阅读说明：本技术 配制的多元醇组合物 (Formulated polyol compositions ) 是由 孟庆浩 L·波切利 D·J·霍恩康普 M·博欧德伟 M·A·斯普林斯 P·库克森 W·L 于 2019-10-07 设计创作，主要内容包括：本公开的实施例涉及包括以下的配制的多元醇组合物：平均羟基数为112至280mg KOH/g的第一聚醚多元醇、平均羟基数为18.5至51mg KOH/g的第二聚醚多元醇、平均羟基数为20至70mg KOH/g的第三聚醚多元醇,和以下中的至少一种：平均羟基数为112至280mg KOH/g的第四聚醚多元醇；和平均羟基数为56至190mg KOH/g的甲氧基聚乙二醇。(Embodiments of the present disclosure relate to a formulated polyol composition comprising: a first polyether polyol having an average hydroxyl number of from 112 to 280mg KOH/g, a second polyether polyol having an average hydroxyl number of from 18.5 to 51mg KOH/g, a third polyether polyol having an average hydroxyl number of from 20 to 70mg KOH/g, and at least one of: a fourth polyether polyol having an average hydroxyl number of from 112 to 280mg KOH/g; and methoxypolyethylene glycol having an average hydroxyl number of 56 to 190mg KOH/g.)

1. A formulated polyol composition comprising:

a first polyether polyol having an average hydroxyl number of from 112 to 280mg KOH/g and an ethylene oxide content of from 45 to 70 weight percent based on a total weight of the first polyether polyol, wherein the first polyether polyol comprises from 20 to 55 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition;

a second polyether polyol having an average hydroxyl number of from 18.5 to 51mg KOH/g and an ethylene oxide content of at least 70 weight percent based on a total weight of the second polyether polyol, wherein the second polyether polyol comprises from 2 to 50 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition;

a third polyether polyol having an average hydroxyl number of 20 to 70mg KOH/g and a propylene oxide content of at least 70 weight percent based on the total weight of the third polyether polyol, wherein the third polyether polyol comprises 5 to 45 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition;

a surfactant;

water;

a catalyst selected from the group consisting of blowing catalysts, gelling catalysts, and combinations thereof; and

at least one of the following:

a fourth polyether polyol having an average hydroxyl number of from 112 to 280mg KOH/g and a propylene oxide content of at least 70 weight percent based on a total weight of the fourth polyether polyol, wherein the fourth polyether polyol comprises from 0.1 to 25 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition; and

a methoxypolyethylene glycol having an average hydroxyl number of 56 to 190mg KOH/g, wherein the methoxypolyethylene glycol comprises 0.1 to 15 weight percent of the formulated polyol composition, based on the total weight of the formulated polyol composition.

2. The formulated polyol composition of claim 1, wherein the fourth polyether polyol has a number average molecular weight of from 500 to 1200g/mol and an average hydroxyl functionality of from 2.6 to 3.4.

3. The formulated polyol composition of claim 1, wherein the methoxypolyethylene glycol has a number average molecular weight of 400 to 700g/mol and an average hydroxyl functionality of 0.6 to 1.4.

4. The formulated polyol composition of any of claims 1-3, wherein

The first polyether polyol having a number average molecular weight of 700 to 1300g/mol and an average hydroxyl functionality of 2.6 to 3.4;

the second polyether polyol having a number average molecular weight of 4000 to 5000g/mol and an average hydroxyl functionality of 2.6 to 3.4; and

the third polyether polyol has a number average molecular weight of 2000 to 4000g/mol and an average hydroxyl functionality of 2.6 to 3.4.

5. A foam formulation comprising:

the formulated polyol composition of any of claims 1 to 4; and

an isocyanate, wherein the foam formulation has an isocyanate index of from 55 to 110.

6. A foam product formed by curing the foam formulation of claim 5.

7. The foam product of claim 6, wherein the foam product comprises a skin, a foam core recovery time of 2 to 120 seconds, a skin airflow rate of 4.0 cubic feet per minute or greater, a core airflow rate of 4.0 cubic feet per minute or greater, and a compression set at 90% compression of 1 to 12%.

8. The foam product according to any one of claims 6 to 7, wherein the foam product has an average cell coverage percentage of 50 to 85 percent and an average cell diameter of 50 to 500 μm.

Technical Field

Embodiments of the present disclosure relate to formulated polyol compositions, more particularly, embodiments relate to formulated polyol compositions comprising: a first polyether polyol having an average hydroxyl number of from 112 to 280mg KOH/g, a second polyether polyol having an average hydroxyl number of from 18.5 to 51mg KOH/g, a third polyether polyol having an average hydroxyl number of from 20 to 70mg KOH/g, and at least one of: a fourth polyether polyol having an average hydroxyl number of from 112 to 280mg KOH/g; and methoxypolyethylene glycol having an average hydroxyl number of 56 to 190mg KOH/g.

Background

A foam is a dispersion in which a gas is dispersed in a liquid material, a solid material, or a gel material. Foams can be formed by the chemical reaction of a polyol and an isocyanate. Foams are useful in many different applications, including mattresses, insulators, bedding, furniture, vehicle seats, and carpet backing, among others.

Disclosure of Invention

The present disclosure provides a formulated polyol composition comprising: a first polyether polyol having an average hydroxyl number of from 112 to 280mg KOH/g and an ethylene oxide content of from 45 to 70 weight percent based on the total weight of the first polyether polyol, wherein the first polyether polyol is from 20 to 55 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition; a second polyether polyol having an average hydroxyl number of from 18.5 to 51mg KOH/g and an ethylene oxide content of at least 70 weight percent based on a total weight of the second polyether polyol, wherein the second polyether polyol is from 2 to 50 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition; a third polyether polyol having an average hydroxyl number of 20 to 70mg KOH/g and a propylene oxide content of at least 70 weight percent based on the total weight of the third polyether polyol, wherein the third polyether polyol is 5 to 45 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition; a surfactant; water; a catalyst selected from the group consisting of blowing catalysts, gelling catalysts, and combinations thereof; and at least one of: a fourth polyether polyol having an average hydroxyl number of from 112 to 280mg KOH/g and a propylene oxide content of at least 70 weight percent based on the total weight of the fourth polyether polyol, wherein the fourth polyether polyol is from 0.1 to 25 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition; and a methoxypolyethylene glycol having an average hydroxyl number of 56 to 190mg KOH/g, wherein the methoxypolyethylene glycol is 0.1 to 15 weight percent of the formulated polyol composition, based on the total weight of the formulated polyol composition.

The present disclosure provides foam formulations comprising a formulated polyol composition and an isocyanate.

The present disclosure provides a foam product formed by curing a foam formulation.

The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The following description more particularly exemplifies illustrative embodiments. Throughout this application, guidance is provided through lists of examples, which examples can be used in various combinations. In each case, the enumerated lists serve only as representative groups and should not be construed as exclusive lists.

Detailed Description

Disclosed herein. A formulated polyol composition comprising: a first polyether polyol having an average hydroxyl number of from 112 to 280mg KOH/g and an ethylene oxide content of from 45 to 70 weight percent based on the total weight of the first polyether polyol, wherein the first polyether polyol is from 20 to 55 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition; a second polyether polyol having an average hydroxyl number of from 18.5 to 51mg KOH/g and an ethylene oxide content of at least 70 weight percent based on a total weight of the second polyether polyol, wherein the second polyether polyol is from 2 to 50 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition; and a third polyether polyol having an average hydroxyl number of from 20 to 70mg KOH/g and a propylene oxide content of at least 70 weight percent based on the total weight of the third polyether polyol, wherein the third polyether polyol is from 5 to 45 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition, and at least one of: a fourth polyether polyol having an average hydroxyl number of from 112 to 280mg KOH/g and a propylene oxide content of at least 70 weight percent based on the total weight of the fourth polyether polyol, wherein the fourth polyether polyol is from 0.1 to 25 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition; and a methoxypolyethylene glycol having an average hydroxyl number of 56 to 190mg KOH/g, wherein the methoxypolyethylene glycol is 0.1 to 15 weight percent of the formulated polyol composition, based on the total weight of the formulated polyol composition. Advantageously, the formulated polyol compositions disclosed herein can be used to form foams having a combination of properties that are advantageous for many applications. For example, the formulated polyol compositions disclosed herein can be used to form foam products that are advantageous for cushions such as pillows, seats, mattresses, and the like. For example, the formulated polyol compositions disclosed herein can form foam products that are desired to form a skin, have a particular foam core recovery time, a particular air flow rate, and a particular compression set at 90% compression.

The formulated polyol compositions disclosed herein include a first polyether polyol. The first polyether polyol has an ethylene oxide content of 45 to 70 weight percent based on the total weight of the first polyether polyol. All individual values and subranges from 45 to 70 weight percent are included; for example, the ethylene oxide content of the first polyether polyol can be from a lower limit of 45, 50, or 55 weight percent to an upper limit of 70, 68, or 65. The first polyether polyol may comprise structural units derived from another alkylene oxide, such as propylene oxide.

The average number of hydroxyl groups of the first polyether polyol may be from 112 to 280mg KOH/g. All individual values and subranges from 112 to 280mg KOH/g are included; for example, the average hydroxyl number of the first polyether polyol can be from a lower limit of 112, 125 or 135mg KOH/g to an upper limit of 280, 240 or 220mg KOH/g. The average hydroxyl number, e.g., KOH, can be determined according to ASTM D4274.

The first polyether polyol may have an average hydroxyl functionality of from 2.6 to 3.4. Including all individual values and subranges from 2.6 to 3.4; for example, the average hydroxyl functionality of the first polyether polyol can range from a lower limit of 2.6, 2.7, or 2.8 to an upper limit of 3.4, 3.3, or 3.2.

The first polyether polyol may have a number average molecular weight of 700 to 1300 g/mol. Including all individual values and subranges from 700 to 1300 g/mol; for example, the first polyether polyol may have a number average molecular weight from a lower limit of 700, 800 or 850g/mol to an upper limit of 1300, 1200 or 1150 g/mol.

The first polyether polyol can be prepared using known equipment, reaction conditions, and reaction components.

The first polyether polyol is commercially available. An example of a first polyether polyol that is commercially available is VORANOL, available from Dow Chemical Company^TMWK 3140, and the like.

The first polyether polyol may be 20 to 55 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition. All individual values and subranges from 20 to 55 weight percent are included; for example, the first polyether polyol can be from a lower limit of 20, 22, or 25 weight percent to an upper limit of 55, 53, or 52 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition.

The formulated polyol compositions disclosed herein include a second polyether polyol. The second polyether polyol has an ethylene oxide content of at least 70, based on the total weight of the second polyether polyol. For example, the second polyether polyol may have an ethylene oxide content of 70 to 98 weight percent, based on the total weight of the second polyether polyol. All individual values and subranges from 70 to 98 weight percent are included; for example, the ethylene oxide content of the second polyether polyol can be from a lower limit of 70, 72, or 75 weight percent to an upper limit of 98, 95, 90, 88, or 85. The second polyether polyol may comprise structural units derived from another alkylene oxide, such as propylene oxide.

The average hydroxyl number of the second polyether polyol may be from 18.5 to 51mg KOH/g. All individual values and subranges from 18.5 to 51mg KOH/g are included; for example, the average hydroxyl number of the second polyether polyol can be from a lower limit of 18.5, 22, or 25mg KOH/g to an upper limit of 51, 48, or 45mg KOH/g.

The second polyether polyol may have an average hydroxyl functionality of from 2.6 to 3.4. Including all individual values and subranges from 2.6 to 3.4; for example, the average hydroxyl functionality of the second polyether polyol can be from a lower limit of 2.6, 2.7, or 2.8 to an upper limit of 3.4, 3.3, or 3.2.

The second polyether polyol may have a number average molecular weight of 4000 to 5000 g/mol. All individual values and subranges from 4000 to 5000g/mol are included; for example, the second polyether polyol may have a number average molecular weight from a lower limit of 4000, 4100 or 4250g/mol to an upper limit of 5000, 4900 or 4750 g/mol.

The second polyether polyol can be prepared using known equipment, reaction conditions, and reaction components.

The second polyether polyol is commercially available. An example of a commercially available second polyether polyol is VORANOL, available from the Dow chemical company^TMCP-1447, and the like.

The second polyether polyol may be 2 to 50 weight percent of the formulated polyol composition, based on the total weight of the formulated polyol composition. All individual values and subranges from 2 to 50 weight percent are included; for example, the second polyether polyol can be from a lower limit of 2, 3, or 5 weight percent to an upper limit of 50, 45, or 40 weight percent of the formulated polyol composition, based on the total weight of the formulated polyol composition.

The formulated polyol compositions disclosed herein include a third polyether polyol. The third polyether polyol has a propylene oxide content of at least 70, based on the total weight of the third polyether polyol. For example, the third polyether polyol may have a propylene oxide content of 70 to 98 weight percent based on the total weight of the third polyether polyol. All individual values and subranges from 70 to 98 weight percent are included; for example, the third polyether polyol may have a propylene oxide content from a lower limit of 70, 72, or 75 weight percent to an upper limit of 98, 95, 90, 88, or 85. The third polyether polyol may comprise structural units derived from another alkylene oxide, such as ethylene oxide. The third polyether polyol may include structural units derived from styrene-acrylonitrile, polyisocyanate, and/or polyurea.

The average hydroxyl number of the third polyether polyol may be from 20 to 70mg KOH/g. All individual values and subranges from 20 to 70mg KOH/g are included; for example, the average hydroxyl number of the third polyether polyol may be from a lower limit of 20, 25 or 30mg KOH/g to an upper limit of 70, 65 or 60mg KOH/g.

The third polyether polyol may have an average hydroxyl functionality of from 2.6 to 3.4. Including all individual values and subranges from 2.6 to 3.4; for example, the average hydroxyl functionality of the third polyether polyol can be from a lower limit of 2.6, 2.7, or 2.8 to an upper limit of 3.4, 3.3, or 3.2.

The third polyether polyol may have a number average molecular weight of 2000 to 4000 g/mol. All individual values and subranges from 2000 to 4000g/mol are included; for example, the third polyether polyol may have a number average molecular weight from a lower limit of 2000, 2250, or 2500g/mol to an upper limit of 4000, 3750, or 3500 g/mol.

The third polyether polyol can be prepared using known equipment, reaction conditions, and reaction components.

The third polyether polyol is commercially available. An example of a commercially available third polyether polyol is VORANOL, available from the Dow chemical company^TM3136, etc.

The third polyether polyol may be 5 to 45 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition. All individual values and subranges from 5 to 45 weight percent are included; for example, the third polyether polyol can be from a lower limit of 5, 8, or 10 weight percent to an upper limit of 45, 43, or 40 weight percent of the formulated polyol composition, based on the total weight of the formulated polyol composition.

The formulated polyol composition disclosed herein includes at least one of a fourth polyether polyol as discussed herein and a methoxypolyethylene glycol as discussed herein. For example, the formulated polyol composition may include a fourth polyether polyol, or methoxypolyethylene glycol, or a fourth polyether polyol and methoxypolyethylene glycol.

The formulated polyol composition disclosed herein may include a fourth polyether polyol. The fourth polyether polyol has a propylene oxide content of at least 70 weight percent based on the total weight of the fourth polyether polyol. For example, the propylene oxide content of the fourth polyether polyol, based on the total weight of the fourth polyether polyol, may be from 70 to 95 weight percent. All individual values and subranges from 70 to 95 weight percent are included; for example, the propylene oxide content of the fourth polyether polyol can be from a lower limit of 70, 72, or 75 weight percent to an upper limit of 95, 90, 88, or 85. The fourth polyether polyol may comprise structural units derived from another alkylene oxide, such as ethylene oxide.

The average hydroxyl number of the fourth polyether polyol may be from 112 to 280mg KOH/g. All individual values and subranges from 112 to 280mg KOH/g are included; for example, the average hydroxyl number of the fourth polyether polyol can be from a lower limit of 112, 125 or 135mg KOH/g to an upper limit of 280, 240 or 220mg KOH/g.

The fourth polyether polyol may have an average hydroxyl functionality of from 2.6 to 3.4. Including all individual values and subranges from 2.6 to 3.4; for example, the average hydroxyl functionality of the fourth polyether polyol can be from a lower limit of 2.6, 2.7, or 2.8 to an upper limit of 3.4, 3.3, or 3.2.

The fourth polyether polyol may have a number average molecular weight of from 500 to 1200 g/mol. Including all individual values and subranges from 500 to 1200 g/mol; for example, the fourth polyether polyol may have a number average molecular weight from a lower limit of 500, 550 or 600g/mol to an upper limit of 1200, 1100, 1000, 900, 850 or 800 g/mol.

The fourth polyether polyol can be prepared using known equipment, reaction conditions, and reaction components.

A fourth polyether polyol is commercially available. An example of a fourth commercially available polyether polyol is VORANOL, available from the Dow chemical company^TM2070, and the like.

The fourth polyether polyol may be from 0.1 to 25 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition. All individual values and subranges from 0.1 to 25 weight percent are included; for example, the fourth polyether polyol can be from a lower limit of 0.1, 1, or 5 weight percent to an upper limit of 25, 20, or 18 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition. Herein, utilizing less than 0.1 weight percent of the fourth polyether polyol is considered to be equivalent to a nominal amount of the fourth polyether polyol that does not utilize any of the fourth polyether polyols.

Formulated polyol compositions disclosed herein may include methoxypolyethylene glycols. The average hydroxyl number of the methoxypolyethylene glycol may be 56 to 190mg KOH/g. All individual values and subranges from 56 to 190mg KOH/g are included; for example, the average hydroxyl number of the methoxypolyethylene glycol may range from a lower limit of 56, 65 or 75mg KOH/g to an upper limit of 190, 175 or 150mg KOH/g.

The average hydroxyl functionality of the methoxypolyethylene glycol may be from 0.6 to 1.4. Including all individual values and subranges from 0.6 to 1.4; for example, the average hydroxyl functionality of the methoxypolyethylene glycol can range from a lower limit of 0.6, 0.7, or 0.8 to an upper limit of 1.4, 1.3, or 1.2.

The methoxypolyethylene glycol may have a number average molecular weight of 400 to 700 g/mol. All individual values and subranges from 400 to 700g/mol are included; for example, the number average molecular weight of the methoxypolyethylene glycol may range from a lower limit of 400, 450 or 500g/mol to an upper limit of 700, 650 or 600 g/mol.

The methoxypolyethylene glycol may be prepared using known equipment, reaction conditions and reaction components.

Methoxypolyethylene glycols are commercially available. An example of a commercially available methoxypolyethylene glycol is CARBOWAX available from the Dow chemical company^TMMPEG 550, and the like.

The methoxypolyethylene glycol may be 0.1 to 15 weight percent of the formulated polyol composition, based on the total weight of the formulated polyol composition. All individual values and subranges from 0.1 to 15 weight percent are included; for example, the methoxypolyethylene glycol may range from a lower limit of 0.1, 1, or 5 weight percent to an upper limit of 15, 13, or 12 weight percent of the formulated polyol composition, based on the total weight of the formulated polyol composition. Herein, the use of less than 0.1 weight percent of methoxypolyethylene glycol is considered equivalent to the nominal amount of methoxypolyethylene glycol without the use of any of the methoxypolyethylene glycols.

One or more embodiments provide that the ethylene oxide content of the formulated polyol composition is 20 weight percent or greater based on the total weight of the first polyether polyol, the second polyether polyol, the third polyether polyol, the fourth polyether polyol, and the methoxypolyethylene glycol, i.e., the total weight of the polyol and the ethylene glycol used in the formulated polyol composition. For example, the ethylene oxide content of the formulated polyol composition may range from a lower limit of 20, 25, 30, 35, or 40 weight percent to an upper limit of 85, 80, 75, or 70 weight percent, based on the total weight of the first polyether polyol, the second polyether polyol, the third polyether polyol, the fourth polyether polyol, and the methoxypolyethylene glycol.

One or more embodiments provide that the formulated polyol composition has a composition such that the combination of the second polyether polyol, the third polyether polyol, the fourth polyether polyol, and the methoxypolyethylene glycol is less than 80 weight percent of the formulated polyol composition based on the total weight of the first polyether polyol, the second polyether polyol, the third polyether polyol, the fourth polyether polyol, and the methoxypolyethylene glycol, i.e., the total weight of the polyol and the ethylene glycol used in the formulated polyol composition. For example, the combination of the second polyether polyol, the third polyether polyol, the fourth polyether polyol, and the methoxypolyethylene glycol, based on the total weight of the first polyether polyol, the second polyether polyol, the third polyether polyol, the fourth polyether polyol, and the methoxypolyethylene glycol, may range from a lower limit of 30, 40, or 50 weight percent of the formulated polyol composition to an upper limit of 79, 75, or 70 weight percent of the formulated polyol composition.

The formulated polyol compositions disclosed herein include a surfactant. Surfactants for preparing polyurethane foams are well known to those skilled in the art and many are commercially available. For example, the surfactant may help provide uniform pore formation and/or gas entrapment. The surfactant can be a silicone surfactant, such as an organosilicone surfactant, a non-silicone surfactant, or a combination thereof. Examples of suitable silicone surfactants include, but are not limited to, NIAX L-620, L-618, L-5130, L-5180, L-5340, L-5440, L-6100, L-6900, L-6980, and L-6989 from Momentive; TEGOSTAB B8427, B-8404, B-8407, B-8409 and B-8462 from Evonik; and DC-193, DC-197, DC-5582 and DC-5598 from Dow Corning. Examples of non-silicone surfactants include, but are not limited to, ethoxylated alkyl phenols, ethoxylated fatty alcohols, paraffin oils, castor oil esters, ricinoleic acid esters, turkey red oil, peanut oil, paraffin waxes, and fatty alcohols.

The surfactant can be 0.1 to 5.0 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition. All individual values and subranges from 0.1 to 5.0 weight percent are included; for example, the surfactant can be from a lower limit of 0.1, 0.3, or 0.5 to an upper limit of 5.0, 4.5, or 4.0 weight percent of the formulated polyol composition, based on the total weight of the formulated polyol composition.

The formulated polyol compositions disclosed herein include water. For example, water may be used as the blowing agent. The water can be 1 to 10 weight percent of the formulated polyol composition, based on the total weight percent of the formulated polyol composition. All individual values and subranges from 1 to 10 weight percent are included; for example, water can be from a lower limit of 1, 2, or 3 to an upper limit of 10, 8, or 6 weight percent of the formulated polyol composition, based on the total weight of the formulated polyol composition.

The formulated polyol 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, a blowing catalyst and a gelling catalyst may be distinguished by a catalytic tendency to favor a urea (blowing) reaction (in the case of a blowing catalyst) or a urethane (gelling) reaction (in the case of a gelling catalyst). Trimerization catalysts can be used to facilitate the reactivity of the composition. One or more embodiments provide that the catalyst is selected from a blowing catalyst, a gelling catalyst, or a combination thereof.

Examples of blowing catalysts (e.g., catalysts that generally facilitate the blowing reaction) include, but are not limited to, short chain tertiary amines or tertiary oxygen-containing amines. For example, blowing catalysts include bis- (2-dimethylaminoethyl) ether; pentamethyldiethylenetriamine, triethylamine, tributylamine, N-dimethylaminopropylamine, dimethylethanolamine, N' -tetramethylethylenediamine, combinations thereof and the like. Examples of commercial blowing catalysts include, but are not limited to, DABCO BL-17 from Windpower and NIAX A1 from Meiji.

Examples of gelling catalysts (e.g., catalysts that generally facilitate the gelling reaction) include, but are not limited to, organometallic compounds, cyclic tertiary amines and/or long chain amines (e.g., containing several nitrogen atoms), and combinations thereof. The organometallic compounds include organotin compounds, such as tin (II) salts of organic carboxylic acids, for example tin (II) diacetate, tin (II) dioctoate, tin (II) diethylhexanoate and tin (II) dilaurate, and dialkyltin (IV) salts of organic carboxylic acids, for example dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate. Bismuth salts of organic carboxylic acids may also be used as gelling catalysts, such as bismuth octoate. The cyclic tertiary amines and/or long chain amines include dimethylbenzylamine, N, N, N ', N' -tetramethylbutanediamine, dimethylcyclohexylamine, triethylenediamine, and combinations thereof. And combinations thereof. Specific examples of commercial gelling catalysts are DABCO 33-LV and DABCO T-12 from the winning group.

Examples of trimerization catalysts include tris (dialkylaminoalkyl) -s-hexahydrotriazines, such as 1,3, 5-tris (N, N-dimethylaminopropyl) -s-hexahydrotriazine; [2,4, 6-tris (dimethylaminomethyl) phenol ]; potassium acetate, potassium caprylate; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; alkali metal hydroxides, such as sodium hydroxide; alkali metal alkoxides such as sodium methoxide and potassium isopropoxide; and alkali metal salts of long chain fatty acids having 10 to 20 carbon atoms and combinations thereof. Some commercially available trimerization catalysts include DABCO TMR, DABCO TMR-2, and DABCO TMR-30 from the winning group.

The catalyst can be 0.01 to 5 weight percent of the formulated polyol composition based on the total weight of the formulated polyol composition. All individual values and subranges from 0.01 to 5 weight percent are included; for example, the catalyst can be from a lower limit of 0.01, 0.1, or 0.2 to an upper limit of 5, 4.5, or 3.5 weight percent of the formulated polyol composition, based on the total weight of the formulated polyol composition.

One or more embodiments of the present disclosure provide that the formulated polyol composition may include one or more additional components. Different additional components and/or different amounts of additional components may be utilized for different applications. Examples of additional components include pigments, colorants, antioxidants, biologic retarders, combinations thereof, and the like. Various amounts of additional components may be utilized for different applications.

The present disclosure provides foam formulations comprising the formulated polyol compositions disclosed herein and an isocyanate. The isocyanate may be a polyisocyanate. As used herein, "polyisocyanate" refers to molecules having an average functionality of greater than 1.0 isocyanate groups per molecule, for example greater than 1.0.

For example, the isocyanate can be an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an aromatic aliphatic polyisocyanate, an aromatic polyisocyanate, or a combination thereof. Examples of isocyanates include, but are not limited to, polymethylene polyphenyl isocyanate, toluene 2,4-/2, 6-diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), polymeric MDI, Triisocyanatononane (TIN), Naphthyl Diisocyanate (NDI), 4 '-diisocyanatodicyclohexylmethane, 3-isocyanatomethyl-3, 3, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate IIPDI), tetramethylene diisocyanate, Hexamethylene Diisocyanate (HDI), 2-methylpentamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate (THDI), dodecamethylene diisocyanate, 1, 4-diisocyanatocyclohexane, 4' -diisocyanato-3, 3 '-dimethyldicyclohexylmethane, 4' -diisocyanato-2, 2-dicyclohexylpropane, 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane (MCI), 1, 3-diisooctylcyanato-4-methylcyclohexane, 1, 3-diisocyanato-2-methylcyclohexane, combinations thereof and the like. In addition to the isocyanates mentioned above, partially modified polyisocyanates may be utilized including uretdione, isocyanurate, carbodiimide, uretonimine, allophanate or biuret structures, combinations thereof and the like.

The isocyanate may be polymeric. As used herein, "polymerized" when describing isocyanates refers to homologues and/or isomers having a higher molecular weight. For example, polymeric methylene diphenyl isocyanate refers to the higher molecular weight homologues and/or isomers of methylene diphenyl isocyanate.

As mentioned, the average functionality of the isocyanate may be greater than 1.0 isocyanate groups per molecule. For example, the average functionality of the isocyanate can be 1.5 to 8.0. Including all individual values and subranges from 1.5 to 8.0; for example, the average functionality of the isocyanate can be 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.

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

The isocyanates can be prepared by known methods. For example, the polyisocyanate may be prepared by phosgenating the corresponding polyamine and forming polycarbamoyl chloride and thermally decomposing it to provide polyisocyanate and hydrogen chloride or by a phosgene-free method, such as by reacting the corresponding polyamine with urea and an alcohol to give polyurethane and thermally decomposing it to give polyisocyanate and alcohol.

Isocyanates are commercially available. Examples of commercial isocyanates include, but are not limited to, those available from the Dow chemical company under the trade name VORANATE^TM、VORACOR^TM(e.g., VORACOR)^TMCL 100) and PAPI^TM(e.g., PAPI)^TM23 and PAPI^TM27) Polyisocyanates of (a), and other commercial isocyanates.

Isocyanates may be utilized such that the isocyanate index of the foam formulation is in the range of 55 to 110. The isocyanate index may be determined as the quotient (multiplied by one hundred) of the actual amount of isocyanate utilized and the theoretical amount of isocyanate used for curing. Including all individual values and subranges from 55 to 110; for example, the isocyanate index of the foam formulation may range from a lower limit of 55, 60, 65, 67, or 69 to an upper limit of 110, 100, or 90.

The foam formulations disclosed herein can be cured to form a foam product. The foam product may be prepared using known methods and conditions, which may vary for different applications.

As mentioned, foam products have a combination of properties that are advantageous for many applications, such as cushions and pillows. For example, the foam products disclosed herein can desirably provide a combination of properties including skin formation, filling of the mold via foaming, having a particular foam core recovery time, a particular air flow rate (e.g., skin and core air flow rates), and a particular compression set at 90% compression.

For many applications, it is critical that the foam formulation be capable of forming a skin. Foam formulations that are not capable of forming a skin can result in undesirable defective foam products. Advantageously, the foam formulations disclosed herein are capable of forming a skin to provide a desired foam product. The advantages of forming the skin will be readily apparent to those skilled in the art, and the formation of the skin can be readily determined by visual inspection.

For many applications, it is crucial that the foam formulation is able to fill the mold via foaming. Foam formulations that are not capable of filling the mold via foaming can result in undesirable defective foam products. Advantageously, the foam formulations disclosed herein are capable of filling a mold via foaming to provide a desired foam product. The advantages of filling the mold will be readily apparent to those skilled in the art, and the filling of the mold can be readily determined by visual inspection.

The foam core recovery time of the foam products disclosed herein can be from 2 seconds to 120 seconds. A foam core recovery time of 2 seconds to 120 seconds indicates that the foam product has the desired viscoelasticity, e.g., the foam product exhibits both viscous and elastic characteristics when subjected to deformation. All individual values and subranges from 2.0 to 120 seconds are included; for example, the foam core recovery time of the foam product can be from a lower limit of 2.0, 2.3, or 2.5 seconds to an upper limit of 120, 90, or 60 seconds.

The skin airflow rate of the foam products disclosed herein may advantageously be 4.0 cubic feet per minute (cfm) or higher. For example, the skin airflow rate of the foam product may be from a lower limit of 4.0cfm to an upper limit of 8.0 cfm. Skin airflow rate may be determined according to ASTM D3574; this air flow rate can be measured with the foam skin remaining on the foam. Herein, a skin airflow rate of 4.0 cubic feet per minute (cfm) or higher indicates that the foam product is chemically perforated. One or more embodiments provide that the skin airflow rate is preferably 5.0cfm or higher.

The core airflow rate of the foam products disclosed herein may advantageously be 4.0 cubic feet per minute (cfm) or higher. For example, the core airflow rate of the foam product may be from a lower limit of 4.0cfm to an upper limit of 14.0 cfm. The core airflow rate may be determined according to ASTM D3574; this air flow rate can be measured with the foam skin removed from the foam. One or more embodiments provide that the core airflow rate is preferably 5.0cfm or higher. Optimally, the core airflow rate is 6.5cfm or more, or 7.0cfm or more.

The compression set of the foam products disclosed herein at 90% compression may advantageously be from 1% to 12%. Compression set is a measure of the permanent set of a foam product after it has been compressed between two metal sheets under controlled time and temperature conditions. The foam product is compressed to a thickness expressed as a percentage of its original thickness that remains "deformed". All individual values and subranges from 1% to 12% are included; for example, the compression set of the foam product at 90% compression can be from a lower limit of 1, 1.5, or 2% to an upper limit of 12, 10, or 9.5%. Compression set at 90% compression can be determined according to ASTM D3574 test D.

The foam products disclosed herein can be open cell foams. As used herein, "open-cell foam" refers to a foam having a core airflow rate of 0.75 cubic feet per minute (cfm) or greater. Open cell foams are desirable for many applications.

The foam products disclosed herein may have one or more desired properties. For example, the foam products disclosed herein may have a density of 1.2 to 3.0 pounds per cubic foot (pcf). All individual values and subranges from 1.2 to 3.0pcf are included; for example, the density of the foam product can be from a lower limit of 1.2, 1.5, 1.8, 2.0, 2.05, or 2.1pcf to an upper limit of 3.0, 2.8, or 2.7 pcf.

The compressive force deflection (25%) of the foam products disclosed herein may be from 1.0 to 2.0 kPa. Including all individual values and subranges from 1.0 to 2.0 kPa; for example, the compressive force deflection (25%) of the foam product may be from a lower limit of 1.0, 1.1, or 1.2kPa to an upper limit of 2.0, 1.9, or 1.85 kPa.

The compressive force deflection (40%) of the foam products disclosed herein may be from 1.3 to 3.5 kPa. All individual values and subranges from 1.3 to 3.5kPa are included; for example, the compressive force deflection (40%) of the foam product may be from a lower limit of 1.3, 1.4, or 1.5kPa to an upper limit of 3.5, 3.4, or 3.3 kPa.

The compression force deflection (65%) of the foam products disclosed herein may be from 2.5 to 20.0 kPa. All individual values and subranges from 2.5 to 20.0kPa are included; for example, the compressive force deflection (65%) of the foam product may be from a lower limit of 2.5, 2.7, or 30kPa to an upper limit of 20.0, 18.0, or 15.0 kPa.

In contrast to previous materials, which may be mechanically perforated to provide more comfort, the foam products disclosed herein may be referred to as chemically perforated. A chemically perforated foam product as disclosed herein may have an average cell diameter of 50 to 500 μm, e.g. the cells in a formed skin. All individual values and subranges from 50 to 500 μm are included; for example, the average cell diameter of the chemically perforated foam product may be from a lower limit of 50, 75, 100, 150, 175, or 200 μm to an upper limit of 500, 475, 450, 425, 400, 375, 350, 325, or 300 μm.

The average pore coverage percentage of a chemically perforated foam product as disclosed herein (e.g., the percentage of the total surface area of the foam product occupied by the pores in the formed skin (chemical perforations)) can be from 50 to 85 percent. All individual values and subranges from 50 to 85 percent are included; for example, the average percent cell coverage of the chemically perforated foam product can be from a lower limit of 50, 55, 60, 62, or 65 percent to an upper limit of 85, 83, or 80 percent. The average percent pore coverage can be determined, for example, by microscopic observation.

The average skin coverage percentage (e.g., the percentage of the total surface area of the foam product occupied by the skin formed) of a chemically perforated foam product as disclosed herein can be 15 to 50 percent. All individual values and subranges from 15 to 50 percent are included; for example, the average skin coverage percentage of the chemically perforated foam product may be from a lower limit of 15, 17, or 20 percent to an upper limit of 50, 45, 40, 38, or 35 percent. The sum of the average percent skin coverage and the average percent pore coverage will be 100 percent.

The foam products disclosed herein may advantageously have an improved interface temperature, i.e., a relatively lower interface temperature, compared to other materials. The interface temperature refers to the temperature between a person and the foam product. The relatively lower interface temperature may make the foam product (e.g., when used as a pillow) desirably more comfortable than a material having a higher interface temperature.

The foam products disclosed herein may advantageously have improved interface relative humidity, i.e., lower interface relative humidity, compared to other materials. Interfacial relative humidity refers to the relative humidity between a person and a foam product. Lower interfacial relative humidity can make the foam product (e.g., when used as a pillow) desirably more comfortable than a material with higher interfacial relative humidity.

The foam products disclosed herein may advantageously have improved wicking times, i.e., lower wicking times, compared to other materials. The wicking time refers to the time for water to disappear from the surface of the foam product. Lower wicking times can make the foam product (e.g., when used as a pillow) desirably more comfortable than a material with a higher wicking time.

Examples of the invention

In examples, various terms and names of materials are used, including, for example, the following:

VORANOL^TMWK 3140 (first polyether polyol; EO content 60%; average hydroxyl functionality 3.0; average hydroxyl number 167mg KOH/g; number average molecular weight 1000 g/mol; available from the Dow chemical company); VORANOL^TM2070 (a fourth polyether polyol; average hydroxyl functionality 3.0; average hydroxyl number 237mg KOH/g; number average molecular weight 708 g/mol; all based on propylene oxide, available from Dow chemical company); VORANOL^TM3136 (third polyether polyol; average hydroxyl functionality 3.0; average hydroxyl number 56.4mg KOH/g; number average molecular weight 3000 g/mol; ethylene oxide content 8% by weight, available from Dow chemical); VORANOL^TMCP-1447 (second polyether polyol; average hydroxyl functionality 3.0; average hydroxyl number 37mg KOH/g; number average molecular weight 4500 g/mol; ethylene oxide content 78 weight percent; available from Dow chemical Co.); CARBOWAX^TMMPEG 550 (methoxypolyethylene glycol; average hydroxyl functionality 1.0; average hydroxyl number 102mg KOH/g; number average molecular weight 550 g/mol; available from Dow chemical); CARBOWAX^TMPEG 600 (commercial polyethylene glycol; average hydroxyl functionality 2.0; average hydroxyl number 190mg KOH/g; number average molecular weight 600 g/mol; available from Dow chemical Co.); IP 625 (commercial polyol; average hydroxyl functionality 3.0; average hydroxyl number 270mg KOH/g; number average molecular weight 623 g/mol; all ethylene oxide based, available from Dow chemical); VORANOL^TMCP-3001 (commercial polyol, average hydroxyl functionality 3.0; average hydroxyl number 56.4mg KOH/g; number average molecular weight 3000 g/mol; end capped with 8.5% ethylene oxide, 54 mole% primary hydroxyl content, available from Dow chemical Co.); NIAX L-620 (organosilicone surfactant; obtained from Mylar chart); DABCO 33-LV (gelling catalyst; obtained from Woods); DABCO BL-17 (blowing catalyst; obtained from Wobo Corp.); PAPI^TM23 (isocyanate; polymethylene polyphenyl isocyanate containing MDI; available from the dow chemical company).

The polyol composition formulated in Example (EX)1 was prepared as follows. For example 1, the formulated polyol composition components listed in table 1 (except for the catalyst added after the first mixing) were combined in a mixing vessel by mixing with a 16-pin mixer at 800rpm for 15 seconds and at 2400rpm for 15 seconds; the catalyst was then added to the contents of the mixing vessel and mixed at 2400rpm for 15 seconds. Examples 2-6 were prepared as in example 1, with the modifications indicated in Table 1, respectively.

Example 7 foam formulations were prepared as follows. The isocyanate was added to example 1 and mixed at 3000rpm for 3 seconds; the isocyanate index is listed in table 1. Examples 8-12 were prepared as in example 7, with the modifications that examples 2-6 were utilized instead of example 1, respectively, and with the modifications that the items indicated in table 1 were utilized, respectively.

Example 13 foam product was prepared as follows. Example 7 was poured into a plastic lined container (38cm x 24cm) for foaming and curing at about 20 ℃ for about 12 hours to provide example 13. Examples 14-18 were prepared as in example 13, with the modification that examples 8-12 were utilized instead of example 7, respectively.

Comparative Examples (CE) A-S were prepared as in examples 1-6, with the modifications that utilized the items indicated in the tables below, respectively.

Comparative examples a-S foam formulations were prepared as in example 7, with the modification that comparative examples a-P were used instead of example 1, respectively.

Comparative examples a-S foam products were prepared as in example 13, with the modification that comparative examples a-P were used instead of example 7, respectively.

A number of characteristics of the examples and comparative examples were determined and are reported in the following table.

Foam core recovery was determined using RESIMAT (mestechnik GmbH, Germany); each sample (4 inches by 2 inches) was compressed to a 78% strain level using a platen and held for 60 seconds, after which 60 seconds the electromagnet released the platen and allowed the foam to recover at least 90% of its original uncompressed height. The recovery time at 90% recovery is referred to as the foam core recovery time.

Compressive force deflection was measured according to ASTM D3574-08.

The airflow rates of the skin and core were determined according to ASTM D3574 and reported in cubic feet per minute (cfm). Each sample (2 inches by 1 inch); three samples were tested per sample and the average value is reported. For skin airflow rate, samples were tested with the foam skin remaining. For core airflow rate, the samples were tested with the foam skin removed, i.e., the foam core was tested. For the comparative example of mechanical perforation, four holes were punched in each sample, each hole having a diameter of 6 mm; the punch holes are symmetrically arranged and each punch hole is located near a corner of the sample. For comparative examples of measured gas flow, comparative examples C, D, N, and P were mechanically perforated, while comparative examples F, J, and M were not mechanically perforated.

Compression set at 90% compression was determined according to ASTM D3574 test D.

TABLE 1

The data of Table 1 advantageously illustrate each of examples 13-18: forming a skin; filling the mold via foaming; the foam core recovery time is from 2 seconds to 120 seconds; a skin airflow rate of 4.0 cubic feet per minute (cfm) or greater; a core airflow rate of 4.0 cubic feet per minute (cfm) or greater; and a compression set at 90% compression of 1% to 12%.

TABLE 2

TABLE 3

TABLE 4

The data of tables 2-4 illustrate that, in contrast to each of examples 13-18, none of comparative examples a-S can provide an advantageous combination of properties as illustrated in table 1. None of comparative examples a-S were able to provide: a formed skin; filling the mold via foaming; the foam core recovery time is from 2 seconds to 120 seconds; a skin airflow rate of 4.0 cubic feet per minute (cfm) or greater; a core airflow rate of 4.0 cubic feet per minute (cfm) or greater; and a compression set at 90% compression of 1% to 12%.

Polyol compositions formulated in examples 20-21 were prepared as in examples 1-6, with the modifications indicated in Table 5, respectively.

Example 22-23 foam formulations were prepared using a Cannon A40 high pressure machine, as discussed further below. The isocyanate index is listed in table 5.

Examples 24-25 foam products were prepared using examples 22-23 and a Cannon A40 high pressure machine equipped with a 14mm FPL mixing head, respectively. Examples 22-23 were each poured into an aluminum pillow mold. The cavity volume of the mold was about 1.4ft³. The temperature of the mold is controlled by resistance heating. A water-based mold release agent was applied to the mold prior to each pour. The set conditions of the machine are: a mold temperature of 120 ° f; a formulated polyol composition temperature of 77 ° f; an isocyanate temperature of 77 ° f; a throughput of 170 grams/second; 170 bar of formulated polyol composition pressure; an isocyanate pressure of 170 bar; a demold time of 210 seconds (3 minutes vented, 3.5 minutes removed); 1.04 specific gravity of the formulated polyol composition; an isocyanate specific gravity of 1.23; 1.5mm orifice of the formulated polyol composition; 0.8mm isocyanate orifice. As previously discussed, a number of characteristics of examples 24-25 were determined. The results are reported in table 5.

TABLE 5

The data of Table 5 advantageously illustrates each of examples 24-25: forming a skin; filling the mold via foaming; the foam core recovery time is from 2 seconds to 120 seconds; a skin airflow rate of 4.0 cubic feet per minute (cfm) or greater; a core airflow rate of 4.0 cubic feet per minute (cfm) or greater; and a compression set at 90% compression of 1% to 12%.

The interfacial temperature and interfacial relative humidity level at the interface between the pillows and human skin of examples 24-25 and various commercially available pillows were determined as follows. The temperature/humidity sensors were inserted between the human head and the pillows of examples 24-25 and commercially available, respectively; the temperature and relative humidity levels were determined after 60 minutes. Examples 24-25 and commercially available pillows each had a respective fabric density of 0.18kg/m²Cotton (55%)/polyester covering (45%) woven fabric covering. The results are reported in table 6.

The wicking time of examples 24-25 and commercially available pillows was determined by placing a drop of dyed water on each surface (1.0 inch thick) of the samples of examples 24-25 and commercially available pillows. The time required for the water droplet to disappear from the surface was visually observed and recorded as the wicking time. The results are reported in table 6.

Commercially available pillows are: pillow 1 (latex pillow from Organic Textiles; 100% latex material, skin airflow rate 10 cfm; core airflow rate 11 cfm; density 2.1 pcf; compression set at 90% 6.2%); pillow 2 (Dream Serenity Ergo Shape Commort from Sinomax; density 2.76 pcf); pillow 3 (Big One Gel Memory Foam from Kohl's company; 10 weight percent Gel particles; density 2.3 pfc); pillow 4 (gel coated pillow from Pharmedc; density 2.45 pcf); pillow 5 (phase change material coated pillow; density 2.5 pcf). As discussed herein, commercially available pillows are mechanically perforated.

Examples 24-25 were performed chemically as discussed herein and had an average pore diameter of about 250 μm; an average pore coverage of about 79 percent and an average skin coverage of about 21 percent. The mechanically perforated material had an average pore diameter of about 6.0 mm; an average pore coverage of about 6.9 percent and an average skin coverage of about 93.1 percent.

TABLE 6

The data of Table 6 illustrates that examples 24-25 have advantageously improved interface temperatures, i.e., relatively lower interface temperatures, compared to each of the commercially available pillows 2-5. The relatively lower interface temperature can make the pillow desirably more comfortable than a pillow having a higher interface temperature.

The data of Table 6 illustrates that examples 24-25 have advantageously improved interface relative humidity, i.e., lower interface relative humidity, as compared to each of the commercially available pillows 2-5. Lower interface relative humidity can make the pillow desirably more comfortable than a pillow having higher interface relative humidity.

The data of table 6 illustrates that examples 24-25 have advantageously improved wicking times, i.e., relatively lower wicking times, compared to each of the commercially available pillows 1-5. Lower wicking times can make the pillow desirably more comfortable than a pillow with a higher wicking time.