Patent Application
20110124759
This invention pertains to polyols that are useful for manufacturing rigid polyurethane foams, as well as rigid foams made from those polyols.
Rigid polyurethane foams have been used widely for several decades as insulation foam in appliances and other applications, as well as a variety of other uses. These foams are prepared in a reaction of a polyisocyanate and one or more polyol, polyamine or aminoalcohol compounds. The polyol, polyamine or aminoalcohol compounds can be characterized as having equivalent weights per isocyanate-reactive group up to about 300 and an average of more than three isocyanate-reactive groups per molecule. The reaction is conducted in the presence of a blowing agent which generates a gas as the reaction proceeds. The gas expands the reacting mixture and imparts a cellular structure.
Originally, the blowing agent of choice was a “hard” chlorofluorocarbon (CFC) such as trichlorofluoromethane or dichlorodifluoromethane. These CFCs processed very easily and produced foam having very good thermal insulation properties. However, the CFC blowing agents have been phased out because of environmental concerns.
CFCs have been replaced with other blowing agents such as hydrofluorocarbons, low-boiling hydrocarbons, hydrochlorofluorocarbons, ether compounds, and water (which reacts with isocyanates to generate carbon dioxide). For the most part, these alternative blowing agents are less effective thermal insulators than their CFC predecessors. The ability of a foam to provide thermal insulation is often expressed in terms of “k-factor”, which is a measure of the amount of heat that is transferred through the foam per unit area per unit time, taking into account the thickness of the foam and the applied temperature difference across the foam thickness. Foams produced using alternative blowing agents tend to have higher k-factors than those produced using “hard” CFC blowing agents. This has forced rigid foam producers to modify their foam formulations in other ways to compensate for the loss of thermal insulation values that result from the changes in blowing agent. Many of these modifications focus on reducing cell size in the foam. Smaller-sized cells tend to provide better thermal insulation properties.
It has been found that modifications to a rigid foam formulation which improve k-factor tend to affect the processing characteristics of the formulation in an undesirable way. The curing characteristics of the formulation are important, especially in pour-in-place application such as appliance foam. Refrigerator and freezer cabinets, for example, are usually insulated by partially assembling an exterior shell and interior liner, and holding them in position such that a cavity is formed between them. This is often done using a jig or other apparatus. The foam formulation is introduced into the cavity, where it expands to fill the cavity. The foam provides thermal insulation and imparts structural strength to the assembly. The way the foam formulation cures is important in at least two respects. First, the foam formulation must cure quickly to form a dimensionally stable foam, so that the finished cabinet can be removed from the jig. This characteristic is generally referred to as “demold” time, and directly affects the rate at which cabinets can be produced.
In addition, the curing characteristics of the system affect a property known as “flow index” or simply “flow”. A foam formulation will expand to a certain density (known as the Tree rise density') if permitted to expand against minimal constraints. When the formulation must fill a refrigerator or freezer cabinet, its expansion is somewhat constrained in several ways. The foam must expand mainly in a vertical (rather than horizontal) direction within a narrow cavity. As a result, the formulation must expand against a significant amount of its own weight. The foam formulation also must flow around corners and into all portions of the wall cavities. In addition, the cavity often has limited or no venting, and so the atmosphere in the cavity exerts additional pressure on the expanding foam. Because of these constraints, a greater amount of the foam formulation is needed to fill the cavity than would be predicted from the free rise density alone. The amount of foam formulation needed to minimally fill the cavity can be expressed as a minimum fill density (the weight of the formulation divided by the cavity volume). The ratio of the minimum fill density to the free rise density is the flow index. The flow index is ideally 1.0, but is on the order of 1.5 in commercially practical formulations. Lower flow index is preferred, all other things being equal, because raw materials costs are lower when a smaller weight of foam is needed.
Modifications to foam formulations that favor low k-factor tend to have an adverse effect on demold time, flow index or both. Therefore, although formulations have been developed which closely match conventional CFC-based formulations in k-factor, the overall cost of using these formulations is often higher due to lower productivity (because of greater demold times), higher raw materials costs (because of higher flow index) or both.
What is desired is a rigid foam formulation that provides a low k-factor foam with a low flow index and a fast cure rate.
The invention is a process for preparing a rigid polyurethane foam, comprising
A) forming a reactive mixture containing at least
1) a polyol mixture containing
a) at least 3% by weight, based on the weight of the polyol mixture, of an ortho-cyclohexanediamine-initiated polyol having an average functionality of greater than 3.0 up to 4.0 and a hydroxyl equivalent weight of from 75 to 560, the ortho-cyclohexanediamine-initiated polyol being produced by reacting at least one C2-C4 alkylene oxide with an ortho-cyclohexanediamine initiator compound or by reacting at least one C2-C4 alkylene oxide with an ortho-phenylenediamine followed by hydrogenation of the aromatic ring of the phenylenediamine group,
2) at least one hydrocarbon, hydrofluorocarbon, hydrochlorofluorocarbon, fluorocarbon, dialkyl ether or fluorine-substituted dialkyl ether physical blowing agent;
3) from 0.5 to 1.9% by weight of one or more tertiary amine catalysts, based on the weight of the polyol mixture; and
4) at least one polyisocyanate; and
b) subjecting the reactive mixture to conditions such that the reactive mixture expands and cures to form a rigid polyurethane foam.
In certain embodiments, the polyol mixture further contains
1b) at least one aromatic amine-initiated polyether polyol having a hydroxyl equivalent weight of from 75 to 560, wherein the weight ratio of component 1a) to 1b) is from 99:1 to 10:90 and components 1a) and 1b) together constitute from 4 to 50% by weight of the polyol mixture.
In other embodiments, the polyol mixture contains from 30 to 70% by weight, based on the weight of the polyol mixture, of a non-amine-initiated polyether polyol having an average hydroxyl functionality of from 4.2 to 7 and a hydroxyl equivalent weight of from 100 to 175.
In still other embodiments, the polyol mixture contains
a) at least 3% by weight, based on the weight of the polyol mixture, of an ortho-cyclohexanediamine-initiated polyol having an average functionality of greater than 3.0 up to 4.0 and a hydroxyl equivalent weight of from 75 to 560, the ortho-cyclohexanediamine-initiated polyol being produced by reacting at least one C2-C4 alkylene oxide with an ortho-cyclohexanediamine initiator compound or by reacting at least one C2-C4 alkylene oxide with an ortho-phenylenediamine followed by hydrogenation of the aromatic ring of the phenylenediamine group and
b) at least one aromatic amine-initiated polyether polyol having a hydroxyl equivalent weight of from 75 to 560, wherein the weight ratio of component 1a) to 1b) is from 99:1 to 10:90 and components 1a) and 1b) together constitute from 4 to 50% by weight of the polyol mixture; and
c) from 30 to 70% by weight, based on the weight of the polyol mixture, of a non-amine-initiated polyether polyol having an average hydroxyl functionality of from 4.2 to 7 and a hydroxyl equivalent weight of from 100 to 175.
In another aspect, the invention is a rigid foam made in accordance with any of the foregoing processes.
It has been found that rigid foam formulations that include the aforementioned polyol mixtures often exhibit desirable curing characteristics (as indicated by flow index of below 1.8 and short demold times), and cure to form a foam having excellent thermal insulation properties (i.e., low k-factor).
The ortho-cyclohexanediamine-initiated polyol is a polyether that can be represented by the structure I:
wherein each R is independently hydrogen or C1-C4 alkyl. Each A is independently hydrogen or (CxHyO)zH where x is from 2 to 4, y is equal to 2x, and z is from 1 to 5, provided that at least 2 of the A groups are (CxHyO)zH groups. At least 3 of the A groups can be (CxHyO)zH groups, and all four A groups can be (CxHyO)zH groups.
The ortho-cyclohexanediamine-initiated polyol can be prepared from an ortho-cyclohexanediamine initiator compound, the term “ortho” indicating that the amino groups are bonded to adjacent carbon atoms on the cyclohexane ring. This initiator compound can be represented by the structure II:
wherein each R is independently hydrogen or C1-C4 alkyl. Each R is preferably hydrogen or methyl. Each R is most preferably hydrogen, such that the initiator compound is 1,2-diaminocyclohexane. Mixtures of two or initiator compounds corresponding to the foregoing structure can be used.
Initiators of the foregoing structure exist in two or more diastereoisomeric forms, as the amino groups may be in the cis-configuration (wherein they reside on the same side of the ring, as illustrated in structure III) or trans-configuration (wherein they reside on the opposite side of the ring, as illustrated in structure IV). In addition, other diastereoisomeric structures are possible when the R groups are not all the same. In such cases, any of the diastereoisomeric forms, or mixtures of any two or more of the diastereoisomeric forms, can be used. Structures III and IV are:
R has the same meaning in structures III and IV as it does with respect to structures I and II above.
Commercially available ortho-cyclohexanediamine compounds tend to contain small amounts (typically less than 3% by weight) of impurities, which tend to be mainly other amine or diamine compounds. These commercially materials are suitable as initiators in the present invention.
The initiator compound is caused to react with at least one C2-C4 alkylene oxide to produce the ortho-cyclohexanediamine-initiated polyol. The alkylene oxide may be ethylene oxide, propylene oxide, 1,2- or 2,3-butylene oxide, tetramethylene oxide or a combination of two or more thereof. If two or more alkylene oxides are used, they may be added to the initiator compound simultaneously (to form a random copolymer) or sequentially (to form a block copolymer). Butylene oxide and tetramethylene oxide are generally less preferred. Ethylene oxide, propylene oxide and mixtures thereof are more preferred. Mixtures of ethylene oxide and propylene oxide may contain the oxides in any proportion. For example, a mixture of ethylene oxide and propylene oxide may contain from 10 to 90 mole percent of ethylene oxide, preferably from 30 to 70 mole percent ethylene oxide or from 40 to 60 mole percent ethylene oxide.
Enough of the alkylene oxide(s) are added to the initiator to produce a polyol having an average functionality of greater than 3.0, up to as many as 4.0 hydroxyl groups/molecule. A preferred average functionality for the polyol is from 3.3 to 4.0, and a more preferred average functionality is from 3.7 to 4.0. The ortho-cyclohexanediamine-initiated suitably has a hydroxyl equivalent weight of from 75 to 560. A preferred hydroxyl equivalent weight is from 90 to 175 and a more preferred hydroxyl equivalent weight for rigid foam production is from 100 to 130.
The alkoxylation reaction is conveniently performed by forming a mixture of the alkylene oxide(s) and the initiator compound, and subjecting the mixture to conditions of elevated temperature and superatmospheric pressure. Polymerization temperatures may be, for example, from 110 to 170° C., and pressures may be, for example, from 2 to 10 bar (200 to 1000 kPa). A catalyst may be used, particularly if more than one mole of alkylene oxide(s) is to be added per equivalent of amine hydrogen on the initiator compound. Suitable alkoxylation catalysts include strong bases such as alkali metal hydroxides (sodium hydroxide, potassium hydroxide, cesium hydroxide, for example), as well as the so-called double metal cyanide catalysts (of which zinc hexacyanocobaltate complexes are most notable). The reaction can be performed in two or more stages, in which no catalyst is used in the first stage, and from 0.5 to 1.0 mole of alkylene oxide is added to the initiator per equivalent of amine hydrogens, followed by one or more subsequent stages in which additional alkylene oxide is added in the presence of a catalyst as described. After the reaction is completed, the catalyst may be deactivated and/or removed. Alkali metal hydroxide catalysts may be removed, left in the product, or neutralized with an acid and the residues left in the product. Residues of double metal cyanide catalysts may be left in the product, but can be removed instead if desired.
Alternatively, the ortho-cyclohexanediamine-initiated polyol can be formed by alkoxylating an ortho-phenylene diamine having the structure
wherein R is as defined before, followed by hydrogenation of the aromatic ring.
Preferred ortho-cyclohexanediamine-initiated polyols are (a) the reaction product of 1,2-diaminocyclohexane with ethylene oxide, (b) the reaction product of 1,2-diaminocyclohexane with propylene oxide and (c) the reaction product of 1,2-diaminocyclohexane with a mixture of from 30 to 70 mole percent ethylene oxide and 70 to 30 mole percent propylene oxide, in each case having a functionality of from 3.3 to 4.0, especially 3.7 to 4.0 and a hydroxyl equivalent weight of from 90 to 175, especially from 100 to 130. In each of the foregoing cases, the 1,2-diaminocyclohexane is most preferably a mixture of the cis- and trans-diastereoisomers having from 25 to 75% of the cis- and 75 to 25% of the trans-diastereoisomer.
Rigid polyurethane foam is prepared from a polyurethane-forming composition that contains at least (1) a polyol mixture that contains the ortho-cyclohexanediamine-initiated polyol, (2) at least one organic polyisocyanate, and (3) at least one physical blowing agent as described more fully below.
The ortho-cyclohexanediamine-initiated polyol is present as part of a polyol mixture. The ortho-cyclohexanediamine-initiated polyol suitably constitutes at least 3 weight percent of all polyols present in the polyol mixture. Below this level, the benefits of using the polyol are slight. In most cases, the ortho-cyclohexanediamine-initiated polyol will constitute from about 3 to about 50% by weight of the polyol mixture. For example, the ortho-cyclohexanediamine-initiated polyol may constitute from 5 to about 40% by weight of the polyol mixture.
In some embodiments of the invention, the polyol mixture includes a) at least 3% by weight, based on the weight of the polyol mixture, of the ortho-cyclohexanediamine-initiated polyol and b) at least one aromatic amine-initiated polyether polyol having a hydroxyl equivalent weight of from 75 to 560, wherein the weight ratio of component a) to b) is from 99:1 to 10:90 and components a) and b) together constitute from 4 to 50% by weight of the polyol mixture. The aromatic amine-initiated polyether polyol may be initiated with one or more isomers of toluene diamine, one or more isomers of phenylene diamine, 2,2′-, 2,4′- and/or 2,6′-diaminodiphenylmethane, diethyltoluenediamine, and the like. 2,6- and/or 2,4-toluene diamine and ortho-phenylenediamine are preferred among these.
The polyol mixture may contain polyols in addition to those already described. Among these are polyether polyols, which are conveniently made by polymerizing an alkylene oxide onto an initiator compound (or mixture of initiator compounds) that has multiple active hydrogen atoms. The initiator compound(s) may include alkylene glycols (e.g., ethylene glycol, propylene glycol, 1,4-butane diol, 1,6-hexanediol and the like), glycol ethers (such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like), glycerine, trimethylolpropane, pentaerythritol, sorbitol, sucrose, glucose, fructose or other sugars, and the like. A portion of the initiator compound may be one containing primary and/or secondary aliphatic amino groups, such as ethylene diamine, hexamethylene diamine, diethanolamine, monoethanolamine, N-methyldiethanolamine, piperazine, aminoethylpiperazine, diisopropanolamine, monoisopropanolamine, methanolamine, dimethanolamine, and the like. Aliphatic amine-initiated polyols of these types tend to be somewhat autocatalytic. The alkylene oxide used to make the additional polyol(s) is as described before with respect to the ortho-cyclohexanediamine-initiated polyol. The alkylene oxide of choice is propylene oxide, or a mixture of propylene oxide and ethylene oxide.
A polyol mixture of particular interest includes a non-amine-initiated polyol that has an average functionality of from 4.5 to 7 hydroxyl groups per molecule and a hydroxyl equivalent weight of 100 to 175. The other polyether polyol may be, for example, a sorbitol-, sorbitol/water or sucrose/glycerine-initiated polyether. Examples of suitable sorbitol-, sorbitol/water or sucrose/glycerine-initiated polyethers that can be used include Voranol® 360, Voranol® RN411, Voranol® RN490, Voranol® 370, Voranol® 446, Voranol® 520, Voranol® 550 and Voranol® 482 polyols, all available from Dow Chemical.
Other polyols that can be present in the polyol mixture includes one or more renewable-resource polyols having from 2 to 6 hydroxyl groups per molecule and a hydroxyl equivalent weight of from 75 to 1000. The renewable-resource polyol in those embodiments constitutes at least 1% by weight of the polyol mixture, and preferably constitutes from 1 to 15% weight percent thereof. A “renewable-resource polyol”, for purposes of this invention, is a polyol that is, or is produced from, a renewable biological resource, such as an animal fat, a vegetable fat, a lignocellulosic material or a carbohydrate such as starch. At least 50% of the mass of the renewable-resource polyol should come from the renewable biological resource. Various types of renewable-resource polyols are useful, including those described in Ionescu, Chemistry and Technology of Polyols for Polyurethanes, Rapra Publishers 2005. These include
1. Castor oil;
2. A hydroxymethyl group-containing polyol as described in WO 2004/096882 and WO 2004/096883. Such polyols are prepared by reacting a hydroxymethyl group-containing fatty acid having from 12-26 carbon atoms, or an ester of such a hydroxymethyl group containing fatty acid, with a polyol or polyamine initiator compound having an average of at least 2 hydroxyl, primary amine and/or secondary amine groups, such that the hydroxymethyl-containing polyester polyol contains an average of at least 1.3 repeating units derived from the hydroxmethyl-group-containing fatty acid or ester per total number of hydroxyl, primary amine and secondary amine groups on the initiator compound, and the hydroxymethyl-containing polyester polyol has an equivalent weight of at least 400 up to 15,000. Preferred such polyols have the following average structure:
[H—X](n-p)—R—[X—Z]p (I)
wherein R is the residue of an initiator compound having n hydroxyl and/or primary or secondary amine groups, where n is at least two; each X is independently —O—, —NH— or —NR′— in which R′ is an inertly substituted alkyl, aryl, cycloalkyl, or aralkyl group, p is a number from 1 to n representing the average number of [X—Z] groups per hydroxymethyl-containing polyester polyol molecule, Z is a linear or branched chain containing one or more A groups, provided that the average number of A groups per molecule is 1.3 times n, and each A is independently selected from the group consisting of A1, A2, A3, A4 and A5, provided that at least some A groups are A1, A2 or A3, wherein A1 is:
wherein B is H or a covalent bond to a carbonyl carbon atom of another group; m is number greater than 3, n is greater than or equal to zero and m+n is from 11 to 19; A2 is:
wherein B is as before, v is a number greater than 3, r and s are each numbers greater than or equal to zero with v+r+s being from 10 to 18, A3 is:
wherein B, v, each r and s are as defined before, t is a number greater than or equal to zero, and the sum of v, r, s and t is from 10 to 18; A4 is
where w is from 10-24, and A5 is
where R′ is a linear or branched alkyl group that is substituted with at least one cyclic ether group and optionally one or more hydroxyl groups or other ether groups.
3. An amide group-containing polyol as described in WO 2007/019063. Among these are amide compounds having hydroxymethyl groups, which are conveniently described as an amide of (1) a primary or secondary amine compound that contains at least one hydroxyl group with (2) a fatty acid that contains at least one hydroxymethyl group. This type of amide has at least one hydroxyl-substituted organic group bonded to the amide nitrogen. A C7-23 hydrocarbon group is bonded to the carbonyl carbon of the amide group. The C7-23 hydrocarbon group is itself substituted with at least one hydroxymethyl group. Other amide group-containing polyols are conveniently described as an amide of a fatty acid (or ester) and a hydroxyl-containing primary or secondary amine, in which the fatty acid group has been modified to introduce one or more (N-hydroxyalkyl)aminoalkyl groups.
4. A hydroxyl ester-substituted fatty acid ester as described in WO 2007/019051. The materials contain at least two different types of ester groups. One type of ester group corresponds to the reaction product of the carboxylic acid group of a fatty acid with a compound having two or more hydroxyl groups. The second type of ester group is pendant from the fatty acid chain, being bonded to the fatty acid chain through the —O— atom of the ester group. The pendant ester group is conveniently formed by epoxidizing the fatty acid (at the site of carbon-carbon unsaturation in the fatty acid chain), followed by reaction with a hydroxy acid or hydroxy acid precursor. The pendant ester group includes at least one free hydroxyl group. These materials can be represented by the structure
[HO](p-x)—R—[O—C(O)—R1]x
wherein R represents the residue, after removal of hydroxyl groups, of a compound having p hydroxyl groups, R1 represents the hydrocarbon portion of a fatty acid, and x is a number from 1 to p. p is 2 or more, as discussed before. Each —R—O—C(O)— linkage represents an ester group of the first type discussed above. At least a portion of the R1 chains are substituted with at least one hydroxyl-containing ester group, which can be represented as
—O—C(O)—R2—OHy
wherein R2 is a hydrocarbyl group that may be inertly substituted, and y is 1 or more, preferably 1 or 2. The bond shown at the left of the structure attaches to a carbon atom of the fatty acid chain. Inert substituents in this context are those which do not interfere with the formation of the material or its use in making a polyurethane.
5. A “blown” soybean oil as described in US Published Patent Applications 2002/0121328, 2002/0119321 and 2002/0090488.
6. An oligomerized vegetable oil or animal fat as described in WO 06/116456. The oil or fat is oligomerized by epoxidizing some or all of the carbon-carbon double bonds in the starting material, and then conducting a ring-opening reaction under conditions which promote oligomerization. Some residual epoxide groups often remain in this materials. A material of this type having a hydroxyl functionality of about 4.4 and a molecular weight of about 1100 is available from Cargill Inc. under the trade name BiOH.
7. Hydroxyl-containing cellulose-lignin materials.
8. Hydroxyl-containing modified starches.
In still other embodiments, the polyol mixture contains at least one polyester polyol. The polyester polyol may have from 2 to 4 hydroxyl groups per molecule and a hydroxyl equivalent weight of from 75 to 560. The polyester polyols include reaction products of polyols, preferably diols, with polycarboxylic acids or their anhydrides, preferably dicarboxylic acids or dicarboxylic acid anhydrides. The polycarboxylic acids or anhydrides may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and may be substituted, such as with halogen atoms. The polycarboxylic acids may be unsaturated. Examples of these polycarboxylic acids include succinic acid, adipic acid, terephthalic acid, isophthalic acid, trimellitic anhydride, phthalic anhydride, maleic acid, maleic acid anhydride and fumaric acid. The polyols used in making the polyester polyols include ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4- and 2,3-butane diol, 1,6-hexane diol, 1,8-octane diol, neopentyl glycol, cyclohexane dimethanol, 2-methyl-1,3-propane diol, glycerine, trimethylol propane, 1,2,6-hexane triol, 1,2,4-butane triol, trimethylol ethane, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, dibutylene glycol and the like.
Some especially preferred polyol mixtures contain:
a) at least 3% by weight, based on the weight of the polyol mixture, of an ortho-cyclohexanediamine-initiated polyol having an average functionality of greater than 3.0 up to 4.0 and a hydroxyl equivalent weight of from 75 to 560, the ortho-cyclohexanediamine-initiated polyol being a reaction product of at least one C2-C4 alkylene oxide with an ortho-cyclohexanediamine initiator compound and
b) at least one aromatic amine-initiated polyether polyol having a hydroxyl equivalent weight of from 75 to 560, wherein the weight ratio of component 1a) to 1b) is from 99:1 to 10:90 and components 1a) and 1b) together constitute from 4 to 50% by weight of the polyol mixture.
Other especially preferred polyol mixtures contain:
a) at least 3% by weight, based on the weight of the polyol mixture, of an ortho-cyclohexanediamine-initiated polyol having an average functionality of greater than 3.0 up to 4.0 and a hydroxyl equivalent weight of from 75 to 560, the ortho-cyclohexanediamine-initiated polyol being a reaction product of at least one C2-C4 alkylene oxide with an ortho-cyclohexanediamine initiator compound and
c) from 30 to 70% by weight, based on the weight of the polyol mixture, of a non-amine-initiated polyether polyol having an average hydroxyl functionality of from 4.2 to 7 and a hydroxyl equivalent weight of from 100 to 175.
Still other especially preferred polyol mixtures contain a) at least 3% by weight, based on the weight of the polyol mixture, of an ortho-cyclohexanediamine-initiated polyol having an average functionality of greater than 3.0 up to 4.0 and a hydroxyl equivalent weight of from 75 to 560, the ortho-cyclohexanediamine-initiated polyol being a reaction product of at least one C2-C4 alkylene oxide with an ortho-cyclohexanediamine initiator compound,
b) at least one aromatic amine-initiated polyether polyol having a hydroxyl equivalent weight of from 75 to 560, wherein the weight ratio of component 1a) to 1b) is from 99:1 to 10:90 and components 1a) and 1b) together constitute from 4 to 50% by weight of the polyol mixture and
c) from 30 to 70% by weight, based on the weight of the polyol mixture, of a non-amine-initiated polyether polyol having an average hydroxyl functionality of from 4.2 to 7 and a hydroxyl equivalent weight of from 100 to 175.
The polyol mixture preferably has an average of 3.5 to about 7 hydroxyl groups/molecule and an average hydroxyl equivalent weight of about 90 to about 175. Any individual polyol within the mixture may have a functionality and/or equivalent weight outside of those ranges, if the mixture meets these parameters. Water is not considered in determining the functionality or equivalent weight of a polyol mixture.
A more preferred average hydroxyl functionality for the polyol mixture is from about 3.8 to about 6 hydroxyl groups/molecule. An even more preferred average hydroxyl functionality for a polyol mixture is from about 3.8 to about 5 hydroxyl groups/molecule. A more preferred average hydroxyl equivalent weight for a polyol mixture is from about 110 to about 130.
Polyol mixtures as described can be prepared by making the constituent polyols individually, and then blending them together. Alternatively, polyol mixtures can be prepared by forming a mixture of the respective initiator compounds, and then alkoxylating the initiator mixture to form the polyol mixture directly. Such “co-initiated” polyols may be prepared using the ortho-cyclohexanediamine and another amine as the initiators, to form a blend of amine-initiated polyols. Combinations of these approaches can also be used.
The polyurethane-forming composition contains at least one organic polyisocyanate. The organic polyisocyanate or mixture thereof advantageously contains an average of at least 2.5 isocyanate groups per molecule. A preferred isocyanate functionality is from about 2.5 to about 3.6 or from about 2.6 to about 3.3 isocyanate groups/molecule. The polyisocyanate or mixture thereof advantageously has an isocyanate equivalent weight of from about 130 to 200. This is preferably from 130 to 185 and more preferably from 130 to 170. These functionality and equivalent weight values need not apply with respect to any single polyisocyanate in a mixture, provided that the mixture as a whole meets these values.
Suitable polyisocyanates include aromatic, aliphatic and cycloaliphatic polyisocyanates. Aromatic polyisocyanates are generally preferred. Exemplary polyisocyanates include, for example, m-phenylene diisocyanate, 2,4- and/or 2,6-toluene diisocyanate (TDI), the various isomers of diphenylmethanediisocyanate (MDI), hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate, hydrogenated MDI (Hi2 MDI), naphthylene-1,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, 4,4′-biphenylene diisocyanate, 3,3′-dimethyoxy-4,4′-biphenyl diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 4,4′,4″-triphenylmethane diisocyanate, polymethylene polyphenylisocyanates, hydrogenated polymethylene polyphenyl polyisocyanates, toluene-2,4,6-triisocyanate and 4,4′-dimethyldiphenylmethane-2,2′,5,5′-tetraisocyanate. Preferred polyisocyanates are the so-called polymeric MDI products, which are a mixture of polymethylene polyphenylene polyisocyanates in monomeric MDI. Especially suitable polymeric MDI products have a free MDI content of from 5 to 50% by weight, more preferably 10 to 40% by weight. Such polymeric MDI products are available from The Dow Chemical Company under the trade names PAPI® and Voranate®.
An especially preferred polyisocyanate is a polymeric MDI product having an average isocyanate functionality of from 2.6 to 3.3 isocyanate groups/molecule and an isocyanate equivalent weight of from 130 to 170. Suitable commercially available products of that type include PAPI™ 27, Voranate™ M229, Voranate™ 220, Voranate™ 290, Voranate™ M595 and Voranate™ M600, all from Dow Chemical.
Isocyanate-terminated prepolymers and quasi-prepolymers (mixtures of prepolymers with unreacted polyisocyanate compounds) can also be used. These are prepared by reacting a stoichiometric excess of an organic polyisocyanate with a polyol, such as the polyols described above. Suitable methods for preparing these prepolymers are well known. Such a prepolymer or quasi-prepolymer preferably has an isocyanate functionality of from 2.5 to 3.6 and an isocyanate equivalent weight of from 130 to 200.
The polyisocyanate is used in an amount sufficient to provide an isocyanate index of from 80 to 600. Isocyanate index is calculated as the number of reactive isocyanate groups provided by the polyisocyanate component divided by the number of isocyanate-reactive groups in the polyurethane-forming composition (including those contained by isocyanate-reactive blowing agents such as water) and multiplying by 100. Water is considered to have two isocyanate-reactive groups per molecule for purposes of calculating isocyanate index. A preferred isocyanate index is from 90 to 400 and a more preferred isocyanate index is from 100 to 150.
The blowing agent used in the polyurethane-forming composition includes at least one physical blowing agent which is a hydrocarbon, hydrofluorocarbon, hydrochlorofluorocarbon, fluorocarbon, dialkyl ether or fluorine-substituted dialkyl ethers, or a mixture of two or more thereof. Blowing agents of these types include, for example, propane, isopentane, n-pentane, n-butane, isobutene, isobutene, cyclopentane, dimethyl ether, 1,1-dichloro-1-fluoroethane (HCFC-141b), chlorodifluoromethane (HCFC-22), 1-chloro-1,1-difluoroethane (HCFC-142b), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1-difluoroethane (HFC-152a), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) and 1,1,1,3,3-pentafluoropropane (HFC-245fa). The hydrocarbon and hydrofluorocarbon blowing agents are preferred. It is generally preferred to further include water in the formulation, in addition to the physical blowing agent.
Blowing agent(s) are preferably used in an amount such that the formulation cures to form a foam with a molded density of from 16 to 160 kg/m3, preferably from 16 to 64 kg/m3 and especially from 20 to 48 kg/m3. To achieve these densities, the hydrocarbon or hydrofluorocarbon blowing agent conveniently is used in an amount ranging from about 10 to about 40, preferably from about 12 to about 35, parts by weight per 100 parts by weight polyol(s). Water reacts with isocyanate groups to produce carbon dioxide, which acts as an expanding gas. Water is suitably used in an amount within the range of 0.5 to 3.5, preferably from 1.5 to 3.0 parts by weight per 100 parts by weight of polyol(s).
The polyurethane-forming composition typically will include at least one catalyst for the reaction of the polyol(s) and/or water with the polyisocyanate. Suitable urethane-forming catalysts include those described by U.S. Pat. No. 4,390,645 and in WO 02/079340, both incorporated herein by reference. Representative catalysts include tertiary amine and phosphine compounds, chelates of various metals, acidic metal salts of strong acids; strong bases, alcoholates and phenolates of various metals, salts of organic acids with a variety of metals, organometallic derivatives of tetravalent tin, trivalent and pentavalent As, Sb and Bi and metal carbonyls of iron and cobalt.
Tertiary amine catalysts are generally preferred. Among the tertiary amine catalysts are dimethylbenzylamine (such as Desmorapid® DB from Rhine Chemie), 1,8-diaza (5,4,0)undecane-7 (such as Polycat® SA-1 from Air Products), pentamethyldiethylenetriamine (such as Polycat® 5 from Air Products), dimethylcyclohexylamine (such as Polycat® 8 from Air Products), triethylene diamine (such as Dabco® 33LV from Air Products), dimethyl ethyl amine, n-ethyl morpholine, N-alkyl dimethylamine compounds such as N-ethyl N,N-dimethyl amine and N-cetyl N,N-dimethylamine, N-alkyl morpholine compounds such as N-ethyl morpholine and N-coco morpholine, and the like. Other tertiary amine catalysts that are useful include those sold by Air Products under the trade names Dabco® NE1060, Dabco® NE1070, Dabco® NE500, Dabco® TMR-2, Dabco® TMR 30, Polycat® 1058, Polycat® 11, Polycat 15, Polycat® 33, Polycat® 41 and Dabco® MD45, and those sold by Huntsman under the trade names ZR 50 and ZR 70. In addition, certain amine-initiated polyols can be used herein as catalyst materials, including those described in WO 01/58976 A. Mixtures of two or more of the foregoing can be used.
The catalyst is used in catalytically sufficient amounts. An advantage of this invention is that the presence of the ortho-cyclohexanediamine-initiated polyol tends to make the polyol mixture more reactive, compared to similar systems in which a toluene diamine-initiated polyol is used in place of the ortho-cyclohexanediamine-initiated polyol. As a result, it is often possible to use catalysts, particularly tertiary amine catalysts, in lesser amounts than are needed in other systems, while at the same time retaining equivalent curing rates and thermal insulation values. Thus, in some embodiments of the invention, the reaction mixture contains from 0.5 to 1.9 parts of tertiary amine catalyst(s) per 100 parts by weight of the polyol mixture. In more preferred cases, the amount of tertiary amine catalyst may be from 0.5 to 0.95 parts per 100 parts by weight of the polyol mixture, and in other embodiments, the amount of tertiary amine catalyst may be from 1.05 to 1.7 parts, or from 1.05 to 1.5 parts, again on the same basis. In all of these cases, the reaction mixture may contain no more than 0.1 parts of a metallic catalyst, and is even more preferably essentially devoid of a metallic catalyst.
The polyurethane-forming composition also preferably contains at least one surfactant, which helps to stabilize the cells of the composition as gas evolves to form bubbles and expand the foam. Examples of suitable surfactants include alkali metal and amine salts of fatty acids, such as sodium oleate, sodium stearate sodium ricinolates, diethanolamine oleate, diethanolamine stearate, diethanolamine ricinoleate, and the like: alkali metal and amine salts of sulfonic acids, such as dodecylbenzenesulfonic acid and dinaphthylmethanedisulfonic acid; ricinoleic acid; siloxane-oxalkylene polymers or copolymers and other organopolysiloxanes; oxyethylated alkylphenols (such as Tergitol NP9 and Triton X100, from The Dow Chemical Company); oxyethylated fatty alcohols such as Tergitol 15-S-9, from The Dow Chemical Company; paraffin oils; castor oil; ricinoleic acid esters; turkey red oil; peanut oil; paraffins; fatty alcohols; dimethyl polysiloxanes and oligomeric acrylates with polyoxyalkylene and fluoroalkane side groups. These surfactants are generally used in amount of 0.01 to 6 parts by weight based on 100 parts by weight of the polyol.
Organosilicone surfactants are generally preferred types. A wide variety of these organosilicone surfactants are commercially available, including those sold by Goldschmidt under the Tegostab® name (such as Tegostab B-8462, B8427, B8433 and B-8404 surfactants), those sold by OSi Specialties under the Niax® name (such as Niax® L6900 and L6988 surfactants) as well as various surfactant products commercially available from Air Products and Chemicals, such as LK-221E, LK-443E, DC-193, DC-198, DC-5000, DC-5043 and DC-5098 surfactants.
In addition to the foregoing ingredients, the polyurethane-forming composition may include various auxiliary components, such as fillers, colorants, odor masks, flame retardants, biocides, antioxidants, UV stabilizers, antistatic agents, viscosity modifiers, and the like.
Examples of suitable flame retardants include phosphorus compounds, halogen-containing compounds and melamine.
Examples of fillers and pigments include calcium carbonate, titanium dioxide, iron oxide, chromium oxide, azo/diazo dyes, phthalocyanines, dioxazines, recycled rigid polyurethane foam and carbon black.
Examples of UV stabilizers include hydroxybenzotriazoles, zinc dibutyl thiocarbamate, 2,6-ditertiarybutyl catechol, hydroxybenzophenones, hindered amines and phosphites.
Except for fillers, the foregoing additives are generally used in small amounts, such as from 0.01 percent to 3 percent each by weight of the polyurethane formulation. Fillers may be used in quantities as high as 50% by weight of the polyurethane formulation.
The polyurethane-forming composition is prepared by bringing the various components together under conditions such that the polyol(s) and isocyanate(s) react, the blowing agent generates a gas, and the composition expands and cures. All components (or any sub-combination thereof) except the polyisocyanate can be pre-blended into a formulated polyol composition, if desired, which is then mixed with the polyisocyanate when the foam is to be prepared. The components may be preheated if desired, but this is usually not necessary, and the components can be brought together at about room temperature (˜22° C.) to conduct the reaction. It is usually not necessary to apply heat to the composition to drive the cure, but this may be done if desired, too.
The invention is particularly useful in so-called “pour-in-place” applications, in which the polyurethane-forming composition is dispensed into a cavity and foams within the cavity to fill it and provide structural and/or thermal insulative attributes to an assembly. The nomenclature “pour-in-place” refers to the fact that the foam is created at the location where it is needed, rather than being created in one step and later assembled into place in a separate manufacturing step. Pour-in-place processes are commonly used to make appliance products such as refrigerators, freezers, and coolers and similar products which have walls that contain thermal insulation foam. The presence of the amine-initiated polyol in the polyurethane-forming composition tends to provide the formulation with good flow and short demold times, while at the same time producing a low k-factor foam.
The walls of appliances such as refrigerators, freezers and coolers are most conveniently insulated in accordance with the invention by first assembling an outer shell and in interior liner together, such that a cavity is formed between the shell and liner. The cavity defines the space to be insulated as well as the dimensions and shape of the foam that is produced. Typically, the shell and liner are bonded together in some way, such as by welding, melt-bonding or through use of some adhesive (or some combination of these) prior to introduction of the foam formulation. The shell and liner may be supported or held in the correct relative positions using a jig or other apparatus. One or more inlets to the cavity are provided, through which the foam formulation can be introduced. Usually, one or more outlets are provided to allow air in the cavity to escape as the cavity is filled with the foam formulation and the foam formulation expands.
The materials of construction of the shell and liner are not particularly critical, provided that they can withstand the conditions of the curing and expansion reactions of the foam formulation. In most cases, the materials of construction will be selected with regard to specific performance attributes that are desired in the final product. Metals such as steel are commonly used as the shell, particularly in larger appliances such as freezers or refrigerators. Plastics such as polycarbonates, polypropylene, polyethylene styrene-acrylonitrile resins, acrylonitrile-butadiene-styrene resins or high-impact polystyrene are used more often to make shells for smaller appliances (such as coolers) or those in which low weight is important. The liner may be a metal, but is more typically a plastic as just described.
The foam formulation is then introduced into the cavity. The various components of the foam formulation are mixed together and the mixture introduced quickly into the cavity, where the components react and expand. It is common to pre-mix the polyol(s) together with the water and blowing agent (and often catalyst and/or surfactant as well) to produce a formulated polyol. The formulated polyol can be stored until it is time to prepare the foam, at which time it is mixed with the polyisocyanate and introduced into the cavity. It is usually not required to heat the components prior to introducing them into the cavity, nor it is usually required to heat the formulation within the cavity to drive the cure, although either or both of these steps may be taken if desired. The shell and liner may act as a heat sink in some cases, and remove heat from the reacting foam formulation. If necessary, the shell and/or liner can be heated somewhat (such as up to 50° C. and more typically 35-40° C.) to reduce this heat sink effect or to drive the cure.
Enough of the foam formulation is introduced such that, after it has expanded, the resulting foam fills those portions of the cavity where foam is desired. Most typically, essentially the entire cavity is filled with foam. It is generally preferred to “overpack” the cavity slightly, by introducing more of the foam formulation than is minimally needed to fill the cavity, thereby increasing the foam density slightly. The overpacking provides benefits such as better dimensional stability of the foam, especially in the period following demold. Generally, the cavity is overpacked by from 4 to 20% by weight. The final foam density for most appliance applications is preferably in the range of from 28 to 40 kg/m3.
After the foam formulation has expanded and cured enough to be dimensionally stable, the resulting assembly can be “demolded” by removing it from the jig or other support that is used to maintain the shell and liner in their correct relative positions. Short demold times are important to the appliance industry, as shorter demold times allow more parts to be made per unit time on a given piece of manufacturing equipment.
Demold times can be evaluated as follows: A 28-liter “jumbo” Brett mold coated with release agent is conditioned to a temperature of 45° C. 896 g±4 g of a foam formulation is injected into the mold in order to obtain a 32 kg/m3 density foam. After a period of 6 minutes, the foam is removed from the mold and the thickness of the foam is measured. After a further 24 hours, the foam thickness is re-measured. The difference between the thickness after 24 hours and the initial thickness is an indication of the post-demold expansion of the foam. The demold time is considered to be sufficiently long if the post-demold expansion is no more than 4 mm on this test.
As mentioned, flow is another important attribute of the foam formulation. For purposes of this invention, flow is evaluated using a rectangular “Brett” mold, having dimensions of 200 cm×20 cm×5 cm (˜6′6″×8″×2″). The polyurethane-forming composition is formed, and immediately injected into the Brett mold, which is oriented vertically (i.e., 200 cm direction oriented vertically) and preheated to 45±5° C. The composition is permitted to expand against its own weight and cure inside the mold. The amount of polyurethane-forming composition is selected such that the resulting foam just fills the mold. The density of the resulting foam is then measured and compared with the density of a free-rise foam made from the same formulation (by injecting the formulation into a plastic bag or open cardboard box where it can expand freely vertically and horizontally against atmospheric pressure). The ratio of the Brett mold foam density to the free rise density is considered to represent the “flow index” of the formulation. With this invention, flow index values are typically below 1.8 and preferably from 1.2 to 1.5.
The polyurethane foam advantageously exhibits a low k-factor. The k-factor of a foam may depend on several variables, of which density is an important one. For many applications, a rigid polyurethane foam having a density of from 28.8 to 40 kg/m3 (1.8 to 2.5 pounds/cubic foot) exhibits a good combination of physical properties, dimensional stability, and cost. Foam in accordance with the invention, having a density within that range, preferably exhibits a 10° C. k-factor of no greater than 22, preferably no greater than 20, and more preferably no greater than 19.5 mW/m-° K. Higher density foam may exhibit a somewhat higher k-factor.
In addition to the appliance and thermal insulation foams described above, the invention is also useful to produce vehicle noise dampening foams, one or more layers of a laminated board, pipe insulation and other foam products. The invention is of special interest when a rapid cure is wanted, and or good thermal insulating properties are wanted in the foam.
If desired, the process of the invention can be practiced in conjunction with the methods described, for example, in WO 07/058,793, in which the reaction mixture is injected into a closed mold cavity which is at a reduced pressure.
The following examples are provided to illustrate the invention, but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated.
Rigid polyurethane foam Examples 1-5 and Comparative Sample A are produced from the components described in Table 1. Catalyst levels are adjusted in each case to obtain a gel time of about 30 seconds. Foam processing is performed using a Cannon HE-60 high pressure machine. The foam formulation is injected into a bag (to measure free rise density) and into a vertical Brett mold which is preheated to 45° C. Component temperatures prior to mixing are ˜21° C.
Gel time is measured for each of the foams, with results as indicated in Table 1.
1A 6.0 functional poly(propylene oxide) having a hydroxyl number of 482, commercially available as Voranol ® RN 482 polyol from Dow Chemical.
2An ethylenediamine-initiated polyol having a hydroxyl number of about 500.
3A polyether diol having a hydroxyl number of about 400.
4A polyol corresponding to an adduct of 5.6 moles of propylene oxide and 1 mole of ortho-cyclohexanediamine.
5An o-toluene diamine-initiated polyol having a hydroxyl number of about 440.
6PAPI ® 27 polymeric MDI, available from Dow Chemical.
The results in Table 1 show that less catalyst is needed to achieve equivalent gel times, as more and more of the ortho-cyclohexanediamine-initiated polyol is substituted for a toluene diamine-initiated polyol.
Rigid polyurethane foam Example 6 and Comparative Samples B and C are produced from the components described in Table 2. Foam processing is performed as described in Examples 1-5. Gel time, tack-free time, free rise density, minimum fill density, flow index, Brett mold density, mean compressive strength and K-factor are all determined for each of the foams. Results are as indicated in Table 2. K-factor is measured on 8″×1″×1″ (20×2.5×2.5 cm) samples of the Brett mold foam, using a Laser Comp Fox 200 device, with an upper cold plate temperature of 10° C. and a lower warm plate temperature of 38° C.
1A 6.0 functional poly(propylene oxide) having a hydroxyl number of 482, commercially available as Voranol ® RN 482 polyol from Dow Chemical.
2A polyether diol having a hydroxyl number of about 110.
3A polyether triol having a hydroxyl number of about 156.
4A polyol corresponding to an adduct of 5.6 moles of propylene oxide and 1 mole of ortho-cyclohexanediamine.
5An o-toluene diamine-initiated polyol having a hydroxyl number of about 440.
6A polyol corresponding to an adduct of 5.6 moles of propylene oxide and 1 mole of o-phenylenediamine.
7PAPI ® 27 polymeric MDI, available from Dow Chemical.
The results in Table 2 show that at equivalent catalyst levels, the formulation containing the ortho-cyclohexanediamine-initiated polyol has shorter gel and tack-free times than do either of the formulations containing instead an aromatic diamine-initiated polyol. Other important properties are nearly equivalent.
Rigid polyurethane foam Example 7 and Comparative Sample D are produced from the components described in Table 3. Foam processing is performed as described in Examples 1-5, and foam testing is performed in the same way as described there with respect to Example 6. Results are as indicated in Table 3.
1A 6.0 functional poly(propylene oxide) having a hydroxyl number of 482, commercially available as Voranol ® RN 482 polyol from Dow Chemical.
2An ethylenediamine-initiated polyol having a hydroxyl number of about 500.
3A polyether diol having a hydroxyl number of about 110.
4A polyol corresponding to an adduct of 5.6 moles of propylene oxide and 1 mole of ortho-cyclohexanediamine.
5An o-toluene diamine-initiated polyol having a hydroxyl number of about 440.
6Stepanpol PS 3152, from Stepan Chemicals.
7PAPI ® 27 polymeric MDI, available from Dow Chemical.
The results in Table 3 show similar trends as seen in Example 6 and Comparative Samples B and C, in a different base formulation. The substitution of an ortho-cyclohexanediamine-initiated polyol for a toluenediamine-initiated polyol, at equivalent catalyst level, reduces gel and tack-free times while causing little change in other important properties.
Rigid polyurethane foam Example 8 and Comparative Samples E and F are produced from the components described in Table 4. Foam processing is performed as described in Examples 1-5, and foam testing is performed in the same way as described there. Results are as indicated in Table 4.
1See note 1, Table 3.
2A polyether diol having a hydroxyl number of about 400.
3A polyether triol having a hydroxyl number of about 156.
4An o-toluene diamine-initiated polyol having a hydroxyl number of about 440.
5A polyol corresponding to an adduct of 5.6 moles of propylene oxide and 1 mole of ortho-cyclohexanediamine.
6A polyol corresponding to an adduct of 5.6 moles of propylene oxide and 1 mole of ortho-cyclohexanediamine.
7PAPI ® 27 polymeric MDI, available from Dow Chemical.
The results in Table 4 again show similar trends as seen in Example 6 and Comparative Samples B and C, in yet another base formulation. The addition of an ortho-cyclohexanediamine-initiated polyol, at equivalent catalyst level, reduces gel and tack-free times while causing little change in other important properties.
| Number | Date | Country | Kind |
|---|---|---|---|
| 61084653 | Jul 2008 | US | national |
This application claims priority from U.S. Provisional Application No. 61/084,653, filed 30 Jul. 2008.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/US09/52076 | 7/29/2009 | WO | 00 | 1/20/2011 |
