking / extension compounds will provide some advantage, and that larger amounts are also usually effective. Specific ranges are preferred in terms of economic as well as performance problems of foams.

The effectiveness of a particular combination of crosslinker / extender and plasticizer will depend on many factors, including the isocyanate index, the amount of water and other ingredients.

Additives

In addition to polyol, water, isocyanate, a plasticizer, and a crosslinker, catalysts are usually used in flexible PU foam board formulations. Typically, a tertiary amine catalyst for a foaming reaction and a thickening agent such as a polyethylene oxide copolymer or a tin (II) compound for a thickening reaction are included.

Other materials may optionally be added to the polyurethane during production to reduce problems during production or to provide the desired properties of the polyurethane product. Among the additives are catalysts such as amines and metal salts; cellularity regulators or surfactants such as silicones (e.g., SILSTAB 2760 or Dabco® DC5604 (a silicone-glycol copolymer available from Air Products and Chemicals, Inc., Allentown, PA)) to help completely blend the ingredients and for regulating cell growth and cell formation in the foam, including silicon dioxide, in particular in amounts ranging from about 1 part per 100 parts to about 10 parts per 100 parts, in particular from about 1.5 parts per 100 parts to about 5 parts per 100 parts inclusive; fillers, including ground PU, calcium carbonate, barium sulfate and the like; dyes; UV stabilizers; flame retardant additives; bacteriostats; cell opening aids and antistatic additives. It is also desirable to include stabilizers and antioxidants, such as hindered amine light stabilizers and benzotriazoles.

Surfactant / Cell Opener

A surfactant, typically a polyester / polysiloxane copolymer, may optionally be included and act as an emulsifier, nucleating agent and foam stabilizer.

Suitable surfactants (also known as surfactants) for block applications include "hydrolyzable" polysiloxane-polyoxyalkylene block copolymers. Another suitable class of foam surfactants is the “non-hydrolyzable” polysiloxane-polyoxyalkylene block copolymers.

A means for opening cells, such as a monohydric alcohol or polyethylene oxide polyol with an equivalent weight of more than about 200 with an amount of two or more hydroxyl functional groups, can be included. For example, one means for opening cells is an adduct of polyethylene oxide and glycerin with a molecular weight of about 990 g / mol, with an equivalent weight of about 330. The means for opening cells should be from about 0.001 to about 20 pphp.

Catalysts

The catalysts that can be used to produce polyurethane foams based on the natural polyols of the present disclosure can be any suitable catalyst known in the art and suitable for use in the manufacture of polyurethane foams, for example, organometallic polyurethane catalysts used to activate the reaction of an isocyanate source with polyol. The catalyst may be an amine, an organometallic compound, an organic acid, a metal salt, tertiary phosphine, an alkali metal compound, radical forming agents, and a similar catalyst used in the formation of polyurethanes.

Amines that can be used as a catalyst in the present invention include, for example, and, without limitation, trialkylamines, such as triethyleneamine; N, N, N ', N'-tetramethyl-1,3-butanediamine; amino alcohols such as dimethylethanolamine; ester amines such as ethoxylamine, ethoxyldiamine, bis- (diethylethanolamine) adipate, 1,3,5-tris- (3-dimethylaminopropyl) -1,3,5-triazine, bis- (3-dimethylaminopropyl) methylamine and bis (2 dimethylaminoethyl) ether; triethylenediamine; cyclohexylamine derivatives such as N, N-dimethylcyclohexylamine; a morpholine derivative such as N-methylmorpholine; piperazine derivatives such as N, N'-diethyl-2-methylpiperazine, N, N'-bis- (2-hydroxypropyl) -2-methylpiperazine, bis (2,2'-dimethylaminoethyl) ether; amidines such as 1,8-diazabicycloundec-7-ene (DBU), and combinations thereof.

Catalysts suitable for use in the methods and compositions of the present disclosure may also be alkali metal compounds and alkali metal salts, including potassium acetate, potassium octoate and similar alkali metal compounds and alkali metal salts. Similarly, alkali metal salts of organic carboxylic acids (alkali metal carboxylates), metal alkoxides, metal phenolates, metal hydroxides and / or quaternary ammonium salts can be used according to the teachings of this document.

Organometallic metals include, for example, tin, lead, bismuth, cadmium, cobalt, aluminum, potassium, chromium and zinc, and can also be used as catalysts in some aspects of the present disclosure. Among them, common embodiments of organotin compounds are dibutyltin dilaurate and dibutyltin bis (2-ethylhexanoate) and the like. Regarding the various salts of organic acids with metals, they are, for example, salts of the organic acid oleic acid, naphthoic acid, caproic acid, caprylic acid, and many other organic acids with tin, lead, bismuth, cadmium, cobalt, aluminum, potassium, chromium and zinc.

Examples of salts of organic tin acids suitable for use herein are tin oleate, tin 2-ethylcaproate, tin naphthoate, tin octylate and the like. Examples of tertiary phosphines suitable for use as catalysts of the present disclosure include trialkylphosphine, dialkylbenzylphosphine and the like, among others. Examples of alkali metal compounds include alkali metal hydroxides or fatty acid salts.

As a typical radical-forming agent, there are, for example, benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile and the like, which are suitable for use according to this document.

These catalysts can be used alone or in combination with each other, as appropriate. For example, according to selected aspects of the present disclosure, it may be more efficient to use an amine together with an organometallic compound or a metal salt of an organic acid.

Suitable catalysts include, but are not limited to, dialkyl tin and carboxylic acid salts, tin salts and organic acids, triethylenediamine, bis (2,2'-dimethylaminoethyl) ether, bis (2-dimethylaminoethyl) ether and the like, which are well known in the art . A typical suitable blowing agent catalyst suitable for use herein is the Dabco® BL-19 catalyst (bis (2-dimethylaminoethyl) ether available from Air Products and Chemicals, Inc., Allentown, PA).

The catalysts should be in an amount in the range of from about 0.0001 to about 5 weight percent (mass%), inclusive, of the reaction mixture in general, if necessary, and depending on the final density of the product from the foam obtained in the reaction process. Typically, amounts of a foaming catalyst for use in these compositions include from about 1 mass. % to about 4.5 wt. % and from about 2 mass. % to about 4 mass. % inclusive.

Emulsifiers

Emulsifiers may be important to add to natural polyol-containing polyurethanes according to the present disclosure, such as TERGITOL ™ NP-9 and BM-400 emulsifier (BASF, Wyandotte, MI) and the like, as well as emulsifiers such as lecithin, including soya lecithin, in a variety of concentrations ranging from about 0.5% (volume / volume) to about 10% (volume / volume), in order to prevent premature exit of any natural polyol from the solution. Other compositions that may be included in order to prevent premature crystallization of natural polyols, such as sucrose, from solution, include an invert solution (eg, 6-10% invert solution), water-soluble proteins, such as albumin; and natural sugar esters such as sorbitan monooleate and sorbitan monolaurate.

Fillers / Modifiers

Solid stabilizing polymers and other additives, including flame retardants, colorants, tinting agents and antistatic additives that are well known in the art, can be used with the sugar polyurethane foam formulations of the present invention. Typical additives listed in US patent No. 4950694 are illustrative and are incorporated herein by reference.

Other excipients and additives, such as esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, can also be used if necessary or desired. Non-limiting examples include acrylates, such as ethylene glycol diacrylate; triethylene glycol diacrylate; tetramethylene glycol diacrylate; trimethylolpropane triacrylate; trimethylol ethane triacrylate; pentaerythritol diacrylate; pentaerythritol triacrylate; pentaerythritol tetraacrylate; dipentaerythritol tetraacrylate; dipentaerythritol pentaacrylate; dipentaerythritol hexaacrylate; tryptaerythritol octaacrylate; glycerol diacrylate; methacrylates such as triethylene glycol dimethacrylate; tetramethylene glycol dimethacrylate; trimethylolpropane trimethacrylate; trimethylol ethane trimethacrylate; pentaerythritol dimethacrylate; pentaerythritol trimethacrylate; pentaerythritol tetramethacrylate; dipentaerythritol dimethacrylate; dipentaerythritol trimethacrylate; dipentaerythritol tetramethacrylate; tryptaerythritol octamethacrylate; ethylene glycol dimethacrylate; 1,4-butanediol dimethacrylate; sorbitol tetramethacrylate and the like; itaconates, such as ethylene glycol diitaconate; propylene glycol diitaconate; 1,2-butanediol diitaconate; tetramethylene glycol diitaconate; pentaerythritol triiitaconate and the like; crotonates, such as ethylene glycol dicrotonate; diethylene glycol dicrotonate; pentaerythritol tetracrotonate and the like; and maleates, such as ethylene glycol dimaleate; triethylene glycol dimaleate; pentaerythritol dimaleate and the like.

According to selected embodiments of the present disclosure, it may be especially advantageous to add an optional antioxidant, such as a hindered phenolic polymer, i.e. IRGANOX ™ 1010 (Ciba-Geigy), an organic phosphite or both, in a polyurethane foam composition. Such antioxidants can act as a moderator of any discoloration associated with high temperatures in the manufacture of foam products. Stabilizers, such as tetrabutylhexamethylenediamine, can also optionally and successfully be added.

Additional additives that may optionally be included in the compositions of the present invention, especially as part B component, include glycerol or glycerol derivatives and analogs, and glycine or glycine derivatives, such as ethoxylated and propoxylated glycine, alone or in combination with one or more high molecular weight ( more than 1000) polyols such as Pluracol® 593 (BASF, Wyandotte, MI). Initial results showed that the use of glycerol or similar compounds provides increased stability of foam products. When included in the composition, the amount of glycerol or glycerol derivatives ranges from about 1 part per 100 parts to about 20 parts per 100 parts, or alternatively from about 2 parts per 100 parts to about 10 parts per 100 parts inclusive.

Foam properties

The polyurethane foam products described herein are composed of one or more natural polyols, such as sucrose, invert sugar solutions, or other natural polyols, as described above; one or more organic isocyanates; blowing agents, in particular water; one or more plasticizers or flame retardants; one or more surfactants and optionally catalysts and / or emulsifiers, as well as other standard ingredients known to those skilled in the art, included, if necessary, depending on the end use of the polyurethane foam product.

Airflow data provides a numerical measure of the amount of air passing through a piece of foam of standard size at standard pressure and air temperature. This provides a measure of the relative openness or closure of a given piece of foam. Foams with large air currents are more open, and conversely, foams with lower air flow are considered more closed or dense. The airflows of the foams disclosed herein are relatively high and indicate good quality open cell foam. Fire-resistant foams will, by definition, be characterized by lower air flows. The preferred air flow for optimal development of physical properties is in the range of about 57-170 L / min at 12.7 mmHg in accordance with ASTM 283.

The polyurethane foam compositions of the present disclosure can be obtained by those characterized by clearly closed cells, core densities ranging from about 4.8 kg / m ³ to about 80 kg / m ³ inclusive, including about 8 kg / m ³ , about 16 kg / m ³ , about 32 kg / m ³ , about 48 kg / m ³ and about 64 kg / m ³ . Typically, low density insulation is characterized as such a foam insulation that exhibits a range in accordance with AC377 of from about 8 kg / m ³ to about 22 kg / m ³ , as determined using ASTM D-1622.

The polyurethane foams of the present disclosure exhibit a number of other desirable properties, including a “green” index, as determined by a value based on the content of biomaterials, the corresponding outdoor combustion characteristics and the corresponding features of industrial foams, as well as the desired core density, tensile strength, dimensional stability and content values of closed cells. Testing of foam products obtained according to the present disclosure was carried out according to ICC-ES AC377, flame propagation was determined using ASTM E-84 standard, smoke emission was determined using ASTM E-84 standard, and biomaterial content was determined according to ASTM D6866-11 .

The polyurethane foams of the present disclosure are suitable for use in a variety of applications ranging from insulation (such as spray insulation) to spray foam for structural panels, indoor sprays and the like. For instance, a polyurethane foam of low density core densities ranging from 16 kg / ^m3 to 48 kg / m ³ can be used in cooling devices, structural insulation panels (SIP), thermal insulating panels, walk-in coolers, refrigeration devices bodies refrigerated, water heaters, foam for spa, heat-insulating wall panels, evaporators, roofing panels, replacement of sheets of a derivative of polyisocyanuric acid and packaging foam. The polyurethane foam of the present disclosure with a core density in the range of 16 kg / m ³ to 80 kg / m ³ can be used in one-to-one packaging foam sprayed on-site packaging, prefabricated packaging boards or household foam. Polyurethane foam of the present disclosure with a core density in the range from 6.4 kg / m ³ to 80 kg / m ³ can be used in the manufacture of mattresses, mattress covers, packaging, toys, accessories, office chairs, car seats, foam for the passenger compartment, carpet bases, profile foam, indicator foam, pre-made foam, pillows, molded low-density foam. Polyurethane foam of the present disclosure with a core density in the range from 24 kg / m ³ to 48 kg / m ³ can be used in the manufacture of molded seats, molded fittings, artificial wood, picture frames, exterior panels for houses, toys, toilet seats, medical devices and the like. Low density structural foam, such a polyurethane foam of the present disclosure with a core density in the range of 24 kg / m ³ to 48 kg / m ³ , can be used in the manufacture of doors, garage doors, automobile panels, car sound insulation, car interior ceilings, foam for filling blocks and inserts in shoes. Polyurethane products obtained according to the present disclosure can also be used to make things, such as low density adhesives, which are used in the artisan industry for dressing.

The following examples are included to illustrate preferred embodiments of the present invention. It will be appreciated by those skilled in the art that the techniques disclosed in the following examples represent the techniques disclosed by the inventor (s) for good work in practicing the invention, and thus can be considered as containing preferred methods for practicing it. However, in the light of the present disclosure, those skilled in the art will appreciate that many changes can be made to the specific embodiments that are disclosed, and yet obtain a similar or similar result without departing from the scope of the present invention.

Examples

According to a presently preferred general method for producing foams according to the present invention, two separate mixtures are first obtained and then mixed together, usually using industrial standard application equipment, such as foam equipment, which mixes part A and part B in a 1: 1 volume ratio (A: B). It will be understood that equipment for producing foams that mixes part A and part B in higher ratios (by volume) can also be used, such as in the ratios 1.25: 1 (A: B), 1.5: 1 (A : B) or 2.0: 1 (A: B) by volume. The first mixture contains at least isocyanate. The second mixture contains a natural polyol, a plasticizer / flame retardant, catalyst (s) and water as a blowing agent. Syrups or solutions of a natural polyol, such as sucrose solutions, are commercially available, contain various amounts of water, up to about 90% by weight of sucrose, and are in the range of about 45% to about 90%, in part, of the resin. These syrups / solutions can be used with or without additional water. Alternatively and equally, it is conceivable that the dry, natural polyol can be absorbed in a selected amount of water.

The final foaming mixture of the present invention will typically contain from about 5 to 60% polyisocyanate, 0.05-1.0% surfactant, 5-30% water, 30-90% natural polyol (dry or in solution), such as sucrose, 0.5-2.5% catalyst, all based on weight relative to total weight. As indicated above, there may be additional additive components in the composition of the mixture, such as flame retardants, tinting agents, pigments and the like. If present, the percentage of flame retardant additives based on the weight is in the range of about 5 masses. % to about 30% by weight.

The desired amounts of each component in the final mixture can be obtained by mixing the first mixture with the second mixture in a first to second ratio of about 0.75: 1 to 2: 1 by weight, if the mixtures contain the following components in parts by weight based on the total weight of each mixture .

Example 1: Obtaining 16 kg / m ³ polyurethane foam

The first mixture, or part B, is a resin part. Sucrose (89%, 67.5 brix), a natural polyol (provided by Imperial Sugar Co., Sugar Land, Texas) is mixed with approximately 5% by weight of water to form a solution. The surfactant (1.75% Dabco DC5604) is then added to the sucrose mixture with stirring. Catalysts such as BL-19 amine catalysts (bis (2-dimethylaminoethyl) ether; available from Air Products), 3%, and Polycat 31 (4%; low emission amine catalyst designed for open-cell foamed water SPF the low density available from Air Products) is then added with stirring, followed by an emulsifier (NP-9) and a chain crosslinker (DEOA LF (diethanolamine 85% and 15% water); available from Air Products). Optional ingredients such as D-400, a polyethylene oxide copolymer of 1,6-diamines added as a thickening agent can also be added at this point.

The second mixture, or part A, is a part of isocyanate. A mixed mixture of a suitable isocyanate, such as MDI or a modified MDI (methylene diphenyl diisocyanate) with a functionality of about 2.3-3.0 (eg, Lupranate® M-10 or Lupranate® M-20 [polymer MDI with a functionality of approximately 2.7], both available from BASF) (approximately 70 parts) and plasticizer, TCP ([Tris (chlorisopropyl) phosphate] at a concentration of approximately 30 parts to bring to a total of 100% (available from ICL-IP called Fyrol PCF) was mixed together.

The resin composition, or part B, is then reacted with part A in a ratio of 1 to 1 using foam spray equipment operating at temperatures from 38 ° C to over 54 ° C to obtain 16 kg / m ³ sprayable polyurethane foam suitable for use in insulating applications for homes and industry.

Production foam was then tested according to ASTM testing protocols, and it showed ACC 377 test data as shown in Figures 1-4, showing that 16 kg / m ³ spray foam can be set at a nominal thickness of up to 25.4 cm and left unprotected on attics and underground. The product also showed an average dry matter content based on biomaterials, as determined using method B of ASTM-D6866-11, about 25%; average bulk density (as determined using ASTM D-1622-98) 16.3 kg / m ³ ; average tensile strength (as determined using ASTM D1623) 22.95 kPa; flame spread (as determined using ASTM E-84) 15 at a spray thickness of 10.2 cm and smoke emission value (as determined using ASTM E-84) 400 at a spray thickness of 10.2 cm.

Example 2: Obtaining 8 kg / m ³ polyurethane foam

The first mixture, or part B, is a resin part. Sucrose (57 parts, 67.5 brix), a natural polyol (provided by Imperial Sugar), either as a solution or as an invert solution, is mixed with about 5% by weight of water and an initial sucrose solution is obtained. The surfactant (1.75% Dabco® DC5604) is then added to the sucrose mixture with stirring. The TMPP plasticizer / flame retardant (tris (2-chloro-1-methylethyl) phosphate; 27 parts) is then added with stirring. Catalysts such as BL-19 amine catalysts (bis (2-dimethylaminoethyl) ether; available from Air Products), 3%, and Polycat 31 (4%; low emission amine catalyst designed for open-cell foamed water SPF the low density available from Air Products) is then added with stirring, followed by an emulsifier (NP-9, EM-400 or the like) and a chain crosslinker (DEOA LF (diethanolamine 85% and 15% water, about 3%; available from Air Products). Optional ingredients such as D-400, 1,6-diamine polyethylene oxide copolymer added as a medium va thickening, may also be added at this point.

The second mixture, or part A, is a part of isocyanate and is a modified MDI (methylene diphenyl diisocyanate) with a functionality of approximately 2.3 (Lupranate M-10, available from BASF) (70 to 100 parts) in water or a suitable solvent or liquid .

The resin composition, or part B, is then reacted with part A in a ratio of 1 to 1 using foam spraying equipment operating at temperatures from 38 ° C to over 54 ° C to obtain 8 kg / m ³ sprayable polyurethane foam suitable for use in insulating applications for homes and industry.

Example 3: Obtaining a modified 8 kg / m ³ polyurethane foam

Part B resin composition: liquid sucrose from the Imperial Sugar Company (55 parts by weight, 67.5 Brix), 5 parts water, 1.5 parts Dabco® DC5604 surfactant (available from Air Products and Chemicals), 24 parts a suitable plasticizer / flame retardant such as TMSP (tris (2-chloro-1-methylethyl) phosphate), 3 parts BL-19 (bis (2-dimethylaminoethyl) ether available from Air Products) as a foaming catalyst, 0 parts Polycat® 31 from Air Products (low emission amine catalyst designed for low-density SPF open-cell), 0.5 h diethanolamine (DEOA), a low molecular weight catalytic chain extender, 7.5 parts of a 9.5 molar nonylphenol plasticizer and 4 parts of 1,3-propanediol, a low molecular weight chain extender. All the ingredients of Part B were mixed together and prepared in a manner similar to that described in Example 2.

Part A component is a modified MDI (methylene diphenyl diisocyanate) (100 parts), in particular Lupranate® M-10 with a functionality of approximately 2.3 or Lupranate® M-20 with a functionality of approximately 2.7 (both available from BASF).

The composition of part B was brought into contact with part A in a weight ratio of 1 to 1 using foam spraying equipment operating at temperatures from 38 ° C to over 54 ° C, obtaining a density of 8 kg / m ³ , a sprayable polyurethane foam suitable for use in insulating applications for homes and industry, which passed the fire resistance tests and insulation properties accepted as an industry standard. The reduction of the reaction catalyst (removal of Polycat® 31) and the addition of 1,3-propanediol effectively increased the thickening time by approximately 2 seconds and improved the flow characteristics of the polymerizable foam, leading to improved adhesion of the tiles and the adhesion between the layers of the final product compared to example No. 2 above .

Example 4: Obtaining a modified 8 kg / m ³ polyurethane foam from sucrose using a high molecular weight plasticizer and a reduced catalyst load

Part B resin composition: liquid sucrose from the Imperial Sugar Company (55 parts by weight, 67.5 Brix), 5 parts water, 1.5 parts Dabco® DC5604 surfactant (available from Air Products and Chemicals), 24 parts TMPP plasticizer / flame retardant (tris (2-chloro-1-methylethyl) phosphate), 3 parts Dabco® BL-19 (bis (2-dimethylaminoethyl) ether, available from Air Products & Chemicals, Inc., Allentown, PA) as a foaming catalyst, 0 parts Polycat® 31 from Air Products (low emission amine catalyst designed for foamed water with low SPF open cells density), 0.5 parts of diethanolamine (DEOA), a low molecular weight catalytic chain extender, 7.5 parts of a 12 molar nonylphenol plasticizer and 4 parts of 1,3-propanediol, a low molecular weight chain extender. All the ingredients of Part B were mixed together and prepared in a manner similar to that described in Example 2.

Part A component is a modified MDI (methylene diphenyl diisocyanate) (100 parts), in particular Lupranate® M-10 with a functionality of approximately 2.3 or Lupranate® M-20 with a functionality of approximately 2.7 (both available from BASF).

The composition of part B was brought into contact with part A in a weight ratio of 1 to 1 using foam spraying equipment operating at temperatures from 38 ° C to over 54 ° C, obtaining a density of 8 kg / m ³ , a sprayable polyurethane foam suitable for use in insulating applications for homes and industry, which passed the fire resistance tests and insulation properties accepted as an industry standard. Reducing the reaction catalyst (removing Polycat® 31) and adding high molecular weight plasticizer (12 molar nonylphenol) effectively increased the thickening time by approximately 5 seconds and improved the flow and tack properties of the polymerizable foam, resulting in improved adhesion of the tiles and adhesion between the layers of the final product compared to Example 3 above.

Example 5: Obtaining a modified 8 kg / m ³ polyurethane foam from sucrose using an emulsifier / plasticizer

Part B resin composition: liquid sucrose from the Imperial Sugar Company (58.5 parts by weight, 67.5 Brix), 5 parts water, 1.0 part Dabco® DC5604 surfactant (available from Air Products & Chemicals, Inc .), 27.5 parts of a plasticizer / flame retardant TMSP (Tris (2-chloro-1-methylethyl) phosphate), 3.5 parts of Polycat® 31 (low emission amine catalyst designed for open-cell foamed water) Low Density SPF, available from Air Products & Chemicals, Inc., Allentown, PA), 2.5 parts Polycat®-140 and 1.0 part Polycat®-141 foaming catalysts, 1.0 part surface stno active agent Dabco® 5350, 6.0 parts of emulsifier VM-400 (BASF Corp., Wyandotte, Michigan) and 0.5 parts of diethanolamine (DEOA), low molecular weight chain extender catalyst. All the ingredients of Part B were mixed together and prepared in a manner similar to that described in Example 2.

Part A component is a modified MDI (methylene diphenyl diisocyanate) (100 parts), in particular Lupranate® M-10 with a functionality of approximately 2.3 or Lupranate® M-20 with a functionality of approximately 2.7 (both available from BASF).

The composition of part B was brought into contact with part A in a weight ratio of 1 to 1 using foam spraying equipment operating at temperatures from 38 ° C to over 54 ° C, obtaining a density of 8 kg / m ³ , a sprayable polyurethane foam suitable for use in insulating applications for homes and industry, which passed the fire resistance tests and insulation properties accepted as an industry standard. The addition of BASF BM-400 effectively emulsified the resin of Part B to give a more uniform mixture. VM-400 also worked as a plasticizer in the process of foam formation, improving the flow characteristics and adhesiveness of the polymerizable foam, thereby improving the adhesion of the tiles and the adhesion between the layers of the final product compared to example No. 4 above.

Example 6: Obtaining 8 kg / m ³ polyurethane foam from an invert solution of sugar (glucose and fructose)

Part B resin composition: Imperial Sugar Company liquid invert solution (glucose and fructose, 55 parts by weight, 72 Brix), 5 parts of water, 1.5 parts of Dabco® DC5604 surfactant, 25 parts of TMPP plasticizer / flame retardant (tris- (2-chloro-1-methylethyl) phosphate), 3 parts of Dabco® BL-19 (bis (2-dimethylaminoethyl) ether, available from Air Products & Chemicals, Inc., Allentown, PA) as a foaming catalyst, 0.5 parts of diethanolamine (DEOA), a low molecular weight catalytic chain extender, 7.5 parts of 12 molar nonylphenol plasticizer and 2.7 parts of the emulsifier BM-400 from BASF were combined. All the ingredients of Part B were mixed together and prepared in a manner similar to that described in Example 2.

Part A component is a modified MDI (methylene diphenyl diisocyanate) (100 parts), in particular Lupranate® M-10 with a functionality of approximately 2.3 or Lupranate® M-20 with a functionality of approximately 2.7 (both available from BASF).

The composition of part B was brought into contact with part A in a weight ratio of 1 to 1 using foam spraying equipment operating at temperatures from 38 ° C to over 54 ° C, obtaining a density of 8 kg / m ³ , a sprayable polyurethane foam suitable for use in insulating applications for homes and industry, which passed the fire resistance tests and insulation properties accepted as an industry standard.

Example 7: Obtaining 8 kg / m ³ polyurethane foam from molasses of sugarcane

Part B resin composition: Reed molasses from Imperial Sugar Company (55 parts by weight, 82 Brix), 5 parts water, 1.3 parts Dabco® DC5604 surfactant, 25 parts TMP plasticizer / flame retardant (Tris- (2 -chloro-1-methylethyl) phosphate), 3 parts of Dabco® BL-19 (bis (2-dimethylaminoethyl) ether, available from Air Products & Chemicals, Inc., Allentown, PA) as a foaming catalyst, 0.5 parts of diethanolamine (DEOA), a low molecular weight catalytic chain extender, 7.5 parts 12 molar nonylphenol plasticizer and 2.7 parts emulsifier BM-400 o BASF pooled. All the ingredients of Part B were mixed together and prepared in a manner similar to that described in Example 2.

Part A component is a modified MDI (methylene diphenyl diisocyanate) (100 parts), in particular Lupranate® M-10 with a functionality of approximately 2.3 or Lupranate® M-20 with a functionality of approximately 2.7 (both available from BASF).

The composition of part B was brought into contact with part A in a weight ratio of 1 to 1 using foam spraying equipment operating at temperatures from 38 ° C to over 54 ° C, obtaining a density of 8 kg / m ³ , a sprayable polyurethane foam suitable for use in insulating applications for homes and industry, which passed the fire resistance tests and insulation properties accepted as an industry standard.

Example 8: Obtaining 8 kg / m ³ polyurethane foam from corn syrup

Part B resin composition: corn syrup from Archer Daniels Midland Corporation (ADM) (55 parts by weight, 75 Brix), 5 parts water, 1.3 parts Dabco® DC5604 surfactant, 25 parts plasticizer / flame retardant TMP ( tris- (2-chloro-1-methylethyl) phosphate), 3 parts Dabco® BL-19 (bis (2-dimethylaminoethyl) ether, available from Air Products & Chemicals, Inc., Allentown, PA) as a foaming catalyst, 0 , 5 parts of diethanolamine (DEOA), a low molecular weight catalytic chain extender, 7.5 parts of 12 molar nonylphenol plasticizer and 2.7 parts of emulsifier and a VM-400 from BASF combined so that the total number of ingredients added to 100 parts by weight. All the ingredients of Part B were mixed together and prepared in a manner similar to that described in Example 2.

Part A component is a modified MDI (methylene diphenyl diisocyanate) (100 parts), in particular Lupranate® M-10 with a functionality of approximately 2.3 or Lupranate® M-20 with a functionality of approximately 2.7 (both available from BASF).

The composition of part B was brought into contact with part A in a weight ratio of 1 to 1 using foam spraying equipment operating at temperatures from 38 ° C to over 54 ° C, obtaining a density of 8 kg / m ³ , a sprayable polyurethane foam suitable for use in insulating applications for homes and industry, which passed the fire resistance tests and insulation properties accepted as an industry standard.

Other and further embodiments in which one or more of the aspects of the present invention described above are used can be changed without departing from the inventors ’inventive concept. For example, polyurethane foams may also contain the addition of dyes or tinting agents, to distinguish between companies during use, if necessary, provided that dyes or tinting agents do not inhibit the formation of foam. Also, various methods and embodiments of the manufacturing process can be included in conjunction with each other to obtain options for the disclosed methods and embodiments. Examining singular elements may include plural elements and vice versa.

The order of the stages may occur in different sequences, unless otherwise specifically limited. The various steps described herein can be combined with other steps, combined with said steps, and / or divided into several steps. Similarly, the elements have been described functionally and can be implemented as separate components or can be combined in components with many functions.

The inventions have been described in the context of preferred and other embodiments, and not all embodiments of the present invention have been described. Obvious modifications and changes to the described embodiments are available to those skilled in the art. The disclosed and undisclosed embodiments are not intended to limit or reduce the scope or applicability of the invention conceived by the applicants, but rather, in accordance with patent law, applicants intend to fully protect all such modifications and improvements that fall within the scope or series of equivalents of the following claims.

Claims (44)

1. Fire-resistant polyurethane foam containing a reaction product: a first reaction mixture consisting of a polyisocyanate and optionally a surfactant, and a second reaction mixture consisting of: a natural polyol in which essentially all hydroxyl groups on the polyol are free; surfactant; aqueous blowing agent and polyurethane formation catalyst; flame retardant additives; and optionally any or any combination of plasticizer, emulsifier, bacteriostat, polyether polyol, halogen-free blowing agent, filler, colorant or tinting agent, glycerin, chain extender / crosslinker, antioxidant, antistatic agent and / or cell opener; moreover, the first reaction mixture and the second reaction mixture are used in such quantities as to obtain an isocyanate index of from 20 to 50. 2. Fire-resistant polyurethane foam according to claim 1, characterized in that the natural polyol is selected from the group consisting of sucrose, fructose, glucose, xylose, corn syrup, dextrose and molasses. 3. Fire-resistant polyurethane foam according to claim 1, characterized in that the second reaction mixture further comprises a plasticizer. 4. Fire-resistant polyurethane foam according to claim 1, characterized in that the flame-retardant additive is a phosphate compound. 5. Fire-resistant polyurethane foam according to claim 1, characterized in that the second reaction mixture further comprises an emulsifier. 6. Fire-resistant polyurethane foam according to claim 1, characterized by a density in the range from about 8 kg / m ³ to about 80 kg / m ³ and showing a percentage of the content of modern carbon (rMS) in the range from about 10% to about 50%, determined according to ASTM-D6866-11. 7. Fire-resistant polyurethane foam according to claim 1, characterized in that the second reaction mixture essentially does not contain hydrocarbons. 8. A method of obtaining a flame retardant polyurethane foam, including: a) mixing a natural polyol in which essentially all hydroxyl groups are free, of a surfactant, a polyurethane formation catalyst, a flame retardant, and water to form a first aqueous solution, optionally the first aqueous solution further comprises any or any combination of plasticizer, emulsifier, bacteriostat , polyether polyol, halogen-free blowing agent, filler, colorant or tint, glycerin, chain extender / crosslinker conductive agents, antioxidant, antistatic agent and / or a means of opening cells; b) contacting the first aqueous solution with a second solution consisting of a polyisocyanate and optionally a surfactant; and c) providing foaming of the mixture; moreover, the first aqueous solution and the second solution are used in such quantities as to provide an isocyanate index of from 20 to 50. 9. The method according to p. 8, characterized in that the halogen-free blowing agent is added to the first aqueous solution. 10. The method of claim 8, further comprising adding an emulsifier to the first aqueous solution. 11. The fire-resistant polyurethane foam according to claim 1, meeting or exceeding the conditions established in accordance with the specification ICC-ES AC377. 12. Fire-resistant polyurethane foam according to claim 1, having a density in the range from about 8 kg / m ³ to about 16 kg / m ³ . 13. Fire-resistant polyurethane foam according to claim 1, having a density of about 8 kg / m ³ . 14. Fire-resistant polyurethane foam according to claim 1, characterized in that the second reaction mixture contains from about 5 mass. % to about 30 mass. % flame retardant additives, calculated on the weight of the flame retardant polyurethane foam. 15. Fire-resistant polyurethane foam according to claim 1, characterized in that the flame-retardant additive is selected from tris- (2-chloro-1-methylethyl) phosphate (TMP), tris (alpha-chloroethyl) phosphate (TCEP), tris- (2 , 3-dichloro-1-propyl) phosphate and tetrakis- (2-chloroethyl) dichloroisopentyl diphosphate (YOKE-V6). 16. Fire-resistant polyurethane foam according to claim 1, characterized in that the second reaction mixture contains from 20 mass. % to about 70 mass. % natural polyol. 17. Fire-resistant polyurethane foam according to claim 1, characterized in that the ratio of the first reaction mixture to the second reaction mixture is from about 0.75: 1 to 2: 1 by weight. 18. Fire-resistant polyurethane foam according to claim 1, characterized in that the second reaction mixture further comprises glycerin or a glycerol-based stabilizer. 19. Fire-resistant polyurethane foam according to claim 1, characterized in that the catalyst for the formation of polyurethane is present in the combined first reaction mixture and the second reaction mixture in an amount of from about 0.0001 mass. % to about 5 mass. % 20. Fire-resistant polyurethane foam according to claim 3, characterized in that the plasticizer is selected from the group consisting of phthalate plasticizers, phosphate or phosphorus-containing plasticizers and benzoate plasticizers. 21. Fire-resistant polyurethane foam according to claim 1, having a density of 4.8 kg / m ³ to 80 kg / m ³ . 22. The method according to p. 8, characterized in that the natural polyol is selected from the group consisting of sucrose, fructose, glucose, xylose, corn syrup, dextrose and molasses. 23. The method according to p. 8, characterized in that the obtained flame retardant polyurethane foam meets or exceeds the conditions established according to the specification ICC-ES AC377. 24. The method according to p. 8, characterized in that the foam has a density in the range from about 8 kg / m ³ to about 16 kg / m ³ . 25. The method according to p. 8, characterized in that the foam has a density in the range from about 8 kg / m ³ to about 80 kg / m ³ and shows a percentage of modern carbon (rMS) in the range from about 10% to about 50 % determined according to ASTM-D6866-11. 26. The method according to p. 8, characterized in that the first aqueous solution contains from about 5 mass. % to about 30 mass. % flame retardant additives, calculated on the weight of the flame retardant polyurethane foam. 27. The method according to p. 8, characterized in that the flame retardant is selected from tris- (2-chloro-1-methylethyl) phosphate (TMPP), tris- (alpha-chloroethyl) phosphate (TCEP), tris- (2,3 -dichloro-1-propyl) phosphate and tetrakis- (2-chloroethyl) dichloroisopentyl diphosphate (YOKE-V6). 28. The method according to p. 8, characterized in that the first aqueous solution contains from 20 mass. % to about 70 mass. % natural polyol. 29. The method according to p. 8, characterized in that the ratio of the first aqueous solution to the second solution is from about 0.75: 1 to 2: 1 by weight. 30. The method according to p. 8, characterized in that the polyurethane formation catalyst is present in the combined first aqueous solution and the second solution in an amount of from about 0.0001 mass. % to about 5 mass. % 31. The method according to p. 8, characterized in that the foam has a density of from 4.8 kg / m ³ to 80 kg / m ³ .

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