Isocyanate-reactive compositions

Abstract

Embodiments of the present disclosure are directed towards isocyanate-reactive compositions including a sorbitol-initiated polyether polyol, a high hydroxyl number glycerin-initiated polyether polyol, an ethylenediamine-initiated polyether polyol, a propylene glycol-initiated polyether polyol, a low hydroxyl number glycerin-initiated polyether polyol, pentafluoro propane, dichloromethane, wherein a combination of the pentafluoro propane and the dichloromethane is from 5 to 14 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition, and water.

Description

ISOCYANATE-REACTIVE COMPOSITIONSField of Disclosure

[0001] This disclosure relates to isocyanate-reactive compositions and foam formulations made with the isocyanate-reactive compositions.Background

[0002] Polyurethane and polyisocyanurate foam is used for a number of applications, including as thermal insulation. Foam of this type is made by reacting one or more polyols and one or more isocyanates.Summary

[0003] The present disclosure provides various embodiments, including the following. An isocyanate-reactive composition including: a sorbitol-initiated polyether polyol; a high hydroxyl number glycerin-initiated polyether polyol; an ethylenediamine-initiated polyether polyol; a propylene glycol-initiated polyether polyol; a low hydroxyl number glycerin-initiated polyether polyol; pentafluoro propane; dichloromethane, wherein a combination of the pentafluoro propane and the dichloromethane is from 5 to 14 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition; and water.Detailed Description

[0004] Isocyanate-reactive compositions are disclosed herein. The isocyanatereactive compositions, as disclosed herein, can provide a combination of desirable properties, as discussed further herein. The isocyanate-reactive compositions disclosed herein can provide a reduced vapor pressure, as compared to other isocyanate-reactive compositions that include similar polyols. A relatively reduced vapor pressure is desirable, for instance, because lower rated pressure storage vessels, which can be less complicated to operate and / or have a relatively lower cost may be utilized, as compared to storage vessels utilized for higher vapor pressure compositions. Further, the isocyanate-reactive compositions disclosed herein can provide a phase stability and a viscosity that are desirable for a number of applications. Also, surprisingly the isocyanatereactive compositions disclosed herein can provide a Free Rise Density that isdesirable for a number of applications, where the isocyanate-reactive compositions disclosed herein utilize less blowing agent, i.e. pentafluoro propane and dichloromethane, than compositions having similar polyols and utilize only either pentafluoro propane or dichloromethane, which cannot provide such Free Range Density.

[0005] Additionally, the isocyanate-reactive compositions, as disclosed herein, can be combined with an isocyanate composition to make a foam formulation. These foam formulations can be cured to make foams that have a combination of desirable properties, as discussed further herein.

[0006] The isocyanate-reactive compositions disclosed herein include a sorbitol- initiated polyether polyol.

[0007] Embodiments provide that the sorbitol-initiated polyether polyol has a PO content equal to or greater than 80 wt%, based on a total weight of alkylene oxides used to make the sorbitol-initiated polyether polyol. For example, the sorbitol-initiated polyether polyol can have a PO content from 80 to 100 wt%. All individual values and subranges from 80 to 100 wt% are included; for example, the sorbitol-initiated polyether polyol can have an PO content from a lower limit of 80, 82, or 85 wt% to an upper limit of 100, 95, or 90, wt% based on the total weight of alkylene oxides used to make the sorbitol-initiated polyether polyol.

[0008] Embodiments provide that the sorbitol-initiated polyether polyol has a non- PO content, e.g., a EO content, from 0 wt% (such as when a non-PO alkylene oxide is not utilized) to 20 wt%, based on a total weight of alkylene oxides used to make the sorbitol-initiated polyether polyol. All individual values and subranges from 0 to 20 wt% are included; for example, the sorbitol-initiated polyether polyol can have a non-PO content from a lower limit of 0, 5, or 10 wt% to an upper limit of 20, 18, 15 wt% based on the total weight of alkylene oxides used to make the sorbitol-initiated polyether polyol.

[0009] Embodiments provide that the sorbitol-initiated polyether polyol has a hydroxyl number from 375 to 600 mg KOH / g. All individual values and subranges from 375 to 600 mg KOH / g are included; for example, the sorbitol-initiated polyether polyol can have a hydroxyl number from a lower limit of 375, 400, 425,or 450 mg KOH / g to an upper limit of 600, 575, 550, or 500 mg KOH / g. Hydroxyl number can be determined by ASTM D4274-21 .

[0010] Embodiments provide that the sorbitol-initiated polyether polyol has a functionality from 5 to 7. As used herein, “functionality” refers to an average hydroxyl functionality, unless stated otherwise. One or more embodiments provide that the sorbitol-initiated polyether polyol has a functionality of 6.

[0011] The sorbitol-initiated polyether polyol may be made by a known process. The sorbitol-initiated polyether polyol may be obtained commercially. A commercial example of the sorbitol-initiated polyether polyol is VORANOL RN 482 available from The Dow Chemical Company, for instance.

[0012] Embodiments provide that the sorbitol-initiated polyether polyol is from 30 to 42 weight percent (wt%) of the isocyanate-reactive composition based upon a total weight (100 wt%) of the isocyanate-reactive composition. All individual values and subranges from 30 to 42 wt% are included; for example, the sorbitol- initiated polyether polyol can be from a lower limit of 30, 32, 34, or 35 wt% to an upper limit of 42, 40, 39, or 37 wt% of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

[0013] The isocyanate-reactive compositions disclosed herein include a high hydroxyl number glycerin-initiated polyether polyol. As used herein, “high hydroxyl number glycerin-initiated polyether polyol” refers to a glycerin-initiated polyether polyol having a hydroxyl number from 325 to 450 mg KOH / g. For instance, the high hydroxyl number glycerin-initiated polyether polyol can have a hydroxyl number from a lower limit of 325, 350, or 375 mg KOH / g to an upper limit of 450, 425, or 400 mg KOH / g.

[0014] Embodiments provide that the high hydroxyl number glycerin-initiated polyether polyol has a PO content equal to or greater than 80 wt%, based on a total weight of alkylene oxides used to make the high hydroxyl number glycerin- initiated polyether polyol. For example, the sorbitol-initiated polyether polyol can have a PO content from 80 to 100 wt%. All individual values and subranges from 80 to 100 wt% are included; for example, the high hydroxyl number glycerin- initiated polyether polyol can have an PO content from a lower limit of 80, 82, or85 wt% to an upper limit of 100, 95, or 90, wt% based on the total weight of alkylene oxides used to make the high hydroxyl number glycerin-initiated polyether polyol.

[0015] Embodiments provide that the high hydroxyl number glycerin-initiated polyether polyol has a non-PO content, e.g., a EO content, from 0 wt% (such as when a non-PO alkylene oxide is not utilized) to 20 wt%, based on a total weight of alkylene oxides used to make the high hydroxyl number glycerin-initiated polyether polyol. All individual values and subranges from 0 to 20 wt% are included; for example, the high hydroxyl number glycerin-initiated polyether polyol can have a non-PO content from a lower limit of 0, 5, or 10 wt% to an upper limit of 20, 18, 15 wt% based on the total weight of alkylene oxides used to make the high hydroxyl number glycerin-initiated polyether polyol.

[0016] Embodiments provide that the high hydroxyl number glycerin-initiated polyether polyol has a functionality from 2 to 4. One or more embodiments provide that the high hydroxyl number glycerin-initiated polyether polyol has a functionality of 3.

[0017] The high hydroxyl number glycerin-initiated polyether polyol may be made by a known process. The high hydroxyl number glycerin-initiated polyether polyol may be obtained commercially. A commercial example of a high hydroxyl number glycerin-initiated polyether polyol is VORANOL 450 N available from The Dow Chemical Company, for instance.

[0018] Embodiments provide that the high hydroxyl number glycerin-initiated polyether polyol is from 10 to 30 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 10 to 30 wt% are included; for example, the high hydroxyl number glycerin-initiated polyether polyol can be from a lower limit of 10, 12, 14, or 16 wt% to an upper limit of 30, 28, 26, or 24 wt% of the isocyanatereactive composition based upon the total weight of the isocyanate-reactive composition.

[0019] The isocyanate-reactive compositions disclosed herein include an ethylenediamine-initiated polyether polyol. The ethylenediamine-initiatedpolyether polyol can be proproxylated ethylenediamine. The ethylenediamine- initiated polyether polyol can be 1 ,2-Ethanediamine, polymer with methyloxirane (CAS 25214-63-5).

[0020] Embodiments provide that the ethylenediamine-initiated polyether polyol has a PO content equal to or greater than 80 wt%, based on a total weight of alkylene oxides used to make the ethylenediamine-initiated polyether polyol. For example, the ethylenediamine-initiated polyether polyol can have a PO content from 80 to 100 wt%. All individual values and subranges from 80 to 100 wt% are included; for example, the ethylenediamine-initiated polyether polyol can have an PO content from a lower limit of 80, 82, or 85 wt% to an upper limit of 100, 95, or 90, wt% based on the total weight of alkylene oxides used to make the ethylenediamine-initiated polyether polyol.

[0021] Embodiments provide that the ethylenediamine-initiated polyether polyol has a non-PO content, e.g., a EO content, from 0 wt% (such as when a non-PO alkylene oxide is not utilized) to 20 wt%, based on a total weight of alkylene oxides used to make the ethylenediamine-initiated polyether polyol. All individual values and subranges from 0 to 20 wt% are included; for example, the ethylenediamine-initiated polyether polyol can have a non-PO content from a lower limit of 0, 5, or 10 wt% to an upper limit of 20, 18, 15 wt% based on the total weight of alkylene oxides used to make the ethylenediamine-initiated polyether polyol.

[0022] Embodiments provide that the ethylenediamine-initiated polyether polyol has a hydroxyl number from 500 to 800 mg KOH / g. All individual values and subranges from 500 to 800 mg KOH / g are included; for example, the ethylenediamine-initiated polyether polyol can have a hydroxyl number from a lower limit of 500, 550, 575, or 600 mg KOH / g to an upper limit of 800, 750, 700, or 675 mg KOH / g.

[0023] Embodiments provide that the ethylenediamine-initiated polyether polyol has a functionality from 3 to 5. One or more embodiments provide that the ethylenediamine-initiated polyether polyol has a functionality of 4.

[0024] The ethylenediamine-initiated polyether polyol may be made by a known process. The ethylenediamine-initiated polyether polyol may be obtained commercially. A commercial example of an ethylenediamine-initiated polyether polyol is VORANOL RA 640 available from The Dow Chemical Company, for instance.

[0025] Embodiments provide that the ethylenediamine-initiated polyether polyol is from 1 to 5 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 1 to 5 wt% are included; for example, the ethylenediamine-initiated polyether polyol can be from a lower limit of 1 .0, 1 .3, 1 .5, or 1 .8 wt% to an upper limit of 5.0, 4.0, 3.5, or 3.0 wt% of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

[0026] The isocyanate-reactive compositions disclosed herein include a propylene glycol-initiated polyether polyol.

[0027] Embodiments provide that the propylene glycol-initiated polyether polyol has a PO content equal to or greater than 80 wt%, based on a total weight of alkylene oxides used to make the propylene glycol-initiated polyether polyol. For example, the propylene glycol-initiated polyether polyol can have a PO content from 80 to 100 wt%. All individual values and subranges from 80 to 100 wt% are included; for example, the propylene glycol-initiated polyether polyol can have an PO content from a lower limit of 80, 82, or 85 wt% to an upper limit of 100, 95, or 90, wt% based on the total weight of alkylene oxides used to make the propylene glycol-initiated polyether polyol.

[0028] Embodiments provide that the propylene glycol-initiated polyether polyol has a non-PO content, e.g., a EO content, from 0 wt% (such as when a non-PO alkylene oxide is not utilized) to 20 wt%, based on a total weight of alkylene oxides used to make the propylene glycol-initiated polyether polyol. All individual values and subranges from 0 to 20 wt% are included; for example, the propylene glycol-initiated polyether polyol can have a non-PO content from a lower limit of 0, 5, or 10 wt% to an upper limit of 20, 18, 15 wt% based on the total weight of alkylene oxides used to make the propylene glycol-initiated polyether polyol.

[0029] Embodiments provide that the propylene glycol-initiated polyether polyol has a hydroxyl number from 40 to 220 mg KOH / g. All individual values and subranges from 40 to 220 mg KOH / g are included; for example, the propylene glycol-initiated polyether polyol can have a hydroxyl number from a lower limit of 40, 60, 75, or 90 mg KOH / g to an upper limit of 220, 200, 140, or 125 mg KOH / g.

[0030] Embodiments provide that the propylene glycol-initiated polyether polyol has a functionality from 2 to 4. One or more embodiments provide that propylene glycol-initiated polyether polyol has a functionality of 2.

[0031] The propylene glycol-initiated polyether polyol may be made by a known process. The propylene glycol-initiated polyether polyol may be obtained commercially. A commercial example of a propylene glycol-initiated polyether polyol is VORANOL 220-110 available from The Dow Chemical Company, for instance.

[0032] Embodiments provide that the propylene glycol-initiated polyether polyol is from 8 to 24 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 8 to 24 wt% are included; for example, the propylene glycol- initiated polyether polyol can be from a lower limit of 8, 10, 12, or 14 wt% to an upper limit of 24, 22, 20, or 18 wt% of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

[0033] The isocyanate-reactive compositions disclosed herein include a low hydroxyl number glycerin-initiated polyether polyol. As used herein, “low hydroxyl number glycerin-initiated polyether polyol” refers to a glycerin-initiated polyether polyol having a hydroxyl number from 10 to 60 mg KOH / g. For instance, the low hydroxyl number glycerin-initiated polyether polyol can have a hydroxyl number from a lower limit of 10, 15, 20, or 25 mg KOH / g to an upper limit of 60, 55, 50, or 40 mg KOH / g.

[0034] Embodiments provide that the low hydroxyl number glycerin-initiated polyether polyol has a EO content equal to or greater than 60 wt%, based on a total weight of alkylene oxides used to make the low hydroxyl number glycerin- initiated polyether polyol. For example, the low hydroxyl number glycerin-initiatedpolyether polyol can have a EO content from 60 to 90 wt%. All individual values and subranges from 60 to 90 wt% are included; for example, the low hydroxyl number glycerin-initiated polyether polyol can have an EO content from a lower limit of 60, 65, or 70 wt% to an upper limit of 90, 85, or 80, wt% based on the total weight of alkylene oxides used to make the low hydroxyl number glycerin- initiated polyether polyol.

[0035] Embodiments provide that the low hydroxyl number glycerin-initiated polyether polyol has a non-EO content, e.g., a PO content, from 10 wt% to 40 wt%, based on a total weight of alkylene oxides used to make the low hydroxyl number glycerin-initiated polyether polyol. All individual values and subranges from 10 to 40 wt% are included; for example, the low hydroxyl number glycerin- initiated polyether polyol can have a non-EO content from a lower limit of 10, 15, or 20 wt% to an upper limit of 40, 35, or 30 wt% based on the total weight of alkylene oxides used to make the low hydroxyl number glycerin-initiated polyether polyol.

[0036] Embodiments provide that the low hydroxyl number glycerin-initiated polyether polyol has a functionality from 2 to 4. One or more embodiments provide that low hydroxyl number glycerin-initiated polyether polyol has a functionality of 3.

[0037] The low hydroxyl number glycerin-initiated polyether polyol may be made by a known process. The low hydroxyl number glycerin-initiated polyether polyol may be obtained commercially. A commercial example of a low hydroxyl number glycerin-initiated polyether polyol is VORANOL CP 1421 available from The Dow Chemical Company, for instance.

[0038] Embodiments provide that the low hydroxyl number glycerin-initiated polyether polyol is from 1 to 5 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 1 to 5 wt% are included; for example, the low hydroxyl number glycerin-initiated polyether polyol can be from a lower limit of 1 .0, 1 .3, 1 .5, or 1 .8 wt% to an upper limit of 5.0, 4.0, 3.5, or 3.0 wt% of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

[0039] The isocyanate-reactive compositions disclosed herein include pentafluoro propane (CAS 460-73-1 ).

[0040] The pentafluoro propane is from 2 to 7 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 2 to 7 wt% are included. One or more embodiments provide that the pentafluoro propane is 2 wt% of the isocyanatereactive composition based upon a total weight of the isocyanate-reactive composition. One or more embodiments provide that the pentafluoro propane is 4 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. One or more embodiments provide that the pentafluoro propane is 7 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition.

[0041] The isocyanate-reactive compositions disclosed herein include dichloromethane (CAS 75-09-2).

[0042] The dichloromethane is from 2 to 7 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 2 to 7 wt% are included. One or more embodiments provide that the dichloromethane is 2 wt% of the isocyanatereactive composition based upon a total weight of the isocyanate-reactive composition. One or more embodiments provide that the dichloromethane is 4 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. One or more embodiments provide that the dichloromethane is 7 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition.

[0043] One or more embodiments provide that that a combination of the pentafluoro propane and the dichloromethane is from 5 to 14 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition. All individual values and subranges from 5 to 14 wt% are included; for example, the combination of the pentafluoro propaneand the dichloromethane can be from a lower limit of 5 or 6 wt% to an upper limit of 14, 12, or 1 1 wt% of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition. For instance, if the pentafluoro propane is 2 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition, then the dichloromethane is at least 3 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition.

[0044] The isocyanate-reactive compositions disclosed herein include water. The water is from 2 to 4 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 2 to 4 wt% are included; for example, the water can be from a lower limit of 2.0, 2.2, 2.5, or 2.8 wt% to an upper limit of 4.0, 3.8, 3.5, or 3.2 wt% of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

[0045] The isocyanate-reactive compositions disclosed herein include a catalyst. The catalyst may be a blowing catalyst, a gelling catalyst, a trimerization catalyst, or a combination thereof. As used herein, blowing catalysts and gelling catalysts may be differentiated by a general tendency to favor either the urea (blow) reaction, in the case of the blowing catalyst, or the urethane (gel) reaction, in the case of the gelling catalyst; or a tendency to generally enhance both the blow reaction and gel reaction, in case of blowing / gelling catalyst.

[0046] Examples of blowing catalysts, include, but are not limited to, short chain tertiary amines or tertiary amines containing an oxygen. The amine-based catalyst may not be sterically hindered. For instance, blowing catalysts include bis-(2-dimethylaminoethyl)ether, pentamethyldiethylene-triamine, triethylamine, tributyl amine, N,N-dimethylaminopropylamine, N,N-dimetilciclohexilamina, dimethylethanolamine, N,N,N',N'-tetra-methylethylenediamine, and combinations thereof, among others. Examples of commercial blowing catalysts are POLYCAT 5 and POLYCAT 8 from Evonik, and NIAX A-1 from Momentive, among other commercially available blowing catalysts.

[0047] Examples of gelling catalysts include, but are not limited to, organometallic compounds, cyclic tertiary amines and / or long chain amines, e.g., that contain several nitrogen atoms, and combinations thereof. Organometallic compounds include organotin compounds, such as tin(ll) salts of organic carboxylic acids, e.g., tin(ll) diacetate, tin(ll) dioctanoate, tin(ll) diethylhexanoate, and tin(ll) dilaurate, and dialkyltin(IV) salts of organic carboxylic acids, e.g., dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate. Bismuth salts of organic carboxylic acids may also be utilized as the gelling catalyst, such as, for example, bismuth octanoate. Cyclic tertiary amines and / or long chain amines include dimethylbenzylamine, triethylenediamine, and combinations thereof. Examples of a commercially available gelling catalysts are POLYCAT SA-2LE, DABCO 33 LV, DABCO BL-1 1 , DABCO EG, and DABCO T- 12 from Evonik, among other commercially available gelling catalysts.

[0048] Examples of a commercially available trimerization catalysts are POLYCAT 41 , DABCO K 2097, and DABCO TMR 30, from Evonik, among other commercially available trimerization catalysts.

[0049] The catalyst can be from 0.1 to 3.0 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 0.1 to 3.0 wt% are included; for example, the catalyst can be from a lower limit of 0.1 , 0.5, 0.75, or 1 .0 wt% to an upper limit of 3, 2, or 1 .5 wt% based upon the total weight of the isocyanate-reactive composition.

[0050] The isocyanate-reactive compositions disclosed herein include a surfactant. Surfactants for use in the preparation of foams are well-known to those skilled in the art, and many are commercially available. The surfactant may be a silicone. Examples of suitable silicone surfactants include, but are not limited to, TEGOSTAB B-8427, B-8454, B-8404, B-8407, B-8409, B-8715, and B- 8462 from Evonik; NIAX L-2171 , L-5130, L-5180, L-5340, L-5440, L-6100, L- 6900, L-6980, and L-6988 from MOMENTIVE, and VORSSURF 5374, VORASURF DC 5164, from The Dow Chemical Company.

[0051] The surfactant can be from 0.1 to 3 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 0.1 to 3 wt% are included; for example, the surfactant can be from a lower limit of 0.1 , 0.5, 0.75, or 1 .0 wt% to an upper limit of 3, 2.5, or 2 wt% of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

[0052] The isocyanate-reactive compositions disclosed herein include an additive.

[0053] Different additives and / or different amounts of the additive may be utilized for various applications. Examples of additives include pigments, colorants, antioxidants, bioretardant agents, flame retardants, and combinations thereof, among others. One or more embodiments provide that the additive is tris (1 - chloro-2-propyl) phosphate, triethyl phosphate, or a combination thereof.

[0054] The additive can be from 5 to 15 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 5 to 15 wt% are included; for example, the additive can be from a lower limit of 5, 7, or 9 wt% to an upper limit of 15, 13, or 11 wt% of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

[0055] As mentioned, the isocyanate-reactive compositions disclosed herein can provide a reduced vapor pressure, as compared to other isocyanate-reactive compositions that include similar polyols. This relatively reduced vapor pressure is desirable for a number of applications. This reduced vapor pressure can help provide reduced packaging costs, among other benefits, as compared to other isocyanate-reactive compositions that include similar polyols and have a higher vapor pressure.

[0056] Embodiments provide that the isocyanate-reactive compositions disclosed have a vapor pressure (55 °C) less than 90 kPa. For instance, the isocyanatereactive compositions can have a vapor pressure (55 °C) from 20 to 89 kPa. All individual values and subranges from 20 to 89 kPa are included; for example, the isocyanate-reactive compositions can have a vapor pressure (55 °C) from alower limit of 20, 25, or 30 kPa to an upper limit of 89, 87, or 85 kPa. Vapor pressure can be determined according to ASTM D 323.

[0057] Further, the isocyanate-reactive compositions disclosed herein can provide a phase stability that is desirable for a number of applications. For instance, the isocyanate-reactive compositions can be phase stable at 3 months storage at 25 °C. Phase stability can be determined by visual inspection.

[0058] Further, the isocyanate-reactive compositions disclosed herein can provide a viscosity that is desirable for a number of applications. The isocyanatereactive compositions disclosed herein can provide a viscosity less than 1 ,000 cP. For instance, the isocyanate-reactive compositions can have viscosity from 200 to 975 cP. All individual values and subranges from 200 to 975 cP are included; for example, the isocyanate-reactive compositions can have a viscosity from a lower limit of 200, 250, or 300 cP to an upper limit of 975, 850, 750, or 650 cP. Viscosity can be determined according to ASTM D445.

[0059] As mentioned, the isocyanate-reactive compositions, as disclosed herein, can be combined with an isocyanate composition to make a foam formulation.

[0060] The isocyanate composition includes an isocyanate. The isocyanate may be a polyisocyanate. As used herein, “polyisocyanate" refers to a molecule having an average of greater than 1 .0 isocyanate groups per molecule, e.g., an average functionality of greater than 1 .0.

[0061] The isocyanate can be an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an aromatic polyisocyanate, or combinations thereof, for example. Examples of isocyanates include, but are not limited to, polymethylene polyphenylisocyanate, toluene 2,4- / 2,6-diisocyanate (TDI), methylenediphenyl diisocyanate (MDI), polymeric MDI, triisocyanatononane (TIN), naphthyl diisocyanate (NDI), 4,4'-diisocyanatodicyclohexylmethane, 3-isocyanatomethyl- 3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanatel IPDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2- methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (THDI), dodecamethylene diisocyanate, 1 ,4-diisocyanatocyclohexane, 4,4'- diisocyanato-3,3'-dimethyldicyclohexylmethane, 4,4'-diisocyanato-2,2-dicyclohexylpropane, 3-isocyanatomethyl-1 -methyl- 1 -isocyanatocyclohexane (MCI), 1 ,3 -diisooctylcyanato -4 -methylcyclohexane, 1 ,3 -diisocyanato-2- methylcyclohexane, and combinations thereof, among others. As well as the isocyanates mentioned above, partially modified polyisocyanates including uretdione, isocyanurate, carbodiimide, uretonimine, allophanate or biuret structure, and combinations thereof, among others, may be utilized.

[0062] The isocyanate can be polymeric. As used herein “polymeric”, in describing the isocyanate, refers to higher molecular weight homologues and / or isomers. For instance, polymeric methylene diphenyl isocyanate refers to a higher molecular weight homologue and / or an isomer of methylene diphenyl isocyanate.

[0063] As mentioned, the isocyanate can have an average functionality of greater than 1 .0 isocyanate groups per molecule. For instance, the isocyanate can have an average functionality from 1 .5 to 8.0. All individual values and subranges from 1 .5 to 8.0 are included; for example, the isocyanate can have an average functionality from a lower limit of 1 .5, 1 .7, 2.0, 2.3, 2.5, 2.7, or 3.0 to an upper limit of 8.0, 7.5, 7.0, 6.7, 6.5, 6.3, 6.0, 5.7 or 5.5.

[0064] The isocyanate can have an isocyanate equivalent weight 80 g / eq to 500 g / eq. All individual values and subranges from 80 to 500 g / eq are included; for example, the isocyanate can have an isocyanate equivalent weight from a lower limit of 80, 82, 84, 90, or 100 to an upper limit of 500, 450, 400, 375, or 350 g / eq.

[0065] The isocyanate may be prepared by a known process. For instance, the polyisocyanate can be prepared by phosgenation of corresponding polyamines with formation of polycarbamoyl chlorides and thermolysis thereof to provide the polyisocyanate and hydrogen chloride, or by a phosgene-free process, such as by reacting the corresponding polyamines with urea and alcohol to give polycarbamates, and thermolysis thereof to give the polyisocyanate and alcohol, for example.

[0066] The isocyanate may be obtained commercially. Examples of commercial isocyanates include, but are not limited to, polyisocyanates under the trade names VORANATE, VORACOR, such as VORACOR CL 100 and VORACORCE 101 , and PAPI, such as PAPI 27, available from The Dow Chemical Company, among other commercial isocyanates.

[0067] The isocyanate composition can be utilized such that the foam formulation has an isocyanate index from 100 to 135. Isocyanate index can be determined as a quotient, multiplied by one hundred, of an actual amount of isocyanate utilized and a theoretical amount of isocyanate for curing. All individual values and subranges from 100 to 135 are included; for example, the foam formulation can have an isocyanate index from a lower limit of 100, 105, or 110 to an upper limit of 135, 130, or 125.

[0068] Theses foam formulations can be cured to make foams that have a combination of desirable properties. This combination of properties is desirable for a number of applications.

[0069] Foams made from the foam formulations, which include the isocyanatereactive compositions disclosed herein, have a Cream Time from 10 to 20 seconds. Cream Time can be determined according to ASTM D7487.

[0070] Foams made from the foam formulations, which include the isocyanatereactive compositions disclosed herein, have a Gel Time from 100 to 140 seconds. Gel Time can be determined according to ASTM D7487.

[0071] Foams made from the foam formulations, which include the isocyanatereactive compositions disclosed herein, have a Free Rise Density from 23 to 28 kg / m3. Free Rise Density can be determined according to ASTM D 6226.

[0072] Surprisingly the isocyanate-reactive compositions disclosed herein can provide a Free Rise Density that is desirable for a number of applications, where the isocyanate-reactive compositions disclosed herein utilize less blowing agent, i.e. pentafluoro propane and dichloromethane, than compositions having similar polyols and utilize only either pentafluoro propane or dichloromethane, which cannot provide such Free Range Density. Foams made from the foam formulations, which include the isocyanate-reactive compositions disclosed herein, have a K-Factor 12.5 °C from 22 to 24 mW / m K. K-Factor (thermal conductivity) can be determined according to ASTM C518.

[0073] The foams can be prepared by combining the isocyanate-reactive compositions disclosed herein and the isocyanate compositions. The components may be combined using know equipment and conditions. In general, the components of the foam formulation are combined and the fully mixed the foam formulation is subjected to known conditions sufficient to allow the foaming reaction to occur.

[0074] Foams of the present disclosure are useful in various types of applications, including thermal insulation applications, as well as other applications.

[0075] The following examples are provided for illustration but are not intended to limit the scope. All parts and percentages are by weight unless otherwise indicated.EXAMPLES

[0076] In the Examples, various terms and designations for materials are used including, for instance, the following.

[0077] Polyol 1 (sorbitol-initiated polyether polyol; PO 100 wt% of the total alkylene oxide content; average hydroxyl number 460-495 mg KOH / g, functionality of 6; VORANOL RN 482, obtained from The Dow Chemical Company).

[0078] Polyol 2 (high hydroxyl number glycerin-initiated polyether polyol; PO 100 wt% of the total alkylene oxide content; functionality 3; average hydroxyl number 370-396 mg KOH / g; VORANOL 450 N, obtained from the Dow Chemical Company).

[0079] Polyol 3 (ethylenediamine-initiated polyether polyol; functionality 3; average hydroxyl number of 615-655 mg KOH / g; VORANOL RA 640, obtained from The Dow Chemical Company).

[0080] Polyol 4 (propylene glycol-initiated polyether polyol; functionality 2; average hydroxyl number of 105-115 mg KOH / g; VORANOL 220-110, obtained from The Dow Chemical Company).

[0081] Polyol 5 (low hydroxyl number glycerin-initiated polyether polyol; average hydroxyl number 31 -36 mg KOH / g; functionality 3; VORANOL CP 1421 , obtained from The Dow Chemical Company).

[0082] Pentafluoro propane (HFC 245FA, obtained from WEGOCHEM MEXICANA S DE RL).

[0083] Dichloromethane (obtained from BLUE CUBE OPERATIONS LLC).

[0084] Water.

[0085] Catalyst 1 (blowing catalyst, NIAX A-1 , 70% bis(2-dimethyl aminoethyl)ether and 30% dipropylene glycol catalyst, obtained from Momentive).

[0086] Catalyst 2 (blowing / gelling catalyst, A / ,A / -dimethylcyclohexylamine, POLYCAT 8, obtained from Evonik).

[0087] Catalyst 3 (trimerization catalyst, 2,4,6-Tris (dimethylaminomethyl) phenol, DABCO TMR 30, obtained from Evonik).

[0088] Silicone Surfactant (VORASURF 5374, obtained from The Dow Chemical Company).

[0089] Additive 1 (triethyl phosphate, obtained from Eastman).

[0090] Additive 2 (tris (1 -chloro-2-propyl) phosphate, obtained from Jiangsu Darning Technology).

[0091] Example 1 (Ex. 1 ), an isocyanate-reactive composition, was made by combining the components shown in Table 1 .

[0092] Examples 2-4, isocyanate-reactive compositions and Comparative Examples A-C (C Ex. A-C) were made as Example 1 with any changes shown in Table 1 .Table 1

[0093] A number of properties were determined for Examples 1 -4 and Comparative Examples A-C, the results are reported in Table 2.Table 2

[0094] The data of Table 2 show that each of Examples 1 -4 each had a respective vapor pressure less than 90 kPa.

[0095] The data of Table 2 show that each of Examples 1 -4 had a phase stability equal to or greater than 3 months.

[0096] The data of Table 2 show that each of Examples 1 -4 had a viscosity less than 1 ,000 cP.

[0097] Example 1 , a foam formulation, was made by mixing isocyanate-reactive composition (Example 1 ) with an isocyanate composition (PAPI 27, obtained from The Dow Chemical Company), to provide the indicated index as shown in Table 3.

[0098] Example 2-4 were respectively used rather than Example 1 .

[0099] Comparative Examples A-C were respectively used rather than Example 1.Table 3

[0100] A number of properties were determined for foams made from Examples 1 -4 and Comparative Examples A-C, the results are reported in Table 4.Table 4

[0101] The data of Table 4 show that foams made from each of Examples 1 -4 had a Cream Time from 10 to 20 seconds.

[0102] The data of Table 4 show that foams made from each of Examples 1 -4 had a Gel Time from 100 to 140 seconds.

[0103] The data of Table 4 show that foams made from each of Examples 1 -4 had a Free Rise Density from 23 to 28 kg / m3.

[0104] As shown in the above Tables, foam made from of Example 1 utilized six wt% of a combination of pentafluoro propane (2 wt%) and dichloromethane (4 wt%); foam made from of Example 2 utilized eleven wt% of a combination of pentafluoro propane (7 wt%) and dichloromethane (4 wt%); foam made from of Example 3 utilized eleven wt% of a combination of pentafluoro propane (4 wt%) and dichloromethane (7 wt%); and foam made from of Example 4 utilized six wt% of a combination of pentafluoro propane (4 wt%) and dichloromethane (2 wt%) to provide the Free Rise Density from 23 to 28 kg / m3.

[0105] In contrast, foam made from Comparative Example A did provide a Free Rise Density from 23 to 28 kg / m3; the foam made from Comparative Example A utilized a greater amount (fourteen wt%) of a combination of pentafluoro propane (14 wt%) and dichloromethane (0 wt%), as compared to foams Examples 1 -4; however, as shown in Table 2, Comparative Example A (utilized to make foam Comparative Example B-C) provided an undesirable vapor pressure greater than90 kPa . Foams made respectively from Comparative Examples B and Comparative Example C did not provide a Free Rise Density from 23 to 28 kg / m3.

[0106] The data of Table 4 show that foams made from each of Examples 1 -4 had a K-Factor 12.5 °C from 22 to 24 mW / m K.

[0107] Vapor pressure at 55 °C was determined in accordance with ASTM D323.

[0108] Phase Stability was determined by visual observation. Phase stable indicated no observed phase separation.

[0109] Viscosity was determined in accordance with ASTM D445.

[0110] Cream time and gel time were determined according to the testing procedure described in ASTM D7487. Cream time was observed visually; gel time was evaluated by touching the surface of the curing reaction mixture periodically with a wood tongue depressor (The gel time was the time after the isocyanate composition and isocyanate-reactive composition are mixed at which strings begin to form when the wood tongue depressor was pulled away).[0011 1 ] Free rise foam density was determined according to ASTM D 6226.

[0112] K-Factor (thermal conductivity) was determined according to ASTM C518.

Claims

What is claimed is:

1. An isocyanate-reactive composition comprising: a sorbitol-initiated polyether polyol; a high hydroxyl number glycerin-initiated polyether polyol; an ethylenediamine-initiated polyether polyol; a propylene glycol-initiated polyether polyol; a low hydroxyl number glycerin-initiated polyether polyol; pentafluoro propane; dichloromethane, wherein a combination of the pentafluoro propane and the dichloromethane is from 5 to 14 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition; and water.

2. The isocyanate-reactive composition of claim 1 , further comprising: a catalyst; a silicone surfactant; and an additive.

3. The isocyanate-reactive composition of claim 2, wherein the pentafluoro propane is from 2 to 7 weight percent of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition and the dichloromethane is from 2 to 7 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition with the proviso that a combination of the pentafluoro propane and the dichloromethane is from 5 to 14 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition .

4. The isocyanate-reactive composition of claim 3, wherein:the sorbitol-initiated polyether polyol is from 30 to 42 weight percent of the isocyanate-reactive composition based upon a total weight of the isocyanatereactive composition; the high hydroxyl number glycerin-initiated polyether polyol is from 10 to 30 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition; the ethylenediamine-initiated polyether polyol is from 1 to 5 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition; the propylene glycol-i nitiated polyether polyol is from 8 to 24 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition; the low hydroxyl number glycerin-initiated polyether polyol is from 1 to 5 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition; the water is from 2 to 4 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition. the catalyst is from 0.1 to 3.0 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition; the silicone surfactant is from 0.1 to 3.0 weight percent of the isocyanatereactive composition based upon the total weight of the isocyanate-reactive composition; and the additive is from 5 to 15 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

5. The isocyanate-reactive composition of any one of the preceding claims, wherein the additive is tris (1 -ch loro-2-propyl) phosphate, triethyl phosphate, or a combination thereof.

6. The isocyanate-reactive composition of any one of the preceding claims, wherein the sorbitol-initiated polyether polyol has a hydroxyl number from 375 to600 mg KOH / g, the high hydroxyl number glycerin-initiated polyether polyol has a hydroxyl number from 325 to 450 mg KOH / g, the ethylenediamine-initiated polyether polyol has a hydroxyl number from 500 to 800 mg KOH / g, the propylene glycol-initiated polyether polyol has a hydroxyl number from 40 to 220 mg KOH / g, and the low hydroxyl number glycerin-initiated polyether polyol has a hydroxyl number from 10 to 60 mg KOH / g.

7. A foam formulation comprising: the isocyanate-reactive composition of any one of the preceding claims; and an isocyanate composition.

8. The foam formulation of claim 7, wherein the foam formulation has an isocyanate index from 100 to 135.

9. A foam product made with the foam formulation of any one of claims 7-8.

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