Alcohol amine compositions and use thereof as polyurethane blowing agents

Abstract

An alcohol amine composition (AC) comprising (1) an asymmetric diol amine (A1) of the secondary amine type having 5-7 carbon atoms which is ethanol isopropanol amine, ethanol butanol amine or isopropanol butanol amine; (2) a tertiary amine type C7-C11 triol amine (A2) having the general formula NR 1 R 2 R 3 wherein R 1 , R 2 and R 3 are each independently an ethanol group, an isopropanol group or a butanol group; and (3) water. Lower CO2 content alcohol amine compositions (AC) are suitable for making spray polyurethane rigid foams while higher CO2 content alcohol amine compositions (AC) are suitable for making cast polyurethane rigid foams.

Description

Technical Field

[0001] This invention relates to aqueous alkanolamine compositions used as blowing agents in the spraying of rigid polyurethane foams, and more specifically, to a chemically-physically combined blowing agent consisting of an alkanolamine composition and a physical blowing agent (e.g., a physical blowing agent with a boiling point in the range of 15-41°C) for the preparation of sprayed or cast rigid PU foams. Background Technology

[0002] Rigid polyurethane foam is a high-quality thermal insulation material widely used in industries such as refrigerators, freezers, water heaters, and cold chain insulation. Currently, in the fields of building exterior wall spraying and pipe wrapping, the requirements for energy conservation and carbon reduction are becoming increasingly stringent. Therefore, the selection of environmentally friendly foaming agents for the preparation of polyurethane insulation materials in these fields is becoming increasingly rigorous.

[0003] In the field of exterior wall spraying and pipe wrapping spraying of polyurethane foam materials, hydrofluorocarbon (HFC) physical blowing agents are often used in the spraying process. Examples include HCFC-141b (dichlorofluoroethane, molecular weight 116.95, boiling point 32℃), HFC-245fa (molecular weight 134, boiling point 15.3℃), HFC-365mfc (molecular weight 148, boiling point 40.2℃), LBA (trans-1-chloro-3,3,3-trifluoropropylene, molecular weight 130.5, boiling point 19℃), and hexafluorobutene (molecular weight 164, boiling point 33℃). Some HFCs or chlorofluorocarbons are expensive. Furthermore, the production of these HFC physical blowing agents also generates chlorofluorocarbon byproducts, which have environmental impacts.

[0004] Generally, rigid polyurethane foam materials formed by spraying are prepared by mixing and spraying a polymer polyol composition (white component) with a polyisocyanate (black component), and then reacting and curing. The white component contains a portion of aromatic polyester polyols (such as polyethylene phthalate polyol) and / or toluene diamine polyether polyol as the main raw material, and contains additives such as foaming agents, catalysts and foam stabilizers.

[0005] US6326412 B1 discloses ammonium carbamate as a polyurethane foaming agent, wherein the viscosity of ammonium carbamate is as high as 2200 mPa·s (see lines 51-55 in column 6 of the specification), and it is in a viscous or semi-solid state.

[0006] Currently, when using composite foaming agents containing a large amount of water, such as foaming agents composed of water and cyclopentane or foaming agents composed of water and hydrofluorocarbon physical foaming agents, if the amount of water is large, the resulting polyurethane foam has a high open cell ratio, its dimensions are unstable (it is prone to shrinkage and deformation), and its thermal insulation performance will decrease.

[0007] In addition, during the spraying process of polyurethane foam, the white component (polymer polyol component A) and the black component (isocyanate component B) are usually mixed by a spraying machine and then sprayed onto the surface of a substrate (such as steel plate, steel pipe, or concrete structure such as wall) via a spray gun. Generally, the foaming is carried out by spraying at a rate of 2-3 cm per layer, with a total thickness of 20-30 cm. The foam is then formed and cured to produce rigid polyurethane foam, which is used as an insulation material layer. If hydrated carbonate amine salts with high activity or high CO2 content are used as the foaming agent component for the spraying of polyurethane foam, it is found that the foam rises too quickly in the early stage of the foaming reaction. The wet foam expands and rises rapidly, and the surface of the foam quickly forms a skin and cures. However, the adhesion strength between the substrate and the foam or between two adjacent foam layers will decrease (due to foam shrinkage). As a result, the (subsequent) polyurethane coatings sprayed on the substrate or on the cured polyurethane foam coating often crack or peel off from the substrate or from the cured polyurethane foam layer.

[0008] Furthermore, existing technologies use hydrous alkanolamines (e.g., carbonates of primary amines (such as ethanolamine) and carbonates of certain secondary amine diethanolamines, such as di(diethanolamine) carbonate, etc.) as blowing agents. These alkanolamines have a significant impact on the ureaalkylation reaction between polymer polyol compositions (white component) containing amine catalysts and polyisocyanates (black component). In particular, some amine blowing agents affect the catalytic activity of amine catalysts, for example, leading to excessively rapid initial reaction rates and insufficient curing in the later stages, affecting the strength of the foam material and causing dimensional instability (high open-cell ratio, easy shrinkage and deformation). In addition, when hydrous alkanolamines (e.g., triethanolamine hydrate) are used as blowing agents to prepare sprayable rigid polyurethane foams with a large thickness, the rapid reaction rate and rapid heat release during spraying cause a "core-burning" phenomenon inside the foam material. This reduces the thermal insulation performance of the foam material and may even cause the foam material to crack from the substrate or between adjacent foam layers.

[0009] In addition, US2622099A, US4169856A, US2051486A, GB448373A, GB710861A, GB1387573A, GB642950A, GB760215A, GB655580A and CA1003358A disclose isopropanolamine, ethanolamine or butanolamine prepared by reacting ammonia with propylene oxide or ethylene oxide.

[0010] CN107663157A and CN103435499A disclose a method for producing ethanol diisopropanolamine by reacting ethanolamine with propylene oxide. Summary of the Invention

[0011] The inventors of this application discovered through extensive research that the cracking problem in the prior art is mainly attributed to the use of carbonate amine salts (e.g., carbonates of diethanolamine, i.e., di(diethanolamine) carbonate) hydrates with high activity and / or high CO2 content as components of the foaming agent. In the early stages of the spray foaming reaction, the foaming reaction mixture sprayed onto the substrate has not yet fully reacted but releases a large amount of CO2 gas, causing the wet foam layer to expand rapidly. However, the subsequent curing reaction is insufficient, resulting in shrinkage and deformation of the foam, which in turn leads to cracking between the cured polyurethane foam layer and the substrate or between two adjacent cured foam layers.

[0012] Water exhibits strong hydrogen bonding with alkanolamines, stronger than the chemical bonds between alkanolamines and carbonate ions. Generally, when the water content in alkanolamine hydrates is below 50 wt% or below 45 wt%, water exists as individual molecules rather than in the form of molecular clusters or groups. Furthermore, in the presence of water, the hydrates of certain tertiary amine triolamines (e.g., triisopropanolamine) hardly absorb CO2 gas.

[0013] To address the technical problems existing in the prior art, the inventors of this application provide an aqueous alkanol composition (AC) (or, an aqueous alkanol mixture or an alkanol hydrate) for polyurethane foam spraying, characterized by its low alkalinity and reactivity with isocyanates, low CO2 content, and high fluidity. A portion of the alkanol amine forms a carbonate with CO2 and water, i.e., the alkanol amine is partially salted. This alkanol amine composition (AC) is used alone as a blowing agent or in combination with a hydrofluorocarbon physical blowing agent (F2) in polyurethane foam spraying. Furthermore, the blowing agent of this invention can delay the gel time of the polyurethane foam and shorten the curing time. For example, when using ordinary alkanolamines as blowing agents, the gel time of the sprayed foam is generally 50-60 seconds; however, when using the aqueous alkanol amine composition (AC) of this invention, the gel time of the sprayed foam is generally 70-90 seconds.

[0014] According to a first aspect of the present invention, an aqueous alkanolamine composition (AC) is provided, comprising, consisting of, or primarily consisting of the following components:

[0015] (1) A secondary amine type asymmetric diolamine (A1) having 5-7 carbon atoms, which is selected from one, two or three of ethanol isopropanolamine, ethanol butanolamine (preferably ethanol sec-butanolamine) and isopropanol butanolamine (preferably isopropanol sec-butanolamine) (i.e., a combination of two or three).

[0016] (2) Has the general formula NR 1 R 2 R 3 Tertiary amine type C7-C11 triolamine (A2), in which R 1 R 2 and R 3 Each is independently an ethanol group, an isopropanol group, or a butanol group, wherein the butanol group is a sec-butanol group, a 1,2-dimethylethanol group, or a combination of both;

[0017] (3) Water; and

[0018] (4) Optional (i.e., optional) other C2-C12 alcohol amines (A3) besides (A1) and (A2) (preferably other C2-C9 alcohol amines, or other C4-C9 alcohol amines (A3)).

[0019] In this application, butanol group is or includes sec-butanol group and / or 1,2-dimethylethanol group.

[0020] Clearly, tertiary amines of the C7-C11 type (A2) with 7-11 carbon atoms do not include triethanolamine and tributanolamine, but may include triisopropanolamine. That is, R 1 R 2 and R 3 It can be either ethanol-based or butanol-based at the same time, but it can also be isopropanol-based.

[0021] Preferably, in triolamine (A2), R 1 Unlike R 2 and R 3 , and R 2 and R 3 They may be the same or different; that is, triolamines (A2) are also asymmetric. Given that triisopropanolamines (R) are completely symmetric... 1 =R 2 =R 3 The crystallization behavior of triisopropanolamine is not preferred, or a combination or mixture of triisopropanolamine with other asymmetric triolamines (A2) is used as the above-mentioned triolamine (A2) component.

[0022] Preferably, at the water content described above and at ambient temperature (e.g., at temperatures between 0 and 40°C, such as 1, 2, 3, 5, 7, 8, 10, 15, 20, 25, 30, 35, or 38°C), the content of the asymmetric triolamine (A2) alone, or the content of both the asymmetric triolamine and the asymmetric diolamine (A1) of the triolamine (A2), should such that the aqueous amine composition (AC) is in a liquid state or a homogeneous liquid state (preferably, a transparent or translucent liquid state, more preferably, a liquid form with low viscosity). More preferably, at ambient temperature (e.g., at temperatures between 0 and 40°C, such as 1, 2, 3, 5, 7, 8, 10, 15, 20, 25, 30, 35, or 38°C), the aqueous alkanolamine composition (AC) is in a (homogeneous) liquid form having a concentration of 200-1000 centipoise (e.g., at 25°C), preferably 250-900 centipoise (e.g., 300, 400, 500, 600, 700, or 800 centipoise).

[0023] In the composition (AC), the higher the content of asymmetric diolamine (A1) and asymmetric triolamine (A2), the lower the content of triisopropanolamine, which is a symmetric triolamine (A2). The doping effect of the asymmetric alkanolamine makes the composition (AC) less prone to crystallization at room temperature and has the lower viscosity described above.

[0024] Generally, the total mol% of asymmetric triolamine (A2) + asymmetric diolamine (A1) is 10-100 mol%, preferably 15-100 mol%, preferably 20-100 mol%, preferably 25-100 mol%, preferably 30-100 mol%, preferably 35-100 mol%, for example, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40 mol%, based on the total molar amount of secondary amine type asymmetric diolamine (A1) and tertiary amine type triolamine (A2). Accordingly, the mol% of the symmetrical triolamine (A2) (i.e., triisopropanolamine) is 0-90 mol%, 0-85 mol%, 0-80 mol%, preferably 0-75 mol%, preferably 0-70 mol%, preferably 0-65 mol%, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 mol%, based on the total molar amount of the secondary amine type asymmetrical diolamine (A1) and the tertiary amine type triolamine (A2).

[0025] The presence of small amounts (e.g., 10, 15, 20 or 25 mol%) of asymmetric alcoholamines (A2) and (A1) can also provide doping for triisopropanolamine as a symmetric triolamine (A2) so that the symmetric triolamine (i.e. triisopropanolamine) does not crystallize, thereby reducing the viscosity of the composition (AC) and making the alcoholamine composition (AC) a (homogeneous) liquid.

[0026] Because the aqueous alkanolamine composition (AC) contains appropriate amounts of asymmetric alkanolamines (A2) and (A1), the composition (AC) has a low viscosity and good compatibility or miscibility in white materials.

[0027] In addition, the composition (AC) has low alkalinity and reactivity with isocyanates to avoid cracking of the foam material from the substrate during the foaming process.

[0028] Preferably, it has the general formula NR 1 R 2 R 3 The asymmetric triolamine (A2) is or includes: diisopropanolamine, isopropanol diethanolamine, dibutanolamine (preferably di-sec-butanolamine), butanol diethanolamine (preferably sec-butanolamine), isopropanol dibutanolamine (preferably di-sec-butanolamine), butanol diisopropanolamine (preferably sec-butanolamine), and / or isopropanol butanolamine (preferably isopropanol sec-butanolamine), that is, having the general formula NR. 1 R 2 R 3The asymmetric triolamine (A2) is selected from one, two, or more of these alcoholamines. More preferably, it is selected from one or two of ethanol diisopropanolamine and isopropanol diethanolamine.

[0029] The isopropanol group is derived from propylene oxide, namely 2-hydroxypropyl (i.e., -CH2-CH(OH)-CH3).

[0030] Generally, in this application, butanol group refers to various isomers of butanol derived from 1,2-butene oxide (epoxybutane) or 2,3-butene oxide (preferably, butanol is sec-butanol or 1,2-dimethyl-ethanol); for example, sec-butanol (i.e., 2-hydroxybutyl, -CH2-CH(OH)-CH2-CH3) or 1-hydroxymethyl-propyl (i.e., -CH(CH2OH)-CH2CH3) derived from 1,2-butene oxide (epoxybutane), or 1,2-dimethyl-ethanol (i.e., 1,2-dimethylhydroxyethyl or 1-methyl-2-hydroxy-propyl, -CH(CH3)-CH(CH3)-OH) derived from 2,3-butene oxide.

[0031] Preferably, the present invention provides an aqueous amine composition (AC) comprising, consisting of, or primarily consisting of the following components:

[0032] (1) Secondary amine type diolamine (A1), which is ethanol isopropanolamine (i.e., hydroxyethyl hydroxyisopropylamine);

[0033] (2) A tertiary amine type triolamine (A2), which is selected from one or more of ethanol diisopropanolamine (i.e., hydroxyethyl di(hydroxyisopropyl)amine), isopropanol diethanolamine (i.e., hydroxyisopropyl di(hydroxyethyl)amine), and triisopropanolamine (a combination thereof); more preferably, it is selected from one or more of ethanol diisopropanolamine and isopropanol diethanolamine (a combination thereof);

[0034] (3) Water; and

[0035] (4) Optionally, other C2-C12 alcohol amines (A3) besides A1 and A2 (preferably other C2-C9 alcohol amines, or other C4-C9 alcohol amines (A3)).

[0036] The above-mentioned alkanolamine composition (AC) is particularly suitable as a blowing agent for the spraying of polyurethane foam.

[0037] Preferably, a portion of the alkanolamine in the composition (AC) of the present invention is neutralized by CO2 to form a carbonated alkanolamine salt (i.e., the alkanolamine reacts with CO2 and water to form carbonated alkanolamines). Neutralization helps to suppress the crystallization of alkanolamines, but it increases the viscosity of the alkanolamines.

[0038] In the alkanolamine composition (AC) of this application, preferably, the molar ratio of A2 to A1 is (0.1-9):1, preferably (0.15-8.5):1, preferably (0.2-8):1, preferably (0.3-7.5):1, preferably (0.4-7):1, preferably (0.5-6.5):1, preferably (0.6-6):1, preferably (0.7-5.5):1, preferably (0.8-5):1, preferably (0.9-4):1. .5):1, preferred (1-4):1, preferred (1.2-3.8):1, preferred (1.4-3.6):1, preferred (1.5-3.5):1, preferred (1.7-3.3):1, preferred (1.8-3.2):1, preferred (2-3):1, preferred (2.1-2.9):1, preferred (2.2-2.8):1, preferred (2.3-2.8):1, preferred (2.4-2.7):1.

[0039] In this application, preferably, the water content in the aqueous alkanolamine composition (AC) is 5-45 wt%, preferably 5-42 wt%, preferably 5-40 wt%, preferably 6-39 wt%, preferably 7-38 wt%, preferably 8-37 wt%, preferably 8.5-36 wt%, preferably 9-35 wt%, preferably 10-33 wt%, preferably 10.5-30 wt%, preferably 11-28 wt%, preferably 11.5-27 wt%, preferably 12-25 wt%, preferably 13-24 wt%, preferably 15-22 wt%, preferably 17-20 wt%, for example 5.5 wt% or 6.5 wt%, based on the total weight of the alkanolamine composition (AC).

[0040] Preferably, the total content of (A1)+(A2)+water is 70-100wt%, preferably 72-99.9%, preferably 73-99.5%, preferably 74-99%, preferably 75-98%, preferably 76-97%, preferably 77-96%, preferably 78-95%, preferably 80-94%, for example 81, 82, 84, 85, 87, 88, 90, 91, 92, 93wt%, based on the total weight of the alkanolamine composition (AC).

[0041] Generally, the content of other C2-C12 alcoholic amines (A3) besides A1 and A2 (preferably other C2-C9 alcoholic amines, or other C4-C9 alcoholic amines (A3)) is 0-30 wt%, preferably 0.1-28%, preferably 0.5-27%, preferably 1-26%, preferably 2-25%, preferably 3-24%, preferably 4-23%, preferably 5-22%, preferably 6-20%, for example 7, 8, 9, 10, 12, 13, 15, 16, 18, 19 wt%, based on the total weight of the alcoholic amine composition (AC). More preferably, the content of other C4-C9 alcoholic amines (A3) is 0-5 wt%, most preferably 0 wt%.

[0042] Preferably, the mol% of the asymmetric triolamine (A2a) (preferably diisopropanolamine ethanol and / or diethanolamine isopropanol) in the tertiary amine type triolamine (A2) is 10-100 mol%, preferably 15-100 mol%, 20-100 mol%, preferably 25-100 mol%, preferably 30-100 mol%, preferably 35-100 mol%, for example, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40 mol%. Therefore, preferably, the mol% of the symmetrical triolamine (A2) (i.e., triisopropanolamine) is 0-90 mol%, preferably 0-85 mol%, 0-80 mol%, preferably 0-75 mol%, preferably 0-70 mol%, preferably 0-65 mol%, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 mol%, based on the total molar amount of all tertiary amine-type triolamines (A2); preferably, this mol% is 0-50 mol%, 0-45 mol%. 1%, preferably 0-40 mol%, preferably 0.1-37 mol%, preferably 0.5-35 mol%, preferably 1-33 mol%, preferably 2-30 mol%, preferably 3-28 mol%, preferably 4-25 mol%, preferably 5-22 mol%, preferably 6-20 mol%, for example 7, 8, 9, 10, 11, 12, 13, 15, 16, 18 mol%, more preferably 0-10 mol%, more preferably 0-5 mol%, based on the total molar amount of all tertiary amine triolamines (A2).

[0043] For example, the other C2-C12 alcoholamine (A3) is a combination of one or more of the following alcoholamines: 1) diethanolamines or triethanolamines: diethanolamine, triethanolamine, tributanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, diisopropanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, N-propyldiisopropanolamine, N-methylethanolisopropanolamine, N-ethylethanolisopropanolamine and N-propylethanolisopropanolamine; and 2) monoethanolamines: ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, isopropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine and N-propylisopropanolamine.

[0044] Because other C2-C12 alcohol amines (A3) may interfere with the catalytic effect of amine gelation catalysts contained in the foaming white material to a certain extent (for example, causing the reaction rate in the early stage of the foaming reaction to be too fast, but the curing reaction in the later stage to be insufficient), the content of other C2-C12 alcohol amines (A3) should be as low as possible.

[0045] Preferably, for the above-described alkanolamine composition (AC), a portion of the alkanolamines (i.e., A1, A2, and optionally A3) in the alkanolamine composition (AC) is neutralized by CO2 to form a carbonate alkanolamine salt (i.e., the alkanolamine, together with CO2 and water, forms a carbonate alkanolamine salt). For example, the degree of neutralization should be such that the CO2 content in the alkanolamine composition (AC) is not higher than 7 wt%. Generally, the CO2 content in the alkanolamine composition (AC) is not higher than 7 wt% (i.e., 0-7 wt%), preferably 0.001-7 wt%, preferably 0.5-7 wt%, 0.8-6.5 wt%, preferably 1-6 wt%, preferably 1.2-6 wt%, preferably 1.5-6.0 wt%, preferably 1.8-5.8 wt%, preferably 2-5 wt%, for example 2.5, 3, 3.5, 4, 4.5 wt%, based on the total weight of the alkanolamine composition (AC).

[0046] If the CO2 content in the amine composition (AC) is higher than 7 wt% or 6 wt%, it may cause the sprayed, cured polyurethane foam layer to crack from the substrate or crack between two adjacent foam layers.

[0047] Generally, the molar percentage (mol%) of the alkanolamines (i.e., A1, A2, and optionally A3) present in the alkanolamine composition (AC) in the form of carbonates is 0 mol% or 0.001-40 mol%, preferably 0.0015-38 mol%, preferably 1-35 mol%, preferably 2-30 mol%, preferably 2.5-28 mol%, preferably 3-25 mol%, preferably 3.5-23 mol%, preferably 4-20 mol%, preferably 5-18 mol%, preferably 6-15 mol%, preferably 7-12 mol%, preferably 8-10 mol%, for example 9 mol%, based on the total molar amount of all alkanolamines in the alkanolamine composition (AC).

[0048] If the molar percentage (mol%) of alkanolamines present in the form of carbonates is higher than 40 mol (i.e., contains too much CO2), this may cause the sprayed, cured polyurethane foam layer to often crack from the substrate or crack between two adjacent foam layers.

[0049] The inventors of this application unexpectedly discovered that the aqueous alkanolamine composition (AC) of the present invention is a low-viscosity liquid at room temperature. Generally, the viscosity or dynamic viscosity (25°C) of the aqueous alkanolamine composition (AC) is 200-900 centipoise (mPa·s), preferably 220-800, more preferably 240-700, and even more preferably 250-600 centipoise, for example 280, 300, 400, 500, 650, 750, or 850 centipoise. For example, as single compounds, diisopropanolamine and triisopropanolamine have freezing points (melting points) of 42°C and 45°C, respectively, and at room temperature, diisopropanolamine and triisopropanolamine are white crystals or solid powders, indicating that symmetrical diisopropanolamine and triisopropanolamine have a strong tendency to crystallize. Therefore, in order to ensure that the alcoholamine composition (AC) of the present invention has a low viscosity, it is desirable to use as little diisopropanolamine as possible in the alcoholamine composition (AC) and to reduce the amount of triisopropanolamine.

[0050] Generally, the pH value of the alcohol amine composition (AC) in which the alcohol amine is partially neutralized by CO2 is in the range of 8-13.5, preferably 8-12, more preferably 8.5-11.5, more preferably 9-11, more preferably 9.1-10.5, and more preferably 9.2-10.

[0051] Preferably, the tertiary amine type triolamine (A2) is selected from one or more (combinations of two or more) of ethanol diisopropanolamine, isopropanol diethanolamine, ethanol dibutanolamine and ethanol isopropanol butanolamine.

[0052] In fact, the aqueous alkanolamine composition (AC) of the present invention comprises alkanolamine carbonate + water + free alkanolamine, and therefore is a low-viscosity composite foaming agent. In this application, "optional" means yes or no (0).

[0053] In addition, the inventors of this application unexpectedly discovered that the above-mentioned aqueous alkanolamine composition (AC) of the present invention has good miscibility (or compatibility) in dry white materials containing aromatic polyester polyols and / or toluene diamine type polyether polyols, and they can form transparent, homogeneous and low-viscosity white materials after being mixed.

[0054] According to a second aspect of the present invention, the present invention provides a method for preparing the above-described alkanolamine composition (AC) (a first method), the method comprising:

[0055] 1) Preparation of the alcoholamine composition (AC): 1a) An alcoholamine composition (AC) is prepared by reacting ethanolamine, or a mixture of isopropanolamine and ethanolamine (e.g., in a molar ratio of (0.1-9):1 or (0.15-8):1) as the starting material, with an epoxide (1) in the presence of water to obtain an alcoholamine composition (AC) containing a tertiary amine type triolamine A2 (e.g., ethanol diisopropanolamine, triisopropanolamine, ethanol isopropanolbutanolamine and / or ethanol dibutanolamine) and a secondary amine type asymmetric diolamine A1 (e.g., ethanol isopropanolamine and / or ethanol butanolamine), wherein the epoxide (1) is selected from propylene oxide, 1,2-epoxybutane and One or more of 2,3-epoxybutane (i.e., a combination of two or more); or, 1b) reacting isopropanolamine, as an alcohol amine starting material, with epoxide (2) in the presence of water to obtain an alcohol amine composition (AC) containing a tertiary amine type triolamine A2 (e.g., isopropanol diethanolamine, ethanol isopropanol butanolamine and / or isopropanol dibutanolamine) and a secondary amine type asymmetric diolamine A1 (e.g., ethanol isopropanolamine and / or isopropanol butanolamine), wherein the epoxide (2) is one or more of ethylene oxide, 1,2-epoxybutane and 2,3-epoxybutane (i.e., a combination of two or more);

[0056] 2) Optionally, an additional tertiary amine triolamine (A2) and an additional secondary amine asymmetric diolamine (A1) are added to the obtained amine composition (AC) to obtain an amine composition (AC), wherein the added tertiary amine triolamine (A2) is selected from one, two, or three of ethanol diisopropanolamine, triisopropanolamine, isopropanol diethanolamine, ethanol dibutanolamine, isopropanol dibutanolamine, butanol diethanolamine, or butanol diisopropanol (preferably ethanol diisopropanolamine, triisopropanolamine, and / or isopropanol diethanolamine); the added secondary amine asymmetric diolamine A1 is selected from one, two, or more of ethanol isopropanolamine, ethanol butanolamine, or isopropanol butanolamine; preferably, the amount of components (A1) and (A2) added should be such that the content range or molar ratio range of triolamine (A2) and asymmetric diolamine (A1) in the obtained composition (AC) is within the range defined above.

[0057] The total amount of water used in step 1) and optional step 2) should be such that the water content in the resulting alkanolamine composition (AC) is as defined above.

[0058] More preferably, a method for preparing the above-mentioned alkanolamine composition (AC) (a first method) is provided, the method comprising:

[0059] 1) Reaction of ethanolamine, as a starting material, with propylene oxide in the presence of water yields an alcoholamine composition (AC) containing a tertiary amine type triolamine A2 (ethanol diisopropanolamine) and ethanol isopropanolamine (A1); and

[0060] 2) Optionally, an additional tertiary amine triolamine (A2) and an additional ethanol isopropanolamine (A1) are added to the resulting amine composition (AC) to obtain an amine composition (AC) containing ethanol isopropanolamine (A1) and a tertiary amine triolamine (A2), wherein the added tertiary amine triolamine (A2) is selected from one, two, or three of ethanol diisopropanolamine, triisopropanolamine, and isopropanol diethanolamine (i.e., ethanol diisopropanolamine, triisopropanolamine, and / or isopropanol diethanolamine). Preferably, the amount of each component (A1) and (A2) added should be such that the content or molar ratio of triolamine (A2) and asymmetric diolamine (A1) in the resulting composition (AC) is within the range defined above.

[0061] Alternatively, the present invention provides a method for preparing the above-mentioned alkanolamine composition (AC) (a second method), the method comprising:

[0062] 1) Reaction of an amine starting material containing ethanolamine with propylene oxide (generally in the presence of water or in the absence of water) yields an amine composition (AC) containing ethanol isopropanolamine (A1) and optionally a tertiary amine type triethanolamine (A2) (e.g., diisopropanolamine ethanol), wherein the amine starting material containing ethanolamine comprises 50-100 mol% ethanolamine and 0-50 mol% diethanolamine; and

[0063] 2) Optionally, an additional tertiary amine triolamine (A2) is added to the resulting amine composition (AC) to obtain an amine composition (AC) containing ethanol isopropanolamine (A1) and tertiary amine triolamine (A2), wherein the added tertiary amine triolamine (A2) is selected from one, two, or three of the amines selected from ethanol diisopropanolamine, triisopropanolamine, and isopropanol diethanolamine (i.e., ethanol diisopropanolamine, triisopropanolamine, and / or isopropanol diethanolamine).

[0064] In step 1) of any of the above methods, the molar ratio of the epoxide (e.g., propylene oxide and / or 1,2-epoxybutane, or ethylene oxide) to the alkanolamine starting material (e.g., ethanolamine and / or isopropanolamine, or ethanolamine + diethanolamine) is (1.2-1.9):1, preferably (1.3-1.85):1, preferably (1.4-1.83):1, preferably (1.5-1.8):1, for example 1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1 or 1.7:1.

[0065] In step 2) of any of the above methods, the amount of tertiary amine triolamine (A2) and diolamine (A1) added should be such that the molar ratio of A2 to A1 in the obtained amine composition (AC) is (0.1-9):1, preferably (0.15-8.5):1, preferably (0.2-8):1, preferably (0.3-7.5):1, preferably (0.4-7):1, preferably (0.5-6.5):1, preferably (0.6):1. -6):1, preferred (0.7-5.5):1, preferred (0.8-5):1, preferred (0.9-4.5):1, preferred (1-4):1, preferred (1.2-3.8):1, preferred (1.4-3.6):1, preferred (1.5-3.5):1, preferred (1.7-3.3):1, preferred (1.8-3.2):1, preferred (2-3):1, preferred (2.2-2.8):1.

[0066] Preferably, in step 2) of the above method, the amount of tertiary amine triolamine (A2) added should be such that: the mol% of the asymmetric triolamine (A2a) in the tertiary amine triolamine (A2) is as described above, for example, 10-100 mol%; and the mol% of the symmetric triolamine (A2) (i.e., triisopropanolamine) is as described above, for example, 0-90 mol%, based on the total molar amount of all tertiary amine triolamine (A2).

[0067] For example, the amount of tertiary amine triolamine (A2) added should be such that the mol% of the sum of diisopropanolamine ethanol and diethanolamine isopropanol is 70-100 mol%, for example, 73, 75, 77, 80, 82, 85, 87, 90, 93, 95, 97, 96, 98, or 99 mol%, based on the total molar amount of tertiary amine triolamine (A2). Therefore, the mol% of triisopropanolamine is the balance, i.e., 0-30 mol%, for example, 27, 25, 23, 20, 18, 15, 13, 10, 7, 5, 4, 3, 2, 1 mol%, based on the total molar amount of tertiary amine triolamine (A2).

[0068] In addition, other C2-C12 alcoholic amines (A3) other than A1 and A2 mentioned above can be added to the obtained alcoholic amine composition (AC). Although this is not preferred for the spraying operation of polyurethane foam, it may be acceptable for the casting operation of polyurethane foam.

[0069] Generally, the amount of other C2-C12 alcoholamines (A3) besides A1 and A2 added should be such that the content of other C2-C12 alcoholamines (A3) besides A1 and A2 is 0-30 wt%, preferably 0.1-28%, preferably 0.5-27%, preferably 1-26%, preferably 2-25%, preferably 3-24%, preferably 4-23%, preferably 5-22%, preferably 6-20%, for example 7, 8, 9, 10, 12, 13, 15, 16, 18 wt%, based on the total weight of the alcoholamine composition (AC).

[0070] The total amount of water used in step 1) and optional step 2) of any of the above methods should be such that the water content in the obtained composition (AC) is as defined above, for example, 5-45 wt%, based on the total weight of the alkanolamine composition (AC).

[0071] In addition, preferably, the total content of (A1)+(A2)+water in the obtained alkanolamine composition (AC) is as defined above, for example, 70-100 wt%, based on the total weight of the alkanolamine composition (AC).

[0072] Generally, ethanolamine and propylene oxide react in a 1:1 molar ratio in the presence of water to obtain ethanol isopropanolamine (hydrate). Reacting ethanolamine and propylene oxide in a 1:2 molar ratio in the presence of water yields ethanol diisopropanolamine (hydrate).

[0073] Alternatively, the present invention provides a method for preparing the above-mentioned alkanolamine composition (AC) (a third method), the method comprising:

[0074] 1) Preparation of secondary amine diolamines: Ethanolamine is reacted with propylene oxide, ethanolamine with 1,2-epoxybutane, ethanolamine with 2,3-epoxybutane, isopropanol with 1,2-epoxybutane, or isopropanol with 2,3-epoxybutane in the presence of water at a molar ratio of about (0.95-1.05):1 (e.g., about 1:1) to obtain secondary amine diolamines (A1) (e.g., ethanol isopropanolamine);

[0075] 2) Preparation of tertiary amine triolamines: Ethanolamine is reacted with propylene oxide, ethanolamine with 1,2-epoxybutane, ethanolamine with 2,3-epoxybutane, isopropanol with 1,2-epoxybutane, isopropanol with 2,3-epoxybutane, or isopropanolamine with propylene oxide in the presence of water at a molar ratio of approximately 1:(1.9-2.1) (e.g., approximately 1:2) to obtain a tertiary amine triolamine (A2) (e.g., diisopropanolamine); or, diethanolamine is reacted with propylene oxide, di... Ethanolamine is reacted with 1,2-epoxybutane, diethanolamine with 2,3-epoxybutane, diisopropanol with 1,2-epoxybutane, diisopropanol with 2,3-epoxybutane, ethanol isopropanol with 1,2-epoxybutane, ethanol isopropanol with 2,3-epoxybutane, or diisopropanolamine with propylene oxide in the presence of water at a molar ratio of about (0.95-1.05):1 (e.g., about 1:1) to obtain a tertiary amine triolamine (A2) (e.g., isopropanol diethanolamine);

[0076] 3) Preparation of the amine composition (AC): The products of step 1) and step 2) are mixed, wherein the amounts of the tertiary amine triolamine and the secondary amine diolamine are such that the content of each component in the composition (AC) is as defined above, or the molar ratio of the tertiary amine triolamine to the secondary amine diolamine (e.g., diisopropanolamine ethanol and isopropanolamine ethanol) is as defined above, for example (0.1-9):1, preferably (0.15-8.5):1, preferably (0.2-8):1, preferably (0.3-7.5):1, preferably (0.4-7):1, preferably (0.5-6.5):1, preferably (… 0.6-6):1, preferably (0.7-5.5):1, preferably (0.8-5):1, preferably (0.9-4.5):1, preferably (1-4):1, preferably (1.2-3.8):1, preferably (1.4-3.6):1, preferably (1.5-3.5):1, preferably (1.7-3.3):1, preferably (1.8-3.2):1, preferably (2-3):1, preferably (2.1-2.9):1, preferably (2.2-2.8):1, preferably (2.3-2.8):1, preferably (2.4-2.7):1, thereby obtaining an alcoholamine composition (AC); and

[0077] 4) Optionally, an additional tertiary amine triolamine (A2) and an additional secondary amine asymmetric diolamine (A1) are added to the obtained amine composition (AC) to obtain an amine composition (AC), wherein the added tertiary amine triolamine (A2) is selected from one, two, or three of ethanol diisopropanolamine, triisopropanolamine, isopropanol diethanolamine, ethanol dibutanolamine, isopropanol dibutanolamine, butanol diethanolamine, or butanol diisopropanol (preferably ethanol diisopropanolamine, triisopropanolamine, and / or isopropanol diethanolamine); the added secondary amine asymmetric diolamine A1 is selected from one, two, or more of ethanol isopropanolamine, ethanol butanolamine, or isopropanol butanolamine; preferably, the amount of components (A1) and (A2) added should be such that the content range or molar ratio range of triolamine (A2) and asymmetric diolamine (A1) in the obtained composition (AC) is within the range defined above.

[0078] Generally, the total amount of water used in steps 1), 2), 3) and optional 4) above should result in a water content in the resulting alkanolamine composition (AC) as defined above, for example, 5-45 wt%, based on the total weight of the composition (AC).

[0079] In addition, preferably, the total content of (A1)+(A2)+water in the obtained alkanolamine composition (AC) is as defined above, for example, 70-100 wt%, based on the total weight of the alkanolamine composition (AC).

[0080] Additionally, triisopropanolamine or isopropanol diethanolamine is formed by reacting isopropanolamine, diisopropanolamine, or diethanolamine with propylene oxide. Specifically, triisopropanolamine can be formed by reacting isopropanolamine with propylene oxide in a molar ratio of approximately 1:2, or by reacting diisopropanolamine with propylene oxide in a molar ratio of approximately 1:1; and isopropanol diethanolamine is obtained by reacting diethanolamine with propylene oxide in a molar ratio of approximately 1:1. This reaction is generally carried out in the presence of water. The obtained triisopropanolamine and / or isopropanol diethanolamine can be added to the product obtained in step 1) of the above method.

[0081] In step 3) "Preparation of the amine composition (AC)" of the above method, the amount of tertiary amine triolamine (A2) added should be such that: the mol% of diisopropanolamine ethanol is as described above; the mol% of isopropanol diethanolamine, triisopropanolamine, or (isopropanol diethanolamine + triisopropanolamine) is as described above; the mol% of the sum of diisopropanolamine ethanol and isopropanol diethanolamine is as described above; and the mol% of triisopropanolamine is as described above.

[0082] The reaction temperature in step 1 of the above method is generally 40-100℃, preferably 45-95℃, more preferably 50-90℃, for example 60-85℃, and preferably 70-80℃. Generally, the reaction is carried out in a closed reactor (e.g., a high-pressure reactor).

[0083] Preferably, in the ethanolamine starting material containing ethanolamine, the mol% of ethanolamine is 50-100 mol%, for example 55, 60, 70, 80, 90, 95, 98 mol%, and therefore, the mol% of diethanolamine is the balance, i.e. 0-50 mol%, for example 45, 40, 30, 20, 10, 5, 2 mol%, based on the total molar amount of all ethanolamines in the ethanolamine starting material.

[0084] Preferably, the method for preparing the alkanolamine composition (AC) of the present invention further includes:

[0085] CO2 gas is introduced into the obtained alkanolamine composition (AC) to partially neutralize the alkanolamine compounds in the composition (AC) (i.e., the alkanolamine forms carbonate alkanolamine salts with CO2 and water), thus obtaining an alkanolamine composition (AC) containing CO2 (in carbonate form). The amount of CO2 introduced or the degree to which the alkanolamine is neutralized by CO2 should be such that the CO2 content in the alkanolamine composition (AC) is not higher than 7 wt% (i.e., 0-7 wt%, or 0 wt% ≤ CO2 content ≤ 7 wt%), preferably 0.001-6.8 wt%, preferably 0.005-6.5 wt%, preferably 0.01-6.3 wt%, preferably 0.05-6.1 wt%, preferably 0.1-6.0 wt%, preferably 0.3-5.8 wt%, preferably 0.5-5.6 wt%, preferably 0.8-5.3 wt%, preferably 1-5 wt%, preferably 1.5-4.5 wt%, preferably 2-4 wt%, for example 3 or 3.5 wt%, based on the total weight of the alkanolamine composition (AC). If the CO2 content is higher than 6 wt% or 7 wt%, a sharp increase in the viscosity of the alkanolamine composition AC is observed, which may be attributed to the gradual increase in the amount of alkanolamine bicarbonate formed. Therefore, the CO2 content should be lower than 4 wt% or 5 wt%.

[0086] Generally, the molar percentage (mol%) of the alkanolamines (i.e., A1, A2 and optionally A3) present in the alkanolamine composition (AC) in the form of carbonates is as defined above, for example, 0 mol% or 0.001-40 mol%, preferably 1-35 mol%, for example, 5, 10, 15, 20, 25, 30 mol%, based on the total molar amount of all alkanolamines in the alkanolamine composition (AC).

[0087] In addition, in the above method, the composition of the alcoholamine composition (AC) is adjusted by adding water and the triolamine (A2) and diolamine (A1) mentioned above, as well as other C2-C12 alcoholamines (A3) other than A1 and A2, to the alcoholamine composition (AC).

[0088] The above-mentioned alkanolamine composition (AC) of the present invention can be used directly as a blowing agent to prepare rigid polyurethane foam, and is particularly suitable for use in the spraying of polyurethane foam.

[0089] According to a third aspect of the invention, the invention also relates to the use of the above-mentioned alkanolamine composition (AC) as a blowing agent in the preparation of (spray-applied) rigid polyurethane foam materials, and particularly to its use as a blowing agent in the spraying of rigid polyurethane foam.

[0090] In addition, the above-described alkanolamine composition (AC) of the present invention can also be used in combination with hydrofluorocarbon physical blowing agents (F2) with boiling points in the range of 15-41°C.

[0091] According to a fourth aspect of the invention, the invention provides a polyurethane blowing agent composition (FC) (particularly suitable for use in the spraying of polyurethane foam), comprising the following components:

[0092] (1) Alkylamine composition (AC) as defined above,

[0093] (2) Hydrofluorocarbon physical blowing agents (F1) with boiling points in the range of 15-41℃; and

[0094] (3) Optional, water (F2).

[0095] The components (1), (2) and (3) are contained in separate storage containers and are added to the white material before spraying and foaming.

[0096] Preferably, the physical blowing agent (F1) is selected from one or more (e.g., a combination of two, three, four or five) of HCFC-141b, HFC-245fa, HFC-365mfc, LBA and hexafluorobutene.

[0097] The relative amounts of each component (e.g., relative to 95-106 parts by weight, such as 96, 97, 98, 99, 100, 101, 102, 103, 104.6, 105 parts by weight of dry white liquor) are:

[0098] The amount of the amine composition (A) is 5-22 parts by weight, preferably 6-21 parts by weight, preferably 7-20 parts by weight, preferably 8-19 parts by weight, preferably 9-18 parts by weight, preferably 10-17 parts by weight, preferably 11-16 parts by weight, preferably 12-15 parts by weight.

[0099] The amount of physical foaming agent (F1) is 0-17 parts by weight, preferably 1-16 parts by weight, preferably 2-15 parts by weight, preferably 3-14 parts by weight, preferably 4-13 parts by weight, preferably 5-12 parts by weight, preferably 6-11 parts by weight, preferably 7-10 parts by weight, preferably 8-9 parts by weight; and

[0100] The amount of water (F2) is 0-2 parts by weight, 0-1.5 parts by weight, more preferably 0-1 parts by weight, even more preferably 0-0.5 parts by weight, and more preferably 0-0.1 parts by weight.

[0101] The water (F2) mentioned herein does not include the water contained in the alcoholamine composition (A).

[0102] Preferably, the weight ratio of the amine composition (A) to the physical blowing agent (F1) is 0.2-5:1, preferably 0.25-4:1, preferably 0.33-3:1, preferably 0.4-2.5:1, preferably 0.5-2:1, preferably 0.7-1.5:1, preferably 0.8-1.3:1, for example 1:1.

[0103] Preferably, the sum of the weights of components (1), (2), and optional component (3) is 80-100 wt%, preferably 85-100 wt%, preferably 88-100 wt%, preferably 90-100 wt%, preferably 92-100 wt%, preferably 93-100 wt%, preferably 95-100 wt%, preferably 98-100 wt%, preferably 98.5-100 wt%, preferably 99-100 wt%, preferably 99.5-100 wt%, preferably 99.8-100 wt%, for example, 96 wt% or 97 wt%, based on the total weight of the polyurethane foam composition (FC).

[0104] When components (1), (2), and optional component (3) are used to formulate white pigment, preferably, the weight percentage (wt%) of the sum of the weights of components (1), (2), and optional component (3) is 8-25 wt%, preferably 10-24 wt%, preferably 12-23 wt%, preferably 13-22 wt%, for example, 9, 11, 14, 15, 16, 17, 18, 19, 20, or 21 wt%, based on the total weight of the dry white pigment (composed of polymeric polyols).

[0105] According to a fifth aspect of the present invention, the present invention provides a white material for polyurethane foaming, comprising: (1) a dry white material for polyurethane foaming containing polymeric polyols and other additives besides a blowing agent, wherein the other additives include a polyurethane catalyst, a foam stabilizer and optionally a flame retardant; and (2) a blowing agent composition (FC) (the above-mentioned alkanolamine composition AC and optionally other physical blowing agents).

[0106] According to a sixth aspect of the invention, the invention also relates to the use of the above-described alkanolamine composition (AC) as a blowing agent in the preparation of castable rigid polyurethane foam. For example, it can be used to prepare rigid polyurethane foam materials for use in the refrigerator, freezer, water heater, and cold chain insulation (refrigerated truck) industries. In this case, preferably, the alkanolamine in the alkanolamine composition (AC) is neutralized by CO2 to such an extent that the alkanolamine composition (AC) contains 7-20 wt% CO2, for example 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19 wt%, based on the total weight of AC.

[0107] When the alkanolamine composition (AC) is used as a blowing agent to prepare cast-type rigid polyurethane foam (in the production of PU foam in industries such as refrigerators, freezers, water heaters, and cold chain insulation (refrigerated trucks)) or to prepare spray-type rigid polyurethane foam, the polymer polyols in the dry white material contain 8-72 wt% (preferably 9-70 wt%, preferably 10-60 wt%, preferably 11-52 wt%, preferably 12-50 wt%, preferably 15-45 wt%, preferably 16-40 wt%, more preferably 18-35 wt%) of aromatic / semi-aromatic polyester polyols (e.g., polyols). The polyols include polyethylene terephthalate (PET), polyethylene isophthalate (PET), or polyethylene terephthalate (PET) and / or toluenediamine-type polyoxypropylene polyols, and 92-28 wt% (preferably 91-30 wt%, preferably 90-40 wt%, preferably 89-48 wt%, preferably 88-50 wt%, preferably 85-55 wt%, more preferably 84-60 wt%, more preferably 82-65 wt%) of (non-toluenediamine-type or non-toluenediamine-initiated) polyoxypropylene polyols, i.e., polyoxypropylene polyols other than toluenediamine polyoxypropylene polyols. The wt% is based on the weight of the polymeric polyols in the dry white material.

[0108] The thermal conductivity λ (w / m·k, 20°C) of the sprayed rigid polyurethane foam of the present invention is generally less than 0.02250, preferably less than 0.02240, more preferably less than 0.02235, more preferably less than 0.02230, more preferably less than 0.02220, and more preferably less than 0.02210.

[0109] The compressive strength of the sprayed rigid polyurethane foam of the present invention (in the direction perpendicular to the substrate, for example when the foam density is about 35 kg / cm³) 3 The pressure (kPa) is 240-285 kPa, preferably 245-270 kPa, preferably 250-267 kPa, and most preferably 255-265 kPa.

[0110] The "asymmetry" mentioned here for alcoholamines refers to "incomplete symmetry".

[0111] Advantages of the present invention

[0112] 1. The foaming agent composition (or alkanolamine composition) of the present invention has low alkalinity and reactivity with isocyanates, and it hardly affects the catalytic effect of amine catalysts in the foaming composition (i.e., white material) for polyurethane foam spraying. Therefore, it can avoid the following problems encountered in the foaming process when using alkanolamine compositions with high reactivity and alkalinity in the prior art as foaming agents: the reaction is too fast and a lot of heat is released in the early stage of the foaming reaction, resulting in the "burnt core" phenomenon inside the foam (i.e. the core of the foam is dark yellow or burnt yellow). However, the crosslinking reaction in the later stage is insufficient, and the strength and dimensional stability of the resulting foam decrease. It often shrinks and deforms, which leads to cracks between the cured foam material and the substrate or between two adjacent cured foam layers.

[0113] 2. In the amine composition of the present invention, only a portion of the amine is neutralized by CO2, or even none at all. Therefore, during the foam spraying process, the following phenomenon often encountered when using amine compositions with high CO2 content as foaming agents in the prior art can be avoided: In the early stage of the foaming reaction during the spraying operation (before the reaction system has fully gelled), the foaming agent composition (or amine composition) with high CO2 content rapidly releases a large amount of CO2 gas upon heating, causing the wet foam sprayed onto the substrate or the cured foam layer to expand rapidly, and causing severe shrinkage and deformation of the cured foam, resulting in cracks forming between the cured foam material and the substrate or between two adjacent cured foam layers. Since the water in the amine composition exists in the form of amine hydrates rather than in the form of molecular clusters, the disadvantages of pure water foaming are avoided.

[0114] 3. In the AC composition of the present invention, the alkanolamine has low alkalinity and reactivity with isocyanates, hardly interfering with the catalytic effect of organic amine polyurethane catalysts in the white material. Furthermore, the alkanolamine and water are beneficial to promoting the later crosslinking reaction of the entire foaming reaction (forming a crosslinking network in the cell wall). The resulting foam has ideal strength and high dimensional stability, and the above-mentioned cracking phenomenon will not occur.

[0115] 4. On the one hand, due to the structural asymmetry of the alkanolamine molecules and the mutual doping effect between different alkanolamines, the alkanolamine composition (AC) of the present invention has a low viscosity, which makes the prepared white material have good flowability. Therefore, it is suitable as a foaming agent for spraying rigid polyurethane foam. On the other hand, they have good compatibility or miscibility with the dry white material for foaming. Therefore, they can be easily and quickly mixed evenly with the dry white material for foaming (achieving molecular-level miscibility) to form a uniform, transparent (homogeneous) foaming system (white material) with good flowability. In the foaming reaction, they have a nucleation effect (foaming point) to promote uniform foaming. Therefore, it is possible to obtain sprayed rigid polyurethane foam with good cell microstructure, closed-cell ratio and strength properties. In particular, when the polymeric polyols in the dry white material contain 8-72 wt% of aromatic / semi-aromatic polyester polyols and / or toluene diamine-type polyoxypropylene polyols and 92-28 wt% of non-toluene diamine-type polyoxypropylene polyols, the alkanolamine composition (AC) of the present invention (wherein the alkanolamine contains methyl or ethyl) has good compatibility or miscibility with the dry white material, and therefore, it is particularly suitable as a foaming agent.

[0116] 5. If the alkanolamine composition (AC) absorbs more CO2 (e.g., CO2 content higher than 7 wt%), it is combined with cyclopentane and / or n-pentane as a blowing agent for the preparation of cast-type rigid polyurethane foam, for example, rigid polyurethane foam materials used in the refrigerator, freezer, water heater and cold chain insulation (refrigerated truck) industries.

[0117] 6. In the early stages of the foaming process using the foaming agent composition, the carbonated amine salt hydrate produces excellent nucleation, i.e., the initial formation of cells. The physical foaming agent, heated and vaporized in the middle and later stages of the foaming process, further expands the cells. This early nucleation results in a superior microstructure in the final PU foam: smaller and more uniform cell size, a greater number of cells per unit volume (SEM images show a greater number of cells per unit area), more thorough cross-linking of the cell walls by the amine and water (resulting in higher strength at lower foam density), thinner cell walls, higher airtightness (attributed to the fully cross-linked network on the cell walls), and a higher closed-cell ratio. Attached Figure Description

[0118] Figure 1 This is an SEM image of the foam from Example 1.

[0119] Figure 2 This is an SEM image of the foam from Example 2.

[0120] Figure 3 This is an SEM image of the foam from Example 3.

[0121] Figure 4 This is an SEM image of the foam from Example 4.

[0122] Figure 5 This is an SEM image of the foam from Example 5.

[0123] Figure 6 This is an SEM image of the foam from Example 6.

[0124] Figure 7 This is a SEM image of the foam from Example 11.

[0125] Figure 8 This is a photograph of the cross-section of the foam in Comparative Example 1.

[0126] Figure reference numerals: 1: Crack between foam and substrate (cement board); 2: Crack between two adjacent foam layers; 3:

[0127] Substrate (cement board).

[0128] Figure 9 This is a photograph of the cross-section of the foam in Comparative Example 2.

[0129] Figure 10 This is a SEM image of the foam in Comparative Example 3.

[0130] Figure 11 This is an SEM image of the foam from Example 14.

[0131] Figure 12 It is the product of preparation Example 8. 1 H-NMR spectrum.

[0132] Figure 13 It is the product of preparation Example 1. 1 H-NMR spectrum. Detailed Implementation

[0133] The present invention will be further described in detail through the following embodiments, but the present invention is not limited to these embodiments.

[0134] The devices used in the embodiments are all commonly used in the art and commercially available, unless otherwise specified.

[0135] Method for measuring the content of alkanolamines: In the examples, the content of various alkanolamines (e.g., ethanol isopropanolamine, ethanol diisopropanolamine, or triisopropanolamine) in aqueous alkanolamine mixtures (AC) (or aqueous alkanolamine compositions or alkanolamine hydrates) can be measured by gas chromatography. The gas chromatograph is equipped with a flame ionization detector (FID), and the mass concentration of the alkanolamine compound is approximately 10 mg / mL, as a standard solution. Gas chromatography conditions: HP-5 capillary column (30m × 0.32mm id × 0.25μm, 5% phenyl methyl-siloxane); column temperature programmed, initial temperature 80℃, held for 3 min, then increased to 250℃ at a rate of 25℃ / min, held for 5 min; injection port temperature 250℃; detector temperature 260℃; carrier gas high-purity nitrogen, flow rate 1.5mL / min; fuel gas hydrogen, flow rate 30mL / min; oxidizing gas air, flow rate 300mL / min; make-up gas nitrogen, flow rate 25mL / min; injection method split injection, split ratio: 30:1; injection volume 1μL.

[0136] In this application, the commonly used polyether polyols (polypropylene oxide polyols) and (aromatic) polyester polyols used in the preparation of polyurethane foams or in foaming compositions are selected from the following varieties: polyether polyols (polypropylene oxide polyols), for example, polyether polyol 4110 (sucrose initiator polypropylene oxide polyol) from Bevar Group Co., Ltd., polyether 450 (sorbitol initiator polypropylene oxide polyol) from Nanjing Hongbaoli Co., Ltd., MN500 (glycerol initiator polypropylene oxide polyol) and SA from Shandong Lanxing Dongda Chemical Co., Ltd. 460 (sorbitol-initiated polyoxypropylene polyol), SA460 (sorbitol-initiated polyoxypropylene polyol), SU380 (sucrose-initiated polyoxypropylene polyol), and SA380 (sorbitol-initiated polyoxypropylene polyol) from Zibo Nuoli Chemical Co., Ltd.; YD8260 (polyoxypropylene polyol with sucrose and diethylene glycol as initiators), YD403 (ethylenediamine-initiated polyoxypropylene polyol, hydroxyl value 770 mg KOH / g), YD460 (toluenediamine-type polyoxypropylene polyol), and YD-4110 (polyether polyol, hydroxyl value 460 mg KOH / g) from Hebei Yadong Chemical Group Co., Ltd. KOH / g), and SD7100 (toluene diamine polyoxypropylene polyol) from Shanghai Dongda Chemical Co., Ltd.; and (aromatic) polyester polyols, such as PS4051, PS4027 or PS3152 from Nanjing Jinling Stepan Chemical Co., Ltd., polyester polyols CF6320 (hydroxyl value 320 mg KOH / g), CF6245, CF6200, CF6300 and CF6255 from Jiangsu Fusheng New Materials Co., Ltd., and polyester polyol DM2003 from Beijing Dongfang Meilong Chemical Technology Co., Ltd.

[0137] Commonly used catalysts are selected from: 33LV(A-33): 33% triethylenediamine in dipropylene glycol solution, N,N-dimethylethanolamine, N,N-dimethylbenzylamine, 70% bis(dimethylaminoethyl) ether in dipropylene glycol solution, 70% potassium octanoate in diethylene glycol solution, dibutyltin dilaurate, PT303, PT304, potassium acetate, PC-8 (N,N-dimethylcyclohexylamine), PC-5 (N,N,N,N,N-pentamethyldiethylenetriamine), PC-41 (tris(dimethylaminopropyl)hexahydrotriazine), triethanolamine, JXP-508, JXP-509, TMR-2 (2-hydroxy-N,N,N-trimethyl-1-propylaminocarbamate), TMR-3, TMR-4. Commonly used silicone oil-based foam stabilizers or silane surfactants include: Evonik Degussa (China) Investment Co., Ltd.'s B8525 and B8408; Jiangsu Meiside Chemical Co., Ltd.'s AK-158, AK-8805, AK-8812, AK-8809, AK-8818, and AK-8860; Gas & Chemicals' DC8545, DC1990, DC5188, DC6070, DC3042, and DC3201; and Shanghai Maihao Chemical Technology Co., Ltd.'s silicone oil 8841. Non-silane surfactants include: Gas & Chemicals' LK-221 and LK-443. Commonly used flame retardants include: TCPP (Qingdao Lianmei Chemical Co., Ltd.), TCEP, DMMP, ammonium chloride, aluminum hydroxide powder, DM1201, DM1301, and tetrabromophthalic anhydride diol.

[0138] The following describes the preparation of carbonate amine salt chemical foaming agents (i.e., carbonate amine salt hydrates) using CO2 ventilation.

[0139] The water content of an alcoholic amine hydrate, as measured by the Karl Fischer method, equals the amount of free water in the hydrate plus the amount of water produced by the decomposition of the carbonate and optionally the bicarbonate. Therefore, the free water content (wt%) in an alcoholic amine hydrate chemical foaming agent (F1) (i.e., alcoholic amine hydrate) = (water content of the alcoholic amine hydrate as measured by the Karl Fischer method) – (amount of water produced by the decomposition of the carbonate and optionally the bicarbonate). For example, the water content in the alcoholic amine composition (AC) described in this application refers to the water content measured by the Karl Fischer method.

[0140] The test methods for various parameters of rigid polyurethane foam are based on the following Chinese national standard GB:

[0141]

[0142] In the table above, the Z direction represents the vertical direction of the foam sample (i.e., the direction perpendicular to the substrate), and the X and Y directions represent two mutually perpendicular directions on the same horizontal plane of the sample.

[0143] Viscosity refers to the kinetic viscosity at 25°C, known as centipoise (cP).

[0144] Preparation Example 1 (Preferred)

[0145] 24.64 kg of ethanolamine (molecular weight 61,404 mol) and 12.24 kg of deionized water were added to a high-pressure reactor and stirred to dissolve. The reactor was then sealed, and the temperature was maintained between 60-95°C with continuous stirring, while keeping the pressure inside the reactor below 0.3 MPa. 41.8 kg of propylene oxide (molecular weight 58,720 mol, molar ratio of propylene oxide to ethanolamine 1.8:1) was added to the reactor in batches. After the addition was complete, the reaction was carried out at a controlled temperature for 3 hours, and then cooled to 40°C. Finally, 78.64 kg of the reaction product (ethanolamine hydrate AA1a, or ethanolamine composition AA1a) was discharged from the reactor, with a viscosity (25°C) of 288 centipoise. A sample of the product was taken and analyzed by gas chromatography. The content of ethanol isopropanolamine in AA1a was 80.9 mol, and the content of ethanol diisopropanolamine was 323.1 mol, with a molar ratio of ethanol diisopropanolamine to ethanol isopropanolamine of 4:1. The sample of the product... 1 The H-NMR spectrum is shown in Figure 13 The water content in the alcohol amine hydrate AA1a was determined to be 15.6 wt% by the Karl Fischer method.

[0146] Then, 40 kg of the obtained amine hydrate AA1a was added to a high-pressure reactor. Carbon dioxide gas was introduced into the amine hydrate AA1a while controlling the pressure of the CO2 gas output from the CO2 storage cylinder to not exceed 0.3 MPa. The temperature was controlled between 40-50°C, and the reaction was carried out for 3 hours. After cooling to below 40°C, the pressure was released, and the product was discharged, yielding a carbonated amine salt composition AA1b (or amine composition AA1b). The CO2 absorption was 440 g (approximately 10 mol, meaning 9.7 mol% of the amine in AA1a was neutralized by CO2 to form carbonated amine salt; CO2 content was 1.088 wt%). The dynamic viscosity (25°C) of product AA1b was 395 centipoise. The pH of product AA1b was measured to be 11.4 using a pH meter (Leici PHS-3C type, Shanghai Yidian Science Instrument Co., Ltd.). Its decomposition temperature is between 45℃ and 70℃.

[0147] Preparation Example 2 (Preferred)

[0148] 24.64 kg of ethanolamine (molecular weight 61,404 mol) and 14.4 kg of deionized water were added to a high-pressure reactor and stirred to dissolve. The reactor was then sealed, and the temperature was maintained between 60-95°C with continuous stirring, while the pressure inside the reactor was kept below 0.3 MPa. 35.148 kg of propylene oxide (molecular weight 58,606 mol, molar ratio of propylene oxide to ethanolamine 1.5:1) was added to the reactor in batches. After the addition was complete, the reaction was carried out at a controlled temperature for 3 hours, and then cooled to 40°C. Then, 74 kg of the reaction product (ethanolamine hydrate AA2a, or ethanolamine composition AA2a) was discharged from the reactor. A sample was taken from the product, and gas chromatography analysis revealed that the content of ethanol isopropanolamine in ethanolamine hydrate AA2a was 201.9 mol, and the content of ethanol diisopropanolamine was 202.1 mol, with a molar ratio of ethanol diisopropanolamine to ethanol isopropanolamine of 1:1. The water content in the alcohol amine hydrate AA2a is 19.4 wt%.

[0149] Then, 40 kg of the obtained amine hydrate AA2a was added to a high-pressure reactor. Carbon dioxide gas was introduced into the amine hydrate AA2a while controlling the pressure of the CO2 gas output from the CO2 storage cylinder to not exceed 0.3 MPa. The temperature was controlled between 40-50°C, and the reaction was carried out for 3 hours. After cooling to below 40°C, the pressure was released, and the product was discharged, yielding the carbonated amine salt composition AA2b. The CO2 absorption was 1.5 kg (approximately 34.1 mol, CO2 content 3.61 wt%, approximately 31 mol% of the amine in AA2a was neutralized by CO2 to form carbonated amine salt). The viscosity of product AA2b (at 25°C) was 614 centipoise. The pH was 10.7, and the decomposition temperature was between 45°C and 70°C.

[0150] Preparation Example 3

[0151] 30 kg of ethanolamine (molecular weight 61, 491.8 mol) and 16.04 kg of deionized water were added to a high-pressure reactor and stirred until dissolved. The reactor was sealed, and the temperature was maintained between 60-95°C with continuous stirring, while keeping the pressure inside the reactor below 0.3 MPa. 34.22 kg of propylene oxide (590 mol, molar ratio of propylene oxide to ethanolamine 1.2:1) was added to the reactor in batches. After the addition was complete, the reaction was carried out at a controlled temperature for 3 hours, then cooled to 40°C. Then, 80.24 kg of the reaction product (ethanolamine hydrate AA3a) was discharged from the reactor. A sample was taken from the product, and gas chromatography analysis revealed that the content of isopropanolamine ethanolate in AA3a was 393.4 mol, and the content of diisopropanolamine ethanolate was 98.4 mol, with a molar ratio of diisopropanolamine ethanolate to isopropanolamine ethanolate of 0.25:1. The water content in AA3a was 20.2 wt%.

[0152] Then, 40 kg of the obtained amine hydrate AA3a was added to a high-pressure reactor. Carbon dioxide gas was introduced into the amine hydrate AA3a while controlling the pressure of the CO2 gas output from the CO2 storage cylinder to not exceed 0.3 MPa. The temperature was controlled between 40-50°C, and the reaction was carried out for 3 hours. After cooling to below 40°C, the pressure was released, and the product was discharged, yielding the carbonated amine salt composition AA3b. The CO2 absorption was 1.94 kg (approximately 44.1 mol, CO2 content was 4.625 wt%, and 35.9 mol% of the amine in AA3a was neutralized by CO2). The viscosity of product AA3b (at 25°C) was 694 centipoise. pH = 11.2.

[0153] Comparative Preparation Example 1 (Comparative)

[0154] A carbonate amine salt composition product with a higher CO2 content was obtained as a comparison.

[0155] 30 kg of the amine hydrate AA3a obtained in Preparation Example 3 was added to a high-pressure reactor. Carbon dioxide gas was introduced into the amine hydrate AA3a while maintaining the CO2 gas pressure from the CO2 storage cylinder at 0.3 MPa. The temperature was controlled between 40-50°C, and the reaction was carried out for 3 hours. After cooling to below 40°C, the pressure was released, and the product was discharged, yielding amine carbonate compound AA3c (or amine composition). The CO2 absorption was 3.003 kg (approximately 68.25 mol, CO2 content was 9.1 wt%, and approximately 74 mol% of the amine was neutralized by CO2). The viscosity (25°C) of product AA3c was 1753 centipoise. pH = 10.2.

[0156] In addition, 10 kg of the amine hydrate AA3a obtained in Preparation Example 3 was added to a high-pressure reactor. Carbon dioxide gas was introduced into the amine hydrate AA3a while controlling the pressure of the CO2 gas output from the CO2 storage cylinder to be no higher than 0.3 MPa. The temperature was controlled between 40-50°C, and the reaction was carried out for 3 hours. After cooling to below 40°C, the pressure was released, and the product was discharged, yielding the carbonate amine salt composition AA3d (or amine composition). The CO2 absorption was 869 g kg (approximately 19.75 mol, CO2 content was 8.0 wt%, and approximately 64 mol% of the amine was neutralized by CO2). The viscosity of product AA3b (at 25°C) was 1255 centipoise. pH = 10.5.

[0157] Preparation Example 4

[0158] 12.32 kg of ethanolamine (molecular weight 61, 202 mol), 21.24 kg of diethanolamine (molecular weight 105.136, 202 mol), and 15.06 kg of deionized water were added to a high-pressure reactor and stirred to dissolve. The reactor was then sealed, and the temperature was controlled between 60-95°C while continuously stirring. The pressure inside the reactor was controlled not to exceed 0.3 MPa. 23.44 kg of propylene oxide (molecular weight 58, 404 mol, with a molar ratio of propylene oxide to ethanolamine of 1:1) was added to the reactor in batches. After the addition was complete, the reaction was carried out at a controlled temperature for 3 hours, and then the temperature was lowered to 40°C. Then, 72.02 kg of the reaction product (alkanolamine hydrate AA4a) was discharged from the reactor. A sample was taken from the product, and gas chromatography analysis revealed that the content of ethanol isopropanolamine and isopropanol diethanolamine in AA4a was 202 mol, with a molar ratio of isopropanol diethanolamine to ethanol isopropanolamine of 1:1. The water content in AA4a was 20.8 wt%.

[0159] Then, 40 kg of the obtained amine hydrate AA4a was added to a high-pressure reactor. Carbon dioxide gas was introduced into the amine hydrate AA4a while controlling the pressure of the CO2 gas output from the CO2 storage cylinder to not exceed 0.3 MPa. The temperature was controlled between 40-50°C, and the reaction was carried out for 3 hours. After cooling to below 40°C, the pressure was released, and the product was discharged, yielding the carbonated amine salt composition AA4b. The CO2 absorption was 1.326 kg (approximately 30 mol, CO2 content was 3.208 wt%, and approximately 26.6 mol% of the amine was neutralized by CO2). The viscosity of product AA4b (at 25°C) was 546 centipoise. pH = 11.2.

[0160] Preparation Example 5

[0161] 12.32 kg of ethanolamine (molecular weight 61, 202 mol), 21.24 kg of diethanolamine (molecular weight 105.136, 202 mol), and 15.8 kg of deionized water were added to a high-pressure reactor and stirred to dissolve. The reactor was then sealed, and the temperature was controlled between 60-95°C and the pressure was controlled not to exceed 0.3 MPa while continuously stirring. 29.3 kg of propylene oxide (molecular weight 58, 505 mol, molar ratio of propylene oxide to ethanolamine is 1.25:1) was added to the reactor in batches. After the addition was complete, the reaction was carried out at a controlled temperature for 3 hours, and then the temperature was lowered to 40°C. Then, 78.6 kg of the reaction product (alkanolamine hydrate AA5a) was discharged from the reactor. A sample was taken from the product and gas chromatography was used to determine the content of ethanol isopropanolamine hydrate AA5a: 101 mol, ethanol diisopropanolamine hydrate 101 mol, and isopropanol diethanolamine hydrate 202 mol. The molar ratio of (ethanol diisopropanolamine + isopropanol diethanolamine) to ethanol isopropanolamine was 3:1. The water content in amine hydrate AA5a was 20 wt%.

[0162] Then, 40 kg of the obtained amine hydrate AA5a was added to a high-pressure reactor. Carbon dioxide gas was introduced into the amine hydrate AA5a while controlling the pressure of the CO2 gas output from the CO2 storage cylinder to not exceed 0.3 MPa. The temperature was controlled between 40-50°C, and the reaction was carried out for 3 hours. After cooling to below 40°C, the pressure was released, and the product was discharged, yielding the carbonated amine salt composition AA5b. The CO2 absorption was 1.06 kg (approximately 24 mol, CO2 content was 2.58 wt%, and approximately 23.3 mol% of the amine was neutralized by CO2). The viscosity of product AA5b (at 25°C) was 462 centipoise. pH = 11.0.

[0163] Preparation Example 6

[0164] Part 1: Preparation of Mono-alcoholic Amines

[0165] 1) Add 30.5 kg of ethanolamine (molecular weight 61,500 mol) and 15.56 kg of deionized water to a high-pressure reactor, stir to dissolve, seal the reactor, and then, while continuously stirring, control the temperature between 60-95℃ and the pressure not exceeding 0.3 MPa. Add 29 kg of propylene oxide (molecular weight 58,500 mol, molar ratio of propylene oxide to ethanolamine 1:1) to the reactor in batches. After the addition is complete, control the temperature and react for 3 hours, then cool to 40℃. Then, discharge 75 kg of the reaction product (ethanolamine hydrate AA6a) from the reactor. Gas chromatography analysis of the product revealed that the content of isopropanolamine ethanol in AA6a was 499.94 mol, and the content of diisopropanolamine ethanol was 0.06 mol. Its viscosity (at 25℃) was 276 centipoise. The water content in AA6a was 20.6 wt%. The pH value was 12.41.

[0166] 2) Add 30.5 kg of ethanolamine (molecular weight 61,500 mol) and 20.58 kg of deionized water to a high-pressure reactor, stir to dissolve, seal the reactor, and then, while continuously stirring, control the temperature between 60-95℃ and the pressure not exceeding 0.3 MPa. Add 58 kg of propylene oxide (1000 mol, molar ratio of propylene oxide to ethanolamine is 2:1) in batches to the reactor. After the addition is complete, control the temperature and react for 3 hours, then cool to 40℃. Then, discharge 109 kg of the reaction product (ethanolamine hydrate AA6b) from the reactor. A sample was taken from the product, and gas chromatography analysis showed that the content of diisopropanolamine ethanol in AA6b was 499.7 mol, and the content of isopropanolamine ethanol was 0.3 mol. Its viscosity (25℃) was 390 centipoise. The water content in AA6b was 18.8 wt%. The pH value was 11.72.

[0167] 3) Add 37.56 kg of isopropanolamine (molecular weight 75.11, 500 mol) and 22.52 kg of deionized water to a high-pressure reactor, stir to dissolve, seal the reactor, and then, while continuously stirring, control the temperature between 60-95℃ and the pressure not exceeding 0.3 MPa. Add 58 kg of propylene oxide (1000 mol, molar ratio of propylene oxide to isopropanolamine is 2:1) in batches to the reactor. After the addition is complete, control the temperature and react for 3 hours, then cool to 40℃. Then, discharge 118 kg of the reaction product (amine hydrate AA6c) from the reactor. Gas chromatography analysis of the product showed that the content of triisopropanolamine in amine hydrate AA6c was 499.9 mol, and the content of diisopropanolamine was 0.1 mol. The water content in amine hydrate AA6c was 19.0 wt%. The pH value was 11.57. It tends to crystallize when left at room temperature, therefore it should be used immediately after synthesis.

[0168] 4) Add 52.58 kg of diethanolamine (molecular weight 105.136, 500 mol) and 18.5 kg of deionized water to a high-pressure reactor, stir to dissolve, seal the reactor, and then, while continuously stirring, control the temperature between 60-95℃ and the pressure not exceeding 0.3 MPa. Add 29.02 kg of propylene oxide (500 mol, propylene oxide to ethanolamine molar ratio 1:1) to the reactor in batches. After the addition is complete, control the temperature and react for 3 hours, then cool to 40℃. Then, discharge 100.02 kg of the reaction product (ethanolamine hydrate AA6d) from the reactor. A sample was taken from the product, and gas chromatography determined that the isopropanol diethanolamine content in ethanolamine hydrate AA6d was approximately 500 mol. Its viscosity (25℃) was 338 centipoise. The water content in ethanolamine hydrate AA6d was 18.4 wt%. The pH value was 11.92.

[0169] Part Two: Blending of Multiple Alkylamines (Formulation Design)

[0170] 1) Product AA6b and product AA6a were mixed at a molar ratio of 4:1 for diisopropanolamine and isopropanolamine to obtain an alcoholamine composition product similar to product AA1a) in Preparation Example 1; then CO2 gas was introduced, and the CO2 content in the alcoholamine composition reached 1.29 wt%, based on the weight of the alcoholamine composition product. Its viscosity (25°C) is 439 centipoise.

[0171] 2) AA6b and AA6a were mixed in a 1:1 molar ratio of diisopropanolamine to isopropanolamine to obtain an alcoholamine composition product similar to product AA2a) in Preparation Example 2; then CO2 gas was introduced, and the CO2 content in the alcoholamine composition was 3.62 wt%. Its viscosity (25°C) was 633 centipoise.

[0172] 3) AA6b and AA6a were mixed at a molar ratio of 0.25:1 for diisopropanolamine ethanol and isopropanolamine ethanol to obtain an alcoholamine composition product similar to product AA3a) in Preparation Example 3; then CO2 gas was introduced, and the CO2 content in the alcoholamine composition was 4.63 wt%. Its viscosity (25°C) was 683 centipoise.

[0173] 4) AA6c and AA6a were mixed in a 1:1 molar ratio of triisopropanolamine to ethanol isopropanolamine to obtain an alcoholamine composition AA6-1; then CO2 gas was introduced, and the CO2 content in the alcoholamine composition was 3.67 wt%. Its viscosity (25℃) was 995 centipoise.

[0174] 5) AA6d and AA6a were mixed in a 1:1 molar ratio of isopropanol diethanolamine to ethanol isopropanolamine to obtain an alcoholamine composition AA6-2; then CO2 gas was introduced, and the CO2 content in the alcoholamine composition was 3.84 wt%. Its viscosity (25℃) was 586 centipoise.

[0175] 6) AA6d, AA6c, and AA6a were mixed in a molar ratio of 0.5:0.5:1 for isopropanol diethanolamine, triisopropanolamine, and ethanol isopropanolamine to obtain an alcoholamine composition AA6-3. CO2 gas was then introduced into the mixture, resulting in a CO2 content of 3.72 wt%. Its viscosity (at 25°C) was 702 centipoise.

[0176] Comparative Preparation Example 2 (Comparative)

[0177] The AA6b from Preparation Example 6 above was mixed with diethanolamine at a molar ratio of ethanol diisopropanolamine to diethanolamine of 2:1. Water was added to make the water content of the mixture 19.5 wt%, thus obtaining an aqueous amine composition. Then, CO2 gas was introduced into the amine composition, and the CO2 content reached 3.60 wt%. An amine composition that absorbs CO2 was obtained.

[0178] Preparation Example 7

[0179] Part 1: Preparation of Mono-alcoholamines

[0180] 1) Add 30.5 kg of ethanolamine (molecular weight 61,500 mol) and 15.5 kg of deionized water to a high-pressure reactor, stir to dissolve, seal the reactor, and then, while continuously stirring, control the temperature between 60-95℃ and the pressure not exceeding 0.25 MPa. Add 36.07 kg of 1,2-epoxybutane (molecular weight 72.11,500 mol) to the reactor in batches. After the addition is complete, control the temperature and react for 3.5 hours, then cool to 40℃. Then, discharge 82.01 kg of the reaction product (ethanolamine hydrate AA7a) from the reactor. Gas chromatography analysis of the product revealed that the content of ethanolamine hydrate AA7a was 499.94 mol of sec-butanolamine and 0.06 mol of di-sec-butanolamine. Its viscosity (25℃) was 372 centipoise. The water content in ethanolamine hydrate AA7a was 18.89 wt%. The pH value was 12.21.

[0181] 2) Add 30.5 kg of ethanolamine (molecular weight 61,500 mol) and 22.55 kg of deionized water to a high-pressure reactor, stir to dissolve, seal the reactor, and then, while continuously stirring, control the temperature between 60-95℃ and the pressure not exceeding 0.25 MPa. Add 72.12 kg of 1,2-epoxybutane (1000 mol) in batches to the reactor. After the addition is complete, control the temperature and react for 3.5 hours, then cool to 40℃. Then, discharge 125.02 kg of the reaction product (ethanolamine hydrate AA7b) from the reactor. Gas chromatography analysis of the product revealed that the content of di-sec-butanolamine in ethanolamine hydrate AA7b was 499.97 mol, and the content of sec-butanolamine was 0.03 mol. Its viscosity (25℃) was 464 centipoise. The water content in ethanolamine hydrate AA7b was 18.0 wt%. The pH value was 11.56.

[0182] 3) 37.56 kg of isopropanolamine (molecular weight 75.11, 500 mol) and 16.6 kg of deionized water were added to a high-pressure reactor, stirred to dissolve, and the reactor was sealed. Under continuous stirring, the temperature was controlled between 60-95℃, and the pressure was controlled not to exceed 0.25 MPa. 36.06 kg of 1,2-epoxybutane (500 mol, molar ratio of 1,2-epoxybutane to isopropanolamine is 1:1) was added to the reactor in batches. After the addition was complete, the reaction was carried out at a controlled temperature for 3 hours, and then cooled to 40℃. Then, 90.02 kg of the reaction product (amine hydrate AA7c) was discharged from the reactor. A sample was taken from the product, and gas chromatography analysis showed that the content of isopropanol sec-butanolamine in amine hydrate AA7c was 499.85 mol, and the content of isopropanol disec-butanolamine was 0.15 mol. Its viscosity (25℃) was 407 centipoise. The water content in the amine hydrate AA7c is 18.4 wt%. The pH value is 11.87.

[0183] 4) Add 37.56 kg of isopropanolamine (molecular weight 75.11, 500 mol) and 23.5 kg of deionized water to a high-pressure reactor, stir to dissolve, seal the reactor, and then, while continuously stirring, control the temperature between 60-95℃ and the pressure not exceeding 0.25 MPa. Add 72.11 kg of 1,2-epoxybutane (1000 mol, molar ratio of 1,2-epoxybutane to isopropanolamine is 2:1) in batches to the reactor. After the addition is complete, control the temperature and react for 3 hours, then cool to 40℃. Then, discharge 133 kg of the reaction product (alkanolamine hydrate AA7d) from the reactor. A sample was taken from the product, and gas chromatography determined that the content of isopropanol di-sec-butanolamine in AA7d was 499.87 mol, and the content of isopropanol sec-butanolamine was 0.13 mol. Its viscosity (25℃) is 519 centipoise. The water content in the amine hydrate AA7d is 17.6 wt%. The pH value is 11.12.

[0184] 5) Add 30.5 kg of ethanolamine (molecular weight 61,500 mol) and 15.7 kg of deionized water to a high-pressure reactor, stir to dissolve, seal the reactor, and then, while continuously stirring, control the temperature between 60-95℃ and the pressure not exceeding 0.25 MPa. Add 36.06 kg of 2,3-epoxybutane (molecular weight 72.11,500 mol, molar ratio of 2,3-epoxybutane to ethanolamine 1:1) in batches to the reactor. After the addition is complete, react at the controlled temperature for 3.5 hours, then cool to 40℃. Then, discharge 82.06 kg of the reaction product (ethanolamine hydrate AA7e) from the reactor. A sample was taken from the product, and gas chromatography determined that the ethanol (1,2-dimethylethanol) amine content in ethanolamine hydrate AA7e was approximately 500 mol. Its viscosity (25℃) was 423 centipoise. The water content in ethanolamine hydrate AA7e was 19.1 wt%. pH value = 12.13.

[0185] Part Two: Blending of Multiple Alkylamines (Formulation Design)

[0186] 1) Product AA7b and product AA7a were mixed at a molar ratio of 4:1 for di-sec-butanolamine and sec-butanolamine to obtain an alcoholamine composition AA7-1; then CO2 gas was introduced, and the CO2 content in the alcoholamine composition was 1.02 wt%, based on the weight of the alcoholamine composition product. Its viscosity (25°C) was 523 centipoise.

[0187] 2) AA7b and AA7a were mixed in a 1:1 molar ratio of di-sec-butanolamine to ethanol to obtain an alcoholamine composition AA7-2; then CO2 gas was introduced, and the CO2 content in the alcoholamine composition was 3.57 wt%. Its viscosity (25℃) was 658 centipoise.

[0188] 3) AA7b and AA6a were mixed in a 1:1 molar ratio of di-sec-butanolamine to isopropanolamine to obtain an alcoholamine composition AA7-3; then CO2 gas was introduced, and the CO2 content in the alcoholamine composition was 3.74 wt%. Its viscosity (25℃) was 641 centipoise.

[0189] 4) AA7b and AA7a were mixed at a molar ratio of 0.25:1 for di-sec-butanolamine and sec-butanolamine to obtain an alcoholamine composition AA7-4; then CO2 gas was introduced, and the CO2 content in the alcoholamine composition was 3.83 wt%. Its viscosity (25℃) was 608 centipoise.

[0190] 5) AA7d and AA6a were mixed in a 1:1 molar ratio of isopropanol disec-butanolamine to ethanol isopropanolamine to obtain an alcoholamine composition AA7-5; then CO2 gas was introduced, and the CO2 content in the alcoholamine composition was 3.61 wt%. Its viscosity (25℃) was 657 centipoise.

[0191] 6) AA7d and AA7c were mixed in a 1:1 molar ratio of isopropanol disec-butanolamine to isopropanol sec-butanolamine to obtain an alcoholamine composition AA7-6; then CO2 gas was introduced, and the CO2 content in the alcoholamine composition was 3.36 wt%. Its viscosity (25℃) was 648 centipoise.

[0192] 7) AA7b and AA7e were mixed at a molar ratio of 0.25:1 for di-sec-butanolamine and ethanol (1,2-dimethylethanol)amine to obtain an alcoholamine composition AA7-7; then CO2 gas was introduced, and the CO2 content in the alcoholamine composition was 3.13 wt%. Its viscosity (25°C) was 577 centipoise.

[0193] 8) AA6b, AA7b, and AA7a were mixed in a molar ratio of 0.5:0.5:1 for diisopropanolamine of ethanol, disec-butanolamine of ethanol, and sec-butanolamine of isopropanol to obtain an alcoholamine composition AA7-8; then CO2 gas was introduced, and the CO2 content in the alcoholamine composition was 2.89 wt%. Its viscosity (25°C) was 534 centipoise.

[0194] Preparation Example 8

[0195] 17.64 kg of 1,4-butanediamine (molecular weight 88.15, 200 mol) and 9.2 kg of deionized water were added to a high-pressure reactor, stirred to dissolve, and the reactor was sealed. Under continuous stirring, the temperature was controlled between 60-95°C, and the pressure was controlled not to exceed 0.3 MPa. 23.232 kg of propylene oxide (molecular weight 58.079, 400 mol) was added to the reactor in batches. After the addition was complete, the reaction was carried out at a controlled temperature for 3 hours, and then cooled to 40°C. Approximately 50 kg of the reaction product (alkanolamine hydrate AA3a) was then discharged from the reactor. The pH of the product was measured to be 13.46. A sample was taken from the product, and gas chromatography analysis revealed that the content of N,N,N'-tris(hydroxyisopropyl)-butanediamine in AA3a was approximately 0.02 mol, and the content of N,N'-di(hydroxyisopropyl)-butanediamine was approximately 199.98 mol. Its viscosity (25°C) is 324 centipoise. The water content in the alcoholamine hydrate AA3a, determined by Karl Fischer chromatography, is 18.4 wt%. A sample was taken from the obtained product for NMR spectroscopy analysis. 1 H-NMR showed Figure 12 . Figure 12 The results of Example 3 indicate that the product is N,N'-di(hydroxyisopropyl)-butanediamine. This demonstrates that the alkanolamine product obtained from the reaction of an organic amine with an epoxide depends on the molar ratio of the organic amine to the epoxide. This alkanolamine product can also be used as a component of a PU foaming agent.

[0196] Application Examples

[0197] Example 1

[0198] 1. Raw materials for the white component (190kg): Weigh out 42.4kg of polyether polyol A (YD-4110, hydroxyl value 460mgKOH / g, Hebei Yadong Chemical Group Co., Ltd.), 53kg of polyester polyol B (type 6320, hydroxyl value 320mgKOH / g, Jiangsu Fusheng Chemical Co., Ltd.), 10.6kg of polyether polyol C (YD-403, hydroxyl value 770mgKOH / g, Hebei Yadong Chemical Group Co., Ltd.), 2.12kg of foam stabilizer B-8545 (Evonik Specialty Chemicals (Shanghai) Co., Ltd.), and catalyst (Evonik Specialty Chemicals (Shanghai) Co., Ltd.). (A mixed catalyst consisting of pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, potassium acetate, triethylenediamine, and dibutyltin dilaurate, in amounts of 2.12 kg, 3.18 kg, 2.12 kg, 2.12 kg, and 0.424 kg, respectively); 27.56 kg of flame retardant TCPP (Qingdao Lianmei Chemical Co., Ltd.); 21 kg of the carbonate amine salt composition AA1b from Preparation Example 1 (wherein the molar ratio of triethanolamine A2 to diethanolamine A1 is 4:1, and the CO2 content is 1.088 wt%); and 21 kg of physical foaming agent HCFC-141b (Zhejiang Sanmei Chemical Co., Ltd.).

[0199] 2. Weigh out the polyether polyol A, polyester polyol B, polyether polyol C, foam stabilizer, carbonate amine salt composition AA1b, physical foaming agent HCFC-141B, catalyst, flame retardant, and additives, and add them to the reaction vessel in sequence. Stir slowly (180 rpm) at room temperature for 1-2 hours to ensure complete mixing and obtain a uniform and transparent mixture.

[0200] 3. Black component B is polymethyl polyphenyl polyisocyanate (PM200, Wanhua Chemical), with a dosage of 220 kg.

[0201] 4. White component A and black component B are sprayed onto the cement board (substrate) using a Graco A-25 sprayer. Each layer of foam is 2-3 cm thick, with a total foam thickness of 20 cm. After the foam has cured and set, rigid polyurethane foam material is obtained. The performance parameters of the obtained foam product are listed in Table 1. SEM images of the foam material are shown below. Figure 1 The foam cells are very uniform in size.

[0202] Example 2

[0203] Example 1 was repeated, except that the same amount of the alkanolamine composition AA2b (where the molar ratio of A2 to A1 is 1:1 and the CO2 content is 3.61 wt%) from Example 2 was used instead of the carbonate alkanolamine salt composition AA1b to prepare a rigid polyurethane foam material. SEM images of the foam material are shown below. Figure 2The cell size is very uniform.

[0204] Example 3

[0205] Example 1 was repeated, except that the same amount of the alkanolamine composition AA3b (A2 to A1 molar ratio of 0.25:1 and CO2 content of 4.625 wt%) from Preparation Example 3 was used instead of the carbonate alkanolamine salt composition AA1b to prepare a rigid polyurethane foam material. SEM images of the foam material are shown below. Figure 3 .

[0206] Example 4

[0207] Example 1 was repeated, except that the same amount of the alkanolamine composition AA4b (A2 to A1 molar ratio of 1:1 and CO2 content of 3.208 wt%) from Preparation Example 4 was used instead of the carbonate alkanolamine salt composition AA1b to prepare a rigid polyurethane foam material. SEM images of the foam material are shown below. Figure 4 The cell size is uniform.

[0208] Example 5

[0209] Example 1 was repeated, except that the same amount of the alkanolamine composition AA5b (A2 to A1 molar ratio of 3:1 and CO2 content of 2.58 wt%) from Preparation Example 5 was used instead of the carbonate alkanolamine salt composition AA1b to prepare a rigid polyurethane foam material. SEM images of the foam material are shown below. Figure 5 The foam cells are of uniform size.

[0210] Example 6

[0211] Example 1 was repeated, except that the same amount of the alkanolamine composition AA6-1 (a molar ratio of triisopropanolamine to ethanol isopropanolamine of 1:1 and a CO2 content of 3.67 wt%) from Preparation Example 6 was used instead of the carbonate alkanolamine salt composition AA1b to prepare a rigid polyurethane foam material. SEM images of the foam material are shown below. Figure 6 .

[0212] The resulting foam has a relatively uniform cell size (i.e., moderately uniform), and a relatively large cell diameter (237 μm). These results are due to the high viscosity of the alkanolamine composition AA6-1.

[0213] Example 7

[0214] Example 1 was repeated, except that the same amount of the alkanolamine composition AA6-3 (A2 to A1 molar ratio of 1:1 and CO2 content of 3.72 wt%) from Preparation Example 6 was used instead of the carbonate alkanolamine salt composition AA1b to prepare a rigid polyurethane foam material. SEM images of the foam (not shown) show that the foam has uniform cell size and a relatively small average cell diameter (221 μm).

[0215] Example 8

[0216] Example 1 was repeated, except that the same amount of the alkanolamine composition AA5b (A2 to A1 molar ratio of 3:1 and CO2 content of 2.58 wt%) from Preparation Example 5 was used instead of the carbonate alkanolamine salt composition AA1b, and the same amount of HFC-245fa was used instead of HCFC-141b to prepare a rigid polyurethane foam material. SEM images of the foam (not shown) show that the foam has uniform cell size and a relatively small average cell diameter (217 μm).

[0217] Example 9

[0218] Example 1 was repeated, except that the same amount of the alkanolamine composition AA7-3 (A2 to A1 molar ratio of 1:1 and CO2 content of 3.74 wt%) from Preparation Example 7 was used instead of the carbonate alkanolamine salt composition AA1b to prepare a rigid polyurethane foam material. SEM images of the foam (not shown) show that the foam has uniform cell size and a relatively small average cell diameter (219 μm).

[0219] Example 10

[0220] Example 1 was repeated, except that the same amount of the alkanolamine composition AA7-4 (A2 to A1 molar ratio of 0.25:1 and CO2 content of 3.83 wt%) from Preparation Example 7 was used instead of the carbonate alkanolamine salt composition AA1b to prepare a rigid polyurethane foam material. The foam cell size was uniform.

[0221] The SEM image of the foam (not shown) shows that the foam has a uniform cell size and a small average cell diameter (223 μm).

[0222] Example 11

[0223] Example 1 was repeated, except that the same amount of the alkanolamine composition AA2a (A2 to A1 molar ratio of 1:1, CO2 content of 0 wt%) from Example 2 was used instead of the carbonate alkanolamine salt composition AA1b, and 22.9 kg of HFC-245fa was used instead of HCFC-141b. Additionally, the amount of black component B (polymethyl polyphenyl polyisocyanate) was 230 kg, resulting in a rigid polyurethane foam material. SEM images of the foam material are shown below. Figure 7 The foam has a uniform cell size, but the average cell size is relatively large (245 μm) and the density is slightly higher.

[0224] Example 12

[0225] Example 1 was repeated, except that the same amount of the amine composition AA1a (or amine hydrate AA1a, wherein the molar ratio of diisopropanolamine to isopropanolamine is 4:1 and the CO2 content is 0 wt%) from Example 1 was used instead of the carbonate amine salt composition AA1b, and 22.3 kg of LBA was used instead of HCFC-141b. Additionally, the amount of black component B (polymethyl polyphenyl polyisocyanate) was 230 kg, resulting in a rigid polyurethane foam material. SEM images of the foam (not shown) show that the foam has a uniform cell size, with an average cell size of 235 μm.

[0226] Example 13

[0227] Example 1 was repeated, except that the same amount of the amine composition AA3a (or amine hydrate AA3a, wherein the molar ratio of diisopropanolamine ethanol to isopropanolamine ethanol is 0.25:1, and the CO2 content is 0 wt%) from Example 3 was used instead of the amine carbonate composition AA1b, and 22.3 kg of LBA was used instead of HCFC-141b. Additionally, the amount of black component B (polymethyl polyphenyl polyisocyanate) was 230 kg, resulting in a rigid polyurethane foam material. The performance parameters of the foam product are listed in Table 1. SEM images of the foam (not shown) show that the foam cell size is uniform, and the average cell size is 231 μm.

[0228] The results in Examples 11-13 show that CO2-free alkanolamine compositions or alkanolamine hydrates can also be used as components of a blowing agent for the preparation of rigid polyurethane foams, but this consumes more polyisocyanate.

[0229] Comparative Example 1

[0230] Example 1 was repeated, except that the same amount of the alkanolamine composition AA3c (molar ratio of diisopropanolamine to isopropanolamine of ethanol is 0.25:1, CO2 content is 9.1 wt%, and water content is 20 wt%) from Comparative Preparation Example 1 was used instead of the carbonate alkanolamine salt composition AA1b to prepare a rigid polyurethane foam material.

[0231] During the application of white component A and black component B onto a cement board (substrate) using a Graco A-25 sprayer, it was observed that the foam expanded rapidly. When the cured polyurethane foam on the cement board (substrate) was cut open with an electric saw, the cross-section revealed that the cured foam cracked from the substrate, and cracks also formed between adjacent foam layers. Figure 8 As shown in the figure. This indicates that if the CO2 content in the carbonate amine salt composition is too high (e.g., above 9 wt%), the resulting foam will experience severe cracking.

[0232] Comparative Example 2

[0233] Example 1 was repeated, except that 20 kg of the CO2-absorbing amine composition obtained in Comparative Preparation Example 2 (in which the molar ratio of diisopropanolamine to diethanolamine was 2:1 and the CO2 content was 3.60 wt%) and 20 kg of physical foaming agent HCFC-141b were used as foaming agents.

[0234] During the application of white component A and black component B onto a cement board (substrate) using a Graco A-25 sprayer, rapid foam expansion was observed. Upon cutting open the cured polyurethane foam on the cement board (substrate) and observing the cross-section, it was found that the cured foam cracked from the substrate, forming fissures, and also cracked between adjacent foam layers. Figure 9 As shown in the figure, although the molar amount of diethanolamine is only 33.3% (i.e., 1 / 3) of the total molar amount of all alcoholamine compounds (i.e., diisopropanolamine + diethanolamine), the resulting foam still exhibited slight cracking. This indicates that diethanolamine has high alkalinity and high reactivity with polyisocyanates, which affects the catalytic activity of the polyurethane catalyst in the white component.

[0235] Comparative Example 3

[0236] Example 1 was repeated, except that 2 kg of water and 38 kg of physical foaming agent HCFC-141b were used as foaming agents and 240 kg of polymethyl polyphenyl polyisocyanate was used.

[0237] The obtained SEM images of the foam are shown in Figure 10The average cell diameter of the foam is 352 micrometers. The cell size of the foam is highly uneven, and there are oversized cells within the foam. Slightly increasing the amount of polyisocyanate results in a higher foam density, but the strength does not increase accordingly.

[0238] Table 1 - Performance parameters of foam materials

[0239]

[0240] Note: Compressive strength is measured for the foam sample in the Z direction (perpendicular to the substrate), and "cracking" refers to the cured foam cracking from the substrate or between two adjacent foam layers. "Slightly uniform" means that the cell size is moderately uniform.

[0241] Example 14 (Preparation of castable rigid PU foam)

[0242] 1. Components used and their relative dosages:

[0243] Foaming agent: 8 parts by weight of the carbonate amine salt composition AA3c prepared in Comparative Preparation Example 1 above (in which the molar ratio of diisopropanolamine ethanol to isopropanolamine ethanol is 0.25:1, the CO2 content is 9.1 wt%, and the water content is 20 wt%) and 18 parts by weight of cyclopentane (CP). The amine composition AA3c is used as a chemical foaming agent (CFA).

[0244] Dry white liquor: It consists of the following components: 40 parts by weight of polyether polyol SD-7100 (toluene diamine type polyoxypropylene polyol, produced by Shanghai Dongda Chemical Co., Ltd.), 20 parts by weight of polyether polyol SA-460 (sorbitol initiator polyoxypropylene polyol, produced by Zibo Nolly Chemical Co., Ltd.). The following are listed as ingredients: 10 parts by weight of aromatic polyester polyol PS-4051 (PET polyol, produced by Nanjing Jinling Stepan Chemical Co., Ltd.), 20 parts by weight of polyether polyol YD-8260 (polyoxypropylene polyol with sucrose and diethylene glycol as initiators, produced by Hebei Yadong Chemical Trading Co., Ltd.), 10 parts by weight of polyether polyol YD-403 (ethylenediamine initiator polyoxypropylene polyol, produced by Hebei Yadong Chemical Trading Co., Ltd.), 3.2 parts by weight of foam stabilizer 8841 (silicone oil, produced by Shanghai Maihao Chemical Technology Co., Ltd.), 0.2 parts by weight of N,N,N,N,N-pentamethyldiethylenetriamine (code name PC-5, produced by Evonik Degussa, Inc.), 0.6 parts by weight of amine catalyst BX-405 (produced by Evonik Degussa, Inc.), and 1 part by weight of tris(dimethylaminopropyl)hexahydrotriazine (code name PC-41, produced by Evonik Degussa, Inc.).

[0245] Black material: 156 parts of polyisocyanate MDI (PM200, Yantai Wanhua Chemical Group Co., Ltd.) as black material.

[0246] Observation on the transparency and compatibility of the white material: The above foaming agent and dry white material were mixed under stirring to obtain a transparent white material, indicating that the foaming agent and the dry white material (polymer polyol) have good compatibility.

[0247] Observation of stratification: The white material was obtained by mixing dry white material and all foaming agent under stirring. The white material was then centrifuged (4500 rpm, 5 minutes) to quickly defoam. The material was then observed to see if there was stratification (i.e., whether there was a thin layer of material at the bottom). The result was that no stratification was found in the white material after centrifugation and defoaming treatment.

[0248] 2. Foaming reaction process:

[0249] Using the same formulation (or composition) as described above, foaming was performed using a high-pressure casting foaming machine (RSC16 / 16, KraussMaffei, Germany). The foaming agent, dry white component, and black component were fed into the casting foaming machine via their respective material pipelines for stirring and mixing. The mixed foaming material was then poured into the Laneige mold through a spray gun for foaming. The specific operation was as follows: First, the initial pouring amount of foaming material was set to 200g. This set amount of foaming material was then poured into a plastic bag through a spray gun for free foaming. The foaming time was measured to be 6 seconds and the nozzle stringing time to be 42 seconds. Then, based on the volume of the Laneige mold, the corresponding amount of foaming material was poured into the mold for foaming. After 180 seconds, the mold was opened (i.e., the inner and outer clamping molds were opened). Foam samples were taken for analysis of the foam's microstructure and thermal insulation properties. Samples were taken from the foam product for SEM analysis. SEM images of the foam are shown below. Figure 11 .

[0250] The SEM images clearly show that there are a large number of cells per unit area, the average pore diameter of the foam sample is small (201 μm), and the pore size is relatively uniform.

[0251] The foaming initiation time was measured to be 6 seconds, and the fiber drawing time was 42 seconds. These initiation and fiber drawing times are consistent with the time ranges in industrial refrigerator production lines (the initiation time for foaming reaction systems in refrigerator or freezer production is generally required to be 6-7 seconds, and the fiber drawing time is required to be 41-55 seconds, preferably 45-50 seconds). Therefore, this foaming system is also suitable for refrigerator foam production.

[0252] Example 15

[0253] Example 14 was repeated, except that the foaming agent consisted of the following components: 8 parts by weight of the carbonate amine salt composition AA3d prepared in Comparative Preparation Example 1 above (in which the molar ratio of diisopropanolamine to isopropanolamine is 0.25:1, the CO2 content is 8.0 wt%, and the water content is 20 wt%) and 18 parts by weight of cyclopentane. The amine composition AA3d was used as a chemical foaming agent (CFA). The resulting rigid foam had an average cell diameter of 219 μm and the cell size was relatively uniform.

[0254] Example 16

[0255] Example 14 was repeated, except that the foaming agent consisted of the following components: 5 parts by weight of the carbonate amine salt composition AA4b prepared in Example 4 above (wherein the molar ratio of diisopropanolamine to isopropanolamine is 1:1, the CO2 content is 3.2 wt%, and the water content is 20 wt%), 3 parts by weight of HFC-245fa, and 17 parts by weight of cyclopentane. The amine composition AA4b served as a chemical foaming agent (CFA). The resulting rigid foam had an average cell diameter of 226 μm and relatively uniform cell size.

[0256] Example 17

[0257] Example 14 was repeated, except that the foaming agent consisted of the following components: 8 parts by weight of the carbonate amine salt composition AA4b prepared in Example 4 above (wherein the molar ratio of diisopropanolamine to isopropanolamine is 1:1, the CO2 content is 3.2 wt%, and the water content is 20 wt%) and 18 parts by weight of cyclopentane. The amine composition AA4b served as a chemical foaming agent (CFA). The resulting rigid foam had an average cell diameter of 221 μm and relatively uniform cell size.

[0258] Table 2 - Foaming Composition and Performance Parameters

[0259]

[0260]

[0261] Note 1: In the table, CFA refers to high-water-content carbonated organic alcohol amine salt foaming agent; the λ value (or K factor) is determined according to GB / T10295-2008, and the foam size is 20*20*2.5cm. The "expansion rate (180s)" in the table refers to the expansion rate measured after opening the Laneige mold 180 seconds (3 minutes) from the start of filling the mold.

[0262] Note 2: The Lance mold size is 1600*300*80mm. The entire foam is divided into two equal parts (left and right sides) along its long side. For each part, a density point (density measurement point) is taken every 20cm from bottom to top, for a total of 16 density points on both sides. The difference between the highest and lowest density values ​​is taken as the density range. The average density of these 16 density points is the average density.

[0263] Note 3: The flow index (cm / g) is determined as follows: A polyethylene (PE) hose with a diameter of approximately 10 cm and a length of 1.8 m is clamped at one end, while the other end (as the upper port) is opened. The foaming agent is poured into the upper part of the hose, and then the upper port is sealed. The hose is then inverted, and the foam rises along the hose. The foam height H (cm) in the hose and the foam mass m (g) in the hose are measured, and the ratio H / m represents the flow index.

[0264] As can be seen from Table 2 above, the alkanolamine composition (AC) of the present invention, when used as a chemical foaming agent in combination with cyclopentane, produces a rigid polyurethane foam material with excellent overall performance, low thermal conductivity, and good thermal insulation properties.

Claims

1. An aqueous alkanolamine composition, the alkanolamine composition (AC) comprising the following components: (1) Secondary amine type asymmetric diolamine (A1) having 5-7 carbon atoms, which is selected from one, two or three of ethanol isopropanolamine, ethanol butanolamine and isopropanol butanolamine; (2) Possesses the general formula NR 1 R 2 R 3 Tertiary amine type C7-C11 triolamine (A2), in which R 1 R 2 and R 3 Each is independently an ethanol group, an isopropanol group, or a butanol group, wherein the butanol group is a sec-butanol group, a 1,2-dimethylethanol group, or a combination of both; (3) Water; in, The molar ratio of (A2) to (A1) is (0.1-9):1; The water content is 5-45 wt%, based on the total weight of the alcoholamine composition (AC); and The total content of (A1)+(A2)+water is 70-100wt%, based on the total weight of the alcoholamine composition (AC). In this composition, a portion of the alkanolamine in the alkanolamine composition (AC) is neutralized by CO2, such that the CO2 content in the alkanolamine composition (AC) is 1-6 wt%.

2. The alkanolamine composition according to claim 1, wherein, The molar ratio of (A2) to (A1) is (0.15-8.5):1; The water content is 5-42 wt%, based on the total weight of the alkanolamine composition (AC); and The total content of (A1)+(A2)+water is 72-99.9%, based on the total weight of the alcoholamine composition (AC).

3. The alkanolamine composition according to claim 2, wherein, The molar ratio of (A2) to (A1) is (0.2-8):1; The water content is 5-40 wt%, based on the total weight of the alcoholamine composition (AC); and The total content of (A1)+(A2)+water is 73-99.5%, based on the total weight of the alcoholamine composition (AC).

4. The alkanolamine composition according to claim 3, wherein, The molar ratio of (A2) to (A1) is (0.5-6.5): 1; The water content is 6-39 wt%, based on the total weight of the alcoholamine composition (AC); and The total content of (A1)+(A2)+water is 74-99%, based on the total weight of the alcoholamine composition (AC).

5. The alkanolamine composition according to claim 4, wherein, The molar ratio of (A2) to (A1) is (0.9-4.5):1; The water content is 7-38 wt%, based on the total weight of the alkanolamine composition (AC); and The total content of (A1)+(A2)+water is 75-98%, based on the total weight of the alcoholamine composition (AC).

6. The alkanolamine composition according to claim 5, wherein, The molar ratio of (A2) to (A1) is (1-4):1; The water content is 9-35 wt%, based on the total weight of the alkanolamine composition (AC); and The total content of (A1)+(A2)+water is 76-97%, based on the total weight of the alcoholamine composition (AC).

7. The alkanolamine composition according to claim 6, wherein, The molar ratio of (A2) to (A1) is (1.5-3.5):1; The water content is 10-33 wt%, based on the total weight of the alkanolamine composition (AC); and The total content of (A1)+(A2)+water is 77-96%, based on the total weight of the alcoholamine composition (AC).

8. The alkanolamine composition according to claim 7, wherein, The molar ratio of (A2) to (A1) is (1.8-3.2):1; The water content is 12-25 wt%, based on the total weight of the alkanolamine composition (AC); and The total content of (A1)+(A2)+water is 78-95%, based on the total weight of the alcoholamine composition (AC).

9. The alkanolamine composition according to claim 8, wherein, The molar ratio of (A2) to (A1) is (2-3):1; The water content is 15-22 wt%, based on the total weight of the alcoholamine composition (AC); and The total content of (A1)+(A2)+water is 80-94%, based on the total weight of the alcoholamine composition (AC).

10. The alkanolamine composition according to claim 1, wherein, In C7-C11 triolamines (A2) with 7-11 carbon atoms, R 1 Unlike R 2 and R 3 , and R 2 and R 3 Are the same or different; and / or At the stated water content and at ambient temperature, the contents of both the asymmetric diolamine (A1) and the asymmetric triolamine (A2) should such that the aqueous alcoholamine composition (AC) is in a liquid state, or a homogeneous liquid state; and / or At an ambient temperature of 25°C, the aqueous alkanolamine composition (AC) is a homogeneous liquid with a viscosity of 200-1000 centipoise at 25°C; and / or The total mol% of the asymmetric triolamine in the asymmetric diolamine (A1) + triolamine (A2) is 10-100 mol%, and the corresponding mol% of the symmetric triolamine, i.e., triisopropanolamine, in the triolamine (A2) is 0-90 mol%, based on the total molar amount of the secondary amine type asymmetric diolamine (A1) and the tertiary amine type triolamine (A2).

11. The alkanolamine composition according to claim 10, wherein, The total mol% of the asymmetric triolamine in the asymmetric diolamine (A1) + triolamine (A2) is 15-100 mol%, and the corresponding mol% of the symmetric triolamine, i.e., triisopropanolamine, in the triolamine (A2) is 0-85 mol%, based on the total molar amount of the secondary amine type asymmetric diolamine (A1) and the tertiary amine type triolamine (A2).

12. The alkanolamine composition according to claim 11, wherein, The total mol% of the asymmetric triolamine in the asymmetric diolamine (A1) + triolamine (A2) is 20-100 mol%, and the corresponding mol% of the symmetric triolamine, i.e., triisopropanolamine, in the triolamine (A2) is 0-80 mol%, based on the total molar amount of the secondary amine type asymmetric diolamine (A1) and the tertiary amine type triolamine (A2).

13. The alkanolamine composition according to claim 12, wherein, The total mol% of the asymmetric triolamine in the asymmetric diolamine (A1) + triolamine (A2) is 25-100 mol%, and the corresponding mol% of the symmetric triolamine, i.e., triisopropanolamine, in the triolamine (A2) is 0-75 mol%, based on the total molar amount of the secondary amine type asymmetric diolamine (A1) and the tertiary amine type triolamine (A2).

14. The alkanolamine composition according to claim 13, wherein, The total mol% of the asymmetric triolamine in the asymmetric diolamine (A1) + triolamine (A2) is 30-100 mol%, and the corresponding mol% of the symmetric triolamine, i.e., triisopropanolamine, in the triolamine (A2) is 0-70 mol%, based on the total molar amount of the secondary amine type asymmetric diolamine (A1) and the tertiary amine type triolamine (A2).

15. The alkanolamine composition according to claim 14, wherein, The total mol% of the asymmetric triolamine in the asymmetric diolamine (A1) + triolamine (A2) is 35-100 mol%, and the corresponding mol% of the symmetric triolamine, i.e., triisopropanolamine, in the triolamine (A2) is 0-65 mol%, based on the total molar amount of the secondary amine type asymmetric diolamine (A1) and the tertiary amine type triolamine (A2).

16. The alkanolamine composition according to any one of claims 1-10, wherein, The tertiary amine type triolamine (A2) is selected from one or more of ethanol diisopropanolamine, isopropanol diethanolamine, ethanol dibutanolamine, butanol diethanolamine, isopropanol dibutanolamine, butanol diisopropanolamine and ethanol isopropanol butanolamine.

17. The alkanolamine composition according to claim 1, wherein, A portion of the alkanolamine in the alkanolamine composition (AC) is neutralized by CO2, such that the CO2 content in the alkanolamine composition (AC) is 1.2-6 wt%, based on the total weight of the alkanolamine composition (AC).

18. The alkanolamine composition according to claim 17, wherein, A portion of the alkanolamine in the alkanolamine composition (AC) is neutralized by CO2, such that the CO2 content in the alkanolamine composition (AC) is 1.5-6 wt%, based on the total weight of the alkanolamine composition (AC).

19. The alkanolamine composition according to claim 18, wherein, A portion of the alkanolamine in the alkanolamine composition (AC) is neutralized by CO2, such that the CO2 content in the alkanolamine composition (AC) is 1.8-5.8 wt%, based on the total weight of the alkanolamine composition (AC).

20. The alkanolamine composition according to claim 19, wherein, A portion of the alkanolamine in the alkanolamine composition (AC) is neutralized by CO2, such that the CO2 content in the alkanolamine composition (AC) is 2-5 wt%, based on the total weight of the alkanolamine composition (AC).

21. The alkanolamine composition according to any one of claims 1-10, wherein, Asymmetric diolamines (A1) are selected from one or both of ethanolisopropanolamine and ethanolbutanolamine; and The tertiary amine type triolamine (A2) is selected from one or more of ethanol diisopropanolamine, isopropanol diethanolamine, ethanol dibutanolamine, butanol diethanolamine and ethanol isopropanol butanolamine.

22. A method for preparing the amine composition according to any one of claims 1-21, the method comprising: 1) Preparation of the alcoholamine composition (AC): 1a) Ethanolamine, or a mixture of isopropanolamine and ethanolamine, as the starting material for an alcoholamine, is reacted with an epoxide (1) in the presence of water to obtain an alcoholamine composition (AC) containing a tertiary amine triolamine (A2) and a secondary amine asymmetric diolamine (A1), wherein the epoxide (1) is selected from one or more of propylene oxide, 1,2-epoxybutane, and 2,3-epoxybutane; or, 1b) isopropanolamine, as the starting material for an alcoholamine, is reacted with an epoxide (2) in the presence of water to obtain an alcoholamine composition (AC) containing a tertiary amine triolamine (A2) and a secondary amine asymmetric diolamine (A1), wherein the epoxide (2) is selected from one or more of ethylene oxide, 1,2-epoxybutane, and 2,3-epoxybutane; wherein the molar ratio of the epoxide to the alcoholamine in the alcoholamine starting material is (1.2-1.9):1; 2) Optionally, an additional tertiary amine triolamine (A2) and an additional secondary amine asymmetric diolamine (A1) are added to the obtained amine composition (AC) to obtain the amine composition (AC), wherein the added tertiary amine triolamine (A2) is selected from one, two, or three of ethanol diisopropanolamine, triisopropanolamine, isopropanol diethanolamine, ethanol dibutanolamine, isopropanol dibutanolamine, butanol diethanolamine, or butanol diisopropanol; and the added secondary amine asymmetric diolamine (A1) is selected from one, two, or more of ethanol isopropanolamine, ethanol butanolamine, or isopropanol butanolamine. The total amount of water used in step 1) and optionally step 2) should result in a water content of 5-45 wt% in the obtained amine composition (AC). The method further includes the step of: passing CO2 gas into the obtained alkanolamine composition (AC) to partially neutralize the alkanolamine compound in the composition (AC), thereby obtaining an alkanolamine composition (AC) containing CO2; The amount of CO2 introduced should be such that the CO2 content in the alcoholamine composition (AC) is 1-6 wt%, based on the total weight of the alcoholamine composition (AC).

23. The method according to claim 22, wherein, The amounts of components (A1) and (A2) added should be such that the molar ratio of triolamine (A2) to asymmetric diolamine (A1) in the resulting composition (AC) is (0.1-9):

1.

24. A method for preparing the amine composition according to any one of claims 1-21, the method comprising: 1) Preparation of secondary amine diolamine: Ethanolamine is reacted with propylene oxide, ethanolamine with 1,2-epoxybutane, ethanolamine with 2,3-epoxybutane, isopropanol with 1,2-epoxybutane, or isopropanol with 2,3-epoxybutane in the presence of water at a molar ratio of (0.95-1.05):1 to obtain secondary amine diolamine (A1); 2) Preparation of tertiary amine triolamines: Ethanolamine is reacted with propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, isopropanol with 1,2-epoxybutane, isopropanol with 2,3-epoxybutane, or isopropanolamine with propylene oxide in a molar ratio of 1:(1.9-2.1) in the presence of water to obtain tertiary amine triolamine (A2); or, diethanolamine is reacted with propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, diisopropanol with 1,2-epoxybutane, diisopropanol with 2,3-epoxybutane, ethanolisopropanol with 1,2-epoxybutane, ethanolisopropanol with 2,3-epoxybutane, or diisopropanolamine with propylene oxide in a molar ratio of (0.95-1.05): The reaction is carried out in the presence of water at a molar ratio of 1 to obtain a tertiary amine triolamine (A2). 3) Preparation of the amine composition (AC): The product of step 1) and the product of step 2) are mixed, wherein the amount of tertiary amine triolamine and secondary amine diolamine should be such that the content of each component in the composition (AC) is as defined in claim 1, or the molar ratio of tertiary amine triolamine to secondary amine diolamine is (0.1-9): 1, thereby obtaining the amine composition (AC); 4) Optionally, an additional tertiary amine triolamine (A2) and an additional secondary amine asymmetric diolamine (A1) are added to the obtained amine composition (AC) to obtain an amine composition (AC) wherein the added tertiary amine triolamine (A2) is selected from one, two, or three of ethanol diisopropanolamine, triisopropanolamine, isopropanol diethanolamine, ethanol dibutanolamine, isopropanol dibutanolamine, butanol diethanolamine, or butanol diisopropanol; the added secondary amine asymmetric diolamine A1 is selected from one, two, or more of ethanol isopropanolamine, ethanol butanolamine, or isopropanol butanolamine, and the amounts of components (A1) and (A2) added should be such that the molar ratio of triolamine (A2) to asymmetric diolamine (A1) in the obtained composition (AC) is (0.1-9): 1; and The total amount of water used in steps 1), 2), 3), and optionally 4) should result in a water content of 5-45 wt% in the obtained amine composition (AC). In the obtained alkanolamine composition (AC), the total content of (A1) + (A2) + water is 70-100 wt%, based on the total weight of the alkanolamine composition (AC). The method also includes the following steps: CO2 gas was introduced into the obtained alkanolamine composition (AC) to partially neutralize the alkanolamine compounds in the composition (AC), thereby obtaining an alkanolamine composition (AC) containing CO2; The amount of CO2 introduced should be such that the CO2 content in the alcoholamine composition (AC) is 1-6 wt%, based on the total weight of the alcoholamine composition (AC).

25. Use of the alkanolamine composition (AC) according to any one of claims 1-21 as a component of a blowing agent in the preparation of sprayable rigid polyurethane foam.

26. A polyurethane foaming agent composition (FC) comprising the following components: (1) The alcoholamine composition (AC) according to any one of claims 1-21, (2) Hydrofluorocarbon physical blowing agents (F1) with boiling points in the range of 15-41℃; and (3) Optional, water (F2); in, The physical blowing agent (F1) is selected from one or more of HCFC-141b, HFC-245fa, HFC-365mfc, LBA and hexafluorobutene; Wherein: the weight ratio of the alkanolamine composition (AC) to the weight of the physical blowing agent (F1) is 0.2-5 : 1; and / or The sum of the weights of components (1), (2) and optional component (3) is 80-100 wt% based on the total weight of the polyurethane foaming agent composition (FC).

27. A white component for polyurethane foaming, comprising: (1) A dry white polyurethane foam comprising a polymeric polyol and other additives besides a blowing agent, wherein the other additives include a polyurethane catalyst, a foam stabilizer, and optionally a flame retardant, optional chain extender, and optional crosslinking agent; and (2) the polyurethane blowing agent composition (FC) according to claim 26. The amount of foaming agent used is 22-30 parts by weight, relative to 95-106 parts by weight of dry white material for polyurethane foaming.

28. The white component for polyurethane foam according to claim 27, wherein, The polymer polyols in the dry white material include 8-72 wt% aromatic / semi-aromatic polyester polyols and / or toluene diamine-type polyoxypropylene polyols and 92-28 wt% non-toluene diamine-type polyoxypropylene polyols.

Images