Isocyanate-reactive compositions and methods for preparing polyurethane and polyisocyanurate foams

Abstract

The present invention provides an isocyanate-reactive composition comprising (i) at least one isocyanate-reactive compound; and (ii) a predetermined amount of at least one T-shaped silicone material; and a foam-forming composition for preparing a polyurethane or polyisocyanurate foam, the foam-forming composition comprising at least one isocyanate component and at least one isocyanate-reactive component; wherein the at least one isocyanate-reactive component is the isocyanate-reactive composition described above.

Description

Technical Field

[0001] The present disclosure relates to the field of thermal insulation rigid foams. More specifically, the present disclosure relates to an isocyanate-reactive composition comprising a liquid siloxane having a T-shaped structure for preparing rigid polyisocyanurate (PIR) and polyurethane (PUR) foams exhibiting excellent thermal insulation properties.

[0002] Preface

[0003] Rigid polyisocyanurate (PIR) and polyurethane (PUR) foams have excellent thermal insulation properties and are therefore used in a variety of applications such as building and construction, roofing, tanks, pipes, appliances, refrigerated transportation, etc. These unique characteristics are due to the combination of a closed-cell honeycomb structure containing specific gases with low thermal conductivity, such as hydrocarbons. With the market demand for better thermal insulation and the requirements for ever-increasing energy efficiency, there is an urgent need and a continuous market demand for further improvements in the thermal insulation properties of PIR / PUR rigid foam products. One such solution is to obtain foams with a finer honeycomb structure to achieve lower thermal conductivity (also known as λδ value or K factor). There remains a need to achieve better thermal insulation while maintaining ease of processing, light weight and good mechanical properties. Summary of the Invention

[0004] The present disclosure is based on the surprising discovery that liquid siloxanes with a T-shaped structure can effectively reduce the K factor of the resulting rigid PIR / PUR foams while maintaining good mechanical properties.

[0005] A first embodiment is an isocyanate-reactive composition comprising at least one isocyanate-reactive compound and at least one liquid silicone material having the following structure:

[0006]

[0007] wherein A1 and B1 are each independently a linear or branched monovalent hydrocarbon group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl, octyl, n-octyl, and the like, and preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl; and

[0008] A2, A3, B2 and B3 are each independently a linear or branched monovalent hydrocarbon group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and preferably methyl, ethyl, propyl or isopropyl; and

[0009] m and n are each independently an integer from 1 to 6; and

[0010] X is a linear or branched monovalent hydrocarbon group having 1 to 4 carbon atoms, such as a methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl group, or a trimethylsilyloxy group; and

[0011] Y is an alkylene oxide-containing group having 2 to 24 alkylene oxide repeating units, preferably 3 to 20 alkylene oxide repeating units, more preferably 3 to 15 alkylene oxide repeating units, even more preferably 3 to 12 alkylene oxide repeating units and still more particularly 5 to 12 alkylene oxide repeating units, and

[0012] Y can also be represented by the following general formula:

[0013] —Z—O—[(C2H4O) a (C3H6O) b (C4H8O) c ] d —W

[0014] wherein Z is a straight or branched divalent hydrocarbon group having 3 to 8 carbon atoms; W is hydrogen, a monovalent hydrocarbon group having 1 to 4 carbon atoms, acetyl, propionyl, or butyrate; subscript a is an integer value from 1 to 15, subscripts b and c are each independently an integer value from 0 or 1 to 14, wherein the sum of the integer values of subscripts a, b, and c is greater than or equal to 2 and less than or equal to 24, and subscript d is 0, 1, or 2.

[0015] The above embodiments (and other embodiments) can be further described as an isocyanate-reactive composition comprising a liquid siloxane material for preparing a rigid polyurethane or polyisocyanurate foam with improved thermal insulation properties, wherein the isocyanate-reactive composition comprises at least one isocyanate-reactive compound; an amount of 0.1 to 5 parts (e.g., an amount of 0.2 to 4 parts, preferably an amount of 0.5 to 3.5 parts, and even more preferably an amount of 0.5 to 3.0 parts) of at least one liquid siloxane material of Formula I, based on 100 parts of the total weight of the isocyanate-reactive compound; and the isocyanate-reactive composition is visually clear without phase separation.

[0016] Another preferred embodiment of the isocyanate-reactive composition can be described as comprising a liquid silicone material for preparing rigid polyurethane or polyisocyanurate foams having improved thermal insulation properties, wherein the isocyanate-reactive composition comprises at least one isocyanate-reactive compound; an amount of 0.1 to 5 parts (e.g., an amount of 0.2 to 4 parts, preferably an amount of 0.5 to 3.5 parts, and even more preferably an amount of 0.5 to 3.0 parts) of at least one T-structured liquid silicone material, based on 100 parts of the total weight of the isocyanate-reactive compound; and the isocyanate-reactive composition is visually clear without phase separation, wherein the at least one liquid silicone material is a T-shaped trisiloxane having the following structure:

[0017]

[0018] R1 and R2 are each independently hydrogen or a C1-C4 alkyl group, p1 is an integer value from 1 to 6, p2 is an integer value from 1 to 12, p3 is an integer value from 0 to 12, and the sum of the values of p1 and p2 is greater than or equal to 2 and less than or equal to 24; R3 is a hydrogen atom, a C1-C4 alkyl group, an acetyl group, a propionyl group, or a butyrate or ester / ether group; and R4 is a C1-C4 alkyl group or a trimethylsiloxy group.

[0019] Another embodiment of the present invention is a foam-forming composition and rigid polyurethane and polyisocyanurate foams prepared from such foam-forming compositions, said foam-forming composition comprising the isocyanate-reactive composition disclosed above, at least one isocyanate component, and optionally auxiliary components such as surfactants, catalysts, blowing agents, etc. The isocyanate index of such foam-forming compositions is preferably between 100 and 600.

[0020] The amount of liquid silicone additive material having a T-shaped structure used in these and other embodiments can range from 0.1 to 5 parts (e.g., 0.2 to 4 parts, 0.5 to 3.5 parts, or 0.5 to 2.5 parts, or 0.5 to 2 parts), based on 100 parts of the total weight of the at least one isocyanate-reactive compound.

[0021] Any optional auxiliary components such as blowing catalysts, gelling catalysts, trimerization catalysts, surfactants, reactive or non-reactive diluents, physical or chemical blowing agents, antioxidants, flame retardant additives, pigments, etc. can be first incorporated into the isocyanate-reactive composition or into the isocyanate component before the isocyanate-reactive composition and the isocyanate component are mixed together for foam preparation, or mixed into the foam-forming composition as a separate stream during the mixing of the isocyanate-reactive composition and the isocyanate component. Not all of these optional auxiliary components are required for foam preparation and should not be construed as limiting the scope of the present disclosure in any way.

[0022] It should be noted that throughout this disclosure, the T-shaped siloxane additive material is sometimes referred to as an additive and sometimes as a material. This is because the siloxane can be present as an additive, as compared to the typical reaction between a polyol (e.g., an isocyanate-reactive compound) and an isocyanate. The siloxane can also be combined with the polyol prior to mixing with the isocyanate and other additives such as blowing agents, making it part of the isocyanate-reactive component rather than an additive added in the same manner as blowing agents, etc. are typically added.

[0023] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the claims. DETAILED DESCRIPTION

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which this method belongs. In addition, all publications, patent applications, patents and other references mentioned herein are incorporated by reference. As disclosed herein, the terms "composition", "formulation" or "mixture" refer to a physical blend of different components, which is obtained by simply mixing the different components in a physical manner. As disclosed herein, "and / or" means "and, or as an alternative". Unless otherwise indicated, all ranges are inclusive.

[0025] In various embodiments, compositions for preparing rigid polyisocyanurate (PIR) and polyurethane (PUR) foams are provided, comprising an isocyanate component having two or more isocyanate groups per molecule, an isocyanate-reactive component such as a polyol that reacts with the isocyanate groups, and a liquid siloxane having a T-shaped structure that is miscible in the isocyanate-reactive component. The isocyanate component and the isocyanate-reactive component are typically stored in separate containers until they are ready to be mixed together and subjected to a polymerization reaction between the isocyanate groups and the hydroxyl groups to form polyisocyanurates and / or polyurethanes. Polyurethanes refer to polymers comprising a backbone formed by repeating units (-NH-C(O)-O-) derived from the reaction between isocyanate groups and hydroxyl groups, while polyisocyanurates comprise an isocyanurate ring structure formed by the trimerization reaction of isocyanate groups. PUR and PIR foams may also contain urea groups due to the use of water as a chemical blowing agent and / or the incorporation of amine compounds into the foam formulation.

[0026] As used herein, the terms "polyisocyanurate and polyurethane," "polyisocyanurate or polyurethane," "PIR and PUR," "PIR or PUR," and "PIR / PUR" are used interchangeably in this disclosure and refer to polymer systems comprising polyurethane chains and groups that lead to cyclotrimerization of isocyanates (sometimes referred to as "polyisocyanurate groups"), the relative proportions of which depend primarily on the stoichiometric ratios of the isocyanate compounds and polyol compounds contained in the raw materials. In addition, ingredients such as catalysts and other additives, as well as processing conditions such as temperature, reaction duration, etc., may also affect the relative amounts of PUR and PIR in the final foam product. Thus, polyisocyanurate and polyurethane foams (PIR / PUR foams) as described in the context of this disclosure refer to foams obtained as the reaction product between the above-mentioned isocyanates and compounds having isocyanate-reactive groups, in particular polyols. In addition, additional functional groups, such as allophanates, biuret, or urea, may be formed during the foaming reaction. PIR / PUR foams may be rigid foams. The compositions of the present disclosure may further comprise catalysts, blowing agents, and other additives.

[0027] According to one embodiment of the present disclosure, the composition of the present disclosure can be prepared and stored as two separate "packages," namely, an isocyanate package containing an isocyanate component and a polyol package containing an isocyanate-reactive composition and, optionally, other auxiliary components such as surfactants, catalysts, blowing agents, and the like, wherein the isocyanate-reactive composition comprises at least one isocyanate-reactive compound and a liquid siloxane having a T-shaped structure. For example, the isocyanate-reactive component, surfactant, catalyst, blowing agent, and other additives can be mixed together to obtain a "polyol package," which is then mixed with the isocyanate component to prepare PUR / PIR foam. According to various embodiments of the present disclosure, the amount, content, or concentration of the isocyanate-reactive component and the isocyanate component in these embodiments is calculated based on the total weight of the foam-forming composition (i.e., the combined weight of the "polyol package" and the "isocyanate package"), while the content of the other components (e.g., T-shaped siloxane, surfactant, catalyst, blowing agent, and other additives) is calculated based on 100 parts (pts) of the total polyol weight in the "polyol package."

[0028] In alternative embodiments, the T-shaped silicone, surfactant, catalyst, blowing agent, and other additives are not premixed with the isocyanate-reactive compound and are added as separate streams, but their amounts are still calculated based on the total weight of polyol in the "polyol package" equal to 100 pts. Any of these optional auxiliary components can be premixed with the isocyanate compound used for foam preparation, as long as they are miscible and chemically compatible with the isocyanate compound. In some embodiments, a gaseous blowing agent can be added to the isocyanate component to cause it to foam, which minimizes leakage of the reactive foaming mixture during application.

[0029] Isocyanate component

[0030] In various embodiments, the isocyanate component of the present invention may include, for example, one or more isocyanate compounds, including, for example, polyisocyanates. As used herein, "polyisocyanate" refers to molecules having an average of greater than 1.0 isocyanate groups per molecule, e.g., an average functionality greater than 1.0.

[0031] The isocyanate compound that can be used in the present invention can be an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an aromatic aliphatic polyisocyanate, an aromatic polyisocyanate, or a combination thereof. Examples of isocyanates that can be used in the present invention 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); 4,4'-diisocyanatodicyclohexyl-methane; 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate IPDI); tetramethylene diisocyanate; hexamethylene diisocyanate (HDI); 2-Methyl-pentamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate (THDI); dodecamethylene diisocyanate; 1,4-diisocyanatocyclohexane; 4,4'-diisocyanato-3,3'-dimethyl-dicyclohexylmethane; 4,4'-diisocyanato-2,2-dicyclohexylpropane; 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane (MCI); 1,3-diisooctylcyano-4-methylcyclohexane; 1,3-diisocyanato-2-methylcyclohexane; and combinations thereof. In addition to the above-mentioned isocyanates, partially modified polyisocyanates including uretdione, isocyanurate, carbodiimide, uretonimine, allophanate, or biuret structures, and combinations thereof, can be used in the present invention.

[0032] Isocyanate compounds can be polymeric. As used herein, when describing isocyanates, "polymeric" refers to homologues and / or isomers having high molecular weights. For example, polymeric methylene diphenyl isocyanate refers to high molecular weight homologues and / or isomers of methylene diphenyl isocyanate.

[0033] Isocyanate compounds that can be used for the present invention can be the polyfunctional isocyanates of modification, the product that promptly obtains by the chemical reaction of isocyanate compounds.Illustrative is the polyisocyanates that contains ester, urea, biuret, allophanate and carbodiimide and / or uretonimine.Also can use the liquid polyisocyanates that contains carbodiimide group, uretonimine group and / or isocyanurate ring of isocyanate group (NCO) content with 10 % by weight to 35 % by weight, 10 % by weight to 32 % by weight, 10 % by weight to 30 % by weight, 15 % by weight to 30 % by weight or 15 % by weight to 28 % by weight. These include, for example, polyisocyanates based on 4,4′-, 2,4′- and / or 2,2′-diphenylmethane diisocyanate and the corresponding isomer mixtures, 2,4- and / or 2,6-toluene diisocyanate and the corresponding isomer mixtures; mixtures of diphenylmethane diisocyanate and PMDI; and mixtures of toluene diisocyanate and PMDI and / or diphenylmethane diisocyanate.

[0034] Alternatively or in addition, the isocyanate component may further comprise an isocyanate prepolymer. Isocyanate prepolymers are known in the art and are typically prepared by reacting (1) at least one isocyanate compound and (2) at least one polyol compound. Isocyanate prepolymers can be obtained by reacting the above-mentioned monomeric isocyanate compounds or polymeric isocyanates with one or more isocyanate-reactive compounds such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,4-butynediol, 1,5-pentanediol, neopentyl glycol, bis(hydroxymethyl)cyclohexanes such as 1,4-bis(hydroxymethyl)cyclohexane, 2-methylpropane-1,3-diol, methylpentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, and polybutylene glycol.

[0035] Prepolymers suitable for use as polyisocyanate components are prepolymers having an NCO group content of 5 % by weight to 30 % by weight or preferably 10 % by weight to 30 % by weight. These prepolymers can be prepared by the reaction of diisocyanates and / or polyisocyanates with the material comprising lower molecular weight diols and triols. Independent example is an aromatic polyisocyanate containing urethane groups, with an NCO content of 5 % by weight to 30 % by weight (for example, 10 % by weight to 30 % by weight or 15 % by weight to 30 % by weight), which is obtained by the reaction of diisocyanates and / or polyisocyanates with for example lower molecular weight diols, triols, oxyalkylene glycols, dioxide alkylene glycols or polyoxyalkylene glycols with a molecular weight of up to about 1000. These polyols can be used alone or with a mixture of dioxide alkylene glycols and / or polyoxyalkylene glycols. For example, diethylene glycol, dipropylene glycol, polyoxyethylene glycol, ethylene glycol, propylene glycol, butylene glycol, polyoxypropylene glycol and polyoxypropylene-polyoxyethylene glycol can be used. Polyester polyols can also be used, as well as alkane diols such as butylene glycol. Other glycols that can also be used include bishydroxyethyl- or bishydroxypropyl-bisphenol A, cyclohexanedimethanol and bishydroxyethylhydroquinone.

[0036] As described above, the isocyanate can have an average functionality greater than 1.0 isocyanate group / molecule. For example, the isocyanate can have an average functionality of 1.75 to 3.50. All individual values and subranges from 1.75 to 3.50 are included; for example, the isocyanate can have an average functionality from a lower limit of 1.5, 1.75, 1.85, or 1.95 to an upper limit of 3.5, 3.4, 3.3, 3.2, 3.1, or 3.

[0037] The isocyanate can have an isocyanate equivalent weight of 80 g / eq to 300 g / eq, including all individual values and subranges from 80 g / eq to 300 g / eq; for example, the isocyanate can have an isocyanate equivalent weight from a lower limit of 80 g / eq, 90 g / eq, or 100 g / eq to an upper limit of 300 g / eq, 290 g / eq, or 280 g / eq.

[0038] The isocyanates used in the present invention can be prepared by known methods. For example, the polyisocyanates can be prepared by phosgenation of the corresponding polyamines, where polycarbamoyl chlorides are formed and thermally decomposed to provide polyisocyanates and hydrogen chloride; or, in another embodiment, the polyisocyanates can be prepared by a phosgen-free process, such as by reacting the corresponding polyamines with urea and an alcohol to give polycarbamates and thermally decomposing them to give, for example, polyisocyanates and alcohols.

[0039] Isocyanates useful in the present invention are commercially available. Examples of commercial isocyanates useful in the present invention include, but are not limited to, VORANATE TM 、PAPI TM and ISONATE TM Such as VORANATE TM M 220 and PAPI TM 27 polyisocyanates, all of which are available from Dow, Inc., and other commercial isocyanates.

[0040] Generally, the amount of the isocyanate component can vary based on the end use of the rigid PIR / PUR foam. For example, as an exemplary embodiment, the concentration of the isocyanate component can be from about 20% to about 80% by weight, or from about 25% to about 80% by weight, or from about 30% to about 75% by weight, based on the total weight of all components in the reactive foam-forming composition used to prepare the rigid PIR / PUR foam.

[0041] The stoichiometric ratio of isocyanate groups in the isocyanate component to hydroxyl groups in the isocyanate-reactive component is between about 1.0 and 6. This ratio multiplied by 100 is generally referred to as the isocyanate index. The isocyanate index can have lower limits of 100, 105, 110, 115, 120, 125, 150, 175, and 180 and upper limits of 600, 575, 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, and 300.

[0042] Isocyanate-reactive components

[0043] In various embodiments of the present disclosure, the isocyanate reactive composition includes one or more isocyanate reactive compounds, such as a polyol selected from the group consisting of: an aliphatic polyol comprising at least two hydroxyl groups, a cycloaliphatic or aromatic polyol comprising at least two hydroxyl groups, an aralkyl group, an aromatic aliphatic polyol comprising at least two hydroxyl groups, a polyether polyol, a polycarbonate polyol, a polyester polyol, a polyester ether polyol, and a mixture thereof. In one example, the polyol is selected from the group consisting of: a C2-C16 aliphatic polyol comprising at least two hydroxyl groups, a C6-C15 cycloaliphatic or aromatic polyol comprising at least two hydroxyl groups, a C7-C15 aromatic aliphatic polyol comprising at least two hydroxyl groups. Polyester polyols typically have an average molecular weight of 200 to 5,000. The average molecular weight of polyether polyols is 50 to 5,000, and combinations thereof.

[0044] In one embodiment, the isocyanate reactive component comprises a mixture of two or more different polyols, such as a mixture of two or more polyether polyols, a mixture of two or more polyester polyols or a mixture of at least one polyether polyol and at least one polyester polyol. The isocyanate reactive component has a functionality (the average number of isocyanate reactive groups, particularly hydroxyl groups, in the polyol molecules) of at least 1.8 and an OH value of 80 mg KOH / g to 2,000 mg KOH / g. For example, 100 mg KOH / g to 1,500 mg KOH / g, 120 mg KOH / g to 1,000 mg KOH / g, 150 mg KOH / g to 1,000 mg KOH / g, 150 mg KOH / g to 750 mg KOH / g, 175 mg KOH / g to 750 mg KOH / g, 175 mg KOH / g to 500 mg KOH / g or 200 mg KOH / g to 500 mg KOH / g.

[0045] Typically, the average hydroxyl functionality of polyol compounds useful in the present invention, such as those described above, can range from as low as 1.8 to as high as 7.5. For example, aromatic polyester polyols can have an average hydroxyl functionality of 1.8 to 3.0; and sucrose / glycerol-initiated polyether polyols can have an average hydroxyl functionality of 3.0 to 7.5. Thus, the average hydroxyl functionality of polyol compounds useful in the present invention can range from 1.8 to 7.5. All individual values and subranges from 1.8 to 7.5 are included; for example, the polyol compound can have an average hydroxyl functionality from a lower limit of 1.8, 2.0, 2.2, 2.5, 2.7, 3.0, or 3.5 to an upper limit of 7.5, 7.0, 6.5, 6.0, 5.7, 5.5, 5.2, 5.0, 4.8, 4.5, 4.2, or 4.0.

[0046] Typically, the polyol compound can have an average hydroxyl number within the range of 75 mg KOH / g to 650 mg KOH / g, including all individual values and subranges therefrom; for example, the polyol compound can have an average hydroxyl number from a lower limit of 75 mg KOH / g, 80 mg KOH / g, 100 mg KOH / g, 125 mg KOH / g, 150 mg KOH / g, or 175 mg KOH / g to an upper limit of 650 mg KOH / g, 600 mg KOH / g, 550 mg KOH / g, 500 mg KOH / g, 450 mg KOH / g, or 400 mg KOH / g.

[0047] Typically, the polyol compound can have a number average molecular weight of 100 g / mol to 1,500 g / mol, including all individual values and subranges from 100 g / mol to 1,500 g / mol; for example, the polyol compound can have a number average molecular weight from a lower limit of 100 g / mol, 150 g / mol, 175 g / mol, or 200 g / mol to an upper limit of 1,500 g / mol, 1250 g / mol, 1,000 g / mol, or 900 g / mol.

[0048] Typically, the polyol compound can have a hydroxyl equivalent molecular weight of 50 g / eq to 750 g / eq, including all individual values and subranges from 50 g / eq to 750 g / eq; for example, the polyol compound can have a hydroxyl equivalent molecular weight of 350 g / eq, 300 g / eq, 275 g / eq, or 250 g / eq, from a lower limit of 50 g / eq, 90 g / eq, 100 g / eq, or 110 g / eq.

[0049] Polyester polyol is obtained by the condensation of polyvalent alcohol and multifunctional carboxylic acid with 2 to 12 carbon atoms (for example, 2 to 6 carbon atoms) conventionally.The typical polyvalent alcohol for the preparation of polyester polyol is diol or triol, and comprises ethylene glycol, diethylene glycol, polyethylene glycol as PEG 200, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, pentanediol or hexylene glycol, polyether glycol, glycerine etc.Typical multifunctional carboxylic acid is selected from the group of being made up of following item: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid and phthalic acid, isophthalic acid, terephthalic acid, isomery naphthalene dicarboxylic acid and their combination.The average OH functionality of polyester polyol is preferably at least 1.8, even more preferably at least 2.0.Aromatic polyester polyol is the polyester polyol of a kind of common type that is used for rigid polyurethane foam.

[0050] As used herein, "aromatic polyester polyol" refers to a polyester polyol that includes aromatic rings. For example, the aromatic polyester polyol can be a phthalic anhydride diethylene glycol polyester or can be prepared by using an aromatic dicarboxylic acid and a diol. The aromatic polyester polyol can be a hybrid polyester-polyether polyol, for example, as discussed in International Publication No. WO 2013 / 053555.

[0051] In one embodiment, the aromatic polyester polyols can be prepared using known equipment and reaction conditions. In another embodiment, the aromatic polyester polyols are commercially available. Examples of commercially available aromatic polyester polyols include, but are not limited to, those available from Stepan Company under the trade name STEPANPOL TM (such as STEPANPOL TM PS-2352) and other polyols sold.

[0052] Polyether polyols typically have a hydroxyl functionality between 2 and 8, specifically 2 to 6, and are typically prepared by polymerization of one or more alkylene oxides selected from propylene oxide (PO), ethylene oxide (EO), butylene oxide, tetrahydrofuran, and mixtures thereof with a suitable starting molecule or a mixture of multiple starting molecules in the presence of a catalyst. Typical starting molecules include compounds having at least two hydroxyl groups or at least one primary amine group in the molecule. Suitable starting molecules can be ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, castor oil, sugar compounds such as glucose, sorbitol, mannitol, and sucrose, aliphatic and aromatic amines, polyphenols, resols, oligomeric condensation products such as phenol and formaldehyde, and Mannich condensates of phenol, formaldehyde, and dialkanolamines, and melamine, etc.

[0053] By means of a starting molecule having at least 2 (e.g., 2 to 8) hydroxyl groups in the molecule, the following non-limiting examples can be further used: trimethylolpropane, glycerol, pentaerythritol, castor oil, sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyphenols, resol resins, oligomeric condensation products such as phenol and formaldehyde and Mannich condensates of phenol, formaldehyde and dialkanolamines, and melamine. The catalyst for preparing the polyether polyol can include a basic catalyst for anionic polymerization, such as potassium hydroxide, or a Lewis acid catalyst for cationic polymerization, such as boron trifluoride. Suitable polymerization catalysts can include potassium hydroxide, cesium hydroxide, boron trifluoride or a dicyanide complex (DMC) catalyst, such as zinc hexacyanocobaltate or a quaternary phosphazenium compound. In one embodiment of the present disclosure, the number average molecular weight of the polyether polyol is in the range of 100 g / mol to 2,000 g / mol. For example, in the range of 125 g / mol to 1,500 g / mol, 150 g / mol to 1,250 g / mol, 150 g / mol to 1,000 g / mol, or 200 g / mol to 1,000 g / mol.

[0054] The polyether polyols suitable for use in the present invention may have an average hydroxyl functionality of 2.0 and are commonly referred to as diols. The diols may be ethylene glycol, propylene glycol, ethoxylates of ethylene glycol or propylene glycol, propoxylates of ethylene glycol or propylene glycol, and the like. Examples of commercially available diols include, but are not limited to, those sold under the trade name VORANOL TM Such as VORANOL TM 2110-TB is available from The Dow Chemical Company as a variety of polyols.

[0055] Polyether polyols suitable for use in the present invention may have an average hydroxyl functionality of 3.0 and are commonly referred to as triols. Triols may be glycerol, trimethylolpropane, ethoxylates or propoxylates of glycerol or trimethylolpropane, and the like. Triols may be prepared using known equipment and reaction conditions. Examples of commercially available triols include, but are not limited to, VORATEC, available from The Dow Chemical Company under the trade name VORATEC. TM , such as VORATEC TM SD 301 sells a variety of polyols, etc.

[0056] Polyether polyols suitable for use in the present invention may include sucrose / glycerol initiated polyether polyols. Sucrose / glycerol initiated polyether polyols may include structural units derived from another alkylene oxide, such as ethylene oxide or propylene oxide. Sucrose / glycerol initiated polyether polyols may include structural units derived from styrene-acrylonitrile, polyisocyanate and / or polyurea. Sucrose / glycerol initiated polyether polyols may be prepared using known equipment and reaction conditions. For example, sucrose / glycerol initiated polyether polyols may be formed from a reaction mixture comprising sucrose, propylene oxide and glycerol. One or more embodiments provide that the sucrose / glycerol initiated polyether polyol is formed by the reaction of sucrose and propylene oxide. In another embodiment, the sucrose / glycerol initiated polyether polyols are commercially available. Examples of commercially available sucrose / glycerol initiated polyether polyols include, but are not limited to, polyether polyols sold under the trade name VORANOL TM Such as VORANOL TM 360、VORANOL TM 490 and VORANOL TM 280 Various polyols purchased from The Dow Chemical Company (Dow).

[0057] Polyether polyols suitable for use in the present invention may include sorbitol-initiated polyether polyols. Sorbitol-initiated polyether polyols may be prepared using known equipment and reaction conditions. For example, a sorbitol-initiated polyether polyol may be formed from a reaction mixture comprising sorbitol and an alkylene oxide, such as ethylene oxide, propylene oxide, and / or butylene oxide. The sorbitol-initiated polyether polyol may be end-capped, for example, the alkylene oxide may be added in stages to preferentially position or end-cap a particular alkylene oxide at a desired position of the polyol. Sorbitol-initiated polyether polyols are commercially available. Examples of commercially available sorbitol-initiated polyether polyols include, but are not limited to, VORANOL®, available from The Dow Chemical Company under the trade name VORANOL TM , such as VORANOL TM RN 482 sells a variety of polyols, etc.

[0058] The polyether polyols suitable for use in the present invention may include polyol compounds including amine-initiated polyols. Amine-initiated polyols may be initiated by aromatic amines or aliphatic amines. For example, the amine-initiated polyols may be o-toluenediamine (o-TDA)-initiated polyols, ethylenediamine-initiated polyols, diethylenetriamine, triisopropanolamine-initiated polyols, or combinations thereof. Amine-initiated polyols may be prepared using known equipment and reaction conditions. For example, the amine-initiated polyols may be formed from a reaction mixture comprising an aromatic amine or aliphatic amine and an alkylene oxide, such as ethylene oxide and / or butylene oxide. The alkylene oxide may be added to the alkoxylation reactor in one step or in several steps, wherein each step may use a single alkylene oxide or a mixture of alkylene oxides.

[0059] Generally speaking, the amount of polyol used herein may range from about 10 wt % to about 80 wt %, or from about 12 wt % to 70 wt %, or from about 15 wt % to 60 wt %, or from about 15 wt % to about 55 wt %, or from about 15 wt % to about 50 wt %, based on the total weight of all components in the foam-forming composition used to prepare the PUR / PIR foam.

[0060] T-shaped siloxane

[0061] Siloxanes are functional materials in organosilicon chemistry, characterized by Si–O–Si bonds. Typical linear and unbranched siloxanes can be represented by the following structure A, where the backbone, consisting of repeating units of -(Si(CH₃)₂-O)-, is terminated at each end with a tri(methyl)siloxy group, and p is an integer, for example, from 1 to 100, such that the unbranched siloxane molecule contains only two tri(methyl)siloxy groups.

[0062]

[0063] Branched siloxanes have more than two tri(methyl)siloxy groups. An example of a branched siloxane is shown below, which contains four tri(methyl)siloxy groups:

[0064]

[0065] Silicone materials are inherently hydrophobic. Unless additional chemical modifications are performed on the silicone molecules, they are insoluble in most common polyols used to make polyisocyanurate / polyurethane foams.

[0066] Surprisingly, it has been discovered that a siloxane having a T-shaped structure is soluble in isocyanate-reactive compounds such as polyols and that, when incorporated in small amounts into foam-forming compositions to prepare rigid polyurethane and / or polyisocyanurate foams, unexpected improvements in thermal insulation properties can be achieved. Specifically, the siloxane useful in the present disclosure has a structure represented by Formula I:

[0067]

[0068] wherein A1 and B1 are each independently a linear or branched monovalent hydrocarbon group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl, octyl, n-octyl, and the like, and preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl; and

[0069] A2, A3, B2 and B3 are each independently a linear or branched monovalent hydrocarbon group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and preferably methyl, ethyl, propyl or isopropyl; and

[0070] m and n are each independently an integer from 1 to 6, preferably from 1 to 3; and

[0071] X is a linear or branched monovalent hydrocarbon group having 1 to 4 carbon atoms, such as a methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl group, or a trimethylsilyloxy group; and

[0072] Y is an alkylene oxide-containing group having 2 to 24 alkylene oxide repeating units, preferably 3 to 20 alkylene oxide repeating units, more preferably 3 to 15 alkylene oxide repeating units, even more preferably 3 to 12 alkylene oxide repeating units, and still even more preferably 5 to 12 alkylene oxide repeating units. Suitable alkylene oxide units may include, but are not limited to, ethylene oxide (—CH2CH2O—), propylene oxide (—CH(CH3)CH2O—), and butylene oxide (—CH2CH2CH2CH2O—).

[0073] Y can also be represented by the following general formula:

[0074] —Z—O—[(C2H4O) a (C3H6O) b (C4H8O) c ] d —W

[0075] Z is a straight or branched divalent hydrocarbon group having 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms, such as propylene, isopropylene, n-butylene, isobutylene, pentylene, isopentylene, hexylene, isohexylene, etc.; W is hydrogen, a monovalent hydrocarbon group having 1 to 4 carbon atoms, acetyl, propionyl, and butyrate; and subscript a is 1 to 15, and subscripts b and c are each independently 0 or 1 to 14, provided that 2≤a+b+c≤24, preferably 3≤a+b+c≤20, more preferably 5≤a+b+c≤15, even more preferably 5≤a+b+c≤12; and subscript d is 0, 1 or 2, preferably 1 or 2. In a preferred embodiment, the siloxane additive may be a T-shaped trisiloxane alkoxylate having the following structure:

[0076]

[0077] Wherein, R1 and R2 may be the same or different and are equal to H, a C1 to C4 alkyl group, p1=1-6, preferably 3-6, p2=1-12, p3=0-12, and 2≤p2+p3≤24, preferably 3≤p2+p3≤20, more preferably 3≤p2+p3≤15, still more preferably 3≤p2+p3≤12, even more preferably 5≤p2+p3≤12; R3 may be an organic group such as H, a C1-C4 alkyl group, an acetyl group, a propionyl group and a butyrate, and R4 may be a C1 to C4 alkyl group or a trimethylsiloxy group.

[0078] The siloxanes of the present invention having a T-shaped structure that are advantageously used have a molecular weight of 350 g / mol to 2,500 g / mol, including all individual values and subranges from 350 g / mol to 2,500 g / mol; for example, the T-shaped siloxane material can have a number average molecular weight from a lower limit of 350 g / mol, 400 g / mol, 425 g / mol, or 450 g / mol to an upper limit of 2,000 g / mol, 1,750 g / mol, 1,500 g / mol, 1,250 g / mol, 1,000 g / mol, 900 g / mol, or 750 g / mol.

[0079] Siloxanes having T-shaped structures of formula (I) and (II) can be prepared using known equipment and reaction conditions. Preparation methods can be found in the patent literature, particularly U.S. Patent Nos. 7,507,775, 7,645,720, and 7,935,842. Examples of commercially available siloxanes having T-shaped structures include OFX-5211 from Dow Chemical.

[0080] According to one embodiment of the present disclosure, a siloxane material having a T-shaped structure can be added as a separate stream or pre-mixed directly into the isocyanate-reactive composition. In one embodiment of the present disclosure, at least one siloxane having a T-shaped structure is directly incorporated into at least one isocyanate-reactive compound to form the isocyanate-reactive composition. Based on the total weight of the at least one isocyanate-reactive compound equal to 100 pts, the amount of the at least one siloxane having a T-shaped structure is 0.1 pts to 5 pts (e.g., 0.2 pts to 4 pts, or 0.5 pts to 3.5 pts, or 0.5 pts to 2.5 pts).

[0081] Optional auxiliary components

[0082] In addition to the at least one isocyanate-reactive component and at least one isocyanate component described above in the foam-forming composition for preparing polyurethane / polyisocyanurate foam, the foam-forming composition of the present invention may further comprise other optional auxiliary components, compounds, agents, or additives as component (C); and such optional component (C) may be added to the reaction mixture together with either component A and / or component B, or added separately as component (C). Component A refers to at least one isocyanate component, and component B refers to at least one isocyanate-reactive component. Optional auxiliary components, compounds, agents, or additives useful in the present invention may include one or more of various optional compounds known in the art for their uses or functions. For example, optional component (C) may include expandable graphite, a physical or chemical blowing agent, a blowing catalyst, a flame retardant, an emulsifier, an antioxidant, a surfactant, a liquid nucleating agent, a solid nucleating agent, an Ostwald ripening inhibitor additive, a pigment, a solvent, including a solvent selected from the group consisting of ethyl acetate, methyl ether ketone, toluene, and mixtures of two or more thereof; and mixtures of two or more of the aforementioned optional additives.

[0083] The amount of optional compounds added to the foam-forming composition of the present invention may be, for example, 0 to 50 parts per 100 parts of polyols in the isocyanate-reactive composition in one embodiment, 0.1 to 40 parts per 100 parts of polyols in another embodiment, and 1 to 35 parts per 100 parts of polyols in yet another embodiment. For example, in one embodiment, a physical blowing agent (if used) may be used in an amount of 1 to 40 parts per 100 parts of polyols in the isocyanate-reactive component. In another embodiment, a chemical blowing agent (if used) may be used in an amount of 0.1 to 10 parts per 100 parts of polyols in the isocyanate-reactive component. In another embodiment, a flame retardant additive (if used) may be used in an amount of 1 to 25 parts per 100 parts of polyols in the isocyanate-reactive component. In yet another embodiment, surfactants (when used) are typically used in an amount of 0.1 to 10 pts based on 100 pts of total polyol in the isocyanate-reactive component. In even another embodiment, blowing catalysts (when used) are used in an amount of 0.05 to 5 pts based on 100 pts of total polyol in the isocyanate-reactive component. And in a general embodiment, other additives (when used) may be used in an amount of 0.1 to 5 pts based on 100 pts of total polyol in the isocyanate-reactive component.

[0084] foaming agent

[0085] In various embodiments, the blowing agent can be selected based at least in part on the desired density of the final foam. The blowing agent can be added to the polyol side before the isocyanate-reactive component is combined with the isocyanate component, or as a separate stream. Without being bound by theory, the blowing agent can absorb heat from the exothermic reaction of the isocyanate component and the isocyanate-reactive component, and evaporate and provide additional gas that can be used to expand the polyurethane foam to the desired low density.

[0086] A variety of conventional blowing agents can be used. For example, the blowing agent can be one or more of the following: water, various hydrocarbons, various hydrofluorocarbons, various hydrofluoroolefins, formic acid, inert gases, various chemical blowing agents that generate nitrogen or carbon dioxide under foaming reaction conditions, and mixtures thereof.

[0087] Chemical blowing agents (such as water) can be used alone or in admixture with other chemical and / or physical blowing agents. Physical blowing agents can be used as low-boiling hydrocarbons. Examples of such liquids are alkanes such as heptane, hexane, n-pentane and isopentane; technical grade mixtures of n-pentane and isopentane and n-butane and isobutane with propane; cycloalkanes such as cyclopentane and / or cyclohexane; ethers such as furan, dimethyl ether and diethyl ether; ketones such as acetone and methyl ethyl ketone; alkyl carboxylates such as methyl formate, dimethyl oxalate and vinyl lactate; and halogenated hydrocarbons such as dichloromethane, dichloromonofluoromethane, Difluoromethane, trifluoromethane, difluoroethane, tetrafluoroethane, chlorodifluoroethane, 1,1-dichloro-2,2,2-trifluoroethane, 2,2-dichloro-2-fluoroethane, pentafluoropropane, heptafluoropropane and hexafluorobutene, (E,Z)1,1,1,4,4,4-hexafluoro-2-butene and trans-1chloro-,3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoroprop-1-ene, 1,3,3,3-tetrafluoropropene, etc. Some of these blowing agents are called LBA, GBA, Opteon TM 1100、Opteon TM 1150 etc. are commercially available materials.

[0088] Mixtures of these low-boiling liquids with each other and / or other substituted or unsubstituted hydrocarbons can also be used. Also suitable are organic carboxylic acids, such as formic acid, acetic acid, oxalic acid and carboxyl-containing compounds.

[0089] In various embodiments, the amount of blowing agent is from about 0.1 pts to about 40 pts (eg, from about 0.5 pts to about 35 pts, 1 pts to 30 pts, or 5 pts to 25 pts) based on 100 pts of total polyol in the isocyanate-reactive composition.

[0090] catalyst

[0091] The catalyst may include a urethane reaction catalyst and an isocyanate trimerization catalyst. The trimerization catalyst may be any trimerization catalyst known in the art that catalyzes the trimerization of an organic isocyanate compound. The trimerization of the isocyanate may produce a polyisocyanurate compound within the polyurethane foam. Without being limited by theory, the polyisocyanurate compound may make the polyurethane foam harder and improve its responsiveness to fire. The trimerization catalyst may include, for example, a glycine salt, a tertiary amine trimerization catalyst, an alkali metal carboxylate, and mixtures thereof. In some embodiments, sodium N-2-hydroxy-5-nonylphenyl-methyl-N-methylglycinate may be used. When used, the trimerization catalyst may be present in an amount of 0.05 pts to 5 pts (e.g., 0.1 pts to 3.5 pts, or 0.2 pts to 2.5 pts, or 0.5 pts to 2.5 pts) based on 100 pts of the total polyol content in the isocyanate reactive component.

[0092] Tertiary amine catalysts include organic compounds containing at least one tertiary nitrogen atom and capable of catalyzing the hydroxyl / isocyanate reaction between an isocyanate component and an isocyanate-reactive component. Tertiary amine catalysts may include, for example, but are not limited to, triethylenediamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl)ether, triethylamine, tripropylamine, tributylamine, tripentylamine, pyridine, quinoline, dimethylpiperazine, piperazine, N-ethylmorpholine, 2-methylpropanediamine, methyltriethylenediamine, 2,4,6-tris(dimethylamino-methyl)phenol, N,N',N"-tris(dimethylamino-propyl)-s-hexahydrotriazine, and mixtures thereof. When used, the tertiary amine catalyst may be present in an amount of 0.05 pts to 5 pts (e.g., 0.1 pts to 3.5 pts, or 0.2 pts to 2.5 pts, or 0.5 pts to 2.5 pts) of "polyol packaging," based on 100 pts of total polyol in the isocyanate-reactive component.

[0093] The compositions of the present disclosure may also contain the following catalysts: tertiary phosphines, such as trialkylphosphines and dialkylbenzylphosphines; chelates of various metals, such as those obtainable from acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, etc., with metals such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, and Ni; acidic metal salts of strong acids, such as ferric chloride, tin chloride; salts of organic acids with various metals, such as alkali metals, alkaline earth metals, Al, Sn, , Pb, Mn, Co, Ni and Cu; organic tin 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, for example, bismuth octoate; organometallic derivatives of trivalent and pentavalent As, Sb and Bi, and metal carbonyls of iron and cobalt. The total amount of the catalyst component used herein can be generally in the range of about 0.01 pts to about 10 pts based on 100 pts of the total polyol amount in the isocyanate-reactive component in one embodiment, and can be in the range of 0.05 pts to about 5 pts in another embodiment.

[0094] surfactants

[0095] The isocyanate-reactive composition of the present invention may contain a surfactant. For example, the surfactant may be added to the isocyanate-reactive composition. The surfactant may be a cell-stabilizing surfactant. Examples of surfactants that can be used in the present invention include silicon-based compounds, such as silicone-polyether copolymers, such as polydimethylsiloxane-polyoxyalkylene block copolymers, such as polyether-modified polydimethylsiloxane, and combinations thereof. Examples of surfactants include non-silicone-based organic surfactants, such as VORASURF® commercially available from The Dow Chemical Company. TM 504. Surfactants are commercially available and include those sold under trade names such as NIAXT TM Such as NIAX TM L 6988 and TEGOSTAB TM Such as TEGOSTAB TM Those purchased from B8462 et al.

[0096] Other surfactants that can be used herein are polyethylene glycol ethers of long-chain alcohols, long-chain allylic acid sulfates, alkyl sulfonates, tertiary amines or alkanolamine salts of alkylarylsulfonic acids, and combinations thereof. Such surfactants are employed in an amount sufficient to stabilize the foaming reaction, prevent collapse, and form larger, non-uniform cells. When used, the amount of surfactant may be from 0.1 pts to 10.0 pts, based on 100 pts of the total polyol combination present in the isocyanate-reactive composition. All individual values and subranges from 0.1 pts to 10.0 pts are included; for example, based on 100 pts of the total polyol combination present in the isocyanate-reactive composition, the surfactant may be an isocyanate-reactive composition with a lower limit of 0.1 pts, 0.2 pts, or 0.3 pts to an upper limit of 10.0 pts, 9.0 pts, 7.5 pts, or 6 pts.

[0097] Other optional / auxiliary additives

[0098] Other optional / auxiliary compounds or additives that can be added to the isocyanate reactive composition and / or foam forming composition of the present invention to prepare polyurethane / polyisocyanurate foams can include, for example, other auxiliary catalysts, auxiliary surfactants, toughening agents, flow modifiers, tackifiers, diluents, stabilizers, plasticizers, catalyst deactivators, dispersants, flame retardants, and mixtures thereof. In various embodiments, fire resistance can be enhanced by including one or more flame retardants. The flame retardant can be brominated or non-brominated and can include, for example, but not limited to, tris(1,3-dichloropropyl) phosphate, tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum oxide trihydrate, and combinations thereof. When used, the flame retardant may be present in an amount of 0.1 pts to about 30 pts, or about 1 pts to 25 pts, or about 2 pts to about 25 pts, or about 5 pts to about 25 pts, based on 100 pts of total polyol in the isocyanate reactive component.

[0099] Other additives, such as fillers and pigments, may be included in the rigid PIR / PUR foam compositions of the present invention. In non-limiting embodiments, such fillers and pigments may include barium sulfate, calcium carbonate, graphite, carbon black, titanium dioxide, iron oxide, microspheres, alumina trihydrate, wollastonite, glass fibers, polyester fibers, other polymeric fibers, combinations thereof, and the like.

[0100] Foam preparation method

[0101] In various embodiments, PIR / PUR foam is prepared by mixing all individual components (including at least one isocyanate-reactive compound, T-shaped siloxane, catalyst, surfactant, blowing agent, and any other additives) with at least one isocyanate compound at room temperature or at an elevated temperature of 25° C. to 120° C. (e.g., 30° C. to 90° C. or 40° C. to 70° C.) for a duration of 1 second to 20 seconds, followed by immediately pouring, spraying, injecting, or laying the resulting mixture into a mold cavity or substrate for foaming. In some embodiments, the isocyanate-reactive component and the T-shaped siloxane may be mixed before or after addition to the isocyanate component. Similarly, optional auxiliary additives such as catalysts, flame retardants, blowing agents, and surfactants may be added to the isocyanate-reactive composition before mixing with the isocyanate component, or may be mixed in-line with the isocyanate component as a separate stream.

[0102] Mixing can be carried out in a spraying device, mixing head or container. Immediately after mixing, the foaming mixture is sprayed or otherwise deposited or injected or poured onto the substrate or into the mold. Regardless of any particular method of foam manufacturing, when the foam expands and solidifies, the amount of foaming mixture introduced into the mold or onto the substrate is sufficient to completely fill the mold or take the shape of a plate or any other functional shape. Even a certain degree of overfilling can be introduced by using a slightly excessive amount of reaction mixture that exceeds the minimum required amount. For example, the cavity can be overfilled by 5%-35%, that is, more than 5% by weight-35% of the reaction system is introduced, which exceeds the minimum required amount to fill the cavity when the reaction mixture expands. This cavity can optionally be maintained at atmospheric pressure or partially evacuated to subatmospheric pressure.

[0103] After the reaction, the foaming mixture is formed into the shape of a mold or adhered to a substrate to produce a PIR / PUR foam, which is then partially or fully cured. Suitable conditions for promoting the curing of PIR / PUR polymers include temperatures of about 20°C to about 150°C. In some embodiments, curing is carried out at a temperature of about 30°C to about 75°C. In other embodiments, curing is carried out at a temperature of about 35°C to about 65°C. In various embodiments, the temperature for curing can be selected at least in part based on the duration required for the PUR / PIR polymer to gel and / or cure at that particular temperature. The curing time will also depend on other factors, including, for example, the amount of specific components used (e.g., the type and amount of their catalysts), as well as the size and shape of the manufactured product. The different products produced may include, but are not limited to, foam boards for roofing, insulation boards for building and construction applications, and door panels for appliances.

[0104] Foam properties

[0105] In one general embodiment, the isocyanate-reactive composition of the present invention for preparing rigid polyurethane or polyisocyanurate foam provides a density of 25 kg / m 3 Up to 200kg / m 3 In an exemplary embodiment, the density of the rigid polyurethane or polyisocyanurate foam may be 25 kg / m 3 Up to 150kg / m 3 In another embodiment, it can be 25 kg / m 3 Up to 100kg / m 3 In another embodiment, it can be 25 kg / m 3 Up to 75kg / m 3 In another embodiment, it can be 25 kg / m 3 Up to 60kg / m 3 , and in even yet another embodiment may be 30 kg / m 3 Up to 60kg / m 3 .

[0106] The rigid polyurethane or polyisocyanurate foams of the present invention also exhibit several beneficial properties, such as low thermal conductivity (improved thermal insulation performance). For example, the foams of the present invention exhibit a low thermal conductivity of no more than 20.5 mW / mK at 10° C. in one general embodiment, 16.0 mW / mK to 20.0 mW / mK in another embodiment, 16.5 mW / mK to 20 mW / mK in another embodiment, and 17.0 mW / mK to 19.5 mW / mK in yet another embodiment. The thermal insulation performance of the rigid foams of the present invention, as measured by thermal conductivity (or "K factor"), is defined and determined by the procedure described in ASTM C518-04 (2010).

[0107] Furthermore, the foams of the present invention advantageously exhibit good mechanical properties, as measured by compressive strength as determined by the procedure described in ASTM D-1621. For example, in one general embodiment, the foam exhibits a compressive strength value of no less than 100 kPa. Foams having a compressive strength below 100 kPa are generally considered to lack sufficient mechanical strength for long-term use.

[0108] The above description is intended to be general and is not intended to include all possible embodiments. Similarly, the examples provided below are illustrative only and are not intended to define or limit the claimed subject matter in any way. It will be fully understood by those skilled in the art that other embodiments within the scope of the claims will be apparent from consideration of the specification and / or practice of the methods as disclosed herein. Such other embodiments may include the selection of specific components and their ingredients and proportions; mixing and reaction conditions, containers, deployment equipment and schemes; performance and selectivity; identification of products and by-products; subsequent processing and use thereof; etc.; and those skilled in the art will recognize that such embodiments may vary within the scope of the claims appended hereto.

[0109] Example

[0110] Material

[0111] Two aromatic polyester polyols were used in the examples. They were prepared using aromatic dicarboxylic acids and polyglycols such as DEG, PEG200, and glycerol. Polyol A had an OH value of 220 mg KOH / g, a number-average molecular weight of 510 g / mol, and an OH functionality of 2.0. Polyol B had an OH value of 315, a number-average molecular weight of 427, and an OH functionality of 2.4.

[0112] Various foaming additives such as catalysts, surfactants, flame retardant (FR) additives, and physical blowing agents were used in the examples. For example, Dabco K-2097 (Catalyst A) is a trimer catalyst purchased from Evonik, and Polycat 5 (Catalyst B) is a foaming catalyst for polyurethane foaming purchased from Evonik. Surfactant A is a silicone polyether surfactant purchased from Evonik, and TEP (FR additive) is a triethyl phosphate flame retardant purchased from ICL-IP. The three T-shaped liquid silicone materials used in the examples are listed in Table 1 below.

[0113] Table 1. Liquid silicone materials used

[0114]

[0115] The polyisocyanate used throughout the examples is commercially manufactured by Dow: PAPI TM 580N (or Voranate TM M 600). PAPI TM 580N is a polymeric MDI having an NCO % of 30.8, an average functionality of 3.0, and a viscosity at 25°C of about 600 mPa.

[0116] The physical blowing agent used in the Examples and Comparative Examples can be cyclopentane, a 70 / 30 blend of cyclopentane and isopentane or sometimes referred to as a cyclo / isopentane blend (70 / 30), or the like.

[0117] General protocol for foam preparation

[0118] Polyol, T-shaped silicone material (if necessary), surfactant, flame retardant, catalyst and water are added to a plastic cup, and the plastic cup and its contents are weighed. The cup contents are then mixed with a high-speed overhead mixer to provide a "polyol package" (i.e., the B side). The target amount of blowing agent is then added to the cup and thoroughly mixed with the polyol package. Subsequently, the required amount of polyisocyanate component (i.e., the A side) is added to the formulation mixture in the cup. The resulting complete formulation is then immediately mixed with a high-speed overhead mixer at 3,000 rpm for 5 seconds, and then poured into a vertical plate mold preheated to 55°C. The dimensions of the mold are 30 cm (height) x 20 cm (length) x 5 cm (width). The mold is placed vertically along its "height" direction for foaming. After curing for about 20 minutes inside the mold, the foam is removed from the mold and then placed on a laboratory bench overnight before physical property testing.

[0119] Characterization and property measurements

[0120] Cream time and gel time were determined according to the test procedure described in ASTM D7487 (2013). The general procedure for cream time and gel time measurement includes the following: free-foaming foam is prepared by the plastic cup method described above. Using this method, polyol, surfactant, flame retardant, catalyst, and water are weighed into a plastic cup. A high-speed mixer is used to mix the polyol component. An appropriate amount of blowing agent is then added to the cup and thoroughly mixed into the polyol side component. The isocyanate component is then added to the cup, followed immediately by mixing at approximately 3,000 rpm for 5 seconds using an overhead mixer. Time is recorded when mechanical mixing of the isocyanate and polyol side mixtures begins. When the foam formulation in the cup shows a noticeable change in color or appearance (or more commonly referred to as creaming) due to the formation of a large number of bubbles, the time is recorded as the "cream time." The tip of a wooden tongue depressor is then immersed in the foam formulation and quickly pulled out to check whether the foaming mixture has become viscous. The time it takes for the foaming formulation to become viscous based on the wooden tongue depressant test is recorded as the "gel time."

[0121] Within 24 hours of foam preparation (after overnight storage on a laboratory bench, table, etc.), cut a foam sample measuring 20 cm x 20 cm x 2.5 cm from the middle interior portion of the molded foam for thermal conductivity measurement. Measure the thermal conductivity (K-factor or lambda value) of each foam sample at 50°F according to the procedure described in ASTM C518-04 (2010). The accuracy of the K-factor measurement is typically within 0.1 mW / m*K. Report the average of the K-factor measurements of at least two test samples.

[0122] The density of rigid foam was measured according to the procedure described in ASTM 1622-03 (2008). Samples of rigid foam were cut into cubic specimens measuring 5 cm x 5 cm x 5 cm. These samples were weighed and the exact dimensions of each sample were measured. Subsequently, the density of the sample was calculated.

[0123] The open cell content of the formed rigid PU foam was measured according to ASTM D-6226. This measurement was performed using a pycnometer AccuPyc 1330 from Micromeretics (Norcross, GA) equipped with the FoamPyc option for calculating open cell content. Five specimens of nominal size 1" x 1" x 1" were taken from various points on the foam sample and measured. Any specimen with obvious defects by visual inspection was excluded from testing. All samples were conditioned under ASTM standard laboratory conditions for a minimum of 24 hours prior to measurement. The average value of the open cell content was then reported.

[0124] The compressive strength of a foam sample is measured by the foam's mechanical resistance to compressive stress. The test is conducted perpendicular to the direction of foam expansion. At least four specimens are used to measure the compressive strength. Each specimen, approximately 2 in x 2 in x 1 in (5 cm x 5 cm x 2.5 cm), is taken from the middle interior portion of the molded foam and measured according to ASTM D-1621.

[0125] Comparative Example A and Examples 1-3

[0126] Comparative Example A: 180 grams of foaming mixture was prepared according to the formulation shown in Table 2 and the general procedure described above and immediately poured into a 5 cm x 20 cm x 30 cm vertical upright mold. For this formulation, approximately 135 grams of the foaming mixture was poured into the mold. The foam was removed from the mold after 20 minutes and allowed to sit overnight on a laboratory bench before the resulting foam product was tested for physical properties. The foam characterization results are summarized in Table 2.

[0127] Example 1: 1.62 parts of liquid silicone additive A was added to a blend of 61 pts of Polyol A and 20.2 pts of Polyol B, respectively, followed by thorough mixing. The resulting polyol mixture was clear and not turbid. This T-type siloxane-containing polyol mixture was stable at room temperature for extended periods of time (>2 weeks) without becoming turbid or undergoing phase separation. This mixture was used to prepare a foam formulation by following the detailed formulation described in Table 2 and using the same (or similar) protocol as Comparative Example A. The foam properties of this example are also shown in Table 2.

[0128] Examples 2-3: The protocol of Example 1 was repeated, except that T-shaped liquid silicone additive B and liquid silicone additive C were used in Examples 2 and 3, respectively. Similar to Example 1, the polyol mixtures containing either liquid silicone additive B or liquid silicone additive C were visually clear, with no turbid appearance, indicating that the mixtures were completely miscible. Both solutions were also stable at room temperature for extended periods of time (>2 weeks) without becoming turbid or experiencing phase separation. The foam properties of these examples are also reported in Table 2.

[0129] Table 2. Formulation Set for Incorporating Liquid Silicone Additives into PIR Systems

[0130] Comparative Example A Example 1 Example 2 Example 3 raw materials Number of copies Number of copies Number of copies Number of copies Polyol A 61 61 61 61 Polyol B 20.2 20.2 20.2 20.2 Catalyst A 1.8 1.8 1.8 1.8 Catalyst B 0.95 0.95 0.95 0.95 Surfactant A 3 3 3 3 FR additives 15 15 15 15 Liquid Silicone Additive A 1.62 Liquid Silicone Additive B 1.62 Liquid Silicone Additive C 1.62 Cyclopentane / Isopentane (70 / 30) 17 17 17 17 water 0.8 0.8 0.8 0.8 Total amount on side B 119.75 121.37 121.37 121.37 <![CDATA[Polyisocyanate A (PAPI TM 580N)]]> 250 250 250 250 Characteristic results Milky time (seconds) 11 12 11 12 Gel time (seconds) 33 33 35 32 Foam density (kg / m3) 42.7 43.2 43.2 43.4 K coefficient at 10℃ (mW / mK) 21.0 19.99 19.76 19.94 K-factor improvement (mW / mK) - 1.01 1.24 1.06 Open cell content (%) 8.8％ 7.7％ 7.6％ 8.0％ Compression strength (KPa) 131 130 114 136

[0131] The results shown in Table 2 indicate that the thermal conductivity or K-factor measured for foams made with all three liquid silicone additives having a T-shaped structure is significantly lower than that of the comparative examples. Additionally, the K-factor improvements provided by the use of the T-shaped silicone materials of the present invention do not compromise other foam properties, such as density, open cell content, and compressive strength.

[0132] Comparative Examples BC and Examples 4-6

[0133] Comparative Examples BC and Examples 4-6: The protocol used in Comparative Example A and Example 1 was repeated, and the detailed formulations for foam preparation shown in Table 3 were followed. For this set of comparative examples and examples, different amounts of liquid silicone additive B (0, 0.5, 1, 2, and 5 pts per 100 pts of polyol) were used. The resulting foam properties are shown in Table 3.

[0134] Table 3. Formulation groups containing different amounts of liquid silicone additives

[0135] Comparative Example B Example 4 Example 5 Example 6 Comparative Example C raw materials Number of copies Number of copies Number of copies Number of copies Number of copies Polyol A 75 75 75 75 75 Polyol B 25 25 25 25 25 Catalyst A 2.24 2.24 2.24 2.24 2.24 Catalyst B 1.18 1.18 1.18 1.18 1.18 Surfactant A 3.53 3.53 3.53 3.53 3.53 FR additives 17.65 17.65 17.65 17.65 17.65 Liquid Silicone Additive B 0 0.5 1 2 5 Cyclopentane 24.71 24.71 24.71 24.71 24.71 water 0.94 0.94 0.94 0.94 0.94 Total amount on side B 150.25 150.75 151.25 152.25 155.25 <![CDATA[Polyisocyanate A (PAPI TM 580N)]]> 308.9 308.9 308.9 308.9 308.9 Characteristic results Milky time (seconds) 12 11 11 12 12 Gel time (seconds) 32 32 31 33 35 Foam density (kg / m3) 43.1 42.7 41.6 42 42.3 K coefficient at 10℃ (mW / mK) 19.8 19.4 19.2 19.1 19.6 K-factor improvement (mW / mK) - 0.4 0.6 0.7 0.2 Open cell content (%) 2.6％ 3.3％ 3.1％ 3.5％ 3.9％ Compression strength (KPa) 127.5 131 138.1 123 95.2

[0136] The results in Table 3 show that the thermal conductivity or K-factor of the foams prepared from the inventive foam-forming compositions of Examples 4-6 is superior to that of Comparative Example B (which does not contain a T-shaped silicone material). In Comparative Example C, the mechanical properties of the foam are slightly negatively impacted by the relatively high amount of T-shaped liquid silicone material used.

Claims

1. An isocyanate-reactive composition, comprising: at least one isocyanate-reactive compound; and At least one T-shaped silicone material having the following structure: ， in, R1 and R2 are each independently hydrogen or a C1-C4 alkyl group, p1 is an integer value of 1-6, p2 is an integer value of 1-12, p3 is an integer value of 0-12, and the sum of the values of p1 and p2 is greater than or equal to 2; R3 is acetyl, propionyl or butyrate; and R4 is a C1-C4 alkyl group or a trimethylsiloxy group, And wherein the amount of the at least one T-shaped siloxane material is 0.1 parts by weight to 4 parts by weight per 100 parts by weight of the at least one isocyanate-reactive compound.

2. The isocyanate-reactive composition of claim 1, wherein the at least one T-shaped siloxane material has a molecular weight of 350 g / mol to 2,500 g / mol.

3. The isocyanate-reactive composition according to claim 1 or 2, wherein the amount of the at least one T-shaped siloxane material is 0.2 parts by weight to 2.5 parts by weight per 100 parts by weight of the at least one isocyanate-reactive compound.

4. The isocyanate-reactive composition according to claim 1 or 2, further comprising at least one auxiliary additive, wherein the auxiliary additive is a surfactant, a catalyst, a physical blowing agent, a chemical blowing agent, a flame retardant additive, or a nucleating agent or a mixture thereof.

5. A foam-forming composition comprising the isocyanate-reactive composition according to any one of claims 1 to 4 and at least one polyisocyanate compound.

6. A method for preparing a polyurethane or polyisocyanurate foam using the foam-forming composition according to claim 5, wherein the isocyanate-reactive composition is mixed with the at least one polyisocyanate compound, wherein the at least one polyisocyanate compound has an isocyanate index of 100 to 600.

7. A polyurethane foam prepared from the isocyanate-reactive composition according to any one of claims 1 to 4 and at least one polyisocyanate compound, wherein the thermal conductivity of the prepared foam measured according to the ASTM C518-04 2010 procedure is less than or equal to 20.5 mW / m·K.

8. The polyurethane foam according to claim 7, wherein the prepared polyurethane has an open cell content of less than 8% and a density of 25-200 kg / m 3 The density between.

9. A polyisocyanurate foam prepared from the isocyanate-reactive composition according to any one of claims 1 to 4 and at least one polyisocyanate compound, wherein the thermal conductivity of the prepared foam measured according to the ASTM C518-04 2010 procedure is less than or equal to 20.5 mW / m·K.

10. The polyisocyanurate foam according to claim 9, wherein the prepared polyisocyanurate foam has an open cell content of less than 8% and a pressure between 25 and 200 kg / m 3 The density between.

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