Additive for polyurethane foam polyol blends and polyurethane foams comprising same

Abstract

The present technology provides a method of making a rigid polyurethane foam having low thermal conductivity from a foam composition comprising a polyol, an isocyanate, a polyurethane catalyst, a surfactant, and a compatibility additive. The compatibility additive enhances the compatibility of one or more components in the foam-forming composition with the polyol component.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 358,640, filed on July 6, 2022, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] The present technology generally relates to polyurethane foam compositions and foams made from such compositions. More particularly, the present technology relates to additives for enhancing the compatibility of components in polyurethane foam compositions and in particular for enhancing the compatibility of components with polyols. The present technology also relates to polyurethane foams formed using such compositions and additives. Background Art

[0004] Rigid polyurethane and polyisocyanurate foams are widely used in the construction industry as insulating materials. These foams exhibit excellent thermal insulation properties.

[0005] Conventional rigid polyurethane foams, such as those useful in thermal insulation applications, are generally prepared by reacting at least one polyol with at least one isocyanate in the presence of a suitable catalyst, surfactant, water, and blowing agent. In admixture with a polyol, whether as the separate polyol component in a two-part composition or in a one-part composition comprising each component, the respective components may separate over time and / or may not be sufficiently compatible, rendering the composition hazy (i.e., lacking clarity). Summary of the invention

[0006] The present technology provides an additive for a polyol used in a polyurethane foam composition. The additive acts as a compatibilizer in a polyol suitable for use in a polyurethane foam composition, such as a rigid polyurethane foam. The additive provides stability to the polyol. In one embodiment, the additive is provided to a polyol pre-blend, thereby providing stability and clarity to the polyol pre-blend. This can be seen in the appearance of the polyol - because separation of components in the pre-blend is reduced or avoided; and / or in the clarity of the polyol pre-blend.

[0007] The additive may also be used to aid in the retention of the blowing agent during the production of the polyurethane foam.

[0008] Additionally, the use of the additive has minimal to no negative impact on the physical properties of the foam produced using the additive of the present invention.

[0009] In one aspect, the present technology provides a polyurethane foam composition comprising a polyol, an isocyanate, a polyurethane catalyst, a surfactant, a compatibility additive according to the present technology, water, optionally a physical blowing agent, optionally a chemical blowing agent, optionally a flame retardant additive or a mixture thereof, and optionally other processing additives. The compatibility additive is a silicone-based compound containing polyether side groups and has been found to reduce or prevent separation of components in a polyol composition (e.g., for polyurethane foam or a one-part polyurethane foam composition).

[0010] In one aspect, a polyurethane or polyisocyanurate foam composition is provided, comprising: a polyol or a mixture thereof; an isocyanate; a compatibility additive; a surfactant; and a polyurethane catalyst or a mixture thereof;

[0011] The compatibility additive is selected from the following compounds:

[0012] M 1 D 1 m D 2 n M 2 (I)

[0013] in:

[0014] M 1 for (R 1 )(R 2 )(R 3 )Si-O 1 / 2

[0015] M 2 for (R 4 )(R 5 )(R 6 )Si-O 1 / 2

[0016] D 1 for (R 7 )(R 8 )Si-O 2 / 2

[0017] D 2 for (R 9 )(R 10 )Si-O 2 / 2

[0018] R 10 is –CH2-CH(R 11 )-CH2-O-[CH2CH(CH3)O] p -[CH2CH2O] q -R 12

[0019] R 1 、R 2 、R 3 、R 4 、R 5 和R 6 are independently selected from C1-C10 alkyl or R 10 ;

[0020] R 7 、R 8 和R 9 are independently selected from C1-C10 alkyl,

[0021] R 11 is H or C1-C10 alkyl;

[0022] R 12 is H, C1-C10 alkyl, or an acetyl group;

[0023] m is from 0 to 100;

[0024] n is from 1 to 50;

[0025] p is from 0 to 35;

[0026] q is from 0 - 45; and

[0027] p + q ≥ 1.

[0028] In one embodiment, the composition is a two-part composition comprising: (i) a first part comprising an isocyanate, and (ii) a second part comprising a polyol and a compatibility additive.

[0029] In one embodiment, m is 0 and n is 1.

[0030] In one embodiment, p is from 1 to 10. In one embodiment, q is 0.

[0031] In one embodiment, q is from 1 to 10. In one embodiment, p is 0.

[0032] In one embodiment, m ≥ 0, and n ≥ 1, where m:n ≤ 6:1.

[0033] In one embodiment, the ratio of m:n is from about 0.1:1 to 6:1.

[0034] In one embodiment, 0 < m ≤ 15 and 1 < n ≤ 5.

[0035] In one embodiment, according to any of the foregoing embodiments, R 11 is H.

[0036] In one embodiment, according to any of the preceding embodiments, R 11 is a C1-C10 alkyl group. 11 It is methyl.

[0037] In one embodiment, according to any of the preceding embodiments, the compound of formula (I) has a silicon content of less than 25% by weight of the weight of formula (I).

[0038] In one embodiment, according to any of the preceding embodiments, the compound of formula (I) has a silicon content of less than 20% by weight of the weight of formula (I).

[0039] In one embodiment, according to any of the preceding embodiments, the compound of formula (I) has a silicon content of about 1 wt % to about 25 wt % based on the weight of formula (I).

[0040] In one embodiment, according to any of the preceding embodiments, the compatibilizing additive is present in an amount of about 0.5 to about 20 parts per hundred parts of polyol.

[0041] In one embodiment, according to any of the preceding embodiments, the compatibilizing additive is present in an amount equivalent to the amount of surfactant present in the composition.

[0042] In one embodiment, according to any of the preceding embodiments, the compatibilizing additive is present in an amount greater than the amount of surfactant present in the composition.

[0043] In one embodiment, according to any of the preceding embodiments, the compatibilizing additive is present in an amount from about 1.2 times to 6 times the amount of surfactant present in the composition.

[0044] In one embodiment, according to any of the preceding embodiments, the composition further comprises a blowing agent.

[0045] In another aspect, there is provided a method of forming a foam comprising reacting a composition according to any one of the preceding embodiments. DETAILED DESCRIPTION

[0046] The present technology provides additives for enhancing the compatibility of components in a foam-forming composition, a foam-forming composition comprising such additives, and foams made from such foam-forming compositions. The composition can be used to provide rigid foams. The foam composition comprises ： (a) a polyol component; (b) an isocyanate component; (c) a compatibilizing additive; (d) a surfactant; and (e) a catalyst component. The polyol component and the isocyanate component may be provided as separate components, as part of a two-part composition, or as a one-part mixture. For example, it has been found that the compatibilizing additive enhances the compatibility of the components employed in the foam-forming composition with the polyol.

[0047] The compatibilizing additive is a silicone-based compound containing polyether side groups. In one embodiment, the compatibilizing additive is selected from compounds of formula (I):

[0048] M 1 D 1 m D 2 n M 2 (I)

[0049] in:

[0050] M 1 for (R 1 )(R 2 )(R 3 )Si-O 1 / 2

[0051] M 2 for (R 4 )(R 5 )(R 6 )Si-O 1 / 2

[0052] D 1 for (R 7 )(R 8 )Si-O 2 / 2

[0053] D 2 for (R 9 )(R 10 )Si-O 2 / 2

[0054] R 10 is –CH2-CH(R 11 )-CH2-O-[CH2CH(CH3)O] p -[CH2CH2O] q -R 12

[0055] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Independently selected from C1-C10 alkyl or R 10 ;

[0056] R 7 , R 8 and R 9 independently selected from C1-C10 alkyl,

[0057] R11 is H or C1-C10 alkyl;

[0058] R 12 is H, a C1-C10 alkyl group, or an acetyl group;

[0059] m is 0 to 100;

[0060] n is 1 to 50;

[0061] p is 0 to 35;

[0062] q is 0-45; and

[0063] p+q≥1.

[0064] In one embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently selected from C1-C10 alkyl, C2-C8 alkyl, or C4-C6 alkyl. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently selected from C1-C4 alkyl or C1-C2 alkyl. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 R is independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, or decyl. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Each is a methyl group.

[0065] In one embodiment, R1 , R 2 , R 3 , R 4 , R 5 and R 6 Independently selected from C1-C10 alkyl or R 10 , where R 1 , R 2 , R 3 , R 4 , R 5 and / or R 6 At least one of R 10 In one embodiment, R 1 , R 2 , or R 3 At least one of R 10 group, and R 4 , R 5 , or R 6 At least one of R 10 Group.

[0066] R 11 is selected from H or C1-C10 alkyl. 11 is H. In one embodiment, R 11 is selected from C1-C10 alkyl, C2-C8 alkyl, or C4-C6 alkyl. 11 is –CH3.

[0067] R 10 The group contains polyethylene and polypropylene units and contains R 12 The polyethylene glycol and / or polypropylene glycol units are formed by the presence of a hydrogen atom. 10 In the group, p is 0 to 35, 1 to 30, 5 to 25, or 10 to 20; and q is 0 to 45, 1 to 40, 5 to 35, 10 to 30, or 15 to 25, wherein p+q≥1. In one embodiment, q is 0 and p≥1. In one embodiment, q is 0 and p is 1 to 10, 2 to 8, or 3 to 5. In one embodiment, p is 0 and q≥1. In one embodiment, p is 0 and q is 1 to 10, 2 to 8, or 3 to 5.

[0068] R 10 The group may have a number average molecular weight of about 85 to about 4000, about 200 to about 2000, or about 400 to about 1500. 10 The molecular weight of the unit can be determined by end group analysis, particularly by titration to obtain hydroxyl and unsaturation values, and further confirmed by NMR analysis.

[0069] The compatibilizing additive comprises at least one D2 groups, i.e., n is at least 1. In one embodiment, the compatibility additive is trisiloxane, where m is 0 and n is 1. In an embodiment, the compatibility additive comprises D 1 and D 2 groups, where n is from 1 to 50, 2 to 40, 5 to 35, 10 to 30, or 15 to 25; and m is from 1 to 100, 5 to 90, 10 to 80, 15 to 75, 20 to 65, 25 to 60, 30 to 50, or 40 to 45. In embodiments where m is greater than 1, the ratio of m:n ≤ 6:1, ≤ 5:1, ≤ 4:1, ≤ 3:1. In one embodiment where m is greater than 1, the ratio of m:n is from about 0.1:1 to 6:1, from about 0.5:1 to about 5:1, from about 1:1 to about 4:1, or from about 2:1 to about 3:1.

[0070] In one embodiment, in the compound of formula (I), 0 < m < 15 and 1 < n ≤ 5; 1 ≤ m ≤ 12 and 2 ≤ n ≤ 4; or 5 ≤ m ≤ 10 and 3 ≤ n ≤ 4.

[0071] Two or more compatibility additives can be employed in the foam-forming composition, and particularly together with the polyol component of the foam-forming composition. In one embodiment, the composition comprises at least one compatibility additive of formula (I), where m is 0 and n is 1. In one embodiment, the polyol composition comprises a first compatibility additive of formula (I) (where m is 0 and n is 1) and a second compatibility additive of formula (I) (where m is 0 and n is 1), where the first compatibility additive and the second compatibility additive are different from each other in terms of the ratio of p:q in any of their R 1 -R 9 groups, their R 10 groups, and / or their R 10 groups.

[0072] In one embodiment, the composition comprises a first compatibility additive of formula (I), where m is 0 and n is 1; and a second compatibility additive, where m ≥ 1 and n ≥ 1 and the ratio of m:n ≤ 9:1, ≤ 7.5:1, ≤ 6:1, ≤ 5:1, or ≤ 4:1. In one embodiment, the ratio of m:n is from about 1:1 to about 9:1, from about 2:1 to about 8:1, from about 3:1 to about 7:1, or from about 4:1 to about 6:1.

[0073] In an embodiment, the compatibilizing additive of formula (I) has a silicon content of less than 25%, less than 20%, less than 17.5%, less than 15%, or less than 10% by weight of the additive of formula (I). In an embodiment, the compatibilizing additive of formula (I) has a silicon content of about 1% to about 25%, about 3% to about 20%, about 5% to about 17.5%, or about 10% to about 15% by weight, based on the weight of the additive of formula (I).

[0074] The compatibilizing additive may be present in an amount of about 0.5 to about 20 parts per hundred parts of polyol (pphp), about 1 to about 15 pphp, about 2.5 to about 10 pphp, or about 5 to about 7.5 pphp, based on the weight of the polyol composition. In one embodiment, the polyol additive is present in an amount of about 1.5 to about 7 pphp, about 2 to about 6 pphp, or about 2.5 to about 5 pphp, based on the total weight of the polyol composition.

[0075] In one embodiment comprising a first compatibilizing additive (wherein m is 0 and n is 1) and a second compatibilizing additive (wherein m≥1 and n≥1), the first compatibilizing additive is present in an amount from about 1 pphp to about 15 pphp, from about 1.5 pphp to about 12 pphp, from about 3 pphp to about 10 pphp, or from about 4 pphp to about pphp, and the second compatibilizing additive is present in an amount from about 0.5 wt % to about 6 wt %, from about 1 pphp to about 5 pphp, or from about 2 pphp to about 4 pphp.

[0076] In one embodiment, the compatibilizing additive is present in an amount from about 1.2 to about 6 times the amount of the surfactant, from about 1.5 to about 5.5 times the amount of the surfactant, from about 2 to about 5 times the amount of the surfactant, or from about 2.5 to about 4 times the amount of the surfactant.

[0077] The polyol component is not particularly limited and can be selected for a specific purpose or intended application as required. In various embodiments, polyol can be selected from polyester polyols, polyether polyols, polycarbonate polyols, hydroxyl-terminated polyolefin polyols, etc. or a combination of two or more thereof. Polyol can be, for example, polyester diols, polyester triols, polyether diols, polyether triols, etc. Alternatively, polyol can be selected from polythioether polyols, polycaprolactones, brominated polyether polyols, acrylic polyols, etc. or a combination of two or more thereof. When using high-functionality polyether polyols, high-functionality polyether polyols can have a functionality of about 3 to about 6. Polyols such as sucrose or sorbitol initiators can be mixed with diols or amines of lower functionality so that the functionality of the polyol is in the range of about 3.5 to about 5.

[0078] Suitable polyols include, but are not limited to, those having 2 to 8 hydroxyl groups per molecule and a number average molecular weight of 200 to 10,000, preferably 500 to 7,500. Examples of suitable polyols include, but are not limited to, polyether diols and triols and polyols, polyester diols and triols and polyols, and hydroxyl-terminated polyolefin polyols, such as polybutadiene diols. Other examples of suitable polyols include sucrose and amine-initiated (initiated) polyols, polymer polyols (also grafted polymer polyols, grafted polyols or copolymer polyols, all of which are used to describe dispersions of vinyl polymers in polyols produced by in-situ polymerization of vinyl monomers (usually styrene and / or acrylonitrile) in a base polyol), polyols derived from naturally occurring materials such as castor oil, chemically modified soybean oil or other chemically modified fatty acid oils, and polyols obtained by alkoxylation of such naturally occurring materials such as castor oil and soybean oil.

[0079] In addition, other particularly suitable polyols include aromatic polyester polyols. Aromatic polyester polyols can be prepared from substantially pure reactant materials, or more complex starting materials, such as polyethylene terephthalate, can be used. In addition, dimethyl terephthalate (DMT) process residues can be used to form aromatic polyester polyols.

[0080] Aromatic polyester polyols may contain halogen atoms. They may be saturated or unsaturated. Aromatic polyester polyols may have an aromatic ring content (expressed as the weight % of groups containing at least one aromatic ring per molecule) of at least about 30 wt%, 35 wt%, or even about 40 wt% based on the total compound weight. Here, as in other positions in the specification and claims, numerical values ​​may be combined to form new or undisclosed ranges. Polyester polyols having an acid component advantageously containing at least about 30 wt% of phthalic acid residues or isomer residues thereof are particularly useful.

[0081] The aromatic polyester polyols may have a hydroxyl number of greater than about 50 mg KOH / g, greater than about 100 mg KOH / g, greater than about 150 mg KOH / g, greater than about 200 mg KOH / g, greater than about 250 mg KOH / g, greater than about 300 mg KOH / g, greater than about 350 mg KOH / g, and even greater than about 400 mg KOH / g. Here, as elsewhere in the specification and claims, numerical values ​​may be combined to form new and undisclosed ranges.

[0082] In one embodiment, the aromatic polyester polyol has a functionality of greater than about 1, greater than about 2, greater than about 3, greater than about 4, greater than about 5, greater than about 6, greater than about 7, and even greater than about 8. Here, as elsewhere in the specification and claims, numerical values ​​can be combined to form new and non-disclosed ranges.

[0083] Exemplary polyols are polyether diols, triols, tetraols and even greater hydroxyl functionalities of polyols employed to date in the manufacture of polyurethane foams. Polyether polyols are typically prepared by reacting starting compounds such as polyols (e.g., ethylene glycol, diethylene glycol, propylene glycol, glycerol, sucrose, etc.) or polyamines (e.g., ethylenediamine, etc.) with one or more alkylene oxides, phenyl-substituted alkylene oxides and / or cyclic ethers (e.g., ethylene oxide, propylene oxide, styrene oxide, tetrahydrofuran, etc.). The selected one or more polyether polyols advantageously have a number average molecular weight value (Mn) of 200 to 10,000 and preferably 250 to 8,000. Mixtures of different polyether polyols are contemplated. Examples of some useful polyether polyols include Voranol 220-028, Voranol 220-094, Voranol 225, Voranol 270, Voranol 490, and Voranol 800 (products of The Dow Chemical Company) and Arcol 1 1-34 (Bayer Material Science), and the like.

[0084] The foam composition also includes an isocyanate composition. The isocyanate may include at least one isocyanate, and may include more than one isocyanate. The isocyanate may be selected from aromatic isocyanates, aliphatic isocyanates, or any combination thereof. The isocyanate composition may include an aromatic isocyanate, such as polymeric MDI. If the isocyanate composition includes an aromatic isocyanate, the aromatic isocyanate may correspond to the formula R 5 (NCO)z, where R 5 is an aromatic polyvalent organic group, and z is a 5 Typically, z is at least 2.

[0085] The isocyanate composition may include, but is not limited to, 1,4-diisocyanatobenzene, 1,3-diisocyanato-o-xylene, 1,3-diisocyanato-p-xylene, 1,3-diisocyanato-m-xylene, 2,4-diisocyanato-1-chlorobenzene, 2,4-diisocyanato-1-nitrobenzene, 2,5-diisocyanato-1-nitrobenzene, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, a mixture of 2,4- and 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, and 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, triisocyanates such as 4,4′,4″-triphenylmethane triisocyanate polymethylene polyphenylene polyisocyanate and 2,4,6-toluene triisocyanate, tetraisocyanates such as 4,4′-dimethyl-2,2′-5,5′-diphenylmethane tetraisocyanate, toluene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, corresponding isomer mixtures thereof, and any combination thereof.

[0086] The foam composition also includes one or more catalysts, such as a gelling catalyst, a foaming catalyst, or a trimerization catalyst. The catalyst generally catalyzes the reaction of a polyol (a main polyol component and / or a modified or unmodified phenolic resin) with an isocyanate composition. Specifically, a gelling catalyst can catalyze the reaction of a hydroxyl group with an isocyanate to generate a urethane bond. A foaming catalyst can promote the reaction of water with an isocyanate to generate a urea bond. A trimerization catalyst can promote the reaction of three isocyanate groups to form an isocyanurate bond. The catalyst of the present technology may include one or more catalysts, and typically includes a combination of catalysts. The catalyst can catalyze the exothermic reaction between the resin composition and the isocyanate composition. The catalyst is generally not consumed in the exothermic reaction. The catalyst may include any suitable catalyst or a mixture of catalysts known in the art. Examples of suitable catalysts include, but are not limited to, amine catalysts in appropriate diluents, for example, bis(dimethylaminoethyl) ether in dipropylene glycol; and metal catalysts, for example, tin, bismuth, lead, etc. If a catalyst is included, it can be included in multiple amounts. In one embodiment, the catalyst is selected from N,N-dimethylcyclohexylamine (DMCHA), N,N,N′,N′,N′′-pentamethyldiethylenetriamine (PMDETA), amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N-methylmorpholine, S-ethylmorpholine, N-cyclohexylmorpholine, N,N,N′,N′-tetramethylethylenediamine, N,N,N ',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, bis(dimethylaminoethyl)ether, bis(dimethylaminopropyl)ureadimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo[3.3.0]octane and typically 1,4-diazabicyclo[2.2.2]octane, alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyl

[0043] The invention also includes the following: 1,2-diethanolamine, 2,4-dimethylethanolamine, 3,4-dialkylaminoalkyl-s-hexahydrotriazines including 3,4-dimethylaminopropyl-s-hexahydrotriazine, 4 ...In various embodiments, the catalyst may be included in an amount of 0.5 to 3, 0.5 to 8, 1 to 7, 3 to 5.5, or even 3.5 to 4.5 weight percent of the foam composition.Here, as elsewhere in the specification and claims, numerical values ​​may be combined to form new or undisclosed ranges.

[0087] Catalysts include, for example, foam-forming organometallic catalysts such as nickel acetylacetonate, iron acetylacetonate, tin-based catalysts, bismuth-based catalysts, and zinc-based catalysts. Other useful urethane catalysts include alkali metal carboxylates such as potassium octoate, potassium acetate, sodium acetate, and sodium octoate, heavy metal-based catalysts such as those of mercury or lead, tertiary amine urethane catalysts such as triethylenediamine and bis(dimethylaminoethyl)ether, and quaternary ammonium salt catalysts such as quaternary ammonium carboxylates such as DABCO from Air Products. ® TMR catalyst. The foam composition may further include a surfactant.

[0088] The surfactant may be an organosilicon surfactant, a non-organosilicon surfactant, or a combination of the two. Any surfactant known in the art may be used in the present invention. In one embodiment, the surfactant is selected from an organosilicon surfactant. Generally, the organosilicon surfactant can control the cell size, closed cell content and shape of the rigid foam produced by the reaction of the resin composition and the isocyanate composition.

[0089] In one embodiment, the surfactant may include a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a combination thereof. In various embodiments, the surfactant may include, but is not limited to, a polyoxyalkylene polyol surfactant, an alkylphenol ethoxylate surfactant, and a combination thereof. In one embodiment, a salt of a sulfonic acid, such as an alkali metal and / or ammonium salt of oleic acid, stearic acid, dodecylbenzene-disulfonic acid or dinaphthylmethane-disulfonic acid and ricinoleic acid, a foam stabilizer such as a silicone oxide copolymer and other organopolysiloxanes, an oxyethylated alkylphenol, an oxyethylated fatty alcohol, paraffin oil, castor oil, castor oil esters and ricinoleic acid esters, and a cell regulator such as a fatty alcohol, dimethylpolysiloxane, and a combination thereof. In one embodiment, the foam composition may include Niax® L-6900.

[0090] If a surfactant is included in the resin composition, the surfactant may be present in any suitable amount. In various embodiments, the surfactant is present in an amount of 0.5 to 3, 1 to 3, or about 2% by weight of the foam composition. Here, as elsewhere in the specification and claims, numerical values ​​may be combined to form new or undisclosed ranges.

[0091] The foam composition may also include a non-silicone surfactant. The non-silicone surfactant may be used together with the silicone surfactant or alone. Any surfactant known in the art may be used in the present invention. Therefore, the surfactant may include a nonionic surfactant, a cationic surfactant, an anionic surfactant, a zwitterionic surfactant, and a combination thereof. In various embodiments, the surfactant may include, but is not limited to, a polyoxyalkylene polyol surfactant, an alkylphenol ethoxylate surfactant, and a combination thereof. If the surfactant is included in the resin composition, the surfactant may be present in any appropriate amount.

[0092] The foam composition may also include one or more blowing agents, including but not limited to physical blowing agents, chemical blowing agents, or any combination thereof. In one embodiment, the blowing agent may include both a physical blowing agent and a co-chemical blowing agent, and the blowing agent may be included in the foam composition. Physical blowing agents typically do not chemically react with the resin composition and / or the isocyanate to provide a foaming gas. The physical blowing agent may be a gas or a liquid. Liquid physical blowing agents may evaporate into a gas when heated and may return to a liquid when cooled. Physical blowing agents may reduce the thermal conductivity of rigid polyurethane foams. Blowing agents may include but are not limited to methylene chloride, acetone and liquid carbon dioxide, aliphatic and / or alicyclic hydrocarbons such as halogenated hydrocarbons and alkanes, acetals, water, alcohols, glycerol, formic acid, and any combination thereof. In an embodiment, the composition comprises a chemical blowing agent selected from water, formic acid, or a combination thereof.

[0093] In various embodiments, the blowing agent may be selected from pentane isomers, hydrofluorocarbons, hydrofluoroolefins, volatile non-halogenated C2-C7 hydrocarbons such as alkanes including n-pentane, olefins, cycloalkanes having up to 6 carbon atoms, dialkyl ethers, cycloalkylene ethers and ketones, and hydrofluorocarbons, C1-C4 hydrofluorocarbons, volatile non-halogenated hydrocarbons such as linear or branched alkanes such as butane, isobutane, 2,3-dimethylbutane, n-pentane and isopentane, n-hexane and isohexane, n-heptane and isoheptane, n-octane and isooctane, n-nonane and isononane, n-decane and isodecane, n-undecane and isondecane and n-dodecane and isododecane, olefins such as 1-pentene, 2-methylbutene, 3-methylbutene and 1-hexene, cycloalkanes such as cyclobutane, cyclopentane and cyclohexane, linear and / or cyclic ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, vinyl methyl ether, vinyl ethyl ether, divinyl ether, tetrahydrofuran and furan, ketones such as acetone, methyl ethyl ketone and cyclopentanone, isomers thereof, hydrofluorocarbons Hydrocarbons such as difluoromethane (HFC-32), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1-difluoroethane (HFC-152a), 1,2-difluoroethane (HFC-142), trifluoromethane, heptafluoropropane (R-227a), hexafluoropropane (R-136), 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, fluoroethane (R-161), 1,1,1,2,2-pentafluoropropane, pentafluoropropylene (R-2125a), 1,1,1,3-tetrafluoropropane, tetrafluoropropylene (R-2134a), difluoropropylene (R-2152b), 1,1,2,3,3-pentafluoropropane, 1,1,1,3,3-pentafluoro-n-butane and 1,1,1,3,3-pentafluoropentane (245fa), isomers thereof, 1,1,1,2-tetrafluoroethane (HFC-134a), isomers thereof, and combinations thereof. In various embodiments, the blowing agent may be further defined as 1,1,1,3,3-pentafluoropropane (245fa), or a combination of HFC 245fa, 365MFC, 227ea, and 134a. In an alternative embodiment, the blowing agent may be further defined as 365 MFC, which may be blended with 227ea.

[0094] In various embodiments, the blowing agent may be present in an amount of 0.1 to 20, 1 to 18, 4 to 16, 7 to 14, 9 to 12, or 10 to 11 weight % of the foam composition. Here, as elsewhere in the specification and claims, values ​​may be combined to form new or undisclosed ranges. Generally, the amount of blowing agent and / or water may be selected based on the desired density of the rigid foam and the solubility of the blowing agent in the resin composition. It may be desirable to minimize the amount of blowing agent used to reduce costs.

[0095] The foam composition may also include a crosslinker and / or a chain extender. The crosslinker may include, but is not limited to, additional polyols, amines, and any combination thereof. If a crosslinker is included in the foam composition, the crosslinker may be present in any suitable amount. Chain extenders contemplated for use in the present technology include, but are not limited to, hydrazines, primary and secondary diamines, alcohols, amino acids, hydroxy acids, diols, and combinations thereof. Specific chain extenders contemplated for use include, but are not limited to, mono- and di-ethylene glycol, mono- and di-propylene glycol, 1,4-butanediol, 1,3-butanediol, propylene glycol, dipropylene glycol, diethylene glycol, methylpropylene glycol, mono-, di- and tri-ethanolamine, NN′-bis-(2-hydroxy-propylaniline), trimethylolpropane, glycerol, hydroquinone bis(2-hydroxyethyl) ether, 4,4′-methylene-bis(2-chloroaniline), diethyltoluenediamine, 3,5-dimethylthio-toluenediamine, hydrazine, isophoronediamine, adipic acid, silane, and any combination thereof.

[0096] The foam composition may also include one or more additives. Suitable additives include, but are not limited to, non-reactive flame retardants (e.g., various phosphates, various phosphonates, triethyl phosphate, trichloropropyl phosphate, triphenyl phosphate, or diethyl ethylphosphonate, tris(2-chloroethyl) phosphate, triethyl-phosphate, tris(2-chloropropyl) phosphate, tris(1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum oxide trihydrate, polyvinyl chloride, and any combination thereof), OH-free / Non-reactive flame retardants, chain terminators, inert diluents, amines, defoamers, air release agents, wetting agents, surface modifiers, waxes, inert inorganic fillers, molecular sieves, reactive inorganic fillers, chopped glass, other types of glass such as glass mats, processing additives, surface active agents, tackifiers, antioxidants, dyes, pigments, UV stabilizers, thixotropic agents, anti-aging agents, antistatic additives, lubricants, coupling agents, solvents, rheology promoters, cell openers, mold release additives, and combinations thereof. One or more additives may be present in the foam composition in any amount.

[0097] Polyurethane foam compositions employing the compatibilizing additives of the present invention can be provided as a one-part or two-part system. In a one-part system, the respective components are provided as parts of a single composition. Polyurethane foam compositions are typically provided as two-part compositions. In a two-part composition, the polyol and isocyanate are provided as separate compositions that are subsequently mixed together for forming the polyurethane. The isocyanate component of the two-part system is typically referred to in the art as the "A-side" component, and the polyol component is typically referred to in the art as the "B-side" component.

[0098] In one embodiment, polyurethane composition is provided as two-part composition, wherein B side component comprises polyol and compatibility additive.B side may include other components such as but not limited to catalyst, surfactant, fire retardant, foaming agent etc.In one embodiment, the presence of compatibility additive can be based on the weight of polyol composition about 0.5 wt % to about 20 wt %, about 1 wt % to about 15 wt %, about 2.5 wt % to about 10 wt %, or about 5 wt % to about 7.5 wt %.In one embodiment, the presence of compatibility additive is based on the gross weight of polyol composition about 1.5 wt % to about 7 wt %, about 2 wt % to about 6 wt %, or about 2.5 wt % to about 5 wt %.

[0099] In one embodiment comprising a first compatibilizing additive (wherein m is 0 and n is 1) and a second compatibilizing additive (wherein m ≥ 1 and n ≥ 1), the first compatibilizing additive is present in an amount from about 1 wt % to about 15 wt %, from about 1.5 wt % to about 12 wt %, from about 3 wt % to about 10 wt %, or from about 4 wt % to about 6 wt %, and the second compatibilizing additive is present in an amount from about 0.5 wt % to about 6 wt %, from about 1 wt % to about 5 wt %, or from about 2 wt % to about 4 wt %.

[0100] In addition to foam compositions, the present technology also provides methods of forming foam and methods of forming foam on a surface.

[0101] The method of forming a rigid foam typically includes the step of combining a polyol composition with an isocyanate composition. Most typically, the polyol and isocyanate composition are combined so that the isocyanate index is about 250 or less. In an embodiment, the isocyanate index is about 225 or less; about 200 or less; about 150 or less; about 125 or less; about 100 or less; even about 90 or less. In an embodiment, the isocyanate index is about 90 to about 250, about 95 to about 240, about 100 to about 200, about 115 to about 180, or even about 125 to about 165. In one embodiment, the isocyanate index is about 90 to about 225; even about 100 to about 200. Here, as elsewhere in the specification and claims, values ​​can be combined to form new or undisclosed ranges. Those skilled in the art will understand that the foam can be a polyurethane foam or a polyisocyanurate foam. Foams with an isocyanate index of about 250 are typically in the category of polyisocyanurate foams. However, it will be appreciated that there is no absolute index value that separates polyurethane foams from polyisocyanurate foams.

[0102] The method of forming a rigid foam on a surface may include the step of combining the components to form a foam mixture. Generally, the combining step may occur in a mixing device such as a static mixer, an impingement mixing chamber, or a mixing pump. In one embodiment, the mixing step occurs in a static mixing tube. Alternatively, the foam composition and the isocyanate composition may be combined in a spray nozzle.

[0103] In one embodiment, the components are combined with an air stream typically having a pressure of 1 to 5 psi. The isocyanate composition can be combined with the air stream prior to being combined with the foam composition. Alternatively, the polyol and modified phenolic resin can be combined with the air stream prior to being combined with the isocyanate composition. Additionally, the components can be combined with the air stream simultaneously. It is believed that the air stream aids in mixing and promotes uniform spraying and distribution of the foam mixture.

[0104] The components can be combined while on or off the surface. In one embodiment, the components can be combined in a spray gun head or in the air above the surface to which the composition is being applied. The components can be combined and applied to the surface by any method known in the art, including spraying, dipping, pouring, coating, painting, etc.

[0105] The present technology provides rigid polyurethane foams ("rigid foams"). The rigid foams may be open-cell or closed-cell and may include a highly cross-linked polymer structure, which allows the foam to have good thermal stability, high compressive strength at low density, low thermal conductivity, and good barrier properties. Typically, the rigid foams of the present technology may have a glass transition temperature greater than room temperature (approximately 23°C + / - 2°C (approximately 73.4°F + / - 3.6°F)) and are typically rigid at room temperature. In general, the foam is rigid at or below its glass transition temperature, particularly in the glassy region of its storage modulus. The rigid foam may have a tensile strength of about 10 to about 1,100 kg / m 3 , about 50 to about 1,000 kg / m 3 , about 100 to about 850 kg / m 3 , about 250 to about 650 kg / m 3 , even about 350 to about 500 kg / m 3 In one embodiment, the rigid foam may have a density of about 10 to about 50 kg / m 3 Here, as elsewhere in the specification and claims, numerical values ​​can be combined to form new or undisclosed ranges.

[0106] The foam mixture can be applied to any suitable surface, such as brick, concrete, masonry, drywall, gypsum sandwich panel, plaster, metal, stone, wood, plastic, polymer composite material or any combination thereof. In addition, the surface can be a mold surface, and thus the rigid foam can be formed in the mold.

[0107] The resulting rigid foam can be used in the form of slabstock, molded parts, or filled cavities. The filled cavities can be, for example, pipes, insulated walls, insulated hull structures. The rigid foam can be spray foam, foamed foam, or a continuously manufactured laminated product or a discontinuously manufactured laminated product, including but not limited to laminates or laminated products formed with other materials such as hardboard, gypsum board, plastic, paper, metal, or combinations thereof.

[0108] The foam mixture can be sprayed at a spray rate of 1 to 30 lbs / min, a rate of 5 to 25 lbs / min, and even a rate of 5 to 20 lbs / min. Moreover, the foam mixture can be sprayed typically at a pressure of less than 3000 psi. Here, as elsewhere in the specification and claims, numerical values ​​can be combined to form new or undisclosed ranges.

[0109] In various embodiments, the foam mixture can be sprayed in a single pass so that the rigid foam formed therefrom has a thickness (in a single pass) of 1 to 10 inches, 2 to 8 inches, 3 to 7 inches, 4 to 6 inches, 4 to 5 inches, or even 6 to 9 inches, with minimal or no visible discoloration and / or scorching. Here, as elsewhere in the specification and claims, numerical values ​​may be combined to form new and undisclosed ranges.

[0110] The rigid foam comprising the above foam composition may be further understood with reference to the following examples.

[0111] Example

[0112] The polyol composition was prepared according to the following formula:

[0113] Table 1

[0114]

[0115]

[0116] Tests were run using different compositions of surfactants. The surfactants were silicone surfactants of the type MDxD'yM, where the D' units contained polyether pendant functional groups. The polyether functional groups may include ethylene oxide and / or propylene oxide units in the polyether chain. The surfactants used in each composition are listed in Table 2:

[0117] Table 2

[0118]

[0119] A compatibilizer is added to the composition. The compatibilizers evaluated are materials according to formula (I). The compatibilizers are trisiloxanes (wherein in formula (I), m is 0) and polysiloxane polyalkylene oxide copolymer additives (wherein in formula (I), m is greater than 0). The compositions of the compatibilizers are listed in Table 3:

[0120] Table 3

[0121]

[0122] The following table identifies the initial appearance of the polyol pre-blends with the corresponding surfactants, and the amount of compatibilizing additives added to obtain a clear homogeneous solution. A comparative example (designated "CE") was also run without any surfactant. In some embodiments, materials belonging to the compositions of formula (I) according to the present invention were evaluated as surfactants alone.

[0123] Table 4 - Polyol Solutions: Example 1

[0124]

[0125] Table 4 shows the evaluation of compatibilizing additives in the case of the polyols of Example 1 using various surfactants. The blowing agent used with the polyols of Example 1 was a hydrofluoroolefin (HFO-1366mzz-Z). In the absence of the compatibilizing additive, the polyol compositions were turbid or clear, but there was separation of the components. Except for Comparative Example CE-1, the addition of the compatibilizing additives in a ratio of at least 1:1 or greater provided clear, uniform solutions. For surfactants 2, 5, and 7, equal amounts of the compatibilizing additives were suitable for obtaining clear, uniform solutions. Equal amounts of the compatibilizing additives were also suitable in the case where the compatibilizing additives were used as surfactants.

[0126] Table 5

[0127]

[0128]

[0129] Table 5 shows the evaluation of compatibilizing additives in the case of the polyols of Example 2 using various surfactants. The blowing agent used with the polyols of Example 2 was a hydrofluoroolefin (HFO-1366mzz-Z). Surfactants with high m:n ratios (greater than 6:1) require the use of compatibilizing additives in an amount of at least twice the amount of surfactant. Surfactants with lower m:n ratios require less compatibilizing additives.

[0130] Table 6

[0131]

[0132] Table 6 shows the evaluation of compatibilizing additives in the case of the polyols of Example 3 with various surfactants. The blowing agent employed with the polyols of Example 3 was a hydrofluoroolefin (HFO-1233zd(E)). With this blowing agent, the polyol solutions were initially clear in the case of Surfactant 2, no surfactant, and when Additives A and B were added as surfactants. These solutions did not require any compatibilizing additives. Surfactant 7, with an m:n ratio of less than 6, required only an equal amount of compatibilizing additive relative to the surfactant. Other surfactants with higher m:n ratios required at least twice the amount of compatibilizing additives.

[0133] Table 7

[0134]

[0135] The polyol solution of Example 4 is similar to Example 3, except that Example 4 uses a higher amount of surfactant. As with Example 3, the polyol solution is clear with Surfactant 2 and Additives A and B as surfactants. Surfactants 1 and 4 require 2 times the amount of compatibilizer compared to the primary surfactant, and Surfactants 3 and 6 require further addition to make the polyol pre-blend clear. Structural analysis shows that those with low m:n (less than 6) require less compatibilizer loading and can be used as compatibilizers by themselves, although not as effective as Additives AF mentioned.

[0136] Table 8

[0137]

[0138]

[0139] Without being bound by any particular theory, Table 8 may indicate that the polarity of the surfactant, polyol pre-blend, blowing agent, and compatibilizing additive are relevant to maintaining the homogeneity of the system.

[0140] Foams were prepared using the polyol pre-blend of Example 1 with either Surfactant 1 or Surfactant 6. The foams were prepared as follows. All B-side (polyol) components were added to a bottle and capped. The bottle was shaken for 30 minutes to provide thorough mixing. The bottle temperature of the B-side composition was controlled to 70°F. This can be accomplished using a water bath or the room itself. If in a water bath, the bottle was shaken thoroughly before weighing the components to keep them mixed. The blend was of very low viscosity and easy to mix.

[0141] In a paper cup on a scale, weigh out the amount of B-side blend needed to fill a 12" x 12" x 3" mold. This amount is typically about 240 g, filling the mold with 10% overloading. Then, add the isocyanate (Papi 27 or similar) to the top of the polyol mixture in the cup. Then, mix the mixture at 3500 RPM for 4 seconds and pour it into the mold for 5 seconds. The mold was closed at 120°F for a demolding period of 4 minutes. The foam pad was removed and stored in the test laboratory at room conditions of 70°F overnight (16 hours) and cut the next day.

[0142] Physical Properties Analysis Procedure: The physical properties of the foams were analyzed as follows.

[0143] K Factor: 8" x 8" x 1" samples were cut from the foam core for analysis of thermal conductivity. They were run per ASTM C-1289 on a Fox 200 instrument (Lasercomp) with a 100°F lower plate and a 50°F upper plate to achieve an average of 75°F.

[0144] Pad density and K factor were evaluated in foams made with polyol pre-blends containing only Surfactant 1 or 6 and those in which Additive A was added to the polyol pre-blend.

[0145] Table 9 shows the foam properties of these foams.

[0146] Table 9

[0147]

[0148]

[0149] Table 9 shows minimal changes in density (due to pour time and viscosity reduction when mixing by hand) and k-factor using the polyol of Example 1. This indicates that at low to moderate usage levels (less than 12%), use of the present invention has minimal impact on the physical properties of rigid foams using a variety of blowing agents, and the material remains clear over extended periods of time.

[0150] Foams were prepared using the polyol pre-blend of Example 3 with Surfactant 1 and Surfactant 6. Foams were prepared without compatibilizing additives and with the addition of 7.5 and 9.0 wt% Additive A. 9.0% Additive A is close to the maximum amount required to obtain the homogeneity of the polyol pre-blend (Example 3) mentioned in Table 4 and is greater than that required to compatibilize Example 5 (Table 8) using Surfactant 2. Foams were prepared using Surfactant 2 as the primary surfactant and with 7.5 and 9.0 wt% Additive A (3% surfactant) added in both Formulations B and F to determine the effect of the higher amounts of the present invention on physical properties when using a more ideal primary surfactant (Table 10).

[0151] Table 10

[0152]

[0153] Additional studies were conducted with other compatibilizing additives. Tables 11-13 show the use of Additives A, B, C, D, E, F, G, I, K, and P to achieve clear homogeneous solutions of the polyol pre-blends of Examples 1, 3, and 5.

[0154] Table 11

[0155]

[0156] Table 12

[0157]

[0158] Table 13

[0159]

[0160]

[0161] Embodiments of the present technology have been described above, and modifications and alterations may occur to others when they read and understand this specification. The following claims are intended to include all modifications and alterations as long as they fall within the scope of the claims or their equivalents.

Claims

1. A polyurethane or polyisocyanurate foam composition, comprising: a polyol or a mixture thereof; an isocyanate; a compatibility additive; a surfactant; and a polyurethane catalyst or a mixture thereof; wherein the compatibility additive is selected from compounds of the following formula: M 1 D 1 m D 2 n M 2 (I) wherein: M 1 is (R 1 )(R 2 )(R 3 )Si-O 1 / 2 M 2 is (R 4 )(R 5 )(R 6 )Si-O 1 / 2 D 1 is (R 7 )(R 8 )Si-O 2 / 2 D 2 is (R 9 )(R 10 )Si-O 2 / 2 R 10 is –CH2-CH(R 11 )-CH2-O-[CH2CH(CH3)O] p -[CH2CH2O] q -R 12 R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Independently selected from C1-C10 alkyl or R 10 ; R 7 , R 8 and R 9 independently selected from C1-C10 alkyl, R 11 is H or C1-C10 alkyl; R 12 is H, a C1-C10 alkyl group, or an acetyl group; m is from 0 to 100; n is from 1 to 50; p is from 0 to 35; q is from 0 - 45; and p + q ≥ 1.

2. The composition according to claim 1, wherein the composition is a two - part composition comprising: (i) a first part comprising the isocyanate, and (ii) a second part comprising the polyol and the compatibility additive.

3. The composition according to claim 1 or 2, wherein m is 0 and n is 1.

4. The composition according to claim 3, wherein p is from 1 to 10.

5. The composition according to claim 4, wherein q is 0.

6. The composition according to claim 3, wherein q is from 1 to 10.

7. The composition according to claim 6, wherein p is 0.

8. The composition according to claim 1 or 2, wherein m ≥ 0 and n ≥ 1, where m:n ≤ 6:

1.

9. The composition according to claim 8, wherein the ratio of m:n is from about 0.1:1 to 6:

1.

10. The composition according to claims 8 and 9, wherein 0 < m ≤ 15 and 1 < n ≤ 5.

11. The composition of any one of claims 1 to 10, wherein R 11 For H.

12. The composition of any one of claims 1 to 10, wherein R 11 It is a C1-C10 alkyl group.

13. The composition of claim 12, wherein R 11 It is methyl.

14. The composition according to any one of claims 1 - 13, wherein the compound of formula (I) has a silicon content of less than 25% by weight of the weight of formula (I).

15. The composition according to any one of claims 1 - 13, wherein the compound of formula (I) has a silicon content of less than 20% by weight of the weight of formula (I).

16. The composition according to any one of claims 1 - 13, wherein the compound of formula (I) has a silicon content of from about 1% to about 25% by weight of the weight of formula (I).

17. The composition according to any one of claims 1 - 16, wherein the compatibility additive is present in an amount of about 0.5 to about 20 parts per hundred parts of polyol.

18. The composition according to any one of claims 1 - 17, wherein the amount of the compatibility additive present is equivalent to the amount of the surfactant present in the composition.

19. The composition according to any one of claims 1 - 17, wherein the amount of the compatibility additive present is greater than the amount of the surfactant present in the composition.

20. The composition according to claim 19, wherein the amount of the compatibility additive present is about 1.2 to 6 times the amount of the surfactant present in the composition.

21. The composition according to any one of claims 1 - 20, further comprising a blowing agent.

22. A method of forming a foam, comprising reacting the composition according to any one of claims 1 - 21.

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