Alcohol amine carbonate salts derived from c4-c6 alkanediamines and blowing agent compositions

Abstract

Disclosed are carbonates of di- and tri-ol amines derived from C4-C6 alkanediamines, and blowing agent compositions comprising the carbonates and C5 alkanes, wherein the C4-C6 alkanediamines include butanediamine, pentanediamine, and hexanediamine. The blowing agent compositions are suitable for use in the production of cast polyurethane rigid foams in the commercial production of refrigerators and freezers.

Description

TECHNICAL FIELD

[0001] The present invention relates to an alcohol amine composition derived from C4-C6 alkanediamine, and a polyurethane blowing agent composition containing it, belonging to the field of blowing agents for polyurethane rigid foam. BACKGROUND

[0002] Polyurethane rigid foam is a high quality thermal insulation material, widely used in the industry of refrigerator, freezer, water heater, cold chain insulation, etc. In order to meet the environmental protection requirements, water and cyclopentane are often used as blowing agents in the production of polyurethane foam in these industries. Since the thermal conductivity of cyclopentane is relatively high, the thermal conductivity of the foam material is also relatively high, resulting in high energy consumption. In order to reduce the thermal conductivity of the foam material, improve the thermal insulation performance of the thermal insulation material, and reduce the energy consumption, other hydrofluorocarbon physical blowing agents, such as HCFC-141b (monofluorodichloroethane, molecular weight 116.95, boiling point 32°C), HFC-245fa (molecular weight 134, boiling point 15.3°C), HFC-365mfc (molecular weight 148, boiling point 40.2°C), LBA (trans-1-chloro-3,3,3-trifluoropropene, molecular weight 130.5, boiling point 19°C), hexafluorobutene (molecular weight 164, boiling point 33°C, FEA1100), etc. are added. The price of some chlorofluorocarbons is expensive. The production process of these hydrofluorocarbon physical blowing agents also produces by-products containing chlorofluorine, which has an impact on the environment.

[0003] The low molecular weight alcohol amine salts used in the prior art often present as solid or semi-solid forms due to their strong crystallization tendency, and the high molecular weight alcohol amine salts also present as solid or semi-solid forms due to their high viscosity and freezing point. US6326412 B1 discloses an ammonium carbamate as a polyurethane blowing agent, wherein the viscosity of the ammonium carbamate salt (of low molecular weight ethanol amine) is as high as 2200 mPa.s (see specification column 6, lines 51-55), which is in a viscous or semi-solid state.

[0004] The thermal insulation performance of polyurethane rigid foam materials used in the refrigerator, freezer, water heater, refrigerated truck (cold chain insulation) and other industries is becoming more and more important. Generally, the Lance thermal conductivity coefficient λ (mW / m-K, 10°C) of the polyurethane rigid foam used in these industries is in the range of 19.00-20.00. If the thermal conductivity coefficient λ is reduced from 19.00 to 18.90, more preferably to 18.80, 18.70, 18.60, 18.50, 18.40, 18.30, 18.20, 18.10, 18.05 or 18.00 (where 18.00 is almost the lowest limit value, and it will be very difficult to continue to reduce this value), each progress will bring huge economic benefits. For example, the world produces at least tens of millions of refrigerators and freezers every year, and through the use of improved rigid foam in these refrigerators and freezers, a refrigerator or freezer saves 0.1-0.3 degrees of electricity per day, and 36.5-109.5 degrees of electricity per year. In terms of the number of refrigerators and freezers produced worldwide every year, the saved electricity is amazing.

[0005] In the industrial production of polyurethane rigid foam in the refrigerator, freezer, water heater, refrigerated truck (cold chain insulation) and other industries, the foaming mixture (mixed by white material and black material in the mixing chamber of the high-pressure casting machine) is injected into the mold through a single pouring port of the mold using a pouring method of a spray gun, and the foaming mixture (foaming material) is subjected to a foaming reaction, curing in the mold, and then demolding. For example, in a refrigerator production line, a refrigerator is taken off the line every 2-3 minutes on average, so the flowability (low viscosity) of the foaming mixture is very important, and it is required to be able to fill every corner of the irregular mold cavity in a short time, to ensure that the foaming mixture is uniformly filled in the mold and no dead corners are left. The foaming process in the refrigerator, freezer, water heater and other industries is actually an online foaming process on an industrial production line.

[0006] The inventors of the present application found that in the production of foam for refrigerators or freezers, if a carbonic acid alcohol amine salt with higher basicity and reactivity with isocyanate is used in the blowing agent, it is possible to interfere with the crosslinking catalysis of the amine gelation catalyst in the PU foaming formula. When using this blowing agent, the early reaction of the foaming reaction is too fast, but the subsequent crosslinking curing reaction (gelation reaction) is affected, so that the strength of the foam material is reduced, causing the foam material to be unstable in size (high open cell rate, easy to shrink and deform), thus the demolding time needs to be greatly extended (to promote sufficient curing), thereby reducing the demolding performance of the foam. SUMMARY

[0007] To solve the problems of the prior art, the present application provides a multifunctional alcohol amine derived from C4-C6 alkane diamine with a medium chain length. The alcohol amine carbonate hydrate formed from the multifunctional alcohol amine and CO2 has a low and suitable reactivity with polyisocyanate and a suitable basicity to avoid the problems of too rapid reaction in the early stage of the blowing reaction and the subsequent crosslinking curing reaction (gelation reaction) being affected. In addition, the alcohol amine carbonate hydrate as a chemical blowing agent and C5 alkane as a physical blowing agent are used as a blowing agent composition for PU. In the early stage of the blowing process using the blowing agent composition, the alcohol amine carbonate hydrate produces good nucleation, i.e. the formation of the embryo of the cells, while the C5 alkane is vaporized by heat in the middle and late stages of the blowing process to further expand the cells. The early nucleation results in a very excellent microstructure of the finally formed PU foam: smaller cell size, more uniform cell size, more number of cells per unit volume (more number of cells per unit area as seen from SEM photos), more fully crosslinked cell walls to make the foam have higher strength at lower foam density, thinner cell walls, higher airtightness of the cells (due to the fully crosslinked network on the cell walls), and higher closed cell rate. Generally, the fine (or fine and dense) cell structure of the foam as seen from the SEM photos of the foam represents the good microstructure of the foam.

[0008] The inventors of the present application have found through research that, relative to the influence of the thermal conductivity coefficient of the gas in the cells on the thermal insulation performance of the polyurethane rigid foam material, the cell microstructure in the polyurethane (PU) rigid foam material has a greater influence on the thermal insulation performance of the foam material.

[0009] In the industrial production of refrigerators, freezers, water heaters or refrigerated trucks, a suitable blowing speed is required in the industrialized polyurethane blowing process, as shown in Table A below:

[0010] Table A: Blowing speed for producing different types of foam

[0011]

[0012] The C4-C6 alkane diamine-derived alcohol amine carbonate hydrate of the present application hardly interferes with the crosslinking catalysis of the amine gelation catalyst in the PU blowing formula, so that the blowing time and the stringing time of the foam meet the above requirements.

[0013] Generally, the polyisocyanate (e.g., polymethylene polyphenyl polyisocyanate, i.e., polymeric MDI) used for preparing the polyurethane rigid foam is referred to as "black material", and the polymer polyol composition to which various aids (e.g., polyurethane catalyst, foam stabilizer, and optional flame retardant) and blowing agent are added is referred to as "white material". Among them, the polymer polyol composition to which various aids (e.g., polyurethane catalyst, foam stabilizer, and optional flame retardant) are added, but only without the blowing agent is referred to as "dry white material". That is, the "dry white material" refers to: a "white material" containing no blowing agent, or a polyurethane foaming dry white material containing polymer polyol and other aids except for the blowing agent.

[0014] Generally, the polyurethane catalyst in the "dry white material" or "white material" includes a primary amine type of pre-catalyst (i.e., pre-catalyst) and a tertiary amine type of post-crosslinking catalyst (i.e., post-catalyst).

[0015] Generally, in the foaming reaction on the production line of the refrigerator, freezer, or refrigerated vehicle, the foaming mixture containing the black material and the white material is injected into the mold via a single injection port using a casting machine (or high, medium, or low pressure casting machine), the foaming mixture has high flowability and can uniformly fill the entire mold, and the foaming is completed within a specified time (the mold opening time or the demolding time is generally about 180 seconds), that is, the pre-, middle-, and post-stage reactions are completed within 3 minutes.

[0016] In the present application, "optional" means with or without. In the present application, the ethanol group refers to hydroxyethyl, or the isopropanol group refers to hydroxyisopropyl or 2-hydroxypropyl.

[0017] The present application is directed to the polyurethane rigid foam for application in the refrigerator, freezer, water heater, cold chain insulation (refrigerated vehicle) industry, a specific foaming agent composition is designed, so that the foaming reaction speed (tack-free time, draw time and skin time) of the foaming reaction mixture containing the foaming agent composition meets the requirements of the foam industrial production in these industries.

[0018] The present application provides an alkanolamine composition (AC) derived from C4-C6 alkanediamine, which is used for formulating a foaming agent composition (FC) for preparing a (cast) polyurethane rigid foam for use in a refrigerator, freezer, or refrigerated vehicle. Part of the alkanolamine is neutralized by CO2 to form a salt.

[0019] The present application provides a C6-C12 diolamine (A1) derived from C4-C6 alkanediamine having the general formula (I):

[0020] R 1HN-Ra-NHR 2 (I).

[0021] In addition, the present application also provides a C10-C15 triolamine (A2) derived from a C4-C6 alkanediamine having the general formula (II):

[0022] R 1 HN-Ra-NHR 2 R 3 (II).

[0023] The present application also provides the use of a compound having the general formula (I) and / or the general formula (II) or a carbonate formed by the partial or total neutralization of the same with CO2 (i.e. a carbonate formed by the reaction of a portion or all of the compound with CO2 and water) as a component in a polyurethane (PU) blowing agent.

[0024] Accordingly, the C4-C6 diamine is one or two or more (e.g. three, four or five) selected from the group consisting of NH2-CH2CH2CH2CH2-NH2, NH2-CH2CH2CH2CH2CH2-NH2, NH2-CH2CH(CH3)CH2CH2-NH2, NH2-CH2CH2CH2CH2CH2CH2-NH2 and NH2-CH2CH2CH(CH3)CH2CH2-NH2. More preferably, the C4-C6 diamine is one or two or three selected from the group consisting of NH2-CH2CH2CH2CH2-NH2, NH2-CH2CH2CH2CH2CH2-NH2 and NH2-CH2CH2CH2CH2CH2CH2-NH2.

[0025] According to a first embodiment of the present application, the present application provides an aqueous alkanolamine composition (AC, alkanolamine composition, wherein the alkanolamine is derived from a C4-C6 alkanediamine) comprising or consisting of or consisting essentially of:

[0026] (1) a C6-C12 diolamine (A1) derived from a C4-C6 alkanediamine having the general formula (I):

[0027] R 1 HN-Ra-NHR 2 (I),

[0028] (2) a C10-C15 triolamine (A2) derived from a C4-C6 alkanediamine having the general formula (II):

[0029] R 1 HN-Ra-NHR 2 R 3 (II),

[0030] (3) water; and

[0031] (4) optionally (i.e., optionally, i.e., not necessarily) other alkanolamines (A3) in addition to A1 and A2, preferably other C2-C15 alkanolamines (A3) or, more preferably, other C2-C9 alkanolamines (A3);

[0032] wherein the molar ratio of the C10-C15 trialkanolamine (A2) of general formula (II) to the C6-C12 dialkanolamine (A1) of general formula (I) is (0.05-2.5):1, preferably (0.0526-2.333):1, preferably (0.075-1.857):1, preferably (0.085-1.5):1, preferably (0.09-1.5):1, preferably (0.111-1.5):1, preferably (0.09-1.4):1, preferably (0.10-1.3):1, preferably (0.11-1.2):1, preferably (0.12-1.0):1, preferably (0.12-0.8):1, preferably (0.1765-1.222):1, preferably (0.2195-1.0):1, preferably (0.23-0.8):1, preferably (0.25-0.6667):1, such as 0.3:1, 0.4:1, 0.5:1, or 0.6:1.

[0033] In general formulae (I) and (II), -Ra- and -Rb- can be the same or different. -Ra- or -Rb- is each independently one or two or more (e.g., three, four, or five) selected from -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, -CH2CH2CH2CH2CH2CH2-, and -CH2CH2CH(CH3)CH2CH2-. That is, -Ra- and -Rb- are each independently (i.e., -Ra- or -Rb-) -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, -CH2CH2CH2CH2CH2CH2-, or -CH2CH2CH(CH3)CH2CH2-.

[0034] R 1 , R 2 , and R 3 are the same or different and are each independently an ethanol group or an isopropanol group. For example, R 1 and R 2 are the same or different; R 3 is the same as or different from R 1 or R 2 ; or, R 1 , R2 and R 3 are both the same.

[0035] The molar ratio of (A2) to (A1) within the above ranges, on the one hand, enables the aqueous alcohol amine composition (AC) to be stored without crystallization at ambient temperature (e.g. 5-35°C, such as 25°C), on the other hand, the composition (AC) has a low viscosity (interdoping between triol amine and diol amine), good flowability, and, appropriate reactivity with isocyanate and appropriate basicity (ensuring a suitable pot life of the reaction mixture in the PU foaming process in the refrigerator or freezer, and ensuring a suitable string time and skin time of the PU foam).

[0036] Preferably, in general formula (I) R 1 and R 2 are not both ethanolic, but can both be isopropanolic.

[0037] Preferably, in general formula (II) R 1 , R 2 and R 3 are not all ethanolic, more preferably R 1 and R 2 are isopropanolic, R 3 is ethanolic or isopropanolic; more preferably R 1 , R 2 and R 3 are isopropanolic.

[0038] In the present application, preferably, the water content in the aqueous alcohol amine 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%, such as 14, 16 or 18 wt%, based on the total weight of (AC).

[0039] In addition, a part of the alcohol amines [i.e. alcohol amines (A1) and (A2) and optionally further alcohol amines (A3)] in the alcohol amine composition (AC) are neutralized by CO2, which can further avoid crystallization of the alcohol amines in the alcohol amine composition (AC).

[0040] Preferably, a portion of the alcohol amines [i.e. alcohol amines (A1) and (A2) and optionally further alcohol amines (A3)] in the alcohol amine composition (AC) are neutralized by CO2(i.e. the alcohol amines form carbonic acid alcohol amine salts with CO2and water), for example, to such an extent that the content of CO2in the alcohol amine composition (AC) is 0.5 to 8.5 wt%, preferably 0.6 to 8 wt%, preferably 0.75 to 7.5 wt%, preferably 0.8 to 7.2 wt%, preferably 1 to 7 wt%, preferably 1.2 to 6.5 wt%, preferably 1.5 to 6 wt%, preferably 1.7 to 5.5 wt%, preferably 2 to 5 wt%, for example 2.5, 3, 3.5, 4 or 4.5 wt%, based on the total weight of (AC).

[0041] A CO2content in the above range prevents crystallization of the alcohol amines, the alcohol amine composition (AC) has a low viscosity (for example, its viscosity (25°C) is in the range of 500 to 1200 centipoise), and, good nucleation during foaming is achieved.

[0042] Preferably, the total content of (A1) + (A2) + water is 70 to 100 wt%, preferably 72 to 99.9%, preferably 73 to 99.5%, preferably 74 to 99%, preferably 75 to 98%, preferably 76 to 97%, preferably 77 to 96%, preferably 78 to 95%, preferably 80 to 94%, for example 81, 82, 84, 85, 87, 88, 90, 91, 92, 93 wt%, based on the total weight of (AC).

[0043] Generally, the content of further alcohol amines (A3) [preferably, further C2-C15 alcohol amines (A3) or, more preferably, further C2-C9 alcohol amines (A3)] other than A1 and A2 is 0 to 30 wt%, preferably 0.1 to 28%, preferably 0.5 to 27%, preferably 1 to 26%, preferably 2 to 25%, preferably 3 to 24%, preferably 4 to 23%, preferably 5 to 22%, preferably 6 to 20%, for example 7, 8, 9, 10, 12, 13, 15, 16, 18, 19 wt%, based on the total weight of the alcohol amine composition (AC). More preferably, the content of further alcohol amines (A3) is 0 to 5 wt%, most preferably 0 wt%.

[0044] The further alcohol amines (A3) [preferably, further C2-C15 alcohol amines (A3) or, more preferably, further C2-C9 alcohol amines (A3)] are, for example, ethanolamine, N-methylethanolamine, isopropanolamine, N-methylisopropanolamine, diethanolamine, diisopropanolamine, ethanolisopropanolamine, triethanolamine and / or triisopropanolamine.

[0045] Preferably, the C6-C12 diolamine of general formula (I) (A1) is one or two or more (e.g., a combination of two or three or more) selected from the group consisting of N,N'-bis(hydroxyisopropyl)-butanediamine, N-hydroxyethyl-N'-hydroxyisopropyl- butanediamine, N,N'-bis(hydroxyethyl)-butanediamine, N,N'-bis(hydroxyisopropyl)- pentanediamine, N-hydroxyethyl-N'-hydroxyisopropyl-pentanediamine, N,N'-bis(hydroxyethyl)- pentanediamine, N,N'-bis(hydroxyisopropyl)-hexanediamine, N-hydroxyethyl-N'- hydroxyisopropyl-hexanediamine, and N,N'-bis(hydroxyethyl)-hexanediamine.

[0046] Preferably, the C10-C15 triolamine of general formula (II) (A2) is one or two or more (e.g., a combination of two or three or more) selected from the group consisting of N,N,N'-tris(hydroxyisopropyl)-butanediamine, N,N,N'-tris(hydroxyethyl)-butanediamine, N-hydroxyethyl-N- hydroxyisopropyl-N'-hydroxyisopropyl-butanediamine, N-hydroxyethyl-N-hydroxyisopropyl-N'- hydroxyethyl-butanediamine, N-hydroxyethyl-N-hydroxyethyl-N'-hydroxyisopropyl- butanediamine, N-hydroxyisopropyl-N-hydroxyisopropyl-N'-hydroxyethyl-butanediamine, N,N,N'-tris(hydroxyisopropyl)-pentanediamine, N,N,N'-tris(hydroxyethyl)-pentanediamine, N-hydroxyethyl-N-hydroxyisopropyl-N'-hydroxyisopropyl-pentanediamine, N-hydroxyethyl-N- hydroxyisopropyl-N'-hydroxyethyl-pentanediamine, N-hydroxyethyl-N-hydroxyethyl-N'- hydroxyisopropyl-pentanediamine, N-hydroxyisopropyl-N-hydroxyisopropyl-N'-hydroxyethyl- pentanediamine, N,N,N'-tris(hydroxyisopropyl)-hexanediamine, N,N,N'-tris(hydroxyethyl)- hexanediamine, N-hydroxyethyl-N-hydroxyisopropyl-N'-hydroxyisopropyl-hexanediamine, N-hydroxyethyl-N-hydroxyisopropyl-N'-hydroxyethyl-hexanediamine, N-hydroxyethyl-N- hydroxyethyl-N'-hydroxyisopropyl-hexanediamine, and N-hydroxyisopropyl-N-hydroxyisopropyl-N'-hydroxyethyl-hexanediamine.

[0047] Preferably, the diolamine compound of general formula (I) is one or two or three (e.g., a combination of two or three) selected from the group consisting of N,N'-bis(hydroxyisopropyl)butanediamine, N,N'-bis(hydroxyisopropyl)pentanediamine, and N,N'-bis(hydroxyisopropyl)hexanediamine. The triolamine compound of general formula (II) is one or two or three (e.g., a combination of two or three) selected from the group consisting of N,N,N'-tris(hydroxyisopropyl)butanediamine, N,N,N'-tris(hydroxyisopropyl)pentanediamine, and N,N,N'-tris(hydroxyisopropyl)hexanediamine.

[0048] The triolamine (A2) of general formula (II) has a doping effect on the diolamine (Al) of general formula (I) and the partial neutralization of the alcoholamine with CO2, which makes the composition (AC) not have a tendency to crystallize and thus have a lower viscosity.

[0049] Generally, the viscosity of the above aqueous alcoholamine composition (AC) is 230-500 centipoises when not neutralized with CO2. When a portion of the alcoholamine in the composition (AC) is neutralized with CO2, the viscosity of the above aqueous alcoholamine composition (AC) is significantly increased, for example, to 700-3000 centipoises, for example, 800-2000 centipoises, such as 900, 1000 or 1500 centipoises.

[0050] When a portion of the alcoholamine in the composition (AC) is neutralized with CO2, the water content in the composition (AC) includes free water and water that forms a carbonic acid alcoholamine salt with CO2 and the alcoholamine.

[0051] According to a second embodiment of the present application, the present application provides a method (i.e., the first method) for preparing the above aqueous alcoholamine composition (AC), which comprises the following steps:

[0052] 1) reacting a C4-C6 diamine with an epoxide in the presence of water to obtain an aqueous alcoholamine composition (AC) comprising the above diolamine (Al) and triolamine (A2), wherein the epoxide is ethylene oxide and / or propylene oxide (i.e., ethylene oxide, propylene oxide or a combination of both), and the molar ratio of the epoxide to the C4-C6 diamine is (2.05-2.7): 1, preferably (2.07-2.65): 1, preferably (2.1-2.6): 1, preferably (2.15-2.55): 1, preferably (2.18-2.5): 1, preferably (2.2-2.4): 1;

[0053] 2) optionally, adding other alcoholamines (A3) to the obtained aqueous alcoholamine composition (AC) in addition to Al and A2, preferably other C2-C15 alcoholamines (A3) or other C2-C9 alcoholamines (A3);

[0054] 3) optionally, bubbling CO2 gas into the obtained aqueous alcoholamine composition (AC) to neutralize the alcoholamine in the composition (AC) to a degree such that the CO2 content in the aqueous alcoholamine composition (AC) is as defined above.

[0055] In the present application, the order of the above step 2) and step 3) can be first performing 2) and then performing step 3), or first performing step 3) and then performing step 2).

[0056] The total water amount in steps 1) and optionally 2) and optionally 3) should be such that the obtained aqueous alcohol amine composition (AC) has the water content as described above.

[0057] Alternatively, the present application provides a second method for preparing the above described aqueous alcohol amine composition (AC), which method comprises:

[0058] 1) reacting a C4-C6 diamine with an epoxide in the presence of water to obtain the above described alcohol amine compound (or mixture of alcohol amines) of general formula (I), wherein the epoxide is ethylene oxide and / or propylene oxide (i.e. ethylene oxide, propylene oxide or a combination of both), and the molar ratio of epoxide to C4-C6 diamine is 2:1;

[0059] 2) reacting a C4-C6 diamine with an epoxide in the presence of water to obtain the above described alcohol amine compound (or mixture of alcohol amines) of general formula (II), wherein the epoxide is ethylene oxide and / or propylene oxide (i.e. ethylene oxide, propylene oxide or a combination of both), and the molar ratio of epoxide to C4-C6 diamine is 3:1;

[0060] 3) mixing the C10-C15 triol amine (A2) of general formula (II) and the C6-C12 diol amine (A1) of general formula (I) in a molar ratio of (0.05-2.5):1, preferably (0.0526-2.333):1, preferably (0.075-1.857):1, preferably (0.085-1.5):1, preferably (0.09-1.5):1, preferably (0.111-1.5):1, preferably (0.09-1.4):1, preferably (0.10-1.3):1, preferably (0.11-1.2):1, preferably (0.12-1.0):1, preferably (0.12-0.8):1, preferably (0.1765-1.222):1, preferably (0.2195-1.0):1, preferably (0.23-0.8):1, preferably (0.25-0.6667):1, such as 0.3:1, 0.4:1, 0.5:1 or 0.6:1, to obtain the aqueous alcohol amine composition (AC); and

[0061] 4) optionally adding to the obtained aqueous alcohol amine composition (AC) a further alcohol amine (A3) than A1 and A2, preferably a further C2-C15 alcohol amine (A3) or a further C2-C9 alcohol amine (A3); and

[0062] 5) optionally, bubbling CO2 gas (in order to partially neutralize the alcohol amine in the obtained aqueous alcohol amine composition (AC)), to obtain a CO2 partially neutralized aqueous alcohol amine composition (AC), wherein the amount of CO2 gas absorbed or bubbled should be such that the CO2 content in the aqueous alcohol amine composition (AC) is as defined above;

[0063] Preferably, the total amount of water used in step 1), step 2), step 3), optional step 4) and optional step 5) should be such that the obtained aqueous alcohol amine composition (AC) has the water content as defined above.

[0064] In the above second method, the order of the above steps 4) and 5) can be first performing 4) and subsequently performing 5), or first performing 5) and subsequently performing 4).

[0065] In the present application, in order to improve the flexibility of the polyurethane foam, preferably, the above C4-C6 diamine is one or two or more (e.g. three, four or five) selected from the group consisting of NH2-CH2CH2CH2CH2-NH2, NH2-CH2CH2CH2CH2CH2-NH2, NH2-CH2CH(CH3)CH2CH2-NH2, NH2-CH2CH2CH2CH2CH2CH2-NH2 and NH2-CH2CH2CH(CH3)CH2CH2-NH2. More preferably, the C4-C6 diamine is one or two or three selected from the group consisting of NH2-CH2CH2CH2CH2-NH2, NH2-CH2CH2CH2CH2CH2-NH2 and NH2-CH2CH2CH2CH2CH2CH2-NH2. More preferably, the C4-C6 diamine is one or two or three (i.e. a combination of two or three) selected from the group consisting of 1,4-butanediamine, 1,5-pentanediamine and 1,6-hexanediamine.

[0066] The amount of the other alcohol amine (A3) added should be such that the obtained composition (AC) has the other alcohol amine (A3) content as defined above.

[0067] According to a third embodiment of the present application, the present application provides a carbonic acid alcohol amine salt foaming agent composition (FC, foaming agent composition), which is especially used for preparing (cast) polyurethane rigid foam, the composition comprising or consisting or consisting essentially of:

[0068] (1) the above aqueous alcohol amine composition (AC);

[0069] (2) a C5 alkane (i.e. a pentane), which C5 alkane is cyclopentane, iso-pentane, n-pentane and / or neopentane, preferably, it is cyclopentane;

[0070] (3) optionally, a physical blowing agent (F1) having a boiling point in the range of 15-41 °C (hydrofluorocarbons), wherein the physical blowing agent (F1) is one or two or more (e.g. a combination of two or three) selected from the group consisting of HFC-245fa, HFC-365mfc, LBA and hexafluorobutene;

[0071] (4) optionally, water (F2);

[0072] wherein the relative amounts (or mass ratios) of the various components are: the amount of water (F2) is 0-2 parts by weight, 0-1.5 parts by weight, more preferably 0-1 parts by weight, further preferably 0-0.5 parts by weight, more preferably 0-0.1 parts by weight; the amount of physical blowing agent (F1) is 0-7 parts by weight, preferably 0-6.5 parts by weight, preferably 0-6 parts by weight, preferably 0-5.5 parts by weight, preferably 0-5 parts by weight, more preferably 0-4.5 parts by weight, preferably 0-4 parts by weight, more preferably 0-3.5 parts by weight, more preferably 0-3 parts by weight, more preferably 0-2.5 parts by weight, most preferably 0 parts by weight; the amount of alcohol amine composition (AC) is 1-10 parts by weight, preferably 1.2-9.5 parts by weight, preferably 1.3-9 parts by weight, preferably 1.4-8.5 parts by weight, preferably 1.5-8 parts by weight, preferably 2.8-8 parts by weight, preferably 3-8 parts by weight, preferably 3.5-7.5 parts by weight, preferably 4-7 parts by weight, preferably 4.5-6.5 parts by weight, preferably 5-6.5 parts by weight, more preferably 5-6 parts by weight, e.g. 5.5 parts by weight; and, the amount of C5 alkane (such as cyclopentane and / or n-pentane) is 10-20 parts by weight, preferably 10.5-19.5 parts by weight, preferably 10.5-19 parts by weight, preferably 11-18.5 parts by weight, preferably 11.5-18 parts by weight, e.g. 12, 13, 14, 15, 16, 17 or 17.5 parts by weight.

[0073] Generally, the sum of the mass of water (F2) + physical blowing agent (F1) + alcohol amine composition (AC), preferably the sum of the mass of water (F2) + alcohol amine composition (AC) (i.e. F1 is 0), more preferably the mass of alcohol amine composition (AC) (i.e. F2 and F1 are 0), is: 4-10 parts by weight, preferably 4-9.5, 4-9, 4.5-9, 4.5-8.5, e.g. 4.7 parts, 5 parts, 5.3 parts, 5.5 parts, 6, 7, 8 or 9 parts. The mass of C5 alkane (such as cyclopentane and / or n-pentane) is 10-20 parts by weight, preferably 10.5-19.5, 11-19, 11.5-18.5, 12-18, 12-17.5, e.g. 13, 14, 15, 16 or 17. Preferably, the mass of physical blowing agent (F1) is 0 parts by weight. More preferably, the mass of both water (F2) and physical blowing agent (F1) is 0 parts by weight.

[0074] Generally, the ratio (or relative amounts) of the sum of the mass of water (F2) + physical blowing agent (Fl) + alcohol amine composition (AC) to the mass of C5 alkane (such as cyclopentane and / or n-pentane), or the ratio (or relative amounts) of the sum of the mass of water (F2) + alcohol amine composition (AC) to the mass of C5 alkane (such as cyclopentane and / or n-pentane) (i.e., Fl is 0), or the ratio (or relative amounts) of the mass of alcohol amine composition (AC) to the mass of C5 alkane (such as cyclopentane and / or n-pentane) (i.e., both F2 and Fl are 0), is: (4-10):(10-20), preferably (4-9.5):(10-20), (4-9):(10-20), (4-9):(10-18), (4-9):(10-16), preferably (4.5-10):(10-20), (5-9.5):(10-20), (5-9.5):(10-18), (5-9.5):(10-16), (5-9):(10-20), (5-9):(10-18), (5-9):(10-16), more preferably (5.5-9):(10-20), (5.5-8.5):(10-20), preferably (5.5-8):(10-20), preferably (5.5-8):(10.5-19.5), (5.5-8):(11-19), (5.5-8):(11.5-18.8), (5.5-8):(12-18.5), (5.5-8):(13-18), preferably (5.6-8):(10.5-19.5), preferably (5.7-8):(11-19), preferably (5.8-8):(11.5-18.8), preferably (5.9-8):(12-18.5), preferably (6-8):(13-18). For example (6-8.5):(14-19), more preferably (6-8.5):(14-18.5), more preferably (6-8.5):(15-18.5), more preferably (6-8):(16-18). Here, (4-10):(10-20) can also be expressed as (1-2.5):(2.5-5), and so on.

[0075] Preferably, when the blowing agent composition (FC) is used for preparing a thermal insulation foam material used at low temperature (e.g. for preparing a thermal insulation foam material for a refrigerator or a freezer), the sum of the mass of water (F2) + physical blowing agent (F1) + alcohol amine composition (AC) is (5.5-10) parts by weight, preferably 6-10 parts by weight (e.g. 7, 8 or 9), and the mass of C5 alkane (e.g. cyclopentane and / or n-pentane) is 10-20 parts by weight, preferably 12-18 parts by weight; or, the ratio (or relative amount) of the sum of the mass of water (F2) + physical blowing agent (F1) + alcohol amine composition (AC) to the mass of C5 alkane (e.g. cyclopentane and / or n-pentane) is (5.5-10):(10-20), preferably (6-10):(12-18) or (5.5-9):(10-20) or (5.5-8.5):(10-20). For example, the alcohol amine composition (AC) is used in an amount of more than 5 parts by weight (e.g. 5, 5.5, 6, 7, 8, 9 or 10 parts by weight) (in addition, for example, F1 or water (F2) is used in an amount of 0-1 parts by weight) so as to make the blowing material (white material + black material) have higher flowability, the blowing material has suitable initiation time and draw time in the polyurethane blowing reaction in the industrial production process of the refrigerator or freezer, the cell size of the obtained foam material is relatively uniform, and the foam material has lower product density (e.g. 28-36 Kg / m3) while significantly improving the mechanical strength (crosslinking density of cell wall and anti-shrinkage deformation) and thermal insulation performance of the obtained foam material. 3 ), while significantly improving the mechanical strength (crosslinking density of cell wall and anti-shrinkage deformation) and thermal insulation performance of the obtained foam material.

[0076] When the CO2 content in the alcohol amine composition (AC) is higher than 9 wt%, the viscosity of the alcohol amine composition (AC) increases significantly, the flowability decreases, and in turn, the white material containing the alcohol amine composition (AC) and the black material (polyisocyanate) are difficult to be uniformly mixed, resulting in the cell size of the foam material being non-uniform, and in particular, the foam material being shrunk and deformed, thus, the demolding performance of the foam material is reduced.

[0077] When the CO2 content in the alcohol amine composition (AC) is lower than 0.5 wt%, good nucleation cannot be generated in the early stage of the blowing reaction, uniform blowing cannot be achieved, and a foam material with smaller cell size and relatively uniform size cannot be obtained. That is, the microstructure of the foam material is not ideal, thereby reducing the thermal insulation performance of the foam material.

[0078] For the blowing agent composition (FC), the weight parts described above are relative to or based on 90 to 115 parts by weight (preferably 95 to 110 parts by weight, more preferably 100 to 105 parts by weight, for example 100, 102 or 104.6 parts by weight) of a dry white material for polyurethane foaming (hereinafter referred to as "dry white material") containing polymeric polyols and other auxiliaries other than blowing agents. The other auxiliaries include a polyurethane catalyst, a blowing stabilizer and optionally a flame retardant. The blowing agent composition (FC) is used for mixing with the dry white material and a polyisocyanate as a black material to carry out a foaming reaction, thereby producing a polyurethane rigid foam.

[0079] When the amount of the composition (AC) is greater than 12 parts by weight and the amount of CP is correspondingly reduced, the viscosity of the obtained white material is significantly increased.

[0080] The physical blowing agents (F2) described herein, i.e. HFC-245fa, HFC-365mfc, LBA and hexafluorobutene, all belong to the class of hydrofluorocarbon physical blowing agents.

[0081] When the blowing agent composition (FC) does not contain the physical blowing agent (F2), the alcohol amine composition (AC) and the C5 alkane (for example, cyclopentane and / or n-pentane) are contained in separate containers, respectively. In addition, when the blowing agent composition (FC) further contains the physical blowing agent (F2), the alcohol amine composition (AC) is contained in a separate container, while the physical blowing agent (F2) and the C5 alkane (for example, cyclopentane and / or n-pentane) are contained in different containers or in the same container, respectively.

[0082] The blowing agent composition (FC) of the present application is used for the production of a cast polyurethane rigid foam, more preferably for the production of a cast polyurethane rigid foam in the production of a refrigerator, a freezer, a water heater or a refrigerated truck.

[0083] In the present application, the amount of the alcohol amine composition (AC) is generally greater than 3 parts by weight, which enables the obtained polyurethane rigid foam to have good thermal insulation performance and strength performance.

[0084] If the alcohol amine composition (AC) is used in an amount of less than 3 parts by weight (for example, 1 to 2.8 parts by weight), it is mainly used for the pre-nucleation of the foaming reaction, because CO2 gas is immediately generated when the white material is mixed with the black material. The physical blowing agent is vaporized to generate bubbles after the foaming mixture is warmed by the reaction heat, which is a kind of delayed foaming, expansion. The pre-nucleation is beneficial to increasing the number of cells and improving the uniformity of cell size, thus also helping to improve the microstructure of the polyurethane rigid foam, thereby improving the thermal insulation performance of the foam to a certain extent. Of course, it is more preferable to use in an amount of more than 3 parts by weight (i.e. 3 to 10 parts by weight) in order to obtain a polyurethane rigid foam with better overall performance.

[0085] When water (F2) is present in the foaming agent composition (FC), it means that by additionally using a small amount (up to 2 parts by weight) of water and correspondingly simultaneously reducing the amount of physical foaming agent to reduce the cost of rigid foam production, but this reduces the strength and deformation resistance of the produced foam, and also reduces the closed cell rate of the foam, resulting in a decrease in the thermal insulation performance. Therefore, it is preferred that the amount of water (F2) should be reduced, more preferably reduced to 0 parts by weight.

[0086] In addition, when the physical foaming agent (F1) is present in the foaming agent composition (FC), it means that the higher the amount of the physical foaming agent (F1), the more significantly the cost of rigid foam production increases, and the strength properties of the rigid foam decrease, but the thermal insulation performance of the produced foam does not significantly increase. Therefore, it is preferred that the amount of the physical foaming agent (F1) should be reduced, more preferably reduced to 0 parts by weight. When the amount of the physical foaming agent (F1) is reduced, the amount of the alcohol amine composition (AC) is correspondingly increased in order to obtain a rigid foam having a prescribed foam density or equivalent foam density.

[0087] Preferably, the blowing agent composition (FC) comprises only component (1) the alcohol amine composition (AC) and component (2) the C5 alkane (e.g. cyclopentane and / or n-pentane), i.e. the amount of component (3) the physical blowing agent (Fl) and component (4) water (F2) is 0 parts by weight. Thus, the mass ratio (or relative amount) of the alcohol amine composition (AC) to the C5 alkane (e.g. cyclopentane and / or n-pentane) is (4-10 parts by weight):(10-20 parts by weight), preferably (4-9.5):(10-20), (4-9):(10-20), (4-9):(10-18), (4-9):(10-16), preferably (4.5-10):(10-20), (5-9.5):(10-20), (5-9.5):(10-18), (5-9.5):(10-16), (5-9):(10-20), (5-9):(10-18), (5-9):(10-16), more preferably (5.5-9):(10-20), (5.5-8.5):(10-20), preferably (5.5-8):(10-20), preferably (5.5-8):(10.5-19.5), (5.5-8):(11-19), (5.5-8):(11.5-18.8), (5.5-8):(12-18.5), (5.5-8):(13-18), preferably (5.6-8):(10.5-19.5), preferably (5.7-8):(11-19), preferably (5.8-8):(11.5-18.8), preferably (5.9-8):(12-18.5), preferably (6-8):(13-18), more preferably (6-8):(14-18), more preferably (6-8):(15-18), more preferably (6-8):(16-18). For example (6-8.5):(14-19), more preferably (6-8.5):(14-18.5), more preferably (6-8.5):(15-18.5), more preferably (6-8):(16-18).

[0088] In these cases, on the one hand the production costs of the rigid foam are significantly reduced, while, unexpectedly, the rigid polyurethane foam formed also has a very low thermal conductivity (λ), i.e. a Lance λ (mW / m-K, 10°C).

[0089] Generally, the blowing agent composition (FC) is used in an amount sufficient to result in a density of the (cast) polyurethane rigid foam produced in the range of 25-38 Kg / cm3, preferably 26-36 Kg / cm3, more preferably 27-35 Kg / cm3, even more preferably 28-34 Kg / cm3, for example 28, 30, 31, 32, 33, 34, 35 or 36 Kg / cm3, relative to or based on 90-115 parts by weight (preferably 95-110 parts by weight, more preferably 100-105 parts by weight, for example 100, 102 or 104.6 parts by weight) of the dry white mix. 3 Kg / cm3, preferably 26-36 Kg / cm3, more preferably 27-35 Kg / cm3, even more preferably 28-34 Kg / cm3, for example 28, 30, 31, 32, 33, 34, 35 or 36 Kg / cm3, relative to or based on 90-115 parts by weight (preferably 95-110 parts by weight, more preferably 100-105 parts by weight, for example 100, 102 or 104.6 parts by weight) of the dry white mix.3 .

[0090] It is preferred in the present application that the sum of the water amounts of both component (1) alcohol amine composition (AC) and component (4) optional water (F2) is 1-4.5 wt% (preferably 1-4, preferably 1-3.7 wt%, preferably 1.1-3.5 wt%, preferably 1.2-3.3 wt%, preferably 1.25-3 wt% or 1.3-2.5 wt% or 1.4-2 wt%, for example 1.5, 1.6, 1.7, 1.8 wt%) (approximately) relative to or based on 100 parts by weight of the dry white material. The water amount within this range enables the foaming composition to have a desirable flowability while ensuring that the prepared rigid foam has excellent strength performance and thermal insulation performance.

[0091] According to a fourth embodiment of the present application, the present application provides a polyurethane foaming white material, which comprises: (1) a polyurethane foaming dry white material comprising polymeric polyols and other auxiliaries other than a blowing agent, wherein the other auxiliaries include a polyurethane catalyst, a foam stabilizer, and optionally a flame retardant; and (2) the above-mentioned alcohol amine carbonate salt blowing agent composition (FC).

[0092] Preferably, the polymeric polyols in the dry white material comprise 8-72 wt% (preferably 9-70 wt%, preferably 10-60 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. polyethylene phthalate polyol, polyethylene isophthalate polyol or polyethylene terephthalate polyol) and / or toluene diamine type polyoxypropylene polyol and 92-28 wt% (preferably 91-30 wt%, preferably 90-40 wt%, preferably 88-50 wt%, preferably 85-55 wt%, more preferably 84-60 wt%, more preferably 82-65 wt%) of (non-toluene diamine type or non-toluene diamine initiated) polyoxypropylene polyol, i.e. polyoxypropylene polyol other than toluene diamine polyoxypropylene polyol. The wt% is based on the weight of the polymeric polyols in the dry white material.

[0093] According to a fifth embodiment of the present application, the present application also provides a polyurethane foaming composition (or mixture), which comprises:

[0094] (1) a polyisocyanate (preferably, a poly-methylene polyphenyl polyisocyanate or polymeric MDI) as a black material;

[0095] (2) a polyurethane foaming dry white material comprising polymeric polyols and other auxiliaries other than a blowing agent; and

[0096] (3) the above-mentioned alcohol amine carbonate blowing agent composition (FC).

[0097] Preferably, the ratio of the mass of the black material (1) to the sum of the mass of the dry white material (2) and the blowing agent composition (3) (i.e. the material ratio) is 1.1-1.36:1, preferably 1.13-1.35:1, preferably 1.15-1.30:1, preferably 1.17-1.27:1, preferably 1.18-1.25:1, most preferably 1.2:1.

[0098] Aromatic / semi-aromatic polyester polyol in the present application means aromatic polyester polyol and / or semi-aromatic polyester polyol, typically having a low viscosity (25°C) (e.g. 250-4000 centipoise, such as 500, 700, 900, 1500, 2000 or 3000, preferably 300-600).

[0099] For the polymeric polyol in the dry white material, since it contains a small amount of aromatic polyester polyol (i.e. PET polyol), preferably polyethylene phthalate and polyethylene isophthalate polyol, more preferably polyethylene phthalate.

[0100] Toluene diamine (type) polyoxypropylene polyol means a polyoxypropylene polyol initiated or started by toluene diamine.

[0101] Preferably, when aromatic / semi-aromatic polyester polyol is used, the amount of toluene diamine polyoxypropylene polyol is reduced or not used.

[0102] The basicity of the A1 and A2 alcohol amine compounds of the present application is lower than that of the alcohol amine compounds prepared from ammonia or ethylene diamine as initiator, and thus the reactivity with isocyanate is also lower, and the tolerance in the process of formulating the white material formulation is better, and thus more catalysts for improving the flowability, demouldability of the foam in the later stage of the foaming reaction can be added in the dry white material.

[0103] On the other hand, the A1 and A2 alcohol amine compounds of the present application have good compatibility or miscibility with the polymeric polyol in the white material (the compatibility between them is even better than that between diisopropanolamine and the polymeric polyol in the white material), so that the blowing agent can be uniformly dispersed in the white material, and a uniform, transparent white material can be formed, achieving the purpose of homogeneous foaming, and further improving the microstructure of the prepared foam and increasing the closed cell rate, so that the thermal conductivity of the foam almost reaches the minimum limit value (e.g. λ value lower than 18.02).

[0104] The present application also provides the use of the carbonic acid alcohol amine salt blowing agent composition (FC) of the present application for formulating a polyurethane foaming composition. The present application also provides the use of the carbonic acid alcohol amine salt blowing agent composition (FC) of the present application as a component of a blowing agent for preparing (cast) rigid polyurethane foam.

[0105] The present application also provides a process for preparing a polyurethane rigid foam, which comprises mixing and foaming a polymer polyol composition white material comprising the above-mentioned blowing agent composition (FC) with a polyisocyanate (preferably, a polymethylene polyphenyl polyisocyanate or polymeric MDI) as a black material; preferably, by using a casting machine to perform cast foaming.

[0106] The present application also provides a polyurethane rigid foam obtained from the above-mentioned process for preparing a polyurethane rigid foam, wherein the density of the polyurethane rigid foam is in the range of 25-38 Kg / cm 3 , preferably 26-37 Kg / cm 3 , preferably 27-36.5 Kg / cm 3 , preferably 28-36 Kg / cm 3 , preferably 28.5-35.5 Kg / cm 3 , preferably 29-35 Kg / cm 3 , for example 30, 31, 32, 33 or 34 Kg / cm 3 .

[0107] The Lance thermal conductivity coefficient λ (mW / m·K, 10°C) of the polyurethane rigid foam is lower than 18.50, preferably lower than 18.40, more preferably lower than 18.30, more preferably lower than 18.20, more preferably lower than 18.10 or 18.05.

[0108] There is a strong hydrogen bonding interaction between water and the alcohol amine, which is stronger or greater than the chemical bond between the alcohol amine and the carbonate radical.

[0109] For the application of the blowing agent composition (FC) in the preparation of polyurethane rigid foams in the refrigerator, freezer, water heater and refrigerated truck industries, when the relative amount of C5 alkanes (such as cyclopentane and / or n-pentane) in the blowing agent (FC) is further increased to more than 22 parts by weight, it will cause the formation of a two-phase system (phase separation phenomenon) in the prepared white material. Among them, oil droplets are found when the white material is stirred, and in addition, stratification occurs when it is left to stand, which means that too much C5 alkanes have escaped from the constraints of water and polymer polyol (or in other words, the solubility of C5 alkanes in the white material is limited), which no longer participates in the formation of a homogeneous polyplex. Thus, a homogeneous foaming system cannot be formed in the foaming reaction, and the cell diameter of the resulting foam is particularly uneven (wherein the oil droplets become vaporization centers, large or super-large pores are generated at the position of the oil droplets), the diameter of the cells is usually greater than 300 microns or even greater than 350 microns, and the thermal insulation performance of the foam is significantly reduced.

[0110] The phase separation phenomenon indicates that the physical blowing agent (F2) and the C5 alkane have good compatibility with the dry white material and can form a transparent and uniform white material only when the content of the physical blowing agent (F2) and / or the C5 alkane (such as cyclopentane or n-pentane) in the foaming composition (FC) is within a certain range. That is, the solubility of the physical blowing agent (F2) and / or the C5 alkane in the dry white material is limited.

[0111] The inventors have found through experiments that due to the presence of a part of the benzene ring-containing polyester polyol and the toluene diamine polyether polyol in the dry white material, the use of such a dry white material can improve the compatibility or solubility of the C5 alkane in the white material system, and can also improve the compatibility of HFC-245fa, HFC-365mfc, LBA and hexafluorobutene in the white material system. However, due to the higher molecular weight, higher density and higher polarity of hexafluorobutene, the higher density will affect the density distribution of hexafluorobutene in the white material, so the compatibility of hexafluorobutene in the white material system is worse than that of HFC-245fa, HFC-365mfc and LBA in the white material. Therefore, in the present application, the use of hexafluorobutene is not preferred.

[0112] In addition, in the refrigerator, freezer, water heater and refrigerated truck industries, when the relative amount of the C5 alkane in the foaming agent (FC) is further reduced to less than 8 parts by weight, it will cause the flowability of the formed white material to decrease, the white material cannot be poured to fill the mold in a short time during the production process of the refrigerator, and it also affects the demolding property of the mold after foaming, resulting in a significant reduction in the production efficiency of the refrigerator production line and a reduction in the thermal insulation performance of the refrigerator.

[0113] When the content of water in the alcohol amine composition (AC) is less than 7wt%, or less than 6wt%, or even less than 5wt%, it will cause the viscosity of the formed foaming agent to increase, the compatibility of the foaming agent in the white material to become poor, the alcohol amine to be precipitated from the white material in solid or viscous form (due to the dehydration of the polymer polyol), the activity of the foaming agent to increase, and the foaming time of the foam in the foaming process of the refrigerator production to be significantly shortened (for example, to 1-3 seconds), and the foaming speed to be too fast to be controlled.

[0114] The suitable foaming time and flowability of the foaming mixture are very important for the in-mold pouring foaming in the field of refrigerators, freezers, water heaters or refrigerated trucks, because the foaming mixture is injected into the complexly structured inner cavity of the mold through a single injection port. If the foaming time is too short or the flowability is too poor, the foaming mixture foams and hardens in the area close to the injection port in the mold, and the foaming mixture cannot reach the more distant areas in the mold, so the entire mold cavity cannot be uniformly filled, which leads to poor demolding performance of the rigid foam and uneven overall density distribution of the foam in the mold.

[0115] For example, in the production of polyurethane rigid foam on the production line of the refrigerator manufacturing industry, the opening time of the mold is often about 180 seconds, therefore, the draw time is also important.

[0116] In addition, when the content of water in the alcohol amine composition (AC) is higher than 45wt%, more black material (polyisocyanate, such as poly-methylene polyphenyl polyisocyanate or polymeric MDI) will be consumed in the foaming reaction, more urea bonds will be produced in the foam material, resulting in the decrease of the dimensional stability of the obtained foam and the decrease of the closed cell rate, which reduces the thermal insulation performance of the foam material.

[0117] The alcohol amines (A1 and A2) in the alcohol amine composition (AC) have lower basicity and suitable reactivity with polyisocyanate, are used to absorb a suitable amount of CO2 gas, hardly affect the catalysis of the amine catalyst in the white material, and they are used together with water as the crosslinking agent in the middle and later stages of the foaming reaction to improve the strength of the inner wall of the cell, thereby improving the foam strength and deformation resistance.

[0118] In addition, if the boiling point of the physical foaming agent (F2) is lower than 15℃ or higher than 41℃, it will affect the smooth progress of the foaming process. In the present application, it is desirable that the CO2 gas produced by the reaction of the carbonate salt of the alcohol amine composition (AC) with the polyisocyanate first plays a role in the early nucleation and foaming, and then the C5 alkane (such as cyclopentane or n-pentane) and the physical foaming agent play the role of expansion in turn as the temperature of the reaction mixture rises, which is conducive to the smooth progress of the foaming process.

[0119] If the boiling point of the physical foaming agent (F2) is lower than 15℃, the low-boiling foaming agent will immediately volatilize and escape when the foaming agent composition (FC) is mixed with the dry white material, in addition, the early foaming effect will also cause the composition of the foaming reaction mixture (i.e., the mixture of black material and white material) to become non-uniform.

[0120] If the boiling point of the physical foaming agent (F2) is higher than 41℃, the foaming effect of the physical foaming agent (F2) is slightly delayed, which affects the smooth progress of the foaming reaction, in addition, when the foam is cooled to room temperature, the high-boiling physical foaming agent (F2) in the cell loses its supporting effect on the cell because it condenses into a liquid, resulting in shrinkage and deformation of the foam in subsequent use.

[0121] In the present application, other alcohol amines (A3) in addition to the above-mentioned specific alcohol amines (A1 and A2) often have higher basicity and higher reactivity and higher viscosity (or freezing point), therefore, the lower their content in the foaming agent composition of the present application is, the better.

[0122] The inventors have found that if the content of the more active carbonic acid alcohol amine salt (for example the carbonates of monoisopropanolamine and diethanolamine) in the alcohol amine composition (AC) is high, then in the early stages of the foaming reaction the reaction is too violent and a large amount of reaction heat is generated, which leads to the phenomenon of "burning core" of the foam, i.e. the core of the foam assumes a dark yellow or burnt yellow colour.

[0123] According to the present application, there is provided a polyurethane rigid foam obtained by the above-mentioned process, in particular when the density of the polyurethane rigid foam is in the range of 25-38 Kg / cm 3 and more preferably 18.30, 18.20, 18.10, 18.04, when the density of the polyurethane rigid foam is in the range of 25-38 Kg / cm

[0124] The inventors of the present application have found, through a large number of experiments, that by optimising the composition of the blowing agent it is possible to optimise the microstructure and the closed cell rate of the rigid foam, thus making it possible to ideally reduce the thermal conductivity of the polyurethane rigid foam, even to the current limit values. When the polyurethane rigid foam obtained according to the present application has a density in the range of 25-38 Kg / cm 3 , preferably 26-37 Kg / cm 3 , preferably 27-36.5 Kg / cm 3 , preferably 28-36 Kg / cm 3 , preferably 28.5-35.5 Kg / cm 3 , preferably 29-35 Kg / cm 3 , and an average cell diameter in the range of 180-230 microns (preferably 185-220 microns, more preferably 190-210), in general the thermal conductivity of the polyurethane rigid foam (Mw / m-k, 10°C) is lower than 18.40, more preferably lower than 18.30, more preferably lower than 18.20, more preferably lower than 18.05 or 18.03.

[0125] Advantages of the present application

[0126] 1. Carbonate salts of diol amines and triol amines derived from butane diamine, pentane diamine or hexane diamine (i.e. partially neutralized aqueous alkanolamine compositions AC with CO2) have lower reactivity with polyisocyanates and lower basicity, they have lower catalytic activity and have little effect on the catalytic activity of amine-based gelation catalysts in PU foaming compositions (white material), resulting in a relatively slow early stage reaction and a faster and more complete later stage curing reaction in the overall polyurethane foaming process, thus improving the release properties of cast foams in the refrigerator or freezer industrial production line. The rise time, draw time and skin time of the foaming reaction mixture formed by mixing the black material with the white material containing the above-mentioned carbonate salt meet the current requirements of such times in the refrigerator or freezer industrial production line, thus without any changes to the existing technology of the refrigerator or freezer industrial production line and the formulation of the dry white material.

[0127] 2. Carbonate salts of diol amines (A1) and triol amines (A2) have better compatibility or miscibility in white material containing aromatic polyester polyol and toluene diamine initiated polyether polyol than carbonate salts of diethanolamine or diisopropanolamine. The carbonate alkanolamine salt of the present invention (i.e. partially neutralized aqueous alkanolamine composition AC with CO2) is used in combination with C5 alkane to form a blowing agent composition (FC), in which the carbonate alkanolamine salt produces good nucleation in the early stage of the PU foaming process, the good compatibility and nucleation result in improved microstructure of the foam (finer cell structure), smaller and more uniform cell size.

[0128] 3. The diol amine (A1) of the present invention has higher basicity, which is beneficial to the absorption of more CO2 by the alkanolamine composition AC and the formation of nucleation, while the triol amine (A2) has a doping effect on (A1) to prevent crystallization in the blowing agent, and (A2) and water are beneficial to the crosslinking of the foam cell wall, thus improving the strength properties of the foam.

[0129] 4. The diol amine (A1) and triol amine (A2) have medium chain length C4-C6 alkylene groups, which participate in the later stage crosslinking reaction of the foaming reaction, which is beneficial to improve the flexibility and elasticity of the molecular chain of the polyurethane.

[0130] 5. In addition, the blowing agent of the present invention has lower cost (e.g. 30-50% lower) compared to the 245fa+CP blowing agent system of the prior art. BRIEF DESCRIPTION OF DRAWINGS

[0131] Figure 1 is the SEM photo of the foam of Example 1.

[0132] Figure 2 is the preparation of diol amine product of Example 3 1H-NMR spectrum.

[0133] Figure 3 is an SEM photograph of the foam of Example 2.

[0134] Figure 4 is an SEM photograph of the foam of Example 3.

[0135] Figure 5 is an SEM photograph of the foam of Example 4.

[0136] Figure 6 is an SEM photograph of the foam of Example 5.

[0137] Figure 7 is an SEM photograph of the foam of Example 6.

[0138] Figure 8 is an SEM photograph of the foam of Example 7.

[0139] Figure 9 is an SEM photograph of the foam of Comparative Example 1.

[0140] Figure 10 is an SEM photograph of the foam of Comparative Example 2.

[0141] Figure 11 is an SEM photograph of the foam of Comparative Example 3.

[0142] Figure 12 is an SEM photograph of the foam of Comparative Example 4.

[0143] Figure 13 is a photograph of the product of the preparation of Example 7. 1 H-NMR spectrum.

[0144] Figure 14 is a photograph of the product of the preparation of Example 12. 1 H-NMR spectrum. DETAILED DESCRIPTION

[0145] The equipment used in the examples is all equipment commonly used in the art and commercially available, unless otherwise specified.

[0146] For the (slow reaction type) foaming reaction of the refrigerator, freezer, water heater or refrigerated vehicle production process, the rise time of the foam is generally 6-7 seconds, and the draw time of the foam is generally 45-55 seconds (preferably 47-52 seconds). The skin time (seconds) of the foam is generally 60-80 seconds (preferably 70-80 seconds).

[0147] In the present application, the common polyether polyols (polyoxypropylene polyols) and (aromatic) polyester polyols used for the preparation of polyurethane foams or in foaming compositions are selected from the following varieties: polyether polyols (polyoxypropylene polyols) such as, for example, polyether polyol 4110 (sucrose initiator polyoxypropylene polyol) of BEFAR GROUP CO., LTD., polyether 450 (sorbitol initiator polyoxypropylene polyol) of Nanjing Hongbaoli Co., Ltd., MN500 (glycerol initiator polyoxypropylene polyol) and SA 460 (sorbitol initiator polyoxypropylene polyol) of Shandong Lansheng Dongda Chemical Co., Ltd., SA 460 (sorbitol initiator polyoxypropylene polyol), SU380 (sucrose initiator polyoxypropylene polyol) and SA380 (sorbitol initiator polyoxypropylene polyol) of Zibo Nuoli Chemical Co., Ltd., YD8260 (polyoxypropylene polyol with sucrose and diethylene glycol as initiators), YD403 (ethylenediamine initiator polyoxypropylene polyol, hydroxyl value 770 mg KOH / g) and YD460 (toluene diamine type polyoxypropylene polyol) and YD4110 (polyether polyol, hydroxyl value 460 mg KOH / g) of Hebei Yadong Chemical Group Co., Ltd., and SD7100 (toluene diamine type polyoxypropylene polyol, functionality 4, hydroxyl value 300-330 mg KOH / g, viscosity 6500-11500 mPa.s (25°C)) of Shanghai Dongda Chemical Co., Ltd.; and (aromatic) polyester polyols such as, for example, PS4051 (PET polyol), PS4027 or PS3152 of Nanjing Jinling Stepan Chemical Co., Ltd., polyester polyols CF6320 (hydroxyl value 320 mg KOH / g), CF6245, CF6200, CF6300 and CF6255 of Jiangsu Fusheng New Material Co., Ltd., and polyester polyol DM2003 of Beijing Dongfang Meilong Chemical Technology Co., Ltd.

[0148] The commonly used catalysts are selected from: 33LV (A-33): 33% triethylenediamine in dipropylene glycol, N,N-dimethylethanolamine, N,N-dimethylbenzylamine, 70% bis(dimethylaminoethyl) ether in dipropylene glycol, 70% potassium octoate 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-propanaminium carbonate), TMR-3, TMR-4. The commonly used silicone oil type foam stabilizers or silane surfactants: B8525 and B8408 of Wacker (China) Investment Co., Ltd., AK-158, AK-8805, AK-8812, AK-8809, AK-8818 and AK-8860 of Jiangsu Meishide Chemical Co., Ltd., DC8545, DC1990, DC5188, DC6070, DC3042 and DC3201 of Air & Chemicals Co., Ltd., and silicone oil 8841 of Shanghai Maihao Chemical Technology Co., Ltd. Non-silane surfactants: LK-221 and LK-443 of Air & Chemicals Co., Ltd. Commonly used flame retardants: TCPP (Qingdao Lianmei Chemical Co., Ltd.), TCEP, DMMP, ammonium chloride, aluminum hydroxide powder, DM1201, DM1301, tetrabromophthalic glycol.

[0149] The method for measuring the water content in the CO2-neutralized alcohol amine composition AC (i.e., the alcohol amine carbonate hydrate in the following examples) prepared by the method of CO2 aeration is described below.

[0150] The water content of the alcohol amine carbonate hydrate (i.e., the CO2-neutralized alcohol amine composition AC) measured by the Karl Fischer method = the amount of free water in the hydrate + the amount of water produced by the decomposition of the carbonate. Therefore, the content (wt%) of free water in the alcohol amine carbonate hydrate (i.e., the CO2-neutralized alcohol amine composition AC) = (the water content of the alcohol amine carbonate hydrate measured by the Karl Fischer method) - (the amount of water produced by the decomposition of the carbonate).

[0151] Method for measuring the content of alcohol amines in alcohol amine composition (AC) (not neutralized by CO2, or already neutralized by CO2): In the examples, for measuring the content of various alcohol amines in the aqueous alcohol amine composition (AC) (or aqueous alcohol amine mixture), gas chromatography can be used. The gas chromatograph is equipped with a hydrogen flame ionization detector (FID), and the mass concentration of the alcohol amine compound is about 10 mg / mL as a standard solution. The gas chromatography conditions are as follows: HP-5 capillary column (30 m x 0.32 mm i.d. x 0.25 μm, 5% phenyl methyl-siloxane); the column temperature is programmed, the initial temperature is 80°C, and after maintaining for 3 min, it is raised to 250°C at a rate of 25°C / min, and maintained for 5 min; the injection port temperature is 250°C; the detector temperature is 260°C; the carrier gas is high-purity nitrogen, with a flow rate of 1.5 mL / min; the combustion gas is hydrogen, with a flow rate of 30 mL / min; the combustion-supporting gas is air, with a flow rate of 300 mL / min; the tail gas is nitrogen, with a flow rate of 25 mL / min; the injection mode is split injection, with a split ratio of 30:1; the injection volume is 1 μL.

[0152] Preparation Example 1

[0153] Into a high-pressure reactor, 17.64 kg of 1,4-butanediamine (molecular weight 88.15, 200 mol) and 13.1 kg of ion-free water were added, dissolved with stirring, the reactor was sealed, and then 30.22 kg of propylene oxide (molecular weight 58.079, 520 mol) was added to the reactor in batches under constant stirring, with the temperature controlled between 60-95°C and the pressure controlled not to exceed 0.3 MPa. After the addition was completed, the temperature was controlled for 3 hours of reaction, and then the temperature was lowered to 40°C. Then, about 60.92 kg of the reaction product (alcohol amine hydrate AA1a) was discharged from the reactor, and the pH value of the product was measured by a pH meter (Ragumin PHS-3C type, Shanghai Yidian Science Instrument Co., Ltd.) to be 12.83. The content of N,N,N’-tris(hydroxyisopropyl)-butanediamine in the alcohol amine hydrate AA1a was about 120 mol, and the content of N,N’-di(hydroxyisopropyl)-butanediamine was about 80 mol, as measured by gas chromatography. The molar ratio of N,N,N’-tris(hydroxyisopropyl)-butanediamine to N,N’-di(hydroxyisopropyl)-butanediamine (i.e., triol amine A2: diol amine A1) was about 1.5:1. Its viscosity (25°C) was 437 centipoise. The water content in the alcohol amine hydrate AA1a was 21.5 wt% as measured by the Karl Fischer method.

[0154] Then, 30 kg of the obtained alcohol amine hydrate AA1a was charged into a high-pressure reactor, and carbon dioxide gas was started to be introduced into the alcohol amine hydrate AA1a under the condition that the pressure of the carbon dioxide gas output from the CO2 storage cylinder was controlled to be 0.2 MPa, and the absorption amount of CO2 was about 2.401 kg (about 54.6 mol, CO2 content was about 7.4 wt%), and the temperature was controlled to be between 40 and 50°C, and the reaction was carried out for 3 hours, and after the temperature was lowered to 40°C or less, the pressure was released, and the product was discharged, and an alcohol amine carbonate compound AA1b (CO2 content was 7.4 wt%) was obtained. The viscosity of the product AA1b (25°C) was about 1319 centipoise. The pH of the product AA1b was 9.86. The decomposition temperature thereof was between 45°C and 70°C.

[0155] Then, 30 kg of the obtained alcohol amine hydrate AA1a was charged into a high-pressure reactor, and carbon dioxide gas was started to be introduced into the alcohol amine hydrate AA1a under the condition that the pressure of the carbon dioxide gas output from the CO2 storage cylinder was controlled to be 0.2 MPa, and the absorption amount of CO2 was about 2.401 kg (about 54.6 mol, CO2 content was about 7.4 wt%), and the temperature was controlled to be between 40 and 50°C, and the reaction was carried out for 3 hours, and after the temperature was lowered to 40°C or less, the pressure was released, and the product was discharged, and an alcohol amine carbonate compound AA1b (CO2 content was 7.4 wt%) was obtained. The viscosity of the product AA1b (25°C) was about 1319 centipoise. The pH of the product AA1b was 9.86. The decomposition temperature thereof was between 45°C and 70°C.

[0156] Observation of crystallization behavior: After being left at room temperature (about 25°C) for 1 month, the alcohol amine hydrate AA1a did not exhibit crystallization, and it was found that the two kinds of alcohol amines were doped with each other. Also, the alcohol amine carbonate compounds AA1b and AA1c did not exhibit crystallization.

[0157] Preparation Example 2

[0158] Into a high-pressure reactor, 17.64 kg of 1,4-butanediamine (molecular weight 88.15, 200 mol), 9.0 kg of ion-free water were added, dissolved with stirring, the reactor was sealed, and then 25.56 kg of propylene oxide (molecular weight 58.079, 440 mol) was added to the reactor in batches while controlling the temperature between 60 and 95°C and the pressure to be not higher than 0.3 MPa with constant stirring. After the addition was completed, the temperature was controlled for 3 hours, and then the temperature was lowered to 40°C. Then, about 52.0 kg of the reaction product (an alcohol amine hydrate AA2a) was discharged from the reactor, and the pH of the product was measured by a pH meter to be 13.34. The content of N,N,N'-tris(hydroxyisopropyl)-butanediamine in the alcohol amine hydrate AA2a was about 40 mol, and the content of N,N'-di(hydroxyisopropyl)-butanediamine was about 160 mol, as measured by gas chromatography from a sample of the product. The molar ratio of N,N,N'-tris(hydroxyisopropyl)-butanediamine to N,N'-di(hydroxyisopropyl)-butanediamine was about 0.25:1. The viscosity (25°C) thereof was 358 centipoise. The water content in the alcohol amine hydrate AA2a was 17.2 wt% as measured by the Karl Fischer method.

[0159] Then, 25 kg of the alcohol amine hydrate AA2a obtained above was added to a high-pressure reactor, and carbon dioxide gas was started to be introduced into the alcohol amine hydrate AA2a while controlling the pressure of the CO2 gas output from a CO2 storage cylinder to be 0.2 MPa, and the absorption amount of CO2 was about 2.322 kg (about 52.77 mol, CO2 content was about 8.5 wt%), the temperature was controlled to be between 40 and 50°C, and the temperature was controlled for 3 hours. After the temperature was lowered to below 40°C, the pressure was released, and the product was discharged, and an alcohol amine carbonate compound AA2b (CO2 content was 8.5 wt%) was obtained. The viscosity (25°C) of the product AA2b was about 1668 centipoise. The pH of the product AA2b was 9.95. The decomposition temperature thereof was between 45°C and 70°C.

[0160] Then, 25 kg of the alcohol amine hydrate AA2a obtained above was added to a high-pressure reactor, and carbon dioxide gas was started to be introduced into the alcohol amine hydrate AA2a while controlling the pressure of the CO2 gas output from a CO2 storage cylinder to be 0.2 MPa, and the absorption amount of CO2 was about 2.322 kg (about 52.77 mol, CO2 content was about 8.5 wt%), the temperature was controlled to be between 40 and 50°C, and the temperature was controlled for 3 hours. After the temperature was lowered to below 40°C, the pressure was released, and the product was discharged, and an alcohol amine carbonate compound AA2b (CO2 content was 8.5 wt%) was obtained. The viscosity (25°C) of the product AA2b was about 1668 centipoise. The pH of the product AA2b was 9.95. The decomposition temperature thereof was between 45°C and 70°C.

[0161] Observation of crystallization behavior: After 1 month at room temperature, no crystallization occurred for the amine alcohol hydrate AA2a, indicating that the two amine alcohols were doped with each other. No crystallization occurred for the amine alcohol carbonate compounds AA2b and AA2c.

[0162] Preparation Example 3

[0163] A high pressure reactor was charged with 17.64 kg of 1,4-butanediamine (molecular weight 88.15, 200 mol), 9.2 kg of ion-free water, and the reactor was sealed and stirred to dissolve the contents. The reactor was then charged with 23.232 kg of propylene oxide (molecular weight 58.079, 400 mol) in portions while maintaining the temperature between 60 and 95 °C and the pressure below 0.3 MPa, and the reactor was stirred while maintaining the temperature for 3 hours after the addition was complete. The reactor was then cooled to 40 °C. About 50 kg of the reaction product (amine alcohol hydrate AA3a) was then removed from the reactor, and the pH of the product was measured to be 13.46. The amine alcohol hydrate AA3a was sampled and analyzed by gas chromatography to determine that it contained about 0.02 mol of N,N,N'-tris(hydroxyisopropyl)-butanediamine and about 199.98 mol of N,N'-di(hydroxyisopropyl)-butanediamine. The viscosity of the amine alcohol hydrate AA3a (25 °C) was 324 centipoise. The water content of the amine alcohol hydrate AA3a was measured by Karl Fischer titration to be 18.4 wt%. A sample of the product was taken for NMR analysis. The NMR of the product is shown in Figure 3. Figure 2 . Figure 2 The product of Preparation Example 3 was shown to be N,N'-di(hydroxyisopropyl)-butanediamine. This indicates that the amine alcohol product obtained from the reaction of a C4-C6 alkylene diamine with an epoxide depends on the molar ratio of the C4-C6 alkylene diamine to the epoxide.

[0164] The amine alcohol hydrate AA3a obtained above was then charged into a high pressure reactor, and carbon dioxide gas was introduced into the amine alcohol hydrate AA3a while controlling the pressure of the CO2 gas from a CO2 storage cylinder to be 0.2 MPa, and the amount of CO2 absorbed was about 2.502 kg (about 56.86 mol, CO2 content about 9.1 wt%). The temperature was controlled to be between 40 and 50 °C, and the reaction was maintained at this temperature for 3 hours. The temperature was then lowered to below 40 °C, and the pressure was released to release the product. An amine alcohol carbonate compound AA3b was obtained (CO2 content 9.1 wt%). The viscosity of the product AA3b (25 °C) was about 1657 centipoise. The pH of the product AA3b was 10.57. The decomposition temperature of the product AA3b was between 45 °C and 70 °C.

[0165] Observation of crystallization behavior: After standing at room temperature for 1 month, the alcohol amine hydrate AA3a completely crystallized. After standing at room temperature for 1 month, the alcohol amine carbonate compound AA3b formed a part of crystallization, which indicates that the crystallization behavior was inhibited to some extent after neutralization with CO2.

[0166] Preparation Example 4

[0167] Into a high-pressure reactor, 17.64 kg of 1,4-butanediamine (molecular weight 88.15, 200 mol), 12.2 kg of ion-free water were charged, dissolved with stirring, the reactor was sealed, and then 34.85 kg of propylene oxide (molecular weight 58.079, 600 mol) was added to the reactor in batches while controlling the temperature between 60 and 95°C and the pressure not higher than 0.3 MPa with continuous stirring, and after the addition was completed, the temperature was controlled for 3 hours, and then the temperature was lowered to 40°C. Then, about 64.66 kg of the reaction product (alcohol amine hydrate AA4a) was discharged from the reactor, and the pH of the product was measured by a pH meter to be 12.37. The content of N,N,N'-tris(hydroxyisopropyl)-butanediamine in the alcohol amine hydrate AA4a was about 199.97 mol, and the content of N,N'-di(hydroxyisopropyl)-butanediamine was about 0.03 mol, which was measured by gas chromatography from the sample of the product. The viscosity (25°C) thereof was 540 centipoise. The water content in the alcohol amine hydrate AA4a was 18.87 wt% which was measured by Karl Fischer method.

[0168] Then, 30 kg of the above obtained alcohol amine hydrate AA4a was charged into a high-pressure reactor, and carbon dioxide gas was started to be introduced into the alcohol amine hydrate AA4a while controlling the pressure of the CO2 gas output from a CO2 storage steel cylinder to be 0.2 MPa, and the absorption amount of CO2 was about 0.309 kg (about 7.02 mol, CO2 content was about 1.02 wt%), and the temperature was controlled between 40 and 50°C for 3 hours, and after the temperature was lowered to below 40°C, the pressure was released, and the product was discharged, and thus an alcohol amine carbonate compound AA4b (CO2 content was 1.02 wt%) was obtained. The viscosity (25°C) of the product AA4b was about 682 centipoise. The pH of the product AA4b was 11.28. The decomposition temperature thereof was between 45 and 70°C.

[0169] Observation of crystallization behavior: After standing at room temperature for 1 month, the alcohol amine hydrate AA4a partially crystallized. After standing at room temperature for 1 month, the alcohol amine carbonate compound AA4b formed a small amount of crystallization.

[0170] Preparation Example 5

[0171] Into a high-pressure reactor, 20.44 kg of 1,5-pentanediamine (molecular weight 102.18, 200 mol), 10.54 kg of ion-free water were added, dissolved with stirring, the reactor was sealed, and then 29.05 kg of propylene oxide (molecular weight 58.079, 500 mol) was added to the reactor in portions while controlling the temperature to be between 60 and 95°C and the pressure to be not higher than 0.3 MPa with constant stirring, and after the addition was completed, the temperature was controlled for 3 hours, and then the temperature was lowered to 40°C. Then, about 60 kg of the reaction product (an alcohol amine hydrate AA5a) was discharged from the reactor, and the pH of the product was measured by a pH meter to be 13.05. The content of N,N,N'-tris(hydroxyisopropyl)-pentanediamine and N,N'-di(hydroxyisopropyl)-pentanediamine in the alcohol amine hydrate AA5a was measured by gas chromatography to be about 100 mol and about 100 mol, respectively, and the molar ratio of N,N,N'-tris(hydroxyisopropyl)-pentanediamine to N,N'-di(hydroxyisopropyl)-pentanediamine was about 1:1. The viscosity (25°C) thereof was 418 centipoise. The water content in the alcohol amine hydrate AA5a was measured by the Karl Fischer method to be 17.6 wt%.

[0172] Then, 30 kg or more of the obtained alcohol amine hydrate AA5a was added to a high-pressure reactor, and carbon dioxide gas was started to be supplied to the alcohol amine hydrate AA5a while controlling the pressure of the CO2 gas output from a CO2 storage cylinder to be 0.2 MPa, and the absorption amount of CO2 was about 2.3 kg (about 52.27 mol, CO2 content was about 7.12 wt%), the temperature was controlled to be between 40 and 50°C, and the temperature was controlled for 3 hours, and then the temperature was lowered to 40°C or less, the pressure was released, and the product was discharged, and an alcohol amine carbonate compound AA5b (CO2 content was 7.12 wt%) was obtained. The viscosity (25°C) of the product AA5b was about 1216 centipoise. The pH of the product AA5b was 9.94. The decomposition temperature thereof was between 45°C and 70°C.

[0173] Then, 30 kg or more of the obtained alcohol amine hydrate AA5a was added to a high-pressure reactor, and carbon dioxide gas was started to be supplied to the alcohol amine hydrate AA5a while controlling the pressure of the CO2 gas output from a CO2 storage cylinder to be 0.2 MPa, and the absorption amount of CO2 was about 2.3 kg (about 52.27 mol, CO2 content was about 7.12 wt%), the temperature was controlled to be between 40 and 50°C, and the temperature was controlled for 3 hours, and then the temperature was lowered to 40°C or less, the pressure was released, and the product was discharged, and an alcohol amine carbonate compound AA5b (CO2 content was 7.12 wt%) was obtained. The viscosity (25°C) of the product AA5b was about 1216 centipoise. The pH of the product AA5b was 9.94. The decomposition temperature thereof was between 45°C and 70°C.

[0174] Observation of crystallization behavior: After being left at room temperature for 1 month, the alcohol amine hydrate AA5a did not show any crystallization, indicating that the two alcohol amines doped each other. The alcohol amine carbonate compounds AA5b and AA5c also did not show any crystallization.

[0175] Preparation Example 6

[0176] Into a high-pressure reactor, 20.44 kg of 1,5-pentanediamine (molecular weight 102.18, 200 mol), 10.5 kg of ion-free water were added, dissolved with stirring, the reactor was sealed, and then 30.22 kg of propylene oxide (molecular weight 58.079, 520 mol) was added to the reactor in batches under constant stirring, temperature control between 60-95°C, and pressure control not higher than 0.3 MPa. After the addition was completed, the temperature was controlled for 3 hours, and then the temperature was lowered to 40°C. Then, about 61 kg of the reaction product (alcohol amine hydrate AA6a) was discharged from the reactor, and the pH value of the product was measured by a pH meter to be 12.73. The content of N,N,N'-tris(hydroxyisopropyl)-pentanediamine in the alcohol amine hydrate AA6a was about 120 mol, and the content of N,N'-di(hydroxyisopropyl)-pentanediamine was about 80 mol, as measured by gas chromatography. The molar ratio of N,N,N'-tris(hydroxyisopropyl)-pentanediamine to N,N'-di(hydroxyisopropyl)-pentanediamine was about 1.5:1. The viscosity (25°C) thereof was 533 centipoise. The water content in the alcohol amine hydrate AA6a was 17.2 wt% as measured by Karl Fischer method.

[0177] Then, 30 kg of the alcohol amine hydrate AA6a obtained above was added to a high-pressure reactor, and carbon dioxide gas was introduced into the alcohol amine hydrate AA6a under the condition that the pressure of the CO2 gas output from a CO2 storage steel cylinder was controlled to be 0.2 MPa, the absorption amount of CO2 was about 1.303 kg (about 29.6 mol, CO2 content was about 4.16 wt%), the temperature was controlled to be between 40-50°C, and the temperature-controlled reaction was carried out for 3 hours. After the temperature was lowered to below 40°C, the pressure was released, and the product was discharged to obtain the alcohol amine carbonate compound AA6b (CO2 content was 4.16 wt%). The viscosity (25°C) of the product AA6b was about 978 centipoise. The pH of the product AA6b was 10.38. The decomposition temperature thereof was between 45°C and 70°C.

[0178] Observation of crystallization behavior: After being left at room temperature for 1 month, the alcohol amine hydrate AA6a did not show any crystallization, indicating that the two alcohol amines doped each other. Similarly, the alcohol amine carbonate compound AA6b also did not show any crystallization.

[0179] Preparation Example 7

[0180] Into a high-pressure reactor, 20.44 kg of 1,5-pentanediamine (molecular weight 102.18, 200 mol), 9.13 kg of ion-free water were added, dissolved with stirring, the reactor was sealed, and then 25.56 kg of propylene oxide (molecular weight 58.079, 440 mol) was added in portions to the reactor while controlling the temperature to be between 60 and 95°C and the pressure to be not higher than 0.3 MPa with constant stirring, and after the addition was completed, the temperature was controlled for 3 hours, and then the temperature was lowered to 40°C. Then, about 55 kg of the reaction product (an alcohol amine hydrate AA7a) was discharged from the reactor, and the pH of the product was measured by a pH meter to be 13.22. The content of N,N,N'-tris(hydroxyisopropyl)-pentanediamine in the alcohol amine hydrate AA7a was measured by gas chromatography to be about 40 mol, and the content of N,N'-di(hydroxyisopropyl)-pentanediamine was about 160 mol, and the molar ratio of N,N,N'-tris(hydroxyisopropyl)-pentanediamine to N,N'-di(hydroxyisopropyl)-pentanediamine was about 0.25:1. The viscosity of the sample of the product was 527 centipoises (25°C). 1 The H-NMR spectrum is shown in Figure 13 The viscosity of the product (25°C) was 527 centipoises. The water content in the alcohol amine hydrate AA7a was measured by the Karl Fischer method to be 16.6 wt%.

[0181] Then, 25 kg of the alcohol amine hydrate AA7a obtained above was added to a high-pressure reactor, and carbon dioxide gas was started to be introduced into the alcohol amine hydrate AA7a while controlling the pressure of the CO2 gas output from a CO2 storage cylinder to be 0.2 MPa, and the absorption amount of CO2 was about 1.882 kg (about 42.77 mol, CO2 content was about 7.0 wt%), the temperature was controlled to be between 40 and 50°C, and the temperature was controlled for 3 hours, and after the temperature was lowered to 40°C or less, the pressure was released, and the product was discharged, and an alcohol amine carbonate compound AA7b (CO2 content was 7.0 wt%) was obtained. The viscosity of the product AA7b (25°C) was about 1281 centipoises. The pH of the product AA7b was 10.16. Its decomposition temperature was between 45°C and 70°C.

[0182] Then, 25 kg or more of the obtained alcohol amine hydrate AA7a was charged into a high-pressure reactor, and carbon dioxide gas was introduced into the alcohol amine hydrate AA7a under conditions that the pressure of the carbon dioxide gas output from a CO2 storage cylinder was controlled to be 0.2 MPa, and the absorption amount of CO2 was about 1.05 kg (about 23.86 mol, CO2 content: about 4.03 wt %), and the temperature was controlled to be between 40 and 50°C, and the reaction was performed for 3 hours while controlling the temperature, and after the temperature was lowered to 40°C or less, the pressure was released, and the product was discharged, and an alcohol amine carbonate compound AA7c (CO2 content: 4.03 wt %) was obtained. The viscosity of the product AA7c (25°C) was about 847 cP. The pH of the product AA7c was 10.63. The decomposition temperature thereof was between 45°C and 70°C.

[0183] Observation of crystallization behavior: After being left at room temperature for 1 month, the alcohol amine hydrate AA7a did not exhibit crystallization, and it was found that the two kinds of alcohol amines were doped with each other. The alcohol amine carbonate compounds AA7b and AA7c also did not exhibit crystallization.

[0184] Preparation Example 8

[0185] Then, 23.242 kg of 1,6-hexanediamine (molecular weight: 116.2, 200 mol), 10.76 kg of ion-free water were charged into a high-pressure reactor, and dissolved with stirring, and the reactor was sealed, and then 29.04 kg of propylene oxide (molecular weight: 58.079, 500 mol) was added to the reactor in batches while controlling the temperature to be between 60 and 95°C and the pressure to be 0.3 MPa or less with continuous stirring, and after the addition was completed, the temperature was controlled for 3 hours, and then the temperature was lowered to 40°C. Then, about 63 kg of the reaction product (alcohol amine hydrate AA8a) was discharged from the reactor, and the pH of the product was measured by a pH meter to be 12.95. The content of N,N,N'-tris(hydroxyisopropyl)-hexanediamine and the content of N,N'-di(hydroxyisopropyl)-hexanediamine in the alcohol amine hydrate AA8a were measured by gas chromatography to be about 100 mol and about 100 mol, respectively, and the molar ratio of N,N,N'-tris(hydroxyisopropyl)-hexanediamine to N,N'-di(hydroxyisopropyl)-hexanediamine was about 1:1. The viscosity of the alcohol amine hydrate AA8a (25°C) was 550 cP. The water content in the alcohol amine hydrate AA8a was measured by the Karl Fischer method to be 17.07 wt %.

[0186] Then, 30 kg of the obtained alcohol amine hydrate AA5a was charged into a high-pressure reactor, and carbon dioxide gas was started to be supplied to the alcohol amine hydrate AA5a under the condition that the pressure of the carbon dioxide gas outputted from the CO2 storage cylinder was controlled to be 0.2 MPa, and the absorption amount of CO2 was about 1.306 kg (about 29.68 mol, CO2 content was about 4.17 wt%), and the temperature was controlled to be between 40 and 50°C, and the reaction was carried out for 3 hours, and after the temperature was lowered to 40°C or less, the pressure was released, and the product was discharged, and the alcohol amine carbonate compound AA8c (CO2 content was 4.17 wt%) was obtained. The viscosity (25°C) of the product AA8c was about 861 centipoise. The pH of the product AA8c was 10.46. The decomposition temperature thereof was in the range of 45°C to 70°C.

[0187] Then, 30 kg of the obtained alcohol amine hydrate AA5a was charged into a high-pressure reactor, and carbon dioxide gas was started to be supplied to the alcohol amine hydrate AA5a under the condition that the pressure of the carbon dioxide gas outputted from the CO2 storage cylinder was controlled to be 0.2 MPa, and the absorption amount of CO2 was about 1.306 kg (about 29.68 mol, CO2 content was about 4.17 wt%), and the temperature was controlled to be between 40 and 50°C, and the reaction was carried out for 3 hours, and after the temperature was lowered to 40°C or less, the pressure was released, and the product was discharged, and the alcohol amine carbonate compound AA8c (CO2 content was 4.17 wt%) was obtained. The viscosity (25°C) of the product AA8c was about 861 centipoise. The pH of the product AA8c was 10.46. The decomposition temperature thereof was in the range of 45°C to 70°C.

[0188] Observation of crystallization behavior: After being left at room temperature for 1 month, the alcohol amine hydrate AA8a did not exhibit crystallization, and it was suggested that the two kinds of alcohol amines were doped with each other. The alcohol amine carbonate compounds AA8b and AA8c also did not exhibit crystallization.

[0189] Preparation Example 9

[0190] Into a high-pressure reactor, 23.242 kg of 1,6-hexanediamine (molecular weight 116.2, 200 mol), 10.7 kg of ion-free water were added, dissolved with stirring, the reactor was sealed, and then 30.22 kg of propylene oxide (molecular weight 58.079, 520 mol) was added in portions to the reactor while controlling the temperature to be between 60 and 95°C and the pressure to be not higher than 0.3 MPa, and after the addition was completed, the temperature was controlled for 3 hours, and then the temperature was lowered to 40°C. Then, about 64 kg of the reaction product (an alcohol amine hydrate AA9a) was discharged from the reactor, and the pH of the product was measured by a pH meter to be 12.65. The content of N,N,N'-tris(hydroxyisopropyl)-hexanediamine in the alcohol amine hydrate AA9a was about 120 mol, and the content of N,N'-di(hydroxyisopropyl)-hexanediamine was about 80 mol, and the molar ratio of N,N,N'-tris(hydroxyisopropyl)-hexanediamine to N,N'-di(hydroxyisopropyl)-hexanediamine was about 1.5:1, as measured by gas chromatography from a sample taken from the product. The viscosity (25°C) thereof was 602 centipoise. The water content in the alcohol amine hydrate AA9a was 16.68 wt% as measured by the Karl Fischer method.

[0191] Then, 30 kg of the alcohol amine hydrate AA6a obtained above was added to a high-pressure reactor, and carbon dioxide gas was started to be supplied to the alcohol amine hydrate AA6a while controlling the pressure of the CO2 gas supplied from a CO2 storage cylinder to be 0.2 MPa, and the absorption amount of CO2 was about 0.96 kg (about 21.82 mol, CO2 content was about 3.1 wt%), and the temperature was controlled to be between 40 and 50°C, and the temperature was controlled for 3 hours, and after the temperature was lowered to 40°C or less, the pressure was released, and the product was discharged, and an alcohol amine carbonate compound AA9b (CO2 content was 3.1 wt%) was obtained. The viscosity (25°C) of the product AA9b was about 980 centipoise. The pH of the product AA9b was 10.57. The decomposition temperature thereof was between 45°C and 70°C.

[0192] Observation of crystallization behavior: After being left at room temperature for 1 month, the alcohol amine hydrate AA9a did not exhibit crystallization, and it was found that the two kinds of alcohol amines were doped with each other. The alcohol amine carbonate compound AA9b also did not exhibit crystallization.

[0193] Preparation Example 10

[0194] Into a high-pressure reactor, 23.242 kg of 1,6-hexanediamine (molecular weight 116.2, 200 mol), 9.33 kg of ion-free water were added, dissolved with stirring, the reactor was sealed, and then 25.56 kg of propylene oxide (molecular weight 58.079, 440 mol) was added in portions to the reactor while controlling the temperature to be between 60 and 95°C and the pressure to be not higher than 0.3 MPa with constant stirring, and after the addition was completed, the temperature was controlled for 3 hours, and then the temperature was lowered to 40°C. Then, about 58 kg of the reaction product (an alcohol amine hydrate AA10a) was discharged from the reactor, and the pH of the product was measured by a pH meter to be 13.15. The content of N,N,N'-tris(hydroxyisopropyl)-hexanediamine in the alcohol amine hydrate AA10a was about 40 mol, and the content of N,N'-di(hydroxyisopropyl)-hexanediamine was about 160 mol, and the molar ratio of N,N,N'-tris(hydroxyisopropyl)-hexanediamine to N,N'-di(hydroxyisopropyl)-hexanediamine was about 0.25:1, as measured by gas chromatography from a sample of the product. The viscosity (25°C) thereof was 548 centipoise. The water content in the alcohol amine hydrate AA10a was 16.05 wt% as measured by the Karl Fischer method.

[0195] Then, 25 kg of the above obtained alcohol amine hydrate AA7a was added to a high-pressure reactor, and carbon dioxide gas was started to be supplied to the alcohol amine hydrate AA7a while controlling the pressure of the CO2 gas output from a CO2 storage cylinder to be 0.2 MPa, and the absorption amount of CO2 was about 1.854 kg (about 42.14 mol, CO2 content was about 6.9 wt%), and the temperature was controlled to be between 40 and 50°C, and the temperature was controlled for 3 hours, and then the temperature was lowered to below 40°C, and then the pressure was released, and the product was discharged, and an alcohol amine carbonate compound AA10b (CO2 content was 6.9 wt%) was obtained. The viscosity (25°C) of the product AA10b was about 1357 centipoise. The pH of the product AA10b was 9.96. The decomposition temperature thereof was between 45°C and 70°C.

[0196] Then, 25 kg of the above obtained alcohol amine hydrate AA7a was added to a high-pressure reactor, and carbon dioxide gas was started to be supplied to the alcohol amine hydrate AA7a while controlling the pressure of the CO2 gas output from a CO2 storage cylinder to be 0.2 MPa, and the absorption amount of CO2 was about 1.854 kg (about 42.14 mol, CO2 content was about 6.9 wt%), and the temperature was controlled to be between 40 and 50°C, and the temperature was controlled for 3 hours, and then the temperature was lowered to below 40°C, and then the pressure was released, and the product was discharged, and an alcohol amine carbonate compound AA10b (CO2 content was 6.9 wt%) was obtained. The viscosity (25°C) of the product AA10b was about 1357 centipoise. The pH of the product AA10b was 9.96. The decomposition temperature thereof was between 45°C and 70°C.

[0197] Observation of crystallization behavior: After 1 month of storage at room temperature, no crystallization was observed for the alkanolamine hydrate AA10a, indicating that the two alkanolamines are doped with each other. No crystallization was observed for the alkanolamine carbonate compounds AA10b and AA10c.

[0198] Preparation Example 11 (comparative)

[0199] Into a high pressure reactor, 20.635 kg of diethylenetriamine (molecular weight 103.17, 200 mol), 10.65 kg of ion-free water were added, dissolved with stirring, the reactor was sealed, and then 29.04 kg of propylene oxide (molecular weight 58.079, 500 mol) was added to the reactor in batches under constant stirring, temperature control between 60-95°C, and pressure control not higher than 0.3 MPa. After the addition was completed, the temperature was controlled for 3 hours, and then the temperature was lowered to 40°C. Then, about 60.1 kg of reaction product (alkanolamine hydrate AA11a) was discharged from the reactor, which was a transparent viscous liquid. The pH of the product was 13.75 as measured by a pH meter. The molar ratio of triolamine to diolamine in the product was about 1:1. Its viscosity (25°C) was 1023 centipoise. The water content in the alkanolamine hydrate AA11a was 17.65 wt% as measured by Karl Fischer method.

[0200] Then, 30 kg of the above obtained alkanolamine hydrate AA11a was added to a high pressure reactor, and carbon dioxide gas was introduced into the alkanolamine hydrate AA11a under the condition that the pressure of the CO2 gas output from the CO2 storage steel cylinder was controlled at 0.2 MPa, the absorption amount of CO2 was about 2.02 kg (about 45.91 mol, CO2 content was about 6.3 wt%), the temperature was controlled between 40-50°C, and the temperature was controlled for 3 hours. After the temperature was lowered to below 40°C, the pressure was released, and the product was discharged to obtain the alkanolamine carbonate compound AA11b (CO2 content was 6.3 wt%). The viscosity (25°C) of the product AA11b was about 2282 centipoise. The pH of the product AA11b was 11.27. Its decomposition temperature was between 45°C-70°C.

[0201] Then, 30 kg or more of the obtained alcohol amine hydrate AA11a was charged into a high-pressure reactor, and carbon dioxide gas was introduced into the alcohol amine hydrate AA11a under the condition that the pressure of the carbon dioxide gas output from a CO2 storage cylinder was controlled to be 0.2 MPa, and the absorption amount of CO2 was about 0.763 kg (about 17.34 mol, CO2 content: about 2.48 wt %). The temperature was controlled to be between 40 and 50°C, and the reaction was carried out for 3 hours. After the temperature was lowered to 40°C or less, the pressure was released, and the product was discharged. Thus, an alcohol amine carbonate compound AA11c (CO2 content: 2.48 wt %) was obtained. The viscosity of the product AA11c (25°C) was about 1326 cP. The pH of the product AA11c was 12.06. The decomposition temperature thereof was between 45°C and 70°C.

[0202] Observation of crystallization behavior: After being left at room temperature for 1 month, the alcohol amine hydrate AA11a was partially crystallized. Also, the alcohol amine carbonate compounds AA11b and AA11c were slightly crystallized, and the viscosity was too high to be used conveniently.

[0203] Preparation Example 12

[0204] Then, 23.242 kg of 1,6-hexanediamine (molecular weight: 116.2, 200 mol) and 12.7 kg of ion-free water were charged into a high-pressure reactor, and dissolved with stirring. After the reactor was sealed, 34.85 kg of propylene oxide (molecular weight: 58.079, 600 mol) was added to the reactor in portions while the temperature was controlled to be between 60 and 95°C and the pressure was controlled to be 0.3 MPa or less with stirring. After the addition was completed, the temperature was controlled for 3 hours, and then the temperature was lowered to 40°C. Then, about 70.52 kg of the reaction product (alcohol amine hydrate AA12a) was discharged from the reactor. The pH of the product was 12.15 as measured with a pH meter. The content of N,N,N'-tris(hydroxyisopropyl)-hexanediamine in the alcohol amine hydrate AA12a was about 199.98 mol, and the content of N,N'-di(hydroxyisopropyl)-hexanediamine was about 0.02 mol as measured with gas chromatography. The viscosity of the sample of the product (25°C) was 577 cP. The water content in the alcohol amine hydrate AA12a was 17.94 wt % as measured with a Karl Fischer method. 1 H-NMR spectrum is shown in Figure 14 The viscosity of the product (25°C) was 577 cP. The water content in the alcohol amine hydrate AA12a was 17.94 wt % as measured with a Karl Fischer method.

[0205] Application Example

[0206] Example 1

[0207] 1. Components used and relative amounts:

[0208] Foaming agent: 8 parts by weight of the alcohol amine carbonate compound AA1c (wherein the CO2 content is 4.15 wt%, the molar ratio of N,N,N'-tris(hydroxyisopropyl)-butane diamine to N,N'-di(hydroxyisopropyl)-butane diamine is about 1.5:1) prepared from Preparation Example 1 above as the alcohol amine composition (AC) and 18 parts by weight of cyclopentane.

[0209] Dry white material: it is composed of the following components: 40 parts by weight of polyether polyol SD7100 (toluene diamine type polyoxypropylene polyol, produced by Shanghai Dongda Chemical Co., Ltd.), 20 parts by weight of YD460 (toluene diamine type polyoxypropylene polyol, Hebei Yadong Chemical Group Co., Ltd.), 10 parts by weight of PS4051 (PET aromatic polyester polyol, Nanjing Jinling Sipernat Chemical Co., Ltd.), 20 parts by weight of polyether polyol YD-8260 (polyoxypropylene polyol with sucrose and diethylene glycol as starter, produced by Hebei Yadong Chemical Trade Co., Ltd.), 10 parts by weight of YD403 (polyoxypropylene polyol with ethylene diamine as starter, hydroxyl value 770 mg KOH / g, Hebei Yadong Chemical Group Co., Ltd.), 3 parts by weight of foam stabilizer 8841 (silicone oil, produced by Shanghai Maihao Chemical Technology Co., Ltd.), 0.1 parts by weight of N,N,N,N,N-pentamethyl diethylene triamine (code PC-5, produced by American Evonik Degussa Co., Ltd.), 0.5 parts by weight of amine catalyst BX-405 (produced by American Evonik Degussa Co., Ltd.), 1 part by weight of tris(dimethylaminopropyl)hexahydro triazine (code PC-41, produced by American Evonik Degussa Co., Ltd.). Total 104.6 parts by weight of dry white material (i.e. 100 parts by weight of polymeric polyol + 4.6 parts by weight of auxiliary).

[0210] Black material: 156 parts of polyisocyanate MDI (PM200, Yantai Wanhua Chemical Group Co., Ltd.) as the black material.

[0211] Observation of 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 (polymeric polyol) had good compatibility.

[0212] Observation of the stratification phenomenon: the dry white material and all the foaming agent were mixed under stirring to obtain a white material, the obtained white material was then quickly defoamed by centrifugal treatment (speed 4500 rpm, centrifugal time 5 minutes), and then the material was observed for stratification phenomenon (i.e. whether there was a thin layer of material at the bottom), and the result was that no stratification phenomenon was found in the white material after centrifugal defoaming treatment.

[0213] 2. Foaming reaction process:

[0214] The foaming process was carried out by using the same formulation as above (or composition) by means of a high pressure injection foaming machine (RSC 16 / 16, Krauss Maffei, Germany). The foaming agent, dry white material and black material were inputted into the injection foaming machine via their respective material lines for stirring and mixing, and then the mixed foaming material was injected into a Lanx foam mold by a spray gun for foaming. The specific operation was as follows: first, the amount of the foaming material for the first injection of the injection machine was set to about 200 g, and then the set amount of the foaming material was injected into a plastic bag by the spray gun for free foaming, and the initiation time of the foaming material was measured to be 7 seconds and the stringing time at the spray gun nozzle was measured to be 48 seconds, and then the amount of the foaming material was set according to the volume of the Lanx mold, and the corresponding set amount of the foaming material was injected into the Lanx mold for foaming. The mold was opened (i.e. the inner and outer mold clamps were opened) after 180 seconds. The foam sample was taken for analyzing the microstructure and thermal insulation performance of the foam. The SEM photo of the sample is shown in Figure 1 .

[0215] From the SEM photo, it can be clearly seen that the number of cells per unit area is large, the average diameter of the cells of the foam sample is small (about 205 μm), and the size of the cells is uniform.

[0216] The initiation time of the foaming process was measured to be 7 seconds, and the stringing time was measured to be 48 seconds. The initiation time and the stringing time are very consistent with the range of the initiation time and the stringing time required in the slow reaction type foaming process on the industrial production line of the refrigerator, and therefore the foam is suitable for use in the refrigerator.

[0217] Example 2

[0218] Example 1 was repeated, except that the foaming agent was 8 parts by weight of an alcohol amine carbonate compound AA2c (wherein the CO2content was 4.29 wt%, and the molar ratio of triol amine to diol amine was 0.25:1) prepared by Preparation Example 2 above as an alcohol amine composition (AC) and 18 parts by weight of cyclopentane.

[0219] Observation of 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 had good compatibility with the dry white material.

[0220] From the SEM photo of the rigid foam ( Figure 3 ), it can be seen that the average diameter of the cells is small (about 212 um) and the size of the cells is uniform.

[0221] Example 3

[0222] Repeat Example 1, except that the foaming agent is: 8 parts by weight of the alcohol amine carbonate compound AA2b prepared in Preparation Example 2 above (wherein the CO2 content is 8.5 wt% and the molar ratio of triolamine to diolamine is 0.25:1) as an alcohol amine composition (AC) and 18 parts by weight of cyclopentane.

[0223] SEM images of rigid foam ( Figure 4 It can be seen that the average diameter of the bubbles is larger (about 245 μm, which is slightly larger than the average bubble diameter of Example 2) and the size uniformity of the bubbles is slightly lower than that of Example 2.

[0224] Example 3 Figure 4 Compared with Example 2 Figure 3 In comparison, it can be found that: compared with the case of AA2c with a CO2 content of 4.29 wt% in Example 2, the case of AA2b with a CO2 content of more than 8 wt% in Example 3 resulted in a higher viscosity of the white material. Therefore, the higher viscosity of the white material and the higher CO2 content led to an increase in the size of the foam cells and a slight decrease in the uniformity of the cell size.

[0225] Example 4

[0226] Repeat Example 1, except that the foaming agent is: 8 parts by weight of the alcoholamine carbonate compound AA5c prepared in Preparation Example 5 above as an alcoholamine composition (AC) (wherein the CO2 content is 4.19 wt%, and the molar ratio of N,N,N'-tris(hydroxyisopropyl)-pentanediamine to N,N'-di(hydroxyisopropyl)-pentanediamine is approximately 1:1) and 18 parts by weight of cyclopentane.

[0227] SEM images of rigid foam ( Figure 5 It can be seen that the average diameter of the pores in the foam is smaller (about 192 μm) and the size of the pores is more uniform compared to the foams in Examples 1-3.

[0228] The results of Example 4 show that when the molar ratio of triolamine A2 to diolamine A1 is approximately 1:1, the resulting foam has a very desirable microstructure and properties.

[0229] Example 5

[0230] Repeat Example 1, except that the foaming agent is: 8 parts by weight of the alcoholamine carbonate compound AA5b prepared in Preparation Example 5 above (wherein the CO2 content is 7.12 wt% and the molar ratio of triolamine to diolamine is approximately 1:1) and 18 parts by weight of cyclopentane as an alcoholamine composition (AC).

[0231] SEM images of rigid foam are shown below Figure 6The average cell diameter of the cells is larger (about 240 um, which is slightly larger than the average cell diameter of the foam of Example 4) and the uniformity of the size of the cells is slightly lower than the uniformity of the cell size of Examples 1 and 4.

[0232] The microstructure of the rigid foam of Example 5 Figure 6 In comparison, it can be found that, in Example 5, AA5b having a CO2 content higher than 7 wt% is used, thus, higher viscosity of the white material and higher CO2 content result in the increase of the cell size of the obtained foam, compared to the case of AA5c having a CO2 content of 4.19 wt% in Example 4. Figure 5 In addition, the microstructure of the rigid foam of Example 5

[0233] In comparison, it can be found that, when the molar ratio of the triol amine A2 to the diol amine Al is about 1:1, the microstructure (e.g. the uniformity of the cell size) and the performance of the obtained foam are more desirable, compared to the case of the molar ratio of the triol amine A2 to the diol amine Al being about 0.25:1. Figure 6 Figure 4 Example 6

[0234] Example 1 is repeated except that the blowing agent is: 8 parts by weight of an alcohol amine carbonate compound AA6b (wherein the CO2 content is 4.16 wt%, the molar ratio of N,N,N'-tris(hydroxyisopropyl)-pentanediamine to N,N'-bis(hydroxyisopropyl)-pentanediamine is about 1.5:1) prepared in Preparation Example 6 above as an alcohol amine composition (AC) and 18 parts by weight of cyclopentane.

[0235] The SEM photograph of the rigid foam is shown in From the SEM photograph, it can be clearly seen that the average diameter of the cells is smaller (about 207 um) and the size of the cells is relatively uniform.

[0236] Figure 7 Example 7

[0237] Example 1 is repeated except that the blowing agent is: 8 parts by weight of an alcohol amine carbonate compound AA7c (wherein the CO2 content is 4.03 wt%, the molar ratio of N,N,N'-tris(hydroxyisopropyl)-pentanediamine to N,N'-bis(hydroxyisopropyl)-pentanediamine is about 0.25:1) prepared in Preparation Example 7 above as an alcohol amine composition (AC) and 18 parts by weight of cyclopentane.

[0238] The SEM photograph of the rigid foam is shown in From the SEM photograph, it can be clearly seen that the average diameter of the cells is smaller (about 213 um, which is slightly larger than the average cell diameter of the foam of Example 6) and the size of the cells is relatively uniform.

[0239] Figure 8 From the SEM photograph, it can be clearly seen that the average diameter of the cells is smaller (about 213 um, which is slightly larger than the average cell diameter of the foam of Example 6) and the size of the cells is relatively uniform. From the SEM photograph, it can be clearly seen that the average diameter of the cells is smaller (about 213 um, which is slightly larger than the average cell diameter of the foam of Example 6) and the size of the cells is relatively uniform.

[0240] Example 8

[0241] Example 1 was repeated except that the blowing agent was: 8 parts by weight of the alcohol amine carbonate compound AA8c (wherein the CO2 content was 4.17 wt%, the molar ratio of N,N,N'-tris(hydroxyisopropyl)-hexanediamine to N,N'-bis(hydroxyisopropyl)-hexanediamine was about 1 : 1) prepared in Preparation Example 8 above as the alcohol amine composition (AC) and 18 parts by weight of cyclopentane.

[0242] From the SEM photograph of the foam sample (not shown), it was clear that the average cell diameter was small (about 208 um) and the size of the cells was uniform.

[0243] Example 9

[0244] Example 1 was repeated except that the blowing agent was: 8 parts by weight of the alcohol amine carbonate compound AA9b (wherein the CO2 content was 3.1 wt%, the molar ratio of N,N,N'-tris(hydroxyisopropyl)-hexanediamine to N,N'-bis(hydroxyisopropyl)-hexanediamine was about 1.5: 1) prepared in Preparation Example 9 above as the alcohol amine composition (AC) and 18 parts by weight of cyclopentane.

[0245] From the SEM photograph of the foam sample (not shown), it was clear that the average cell diameter was small (about 214 um) and the size of the cells was uniform.

[0246] Example 10

[0247] Example 1 was repeated except that the blowing agent was: 8 parts by weight of the alcohol amine carbonate compound AA10c (wherein the CO2 content was 4.0 wt%, the molar ratio of N,N,N'-tris(hydroxyisopropyl)-hexanediamine to N,N'-bis(hydroxyisopropyl)-hexanediamine was about 0.25: 1) prepared in Preparation Example 9 above as the alcohol amine composition (AC) and 18 parts by weight of cyclopentane.

[0248] From the SEM photograph of the foam sample (not shown), it was clear that the average cell diameter was small (about 218 um) and the size of the cells was uniform.

[0249] Example 11

[0250] Example 1 was repeated except that the blowing agent was: 4 parts by weight of the alcohol amine carbonate compound AA2c (wherein the CO2content was 4.29 wt%, the molar ratio of N,N,N'-tris(hydroxyisopropyl)-butanediamine to N,N'-di(hydroxyisopropyl)-butanediamine was about 0.25:1) prepared in Preparation Example 2 above as the alcohol amine composition (AC), 4 parts by weight of the alcohol amine carbonate compound AA7c (wherein the CO2content was 4.03 wt%, the molar ratio of N,N,N'-tris(hydroxyisopropyl)-pentanediamine to N,N'-di(hydroxyisopropyl)-pentanediamine was about 0.25:1) prepared in Preparation Example 7 above as the alcohol amine composition (AC), and 18 parts by weight of cyclopentane.

[0251] From the SEM photograph of the foam sample (not shown), it was clear that the average diameter of the cells was small (about 217 um) and the size of the cells was uniform.

[0252] Example 12

[0253] Example 1 was repeated except that the blowing agent was: 4 parts by weight of the alcohol amine carbonate compound AA2c (wherein the CO2content was 4.29 wt%, the molar ratio of N,N,N'-tris(hydroxyisopropyl)-butanediamine to N,N'-di(hydroxyisopropyl)-butanediamine was about 0.25:1) prepared in Preparation Example 2 above as the alcohol amine composition (AC), 4 parts by weight of the alcohol amine carbonate compound AA10c (wherein the CO2content was 4.0 wt%, the molar ratio of N,N,N'-tris(hydroxyisopropyl)-hexanediamine to N,N'-di(hydroxyisopropyl)-hexanediamine was about 0.25:1) prepared in Preparation Example 10 above as the alcohol amine composition (AC), and 18 parts by weight of cyclopentane.

[0254] From the SEM photograph of the foam sample (not shown), it was clear that the average diameter of the cells was small (about 215 um) and the size of the cells was uniform.

[0255] Example 13

[0256] Example 1 was repeated except that the blowing agent was: 3 parts by weight of the alcohol amine carbonate compound AA2c (wherein the CO2content was 4.29 wt%, the molar ratio of N,N,N'-tris(hydroxyisopropyl)-butanediamine to N,N'-di(hydroxyisopropyl)-butanediamine was about 0.25:1) prepared in Preparation Example 2 above as the alcohol amine composition (AC), 2 parts by weight of the alcohol amine carbonate compound AA7c (wherein the CO2content was 4.03 wt%, the molar ratio of N,N,N'-tris(hydroxyisopropyl)-pentanediamine to N,N'-di(hydroxyisopropyl)-pentanediamine was about 0.25:1) prepared in Preparation Example 7 above as the alcohol amine composition (AC), 3 parts by weight of the alcohol amine carbonate compound AA10c (wherein the CO2content was 4.0 wt%, the molar ratio of N,N,N'-tris(hydroxyisopropyl)-hexanediamine to N,N'-di(hydroxyisopropyl)-hexanediamine was about 0.25:1) prepared in Preparation Example 10 above as the alcohol amine composition (AC), and 18 parts by weight of cyclopentane.

[0257] From the SEM photograph of the foam sample (not shown), it can be clearly seen that the average diameter of the cells was small (about 214 um) and the size of the cells was uniform.

[0258] Comparative Example 1

[0259] Example 1 was repeated except that the blowing agent was: 8 parts by weight of the alcohol amine carbonate compound AA3b (wherein the CO2content was 9.1 wt%, N,N'-di(hydroxyisopropyl)-butanediamine. It had been left at room temperature for 5 days) prepared in Preparation Example 3 above as the alcohol amine composition (AC), and 18 parts by weight of cyclopentane.

[0260] The SEM photograph of the rigid foam is shown in Figure 9 From the SEM photograph, it can be clearly seen that the average diameter of the cells was large (about 243 um) and the size of the cells was not uniform.

[0261] Comparative Example 2

[0262] Example 1 was repeated except that the blowing agent was: 8 parts by weight of the alcohol amine carbonate compound AA4b (wherein the CO2content was 1.02 wt%, N,N,N'-tris(hydroxyisopropyl)-butanediamine. It had been left at room temperature for 2 days) prepared in Preparation Example 4 above as the alcohol amine composition (AC), and 18 parts by weight of cyclopentane.

[0263] The SEM photograph of the rigid foam is shown in Figure 10 From the SEM photograph, it can be clearly seen that the average diameter of the cells was large (about 233 um) and the size of the cells was not uniform.

[0264] Comparative Example 3

[0265] Example 1 was repeated except that the blowing agent was 7 parts by weight of HFC- 245fa and 16 parts by weight of cyclopentane. The SEM photograph of the foam is shown in Figure 11 The cells of the foam were coarse and the size of the cells was not uniform.

[0266] Observation of the transparency and compatibility of the white material: The blowing agent (245fa + CP) and the dry white material were mixed under stirring to obtain a slightly turbid white material (with oil droplets). The turbidity phenomenon indicates that the blowing agent (245fa + CP) has a slightly lower compatibility in the dry white material containing a larger amount of toluene diamine type polyoxypropylene polyol and aromatic polyester polyol.

[0267] From the SEM photograph of the rigid foam ( Figure 11 ), it can be clearly seen that the average cell diameter of the cells was large (about 260 um) and the size of the cells was not uniform.

[0268] Comparative Example 4

[0269] Example 1 was repeated except that the blowing agent was 8 parts by weight of the alcohol amine carbonate compound AA11c (wherein the CO2 content was 2.48 wt%) prepared in Preparation Example 11 above as an alcohol amine composition (AC) and 18 parts by weight of cyclopentane.

[0270] The SEM photograph of the foam is shown in Figure 12 . The cells of the foam were coarse (about 263 um) and the size of the cells was not uniform, which indicates that since AA11c has a higher viscosity, the white material containing it has a higher viscosity and a decreased flowability. The foaming reaction mixture was difficult to mix uniformly, so that the size of the cells of the foam was increased.

[0271] Table 1 - Comparison of the foaming composition and the performance parameters of the foam:

[0272]

[0273]

[0274] Note 1 : 104.6 parts by weight of dry white material includes 100 parts by weight of polymeric polyol and 4.6 parts by weight of auxiliary agent (foam stabilizer, PU catalyst); CP means cyclopentane; CFA refers to alcohol amine carbonate compound (i.e. AC containing alcohol amine being fully or partially neutralized by CO2, such as AA1c, AA2c, etc. in Preparation Example 1-2) as chemical foaming agent; A2:A1 refers to the molar ratio of triol amine A2 to diol amine A1 in CFA; the value of λ (or K factor) is determined according to GB / T 10295-2008, foam size 20*20*2.5 cm. The "expansion rate (180s)" in the table refers to the expansion rate measured after opening the Lanxess mold from the start of timing from the start of injecting material into the Lanxess mold to 180 seconds (3 minutes).

[0275] Note 2: The size of Lance mold is 1600*300*80 mm. The overall foam is divided into left and right parts (i.e. left and right sides) in the direction of long side, and each part is divided into 16 density points (density measurement points) from bottom to top at intervals of 20 cm, and the difference between the highest and lowest values of the 16 density points is the density range. The average of the 16 density points is the average density.

[0276] Note 3: The flow index cm / g is determined by the following method: a polyethylene (PE) hose with a diameter of about 10 cm and a length of 1.8 m is used, one end is clamped with a clamp, and the other end (as the upper port) is stretched open, the foaming solution is poured into the upper part of the hose, then the upper port is sealed, and the hose is turned over, and the foam rises along the hose. The ratio of the height H (cm) of the foam in the hose to the mass m (g) of the foam in the tube represents the flow index.

[0277] Table 1 (continued) - Comparison of foaming composition and performance parameters of foam:

[0278]

[0279]

[0280]

[0281] From the relationship between CO2 and viscosity in Preparation Example 1-11, it can be seen that although high CO2 content can help to inhibit the crystallization of alcohol amine and improve the foaming efficiency, too high CO2 content can significantly increase the viscosity of alcohol amine, resulting in too high viscosity of the white material containing it, and thus the black material and white material cannot be uniformly mixed during foaming.

[0282] Based on the relationship between the microstructure of the cells and the thermal insulation performance of the foam from the SEM photos, the excellent cell microstructure (smaller cell size, more uniform cell size, but more number of cells in unit volume) makes the foam have good thermal insulation performance. The inventors have found through experiments that the higher the CO2 content in the blowing agent and the slight decrease in the density of the PU foam do not necessarily make the foam have better thermal insulation performance.

[0283] The triol amine A2 and water are beneficial to the crosslinking of the cell wall, and the diol amine A1 is beneficial to the absorption of more CO2 gas, both of which exist in a molar ratio of 1.5-0.25:1, are doped with each other, and can obtain a PU rigid foam with more excellent performance.

[0284] As can be seen from Table 1, the draw time (s) of the foam of Comparative Example 1 is only 44 seconds, which does not meet the requirements of the production of PU foam in the production of refrigerators and freezers. The triol amine A2 in Comparative Example 2 can only absorb a small amount of CO2 gas, resulting in too low foaming efficiency and low thermal insulation performance of the foam. In Comparative Example 3, because the microstructure of the cells is not ideal, the thermal insulation performance of the foam is not good.

[0285] In Comparative Example 4, because the viscosity of the alcohol amine is too high, the white material containing it has too high viscosity, so that the black material and the white material cannot be uniformly mixed during the foaming process, resulting in poor thermal insulation performance of the foam.

[0286] In summary, under the conditions that the CO2 content in the CO2 neutralized AC is 3-4.5wt% (AC produces good nucleation in the early stage of the foaming process) and the molar ratio of A2 to A1 is 1:1, a PU rigid foam with more excellent performance can be obtained.

Claims

1. An alkanolamine composition (AC) comprising, consisting of, or primarily consisting of the following components: (1) C6-C12 diolamines derived from C4-C6 alkyl diamines having the general formula (I): R 1 HN-Ra-NHR 2 (YOUR); (2) C10-C15 triolamines (A2) derived from C4-C6 alkyldiamines of general formula (II): R 1 HN-Rb-NR 2 R 3 (II); (3) Water; (4) Any other alcoholamines other than (A1) and (A2) (A3); In general formulas (I) and (II), -Ra- and -Rb- are the same or different, and -Ra- and -Rb- are independently: -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, -CH2CH2CH2CH2CH2CH2- or -CH2CH2CH(CH3)CH2CH2-; Where R 1 R 2 and R 3 They may be the same or different, and each is independently either ethanol-based or isopropanol-based; The molar ratio of C10-C15 triolamine (A2) of general formula (II) to C6-C12 diolamine (A1) of general formula (I) is (0.05-2.5):

1. The total content of (A1)+(A2)+water is 70-100wt%, based on the total weight of the alcoholamine composition (AC); The water content in the aqueous alkanolamine composition (AC) is 5-45 wt%, based on the total weight of the alkanolamine composition (AC).

2. The alkanolamine composition according to claim 1, wherein, The molar ratio of C10-C15 triolamine (A2) of general formula (II) to C6-C12 diolamine (A1) of general formula (I) is (0.0526-2.333): 1; The total content of (A1)+(A2)+water is 72-99.9%, based on the total weight of the alcoholamine composition (AC); The water content in the aqueous alkanolamine composition (AC) is 5-42 wt%, based on the total weight of the alkanolamine composition (AC).

3. The alkanolamine composition according to claim 1, wherein, The molar ratio of C10-C15 triolamine (A2) of general formula (II) to C6-C12 diolamine (A1) of general formula (I) is (0.075-1.857):1; The total content of (A1)+(A2)+water is 73-99.5%, based on the total weight of the alcoholamine composition (AC); The water content in the aqueous alkanolamine composition (AC) is 5-40 wt%, based on the total weight of the alkanolamine composition (AC).

4. The alkanolamine composition according to claim 1, wherein, The molar ratio of C10-C15 triolamine (A2) of general formula (II) to C6-C12 diolamine (A1) of general formula (I) is (0.085-1.5):1; The total content of (A1)+(A2)+water is 74-99%, based on the total weight of the alcoholamine composition (AC); The water content in the aqueous alkanolamine composition (AC) is 6-39 wt%, based on the total weight of the alkanolamine composition (AC).

5. The alkanolamine composition according to claim 1, wherein, The molar ratio of C10-C15 triolamine (A2) of general formula (II) to C6-C12 diolamine (A1) of general formula (I) is (0.09-1.5):1; The total content of (A1)+(A2)+water is 75-98%, based on the total weight of the alcoholamine composition (AC); The water content in the aqueous alkanolamine composition (AC) is 7-38 wt%, based on the total weight of the alkanolamine composition (AC).

6. The alkanolamine composition according to claim 1, wherein, The molar ratio of C10-C15 triolamine (A2) of general formula (II) to C6-C12 diolamine (A1) of general formula (I) is (0.111-1.5): 1; The total content of (A1)+(A2)+water is 76-97%, based on the total weight of the alcoholamine composition (AC); The water content in the aqueous alkanolamine composition (AC) is 8-37 wt%, based on the total weight of the alkanolamine composition (AC).

7. The alkanolamine composition according to claim 1, wherein, The molar ratio of C10-C15 triolamine (A2) of general formula (II) to C6-C12 diolamine (A1) of general formula (I) is (0.10-1.3):1; The total content of (A1)+(A2)+water is 77-96%, based on the total weight of the alcoholamine composition (AC); The water content in the aqueous alkanolamine composition (AC) is 8.5-36 wt%, based on the total weight of the alkanolamine composition (AC).

8. The alkanolamine composition according to claim 1, wherein, The molar ratio of C10-C15 triolamine (A2) of general formula (II) to C6-C12 diolamine (A1) of general formula (I) is (0.12-1.0): 1; The total content of (A1)+(A2)+water is 78-95%, based on the total weight of the alcoholamine composition (AC); The water content in the aqueous amine composition (AC) is 9-35 wt%, based on the total weight of the amine composition (AC).

9. The alkanolamine composition according to claim 1, wherein, The molar ratio of C10-C15 triolamine (A2) of general formula (II) to C6-C12 diolamine (A1) of general formula (I) is (0.12-0.8):1; The total content of (A1)+(A2)+water is 80-94%, based on the total weight of the alcoholamine composition (AC); The water content in the aqueous amine composition (AC) is 10-33 wt%, based on the total weight of the amine composition (AC).

10. The alkanolamine composition according to claim 9, wherein, The molar ratio of C10-C15 triolamine (A2) of general formula (II) to C6-C12 diolamine (A1) of general formula (I) is (0.25-0.6667):1; The water content in the aqueous alkanolamine composition (AC) is 12-25 wt%, based on the total weight of the alkanolamine composition (AC).

11. The alkanolamine composition according to claim 1, wherein, The content of other alkanolamines (A3) besides (A1) and (A2) is 0-30 wt%, based on the total weight of the alkanolamine composition (AC); and / or in, Other alkanolamines (A3) are other C2-C15 alkanolamines (A3) or other C2-C9 alkanolamines (A3); and / or In general formula (I), R 1 and R 2 It is not simultaneously an ethanol group, but can simultaneously be an isopropanol group; in general formula (II) R 1 R 2 and R 3 They are not both ethanol groups.

12. The alkanolamine composition according to claim 1, wherein, R 1 and R 2 It is both isopropanol group and R 3 It is either ethanol-based or isopropanol-based.

13. The alkanolamine composition according to claim 1, wherein, R 1 R 2 and R 3 They are all isopropanol groups.

14. The alkanolamine composition according to any one of claims 1-13, wherein, A portion of the alkanolamine in the alkanolamine composition (AC) is neutralized by CO2, to the extent that the CO2 content in the alkanolamine composition (AC) is 0.5-8.5 wt%, based on the total weight of the alkanolamine composition (AC); and / or Other alcoholamines (A3) are ethanolamine, N-methylethanolamine, isopropanolamine, N-methylisopropanolamine, diethanolamine, diisopropanolamine, ethanolisopropanolamine, triethanolamine and / or triisopropanolamine.

15. The alkanolamine composition according to claim 14, wherein, In the amine composition (AC), a portion of the amine is neutralized by CO2, and the degree of neutralization should be such that the CO2 content in the amine composition (AC) is 0.6-8 wt%.

16. The alkanolamine composition according to claim 14, wherein, A portion of the alkanolamine in the alkanolamine composition (AC) is neutralized by CO2, and the degree of neutralization should be such that the CO2 content in the alkanolamine composition (AC) is 0.75-7.5 wt%.

17. The alkanolamine composition according to claim 14, wherein, A portion of the alkanolamine in the alkanolamine composition (AC) is neutralized by CO2, and the degree of neutralization should be such that the CO2 content in the alkanolamine composition (AC) is 0.8-7.2 wt%.

18. The alkanolamine composition according to claim 14, wherein, A portion of the alkanolamine in the alkanolamine composition (AC) is neutralized by CO2, and the degree of neutralization should be such that the CO2 content in the alkanolamine composition (AC) is 1-7 wt%.

19. The alkanolamine composition according to claim 14, wherein, A portion of the alkanolamine in the alkanolamine composition (AC) is neutralized by CO2, and the degree of neutralization should be such that the CO2 content in the alkanolamine composition (AC) is 1.7-5.5 wt%.

20. The alkanolamine composition according to claim 14, wherein, In the alcoholamine composition (AC), a portion of the alcoholamine is neutralized by CO2, and the degree of neutralization should be such that the CO2 content in the alcoholamine composition (AC) is 2-5 wt%.

21. A method for preparing the amine composition according to any one of claims 1-20, the method comprising the following steps: 1) A C4-C6 diamine is reacted with an epoxide in the presence of water to obtain an aqueous amine composition (AC) comprising the above-mentioned diolamine (A1) and triolamine (A2), wherein the epoxide is ethylene oxide and / or propylene oxide, and the molar ratio of the epoxide to the C4-C6 diamine is (2.05-2.7):1; 2) Optionally, other alkanolamines (A3) other than (A1) and (A2) are added to the aqueous alkanolamine composition (AC). 3) Optionally, CO2 gas is introduced into the aqueous alkanolamine composition (AC) obtained in step 1) to neutralize the alkanolamine in the composition (AC), the degree of neutralization being such that the CO2 content in the aqueous alkanolamine composition (AC) is as defined in claim 14; Wherein, the total amount of water used in step 1) and optionally steps 2) and optionally steps 3) should be such that the obtained aqueous amine composition (AC) has the water content described above.

22. The method according to claim 21, wherein, The molar ratio of epoxide to C4-C6 diamine is (2.07-2.65):

1.

23. The method according to claim 21, wherein, The molar ratio of epoxide to C4-C6 diamine is (2.1-2.6):

1.

24. The method according to claim 21, wherein, The molar ratio of epoxide to C4-C6 diamine is (2.15-2.55):

1.

25. The method according to claim 21, wherein, The molar ratio of epoxide to C4-C6 diamine is (2.18-2.5):

1.

26. The method according to claim 21, wherein, The molar ratio of epoxide to C4-C6 diamine is (2.2-2.4):

1.

27. A method for preparing the amine composition according to any one of claims 1-20, the method comprising the following steps: 1) React C4-C6 diamine with epoxide in the presence of water to obtain an alcoholamine compound of the above general formula (I), wherein the epoxide is ethylene oxide and / or propylene oxide, and the molar ratio of epoxide to C4-C6 diamine is 2:

1. 2) React C4-C6 diamine with epoxide in the presence of water to obtain an alcohol amine compound of the above general formula (II), wherein the epoxide is ethylene oxide and / or propylene oxide, and the molar ratio of epoxide to C4-C6 diamine is 3:1; 3) The triolamine (A2) of general formula (II) and the diolamine (A1) of general formula (I) are mixed according to a molar ratio of (0.05-2.5):1 to obtain an aqueous amine composition (AC). 4) Optionally, other alkanolamines (A3) other than (A1) and (A2) are added to the aqueous alkanolamine composition (AC). 5) Optionally, CO2 gas is passed into the obtained aqueous alkanolamine composition (AC) to partially neutralize the alkanolamine in the composition (AC), resulting in an aqueous alkanolamine composition (AC) partially neutralized by CO2, wherein the amount of CO2 gas absorbed or passed should be such that the CO2 content in the aqueous alkanolamine composition (AC) is as defined in claim 14. The total amount of water used in steps 1), 2), 3), optional 4), and optional 5) should be such that the obtained aqueous amine composition (AC) has the water content described above.

28. The method according to claim 27, wherein, Other alcohol amines (A3) are C2-C15 alcohol amines.

29. The method according to claim 28, wherein, Other alcohol amines (A3) are C2-C9 alcohol amines.

30. Use of diolamine compounds having general formula (I) and / or triolamine compounds having general formula (II), or carbonates formed by the partial or complete neutralization of these compounds by CO2, as components in polyurethane foaming agents; wherein (1) C6-C12 diolamines derived from C4-C6 alkyl diamines (A1) having the general formula (I): R 1 HN-Ra-NHR 2 (YOUR), (2) C10-C15 triolamines (A2) derived from C4-C6 alkyldiamines of general formula (II): R 1 HN-Rb-NR 2 R 3 (II), In general formulas (I) and (II), -Ra- and -Rb- may be the same or different, and -Ra- and -Rb- are independently: -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, -CH2CH2CH2CH2CH2CH2- or -CH2CH2CH(CH3)CH2CH2-; Where R 1 R 2 and R 3 They may be the same or different, and each is independently either ethanol-based or isopropanol-based.

31. A carbonate amine salt foaming agent composition, the foaming agent composition (FC) comprising, being composed of, or primarily composed of the following components: (1) The alkanolamine composition (AC) according to claim 1 or 11; (2) C5 alkane, which is cyclopentane, isopentane, n-pentane and / or neopentane; (3)Optional, physical foaming agent (F1) with a boiling point in the range of 15-41°C, wherein the physical foaming agent (F1) is selected from one or more of HFC-245fa, HFC-365mfc, LBA and hexafluorobutene; (4) Optional, water (F2); The relative amounts of each component are as follows: The amount of water (F2) is 0-2 parts by weight; The amount of physical foaming agent (F1) is 0-7 parts by weight; The amount of the alkanolamine composition (AC) is 1-10 parts by weight; and, The amount of C5 alkanes is 10-20 parts by weight; The parts by weight mentioned therein refer to 90-115 parts by weight of a dry white polyurethane foam containing polymeric polyols and other additives other than a foaming agent.

32. The carbonate amine salt foaming agent composition according to claim 31, wherein, The amount of water (F2) is 0-1.5 parts by weight; The amount of physical foaming agent (F1) is 0-6.5 parts by weight; The amount of the alkanolamine composition (AC) is 1.2-9.5 parts by weight; and, The amount of C5 alkanes is 10.5-19.5 parts by weight; The parts by weight mentioned herein are relative to 100 parts by weight of a dry white polyurethane foam containing polymeric polyols and other additives other than a blowing agent.

33. The carbonate amine salt foaming agent composition according to claim 32, wherein, The amount of water (F2) is 0-0.5 parts by weight; The amount of physical foaming agent (F1) is 0-5 parts by weight; The amount of the alkanolamine composition (AC) is 1.3-9 parts by weight; and, The amount of C5 alkanes is 11-18.5 parts by weight.

34. The carbonate amine salt foaming agent composition according to claim 33, wherein, The amount of water (F2) is 0-0.1 parts by weight; The amount of physical foaming agent (F1) is 0-2.5 parts by weight; The amount of the alkanolamine composition (AC) is 3-8 parts by weight; and, The amount of C5 alkanes is 11.5-18 parts by weight.

35. The carbonate amine salt foaming agent composition according to claim 31, wherein, The ratio of the total mass of water (F2) + physical foaming agent (F1) + alcohol amine composition (AC) to the mass of C5 alkane is (5.5-10): (10-20).

36. The carbonate amine salt foaming agent composition according to claim 35, wherein, The mass of water (F2) and physical foaming agent (F1) is 0 parts by weight, and the mass ratio of the alkanolamine composition (AC) to the mass of C5 alkane is (5.5-10): (10-20).

37. The carbonate amine salt foaming agent composition according to claim 35, wherein, The ratio of the total mass of water (F2) + physical foaming agent (F1) + alkanolamine composition (AC) to the mass of C5 alkane is (6-10) : (12-18); The mass of water (F2) and physical foaming agent (F1) is 0 parts by weight, and the mass ratio of the alkanolamine composition (AC) to the mass of C5 alkane is (6-10): (12-18).

38. The carbonate amine salt foaming agent composition according to claim 35, wherein, The ratio of the total mass of water (F2) + physical foaming agent (F1) + alkanolamine composition (AC) to the mass of C5 alkane is (5.5-9) : (10-20); The mass of water (F2) and physical foaming agent (F1) is 0 parts by weight, and the mass ratio of the alkanolamine composition (AC) to the mass of C5 alkane is (5.5-9): (10-20).

39. The carbonate amine salt foaming agent composition according to claim 35, wherein, The ratio of the total mass of water (F2) + physical foaming agent (F1) + alkanolamine composition (AC) to the mass of C5 alkane is (5.5-8.5) : (10-20); The mass of water (F2) and physical foaming agent (F1) is 0 parts by weight, and the mass ratio of the alkanolamine composition (AC) to the mass of C5 alkane is (5.5-8.5): (10-20).

40. The carbonate amine salt foaming agent composition according to claim 31, 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% of polyoxypropylene polyols other than toluene diamine polyoxypropylene polyol, Wherein, the wt% is based on the weight of polymeric polyols in the dry white material.

41. The carbonate amine salt foaming agent composition according to claim 40, wherein, The polymer polyols in the dry white material include: 9-70 wt% aromatic / semi-aromatic polyester polyols and / or toluene diamine-type polyoxypropylene polyols, and 91-30 wt% of polypropylene oxide polyols other than toluene diamine polypropylene oxide polyol, Wherein, the wt% is based on the weight of polymeric polyols in the dry white material.

42. The carbonate amine salt foaming agent composition according to claim 41, wherein, The polymer polyols in the dry white material include: 18-35 wt% aromatic / semi-aromatic polyester polyols and / or toluene diamine-type polyoxypropylene polyols, and 82-65 wt% of polyoxypropylene polyols other than toluene diamine polyoxypropylene polyol, Wherein, the wt% is based on the weight of polymeric polyols in the dry white material.

43. 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 an optional flame retardant; and (2) a carbonate amine salt blowing agent composition (FC) according to any one of claims 31-42. The amount of foaming agent used is 22-30 parts by weight, relative to 90-115 parts by weight of dry white material for polyurethane foaming.

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