Additive for polyurethane foam polyol blend and polyurethane foam containing the same

Abstract

The present technology provides a method for producing a rigid polyurethane foam having a low thermal conductivity from a foam composition containing a polyol, an isocyanate, a polyurethane catalyst, a surfactant, and a compatibility additive. The compatibility additive improves the compatibility between one or more components in the foam-forming composition and the polyol component.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the priority and benefit of U.S. Provisional Patent Application No. 63 / 358,640, filed on July 6, 2022, the disclosure of which is hereby incorporated by reference in its entirety.

[0002] The present technology generally relates to polyurethane foam compositions and foams made from such compositions. More specifically, the present technology relates to additives that improve the compatibility of components in polyurethane foam compositions, particularly the compatibility between components and polyols. This technology also relates to polyurethane foams formed using such compositions and additives.

Background Art

[0003] Rigid polyurethane foams and polyisocyanurate foams are widely used as insulation materials in the construction industry. Such foams exhibit excellent insulation properties.

[0004] Conventional rigid polyurethane foams that can be used for insulation applications are generally prepared by the reaction of at least one polyol and at least one isocyanate in the presence of a suitable catalyst, surfactant, water, and blowing agent. In a mixture with a polyol, whether as a separate polyol component in a two - component composition or as a one - component composition containing each component, the respective components separate over time and / or are not fully compatible, and thus the composition becomes cloudy (i.e., loses transparency).

Summary of the Invention

[0005] The present technology provides an additive for polyols used in polyurethane foam compositions. This additive functions as a compatibilizer in polyols suitable for use in polyurethane foam compositions such as, for example, rigid polyurethane foams. This additive provides stability to the polyol. In one embodiment, the additive is provided to a polyol blend, providing stability and transparency to the polyol blend. This can be seen in the appearance of the polyol, where separation of the components in the blend is reduced or avoided, and / or can be seen in the transparency of the polyol blend.

[0006] This additive also acts to help retain blowing agents during the manufacture of polyurethane foams.

[0007] In addition, the adverse effects that the use of this additive has on the physical properties of the foam produced using this additive are minimal or non - existent.

[0008] In one embodiment, the present technology provides a polyurethane foam composition comprising a polyol, an isocyanate, a polyurethane catalyst, a surfactant, a compatibilizing 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 compatibilizing additive is a silicone - based compound containing pendant polyol groups and has been found to reduce or prevent separation of components in polyol compositions, such as polyol blends for polyurethane foams or one - component polyurethane foam compositions.

[0009] Provided in one embodiment is a polyurethane or polyisocyanurate foam composition comprising: a polyol or a mixture thereof; an isocyanate; a compatibilizing additive; a surfactant; and a catalyst for polyurethane or a mixture thereof; where the compatibilizing additive has the formula: M 1 D 1m D 2 n M 2 (I) selected from the compounds of: 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 are independently selected from C1 - C10 alkyl or R 10 ; R 7 、R 8 、and R 9 are independently selected from C1 - C10 alkyl, R 11 is H or C1 - C10 alkyl; R 12 is H, C1 - C10 alkyl, or an acetyl group; m is from 0 to 100; n is from 1 to 50; p is from 0 to 35; q is 0 - 45; and p + q ≥ 1.

[0010] In one embodiment, the composition is a two-component composition containing (i) a first component containing an isocyanate and (ii) a second component containing a polyol and a compatibilizing additive.

[0011] In one embodiment, m is 0 and n is 1.

[0012] In one embodiment, p is from 1 to 10. In one embodiment, q is 0.

[0013] In one embodiment, q is from 1 to 10. In one embodiment, p is 0.

[0014] In one embodiment, m ≧ 0 and n ≧ 1, where m:n ≦ 6:1.

[0015] In one embodiment, the ratio of m:n is from about 0.1:1 to 6:1.

[0016] In one embodiment, 0 < m ≦ 15 and 1 < n ≦ 5.

[0017] In one embodiment according to any of the above embodiments, R 11 is H.

[0018] In one embodiment according to any of the above embodiments, R 11 is C1-C10 alkyl. In one embodiment, R 11 is methyl.

[0019] In one embodiment according to any of the above embodiments, the compound of formula (I) has a silicon content of less than 25% by weight of the weight of formula (I).

[0020] In one embodiment according to any of the above embodiments, the compound of formula (I) has a silicon content of less than 20% by weight of the weight of formula (I).

[0021] In one embodiment according to any of the above embodiments, the compound of formula (I) has a silicon content of about 1 wt% to 25 wt% of the weight of formula (I).

[0022] In one embodiment according to any of the above embodiments, the compatibilizing additive is present in an amount of about 0.5 to about 20 parts per 100 parts of polyol.

[0023] In one embodiment according to any of the above embodiments, the compatibilizing additive is present in an amount equal to the amount of surfactant present in the composition.

[0024] In one embodiment according to any of the above embodiments, the compatibilizing additive is present in an amount exceeding the amount of surfactant present in the composition.

[0025] In one embodiment according to any of the above embodiments, the compatibilizing additive is present in an amount of about 1.2 to 6 times the amount of surfactant present in the composition.

[0026] In one embodiment according to any of the above embodiments, the composition further comprises a blowing agent.

[0027] In yet another embodiment, there is provided a method for forming a foam, comprising reacting a composition according to any of the above embodiments.

Mode for Carrying Out the Invention

[0028] The present technology provides an additive for improving the compatibility of components in a foam-forming composition, a foam-forming composition containing such an additive, and a foam made from such a foam-forming composition. This composition may be used to provide a rigid foam. The foam composition comprises: (a) a polyol component; (b) an isocyanate component; (c) a compatibility additive; (d) a surfactant; and (e) a catalyst component. The polyol component and the isocyanate component can be provided as separate components of each component of a two-component composition or as a one-component mixture. The compatibility additive has been found to improve, for example, the compatibility of the components used in the foam-forming composition with the polyol.

[0029] The compatibility additive is a silicone-based compound and contains pendant polyol groups. In one embodiment, the compatibility additive has the formula (I): M 1 D 1 m D 2 n M 2 (I) and is selected from compounds of: 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 R1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently C1-C10 alkyl or R 10 Selected from; R 7 , R 8 , and R 9 is independently selected from C1-C10 alkyl; R 11 is H or C1-C10 alkyl; R 12 is H, C1-C10 alkyl, or acetyl group; m is from 0 to 100; n is 1 to 50; p ranges from 0 to 35; q is 0-45; and p+q≧1.

[0030] 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. 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-C4 alkyl or C1-C2 alkyl. In one embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9is independently selected from methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, or decyl. In one embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each methyl.

[0031] In one embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from C1-C10 alkyl or R 10 , where at least one of R 1 , R 2 , R 3 , R 4 , R 5 , and / or R 6 is an R 10 group. In one embodiment, at least one of R 1 , R 2 , or R 3 is an R 10 group, and at least one of R 4 , R 5 , or R 6 is an R 10 group.

[0032] R 11 is selected from H or C1-C10 alkyl. In one embodiment, R 11 is H. In one embodiment, R 11 is selected from C1-C10 alkyl, C2-C8 alkyl, or C4-C6 alkyl. In one embodiment, R 11 is -CH3.

[0033] R 10The base contains polyethylene and polypropylene units and is hydrogen for R 12 and includes polyethylene glycol and / or polypropylene glycol units formed with a group. In R 10 the group, p is from 0 to 35, 1 to 30, 5 to 25, or 10 to 20; and q is from 0 to 45, 1 to 40, 5 to 35, 10 to 30, or 15 to 25, where p + q ≥ 1. In one embodiment, q is 0 and p ≥ 1. In one embodiment, q is 0 and p is from 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 from 1 to 10, 2 to 8, or 3 to 5.

[0034] R 10 the group can have a number average molecular weight from about 85 to about 4000, about 200 to about 2000, or about 400 to about 1500. R 10 The molecular weight of the unit can be determined by analysis of the end groups, in particular the hydroxyl value and the unsaturation value obtained by titration, and can be further verified through NMR analysis.

[0035] The compatibilizing additive contains at least one D 2 group, i.e., n is at least 1. In one embodiment, the compatibilizing additive is trisiloxane, where m is 0 and n is 1. In an embodiment, the compatibilizing additive contains D 1 group and D 2 group, 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 exceeds 1, the ratio of m:n is ≤ 6:1, ≤ 5:1, ≤ 4:1, ≤ 3:1. In one embodiment where m exceeds 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.

[0036] 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.

[0037] Two or more compatible additives can be used in the foam-forming composition, and in particular with the polyol component of the foam-forming composition. In one embodiment, the composition comprises at least one compatible additive of formula (I), where m is 0 and n is 1. In one embodiment, the polyol composition comprises a first compatible additive of formula (I), where m is 0 and n is 1, and also a second compatible additive of formula (I), where m is 0 and n is 1, wherein the first compatible additive and the second compatible additive are R 1 -R 9 any of the groups, their R 10 groups, and / or R 10 groups are different from each other with respect to the p:q ratio.

[0038] In one embodiment, the composition comprises a first compatible additive of formula (I), where m is 0 and n is 1, and also a second compatible additive, where m ≥ 1 and n ≥ 1, and the ratio of m:n is ≤ 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.

[0039] The compatible additive of formula (I) has, in embodiments, a silicon content of less than 25 wt%, less than 20 wt%, less than 17.5 wt%, less than 15 wt%, or less than 10 wt% of the additive of formula (I). The compatible additive of formula (I) has, in one embodiment, a silicon content of from about 1 wt% to about 25 wt%, from about 3 wt% to about 20 wt%, from about 5 wt% to about 17.5 wt%, or from about 10 wt% to about 15 wt% based on the weight of the additive of formula (I).

[0040] The compatibilizing additive can be present in an amount of from about 0.5 parts to about 20 parts per 100 parts of polyol (pphp), from about 1 pphp to about 15 pphp, from about 2.5 pphp to about 10 pphp, or from about 5 pphp 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 from about 1.5 pphp to about 7 pphp, from about 2 pphp to about 6 pphp, or from about 2.5 pphp to about 5 pphp, based on the total weight of the polyol composition.

[0041] In one embodiment, it includes a first compatibilizing additive where m is 0 and n is 1, and a second compatibilizing additive where m is ≧1 and n is ≧1. The first compatibilizing additive is present in an amount of 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 of 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.

[0042] In one embodiment, the compatibilizing additive is present in an amount that is about 1.2 to about 6 times the amount of the surfactant, about 1.5 to about 5.5 times the amount of the surfactant, about 2 to about 5 times the amount of the surfactant, or about 2.5 to about 4 times the amount of the surfactant.

[0043] The polyol component is not particularly limited and may be selected as desired depending on a specific purpose or intended use. In various embodiments, the polyol may be selected from polyester polyols, polyether polyols, polycarbonate polyols, hydroxyl-terminated polyolefin polyols, and others, or combinations of two or more thereof. The polyol may be, for example, a polyester diol, a polyester triol, a polyether diol, a polyether triol, or others. Alternatively, the polyol may be selected from the group consisting of polythioether polyols, polycaprolactone, brominated polyether polyols, acrylic polyols, and others, or combinations of two or more thereof. When a highly functional polyether polyol is used, the highly functional polyether polyol may have a functionality of from about 3 to about 6. Polyols such as sucrose or sorbitol initiators may be mixed with less functional glycols or amines to make the functionality of the polyol in the range of from about 3.5 to about 5.

[0044] Suitable polyols include, but are not limited to, those having from 2 to 8 hydroxyl groups per molecule and a number average molecular weight of from 200 to 10,000, preferably from 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 diol. Other examples of suitable polyols include polyols derived from naturally occurring substances such as sucrose and amine-initiated polyols, polymer polyols (also referred to as graft polymer polyols, graft polyols, or copolymer polyols, which are all names used to describe vinyl polymer dispersions in polyols produced by in-situ polymerization of vinyl monomers (usually styrene and / or acrylonitrile) in a base polyol), castor oil, chemically modified soybean oil, or other chemically modified fatty acid oils, and polyols obtained from the alkoxylation of naturally occurring substances such as castor oil and soybean oil.

[0045] In addition, other particularly suitable polyols include aromatic polyester polyols. Aromatic polyester polyols may be prepared from substantially pure reactant materials or more complex starting materials, for example polyethylene terephthalate may be used. In addition, residues from the dimethyl terephthalate (DMT) process may be used to form aromatic polyester polyols.

[0046] The aromatic polyester polyol may contain halogen atoms. It may be saturated or unsaturated. The aromatic polyester polyol may have an aromatic ring content (expressed as the weight percentage 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 weight of the compound. Here, also at any place in the specification and claims, the 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.

[0047] The aromatic polyester polyol may have a hydroxyl value exceeding about 50 mg KOH / g, exceeding about 100 mg KOH / g, exceeding about 150 mg KOH / g, exceeding about 200 mg KOH / g, exceeding about 250 mg KOH / g, exceeding about 300 mg KOH / g, exceeding about 350 mg KOH / g, and even exceeding about 400 mg KOH / g. Here, also at any place in the specification and claims, the numerical values may be combined to form new or undisclosed ranges.

[0048] In one embodiment, the aromatic polyester polyol has a functionality exceeding about 1, exceeding about 2, exceeding about 3, exceeding about 4, exceeding about 5, exceeding about 6, exceeding about 7, and even exceeding about 8. Here, also at any place in the specification and claims, the numerical values may be combined to form new or undisclosed ranges.

[0049] Exemplary polyols are polyether diols, triols, tetraols, and polyols with greater hydroxyl functionality that have been used heretofore in the manufacture of polyurethane foams. Polyether polyols are typically prepared by reacting a starting compound such as a polyhydroxyl compound, e.g., ethylene glycol, diethylene glycol, propylene glycol, glycerin, sucrose, etc., or a polyamine such as ethylenediamine, with one or more alkylene oxides, phenyl-substituted alkylene oxides, and / or cyclic ethers such as ethylene oxide, propylene oxide, styrene oxide, tetrahydrofuran, etc. The polyether polyol(s) selected advantageously have a number average molecular weight (Mn) of from 200 to 10,000, and preferably from 250 to 8,000. Mixtures of different polyether polyols are also 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 11-34 (Bayer MaterialScience), and others.

[0050] 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. When the isocyanate composition includes an aromatic isocyanate, the aromatic isocyanate may correspond to the formula R 5 (NCO)z where R 5 is a polyvalent organic radical, i.e., aromatic, and z is an integer corresponding to the valence of R 5 . Generally, z is at least 2.

[0051] The isocyanate composition may include, but is not limited to, 1,4-diisocyanatobenzene, 1,3-diisocyanate-o-xylene, 1,3-diisocyanate-p-xylene, 1,3-diisocyanate-m-xylene, 2,4-diisocyanate-1-chlorobenzene, 2,4-diisocyanate-1-nitrobenzene, 2,5-diisocyanate-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 diisocyanates, 1,5-naphthalene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-bisphenylene 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, mixtures of isomers corresponding thereto, and any combination thereof.

[0052] The foam composition also contains one or more catalysts, such as a gelling catalyst, a blowing agent catalyst, or a trimerization catalyst. The catalyst generally catalyzes the reaction between the polyol (the main polyol component and / or a modified or unmodified phenolic resin) and the isocyanate composition. Specifically, the gelling catalyst may catalyze the reaction between the hydroxyl and the isocyanate to form a urethane bond. The blowing agent catalyst may promote the reaction between water and the isocyanate to form a urea bond. The trimerization catalyst may promote the reaction of three isocyanate groups to form an isocyanurate bond. The catalyst of the present technology may contain one or more catalysts and typically contains a combination of catalysts. These catalysts may catalyze the exothermic reaction between the resin composition and the isocyanate composition. These catalysts are generally not consumed in the exothermic reaction. The catalyst may contain any suitable catalyst or mixture of catalysts known in the art. Examples of suitable catalysts include, but are not limited to, amine catalysts in a suitable diluent, such as bis(dimethylaminoethyl)ether dipropylene glycol; and metal catalysts, such as tin, bismuth, lead, and others. When included, the catalyst may be included in various amounts.In one embodiment, the catalyst is selected from the group consisting of 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)urea dimethylpiperazine, 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-ethyldiethanolamine, dimethylethanolamine, tris(dialkylaminoalkyl)-s-hexahydrotriazines such as tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal alkoxides such as sodium methoxide and potassium isopropoxide, alkali metal salts of long-chain fatty acids having 10 to 20 carbon atoms and / or side-chain hydroxyl groups, tin, iron, lead, bismuth, mercury, titanium, hafnium, zirconium, iron(II) chloride, zinc chloride, lead octylate stannous octylate, tin(II) salts of organic carboxylic acids such as tin(II) acetate, tin(II) octylate, tin(II) ethylhexanoate, and tin(II) laurate, and dialkyltin(IV) salts of organic carboxylic acids such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin maleate, and dioctyltin diacetate, potassium salts, potassium octanoate, potassium acetate, and any combination thereof.In various embodiments, the catalyst may be included in an amount of from 0.5 to 3 wt%, from 0.5 to 8 wt%, from 1 to 7 wt%, from 3 to 5.5 wt%, or even from 3.5 to 4.5 wt% of the foam composition. Here, also, at any place in the specification and claims, the numerical values may be combined to form new or undisclosed ranges.

[0053] The catalyst may include, for example, a foam-forming organometallic catalyst 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 octylate, potassium acetate, sodium acetate, and sodium octylate, heavy metal-based catalysts such as mercury-based and lead-based catalysts, tertiary amine urethane catalysts such as triethylenediamine and bis(dimethylaminoethyl) ether, quaternary ammonium salt catalysts such as quaternary ammonium carboxylates, for example: DABCO® TMR catalyst manufactured by Air Products. The foam composition may also include a surfactant.

[0054] The surfactant may be a silicone surfactant, a non-silicone surfactant, or a combination of both. Any surfactant known in the art may be used in the present invention. In one embodiment, the surfactant is selected from the group of silicone surfactants. Generally, the silicone surfactant may control the cell diameter, the content of closed cells, and the shape in the rigid foam produced from the reaction of the resin composition and the isocyanate composition.

[0055] In one embodiment, the surfactant may include a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and combinations thereof. In various embodiments, the surfactant may include, but is not limited to, polyoxyalkylene polyol surfactants, alkylphenol ethoxylate surfactants, and combinations thereof. In one embodiment, sulfonic acid and other salts, such as oleic acid, stearic acid, dodecylbenzenedisulfonic acid, or dinaphthalenemethanedisulfonic acid, and alkali metal salts and / or ammonium salts of ricinoleic acid form foam stabilizers with siloxane oxyalkylene copolymers and other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oil, castor oil, castor oil esters, ricinoleic acid esters, and cell regulators such as aliphatic alcohols, dimethylpolysiloxanes, and combinations thereof. In one embodiment, the foam composition may include Niax® L-6900.

[0056] When the 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 wt%, 1 to 3 wt%, or about 2 wt% of the foam composition. Here, also at any place in the specification and claims, the numerical values may form new or undisclosed ranges in combination.

[0057] The foam composition may also contain 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. Thus, the surfactant may include nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and combinations thereof. In various embodiments, the surfactant may include, but is not limited to, polyoxyalkylene polyol surfactants, alkylphenol ethoxylate surfactants, and combinations thereof. When the surfactant is included in the resin composition, the surfactant may be present in any suitable amount.

[0058] The foam composition may also contain one or more blowing agents which are, but are 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. The physical blowing agent typically does not chemically react with the resin composition and / or the isocyanate to produce a foaming gas. The physical blowing agent may be a gas or a liquid. The liquid physical blowing agent may evaporate and gasify when heated and may return to a liquid when cooled. The physical blowing agent may reduce the thermal conductivity of the rigid polyurethane foam. This blowing agent may include, but is not limited to, methylene chloride, acetone, and liquid carbon dioxide, aliphatic and / or cycloaliphatic hydrocarbons such as halogenated hydrocarbons and alkanes, acetals, water, alcohols, glycerin, formic acid, and any combination thereof. In embodiments, the composition includes a chemical blowing agent selected from water, formic acid, or a combination thereof.

[0059] In various embodiments, the blowing agent is a pentane isomer, a hydrofluorocarbon, a hydrofluoroolefin, a volatile non-halogenated C2-C7 hydrocarbon, such as an alkane like N-pentane, an alkene, a cycloalkene having up to 6 carbon atoms, a dialkyl ether, a cycloalkylene ether and a ketone, and a hydrofluorocarbon, a C1-C4 hydrofluorocarbon, a volatile non-halogenated hydrocarbon, 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 isoundecane, and n-dodecane and isododecane like linear or branched alkanes, alkenes like 1-pentene, 2-methylbutene, 3-methylbutene, and 1-hexene, cycloalkanes like cyclobutane, cyclopentane, and cyclohexane, linear and / or cyclic ethers like dimethyl ether, diethyl ether, methyl ethyl ether, vinyl methyl ether, vinyl ethyl ether, divinyl ether, tetrahydrofuran, and furan, ketones like acetone, methyl ethyl ketone, cyclopentanone, and isomers thereof, 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-pentafluoron-butane, and 1,1,1,3,3-pentafluoropentane (245fa), its isomers, 1,1,1,It may be selected from hydrofluorocarbons such as 2-tetrafluoroethane (HFC-134a), its isomers, and combinations thereof. In various embodiments, the blowing agent may further be defined as a combination of 1,1,1,3,3-pentafluoropentane (245fa) or HFC245fa, 365MFC, 227ea, and 134a. In alternative embodiments, the blowing agent may further be defined as 365MFC, which may be blended with 227ea.,

[0060] In various embodiments, the blowing agent may be present in an amount of from 0.1 to 20 wt%, from 1 to 18 wt%, from 4 to 16 wt%, from 7 to 14 wt%, from 9 to 12 wt%, or from 10 to 11 wt% of the foam composition. Here, also at any place in the specification and claims, the numerical values may combine to form new or undisclosed ranges. Generally, the amount of the 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. To reduce costs, it would be desirable for the amount of the blowing agent to be minimal.,

[0061] The foam composition may also include a crosslinking agent and / or a chain extender. The crosslinking agent may include, but is not limited to, additional polyols, amines, and any combination thereof. When the crosslinking agent is included in the foam composition, the crosslinking agent may be present in any suitable amount. Chain extenders contemplated for use in the present technology include, but are not limited to, hydrazine, primary and secondary diamines, alcohols, amino acids, hydroxy acids, glycols, and combinations thereof. Specific chain extenders contemplated for use include, but are not limited to, monoethylene glycol and diethylene glycol, monopropylene glycol and dipropylene glycol, 1,4 - butanediol, 1,3 - butanediol, propylene glycol, dipropylene glycol, diethylene glycol, methylpropylene diol, monoethanolamine, diethanolamine, and triethanolamine, N - N'-bis-(2 - hydroxy - propylaniline), trimethylolpropane, glycerin, hydroquinone bis(2 - hydroxyethyl) ether, 4,4'-methylene - bis(2 - chloroaniline, diethyltoluenediamine, 3,5 - dimethylthio - toluenediamine, hydrazine, isophoronediamine, adipic acid, silanes, and any combination thereof.

[0062] The foam composition may also contain 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, trisethyl phosphate, tris(2-chloropropyl) phosphate, tris(1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, alumina 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, surfactants, adhesion promoters, antioxidants, dyes, pigments, UV stabilizers, thixotropic agents, anti-aging agents, antistatic agents, lubricants, coupling agents, solvents, rheology improvers, bubble release agents, release additives, and combinations thereof. The one or more additives may be present in any amount in the foam composition.

[0063] The polyurethane foam composition using the compatibilizing additive of the present invention can be provided as a one-component system or a two-component system. In the one-component system, each component is provided as part of a single composition. The polyurethane foam composition is often provided as a two-component type composition. In the two-component type composition, the polyol and the isocyanate are provided in separate compositions and then mixed with each other to form polyurethane. The isocyanate component in the two-component system is typically referred to as the "A agent" component in the art, and the polyol component is often referred to as the "B agent" component in the art.

[0064] In one embodiment, the polyurethane composition is provided as a two-component composition, where the component B contains a polyol and a compatibility additive. The component B can contain other components such as, but not limited to, a catalyst, a surfactant, a flame retardant, a blowing agent, and others. In one embodiment, the compatibility additive can be present in an amount of from about 0.5 wt% to about 20 wt%, from about 1 wt% to about 15 wt%, from about 2.5 wt% to about 10 wt%, or from about 5 wt% to about 7.5 wt% based on the weight of the polyol composition. In one embodiment, the compatibility additive is present in an amount of from about 1.5 wt% to about 7 wt%, from about 2 wt% to about 6 wt%, or from about 2.5 wt% to about 5 wt% based on the total weight of the polyol composition.

[0065] In one embodiment including a first compatibility additive where m is 0 and n is 1, and a second compatibility additive where m is ≧1 and n is ≧1, the first compatibility additive is present in an amount of 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%, and the second compatibility additive is present in an amount of 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%.

[0066] In addition to the foam composition, this technology also provides a method for forming a foam and a method for forming a foam on a surface.

[0067] Methods for forming rigid foams typically include the step of combining a polyol composition and an isocyanate composition. More typically, the polyol composition and the isocyanate composition are combined such that the isocyanate index is about 250 or less. In embodiments, the isocyanate index is about 225 or less; about 200 or less; about 150 or less; about 125 or less; about 100 or less; and even about 90 or less. In embodiments, the isocyanate index is from about 90 to about 250, from about 95 to about 240, from about 100 to about 200, from about 115 to about 180, and even from about 125 to about 165. In one embodiment, the isocyanate index is from about 90 to about 225; and even from about 100 to about 200. Here, also in any part of the specification and claims, the numerical values may be combined to form new or undisclosed ranges. As will be understood by those skilled in the art, the foam may be a polyurethane foam or a polyisocyanurate foam. A foam with an isocyanate index of about 250 typically falls within the category of polyisocyanurate foams. However, as will be understood, there is no absolute value of the isocyanate index that describes polyurethane foams and polyisocyanurate foams.

[0068] A method for forming a rigid foam on a surface may include the step of combining components to form a foam mixture. Generally, this combining step may be performed within a mixing device such as a static mixer, an impingement mixing chamber, or a mixing pump. In one embodiment, the mixing step is performed within the tube of a static mixer. Alternatively, the foam composition and the isocyanate composition may be combined within a spray nozzle.

[0069] In one embodiment, the components of the composition are typically combined with an air stream having a pressure of 1 to 5 psi. The isocyanate composition may be combined with the air stream before being combined with the foam composition. Alternatively, the polyol and the modified novolak type resin may be combined with the air stream before being combined with the isocyanate composition. Further, the components of the composition may be combined simultaneously with respect to the air stream. The air stream is thought to aid in mixing and to promote uniform spraying and distribution of the foam mixture.

[0070] The components of the composition may be combined while on the surface or away from the surface. In one embodiment, the components of the composition may be combined at the head of a spray gun or in the air above the surface to which the composition is applied. The components of the composition may be combined by any technically known method including spraying, dipping, injecting, coating, applying, etc. and applied to the surface.

[0071] This technology provides rigid polyurethane foam (“rigid foam”). The rigid foam may be open cell or closed cell and may include a highly cross-linked polymer structure, enabling the foam to have good thermal stability, high compressive strength at low density, low thermal conductivity, and good barrier properties. Typically, the rigid foam of this technology may have a glass transition temperature higher than room temperature (approximately 23 °C + / - 2 °C (about 73.4 °F + / - 3.6 °F)) and is typically rigid at room temperature. Generally, the foam is rigid at or below the glass transition temperature, particularly in the glass region of the storage modulus. The rigid foam may have a density of from about 10 to about 1,100 kg / m 3 , from about 50 to about 1,000 kg / m 3 , from about 100 to about 850 kg / m 3 , from about 250 to about 650 kg / m 3 , and further from about 350 to about 500 kg / m 3 In one embodiment, the rigid foam is from about 10 to about 50 kg / m 3It may have a density. Here, also in any part of the specification and the claims, the numerical values may combine to form new or undisclosed ranges.

[0072] The foam mixture may be applied to any suitable surface, such as brick, concrete, masonry, drywall, gypsum board, plaster, metal, stone, wood, plastic, polymer composite, or any combination thereof. Also, this surface may be a mold surface, and thus the rigid foam may be formed in a mold.

[0073] The resulting rigid foam may be used in the form of slab stock, molding, or cavity filling. The cavity filling may be, for example, a pipe, a heat-insulating wall, or a heat-insulating hull structure. The rigid foam may be a sprayed foam, a foamed foam, or a continuously manufactured laminate product or a discontinuously manufactured laminate product, including, but not limited to, laminates or laminate products formed with other materials, such as rigid fiberboard, gypsum board, plastic, paper, metal, or combinations thereof.

[0074] The foam mixture may be sprayed at a spraying rate of 1 to 30 pounds per minute, 5 to 25 pounds per minute, and even 5 to 20 pounds per minute. Also, the foam mixture may generally be sprayed at a pressure of less than 3000 psi. Here, also in any part of the specification and the claims, the numerical values may combine to form new or undisclosed ranges.

[0075] In various embodiments, the foam mixture is sprayed in one pass to minimize or zero visible discoloration and / or scorching, such that the rigid foam to be foamed has a thickness 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 (in one pass). Here, also in any part of the specification and the claims, the numerical values may combine to form new or undisclosed ranges.

[0076] The rigid foam containing the foam composition described above can be further understood by referring to the following examples.

Examples

[0077] The polyol composition was prepared according to the following formulation:

Table 1

[0078] The experiments were conducted using compositions with different surfactants. The surfactant is a silicone surfactant of the MDxD'yM type, where the D' unit contains a pendant polyol functional group. This polyether functional group can contain ethylene oxide and / or propylene oxide units in the polyether chain. The surfactants used in each of the compositions are listed in Table 2.

Table 2

[0079] A compatibilizer was added to the composition. The compatibilizing additives evaluated were substances according to formula (I). The compatibilizing additives were trisiloxane additives (where m = 0 in formula (I)) and polysiloxane polyalkylene oxide copolymer additives (where m > 0 in formula (I)). The composition of the compatibilizing additives is listed in Table 3:

Table 3

[0080] The following table shows the initial appearance of the polyol preblends with each surfactant and the amount of compatibilizing additive added to obtain a clear and homogeneous solution. A comparative example without surfactant (designated "CE") was also run. In some examples, the substances corresponding to the composition of formula (I) according to the present invention were evaluated with surfactant only.

Table 4

[0081] Table 4 shows the evaluation of compatibility additives with the polyol of Example 1 using various surfactants. The blowing agent used with the polyol of Example 1 is hydrofluoroolefin (HFO-1366mzz-Z). Without the compatibility additive, the polyol composition is cloudy or transparent but accompanied by component separation. When the compatibility additive was added at a ratio of at least 1:1 or more, a transparent and homogeneous solution was obtained except for Comparative Example CE-1. For surfactants 2, 5, and 7, the same amount of compatibility additive was appropriate to obtain a transparent and homogeneous solution. The same amount of compatibility additive was also appropriate when the compatibility additive was used as a surfactant.

Table 5

[0082] Table 5 shows the evaluation of compatibility additives with the polyol of Example 2 using various surfactants. The blowing agent used with the polyol of Example 2 is hydrofluoroolefin (HFO-1366mzz-Z). Surfactants with a high m:n ratio (greater than 6:1) required the use of at least twice the amount of compatibility additive as the amount of surfactant. Less compatibility additive was required for surfactants with a lower m:n ratio.

Table 6

[0083] Table 6 shows the evaluation of the compatibility additives with the polyol of Example 3 using various surfactants. The blowing agent used with the polyol of Example 3 is hydrofluoroolefin (HFO-1233zd(E)). When this blowing agent was used, the polyol solutions were initially transparent for Surfactant 2, no surfactant, and when Additives A and B were added as surfactants. These solutions did not require compatibility additives. Surfactant 7 with an m:n ratio less than 6 required only the same amount of compatibility additive as the surfactant. Other surfactants with higher m:n ratios required at least twice the amount of the compatibility additive.

Table 7

[0084] The polyol solution of Example 4 is similar to Example 3 except that Example 4 uses a larger amount of surfactant. As in the case of Example 3, the polyol solutions were transparent when Surfactant 2 and Additives A and B were used as surfactants. Surfactants 1 and 4 required compatibilizers at twice the usage level compared to the main surfactant, and Surfactants 3 and 6 required further addition to impart transparency to the polyol blend. As shown by the structural analysis, the loading amount of the compatibilizer required in the case of a small m:n (less than 6) is smaller and may be useful as the compatibilizer itself but is less efficient than Additives A - F.

Table 8

[0085] Without being bound by a particular theory, Table 8 may indicate that the polarity of the surfactant, the polyol blend, the blowing agent, and the compatibility additive are relevant to maintaining the homogeneity of the system.

[0086] Preparation of Foam

[0087] The polyol preblend of Example 1 was used with either Surfactant 1 or Surfactant 6 to prepare a foam. The foam was prepared as follows. All of the Component B (polyol) ingredients were added to a bottle and the cap was closed. The bottle was rolled for 30 minutes for proper mixing. The temperature of the bottle of this Component B composition was controlled at 70°F. This can be achieved using a water bath or by room temperature itself. When in the water bath, the bottle was shaken well before weighing out the ingredients to maintain their mixed state. This blend has a very low viscosity and is easily mixed.

[0088] The Component B blend is weighed out onto a paper cup on a balance in an amount necessary to fill a 12-inch × 12-inch × 3-inch mold. This amount is typically around 240 g and the mold is filled 10% over. The isocyanate (Dow Chemical's Papi 27 or the like) is then added to this paper cup on top of the polyol mixture. This mixture is then mixed at 3500 RPM for 4 seconds and injected into the mold over 5 seconds. The mold is closed for a demolding time of 4 minutes at 120°F. The foam pad is removed and stored in the experimental laboratory overnight (16 hours) at room temperature conditions of 70°F and cut the next day.

[0089] Physical property analysis procedure: The physical properties of the foam are analyzed as follows.

[0090] K factor: An 8-inch × 8-inch × 1-inch sample is cut from the center (core) of the foam and the thermal conductivity is analyzed. The analysis was performed on a Lasercomp Fox200 thermal conductivity measuring device with the lower isothermal plate at 100°F, the upper isothermal plate at 50°F, and the average being 75°F in accordance with ASTM C-1289.

[0091] The pad density and K factor of the foam were evaluated for foams made with polyol preblends containing only Surfactant 1 or 6, and also for cases where Additive A was added to the polyol preblend.

[0092] Table 9 shows the form characteristics for these forms. [Table 9]

[0093] Table 9 shows the minimal change in density (due to injection time and reduction in viscosity when mixed by hand) and the k - factor when using the polyol of Example 1. This indicates that at low to moderate usage levels (less than 12%), the impact of using the present invention on the physical properties of rigid foams using various blowing agents is minimal, and the material remains transparent over a long period.

[0094] The polyol pre - blend of Example 3 was used with Surfactant 1 and Surfactant 6 to create foams. The foams were created without including compatibilizing additives and also by adding Additive A at 7.5 wt% and 9.0 wt%. 9.0% of Additive A is close to the maximum usage level (Example 3) to obtain the uniformity of the polyol pre - blend as described in Table 4 and is also greater than the level required to compatibilize with Example 5 (Table 8) using Surfactant 2. In both Formulations B and F (Surfactant 3%), Surfactant 2 was used as the main surfactant, and Additive A was added at 7.5 wt% and 9.0 wt% to create foams, and the impact on the physical properties at high usage levels of the present invention when using a more optimal main surfactant was determined (Table 10). [Table 10]

[0095] Additional experiments were conducted on other compatibilizing additives. Tables 11 to 13 show that using Additives A, B, C, D, E, F, G, I, K, and P achieves transparent and homogeneous solutions for the polyol pre - blends of Examples 1, 3, and 5. [Table 11]

Table 12

Table 13

[0096] In the above, embodiments of the present technology have been described. For those skilled in the art, modifications and changes may be envisioned upon reading and understanding this specification. The following claims are intended to cover all such modifications and changes as long as they fall within the scope of the claims or their equivalents.

Claims

1. A polyurethane or polyisocyanurate foam composition, comprising: Polyols or mixtures thereof; isocyanate; Compatibility additives; surfactants; and Includes a catalyst for polyurethane or a mixture thereof; Here, the formula for compatible additives is: M １ D １ ｍ D ２ ｎ M ２ (I) Selected from the compounds, here: M １ は (R １ )(R ２ )(R ３ )Si-O １／２ M ２ は (R ４ )(R ５ )(R ６ )Si-O １／２ D １ は (R ７ )(R ８ )Si-O ２／２ D ２ は (R ９ )(R １０ )Si-O ２／２ R １０ は-CH ２ -CH(R １１ )-CH ２ -O-[CH ２ CH(CH ３ )O] ｐ -[CH ２ CH ２ O] ｑ -R １２ R １ , R ２ , R ３ , R ４ , R ５ , and R ６ These are independently C1-C10 alkyl or R １０ Selected from; R ７ , R ８ , and R ９ These are independently selected from C1-C10 alkyl groups. R １１ is H or C1-C10 alkyl; R １２ is an H, C1-C10 alkyl, or acetyl group; m is between 0 and 100; n is between 1 and 50; p is between 0 and 35; q is 0-45; and A composition in which p + q ≥ 1.

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

3. The composition of claim 1, wherein m is 0 and n is 1.

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

5. The composition of claim 4, wherein q is 0.

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

7. The composition of claim 6, wherein p is 0.

8. The composition of claim 1, wherein m ≥ 0 and n ≥ 1, where m:n ≤ 6:

1.

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

1.

10. The composition of claim 8, wherein 0 < m ≤ 15 and 1 < n ≤ 5.

11. R １１ The composition of claim 1, wherein is H.

12. R １１ The composition according to claim 1, wherein is a C1-C10 alkyl group.

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

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

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

16. The composition according to claim 1, wherein the compound of formula (I) has a silicon content of about 1% to 25% by weight of the compound of formula (I).

17. The composition according to claim 1, wherein the compatible additive is present in an amount of about 0.5 to about 20 parts per 100 parts of polyol.

18. The composition according to claim 1, wherein the compatible additive is present in an amount equal to the amount of surfactant present in the composition.

19. The composition according to claim 1, wherein the compatible additive is present in an amount exceeding the amount of surfactant present in the composition.

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

21. Furthermore, the composition of claimant 1 includes a foaming agent.

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