CN114805902A

CN114805902A - Carbonic acid alkanolamine salt foaming agent composition for polyurethane rigid foam

Info

Publication number: CN114805902A
Application number: CN202110315460.3A
Authority: CN
Inventors: 毕戈华; 毕玉遂
Original assignee: Butian New Material Technology Co ltd; Shandong University of Technology
Current assignee: Butian New Material Technology Co ltd; Shandong University of Technology
Priority date: 2021-01-27
Filing date: 2021-03-24
Publication date: 2022-07-29
Anticipated expiration: 2041-03-24
Also published as: CN114805902B; WO2022160439A1

Abstract

A chemical-physical combination carbonate alkanolamine salt blowing agent composition for use in the preparation of cast polyurethane rigid foams comprising: 1) a high water content and low bicarbonate content alkanolamine carbonate chemical blowing agent (F1); and 2) cyclopentane; 3) optionally, a physical blowing agent (F2) having a boiling point in the range of 15-41 ℃, wherein the physical blowing agent (F2) is one or more (two or three) selected from HFC-245fa, HFC-365mfc, LBA and hexafluorobutene; wherein the chemical blowing agent (F1) comprises: A)67-90 wt% of a di (C2-C9 alcohol amine) carbonate salt; B)10-33 wt% water; C)0-20 wt% of C2-C9 alcohol amine.

Description

Carbonic alcohol amine salt foaming agent composition for polyurethane rigid foam

Technical Field

The present invention relates to a carbonate alkanolamine salt composite blowing agent for (pour-on) polyurethane rigid foams used in the refrigerator, freezer, water heater, cold chain insulation (refrigerator car) and like industries, and more particularly to a chemical-physical combination type blowing agent comprising a high water content carbonate alkanolamine salt chemical blowing agent in combination with cyclopentane and optionally a physical blowing agent having a boiling point in the range of 15 to 41 ℃, particularly the polyurethane rigid foam prepared using as white material a polymer polyol comprising a portion of an aromatic polyester polyol such as a polyethylene phthalate polyol and/or a toluene diamine polyether polyol.

Background

The polyurethane rigid foam material is a high-quality heat insulation material and is widely applied to the industries of refrigerators, freezers, water heaters, cold chain heat insulation and the like. For the environmental protection, in these industries, water and cyclopentane are commonly used as blowing agents in the production process of polyurethane foams, because the high thermal conductivity of cyclopentane results in the high thermal conductivity of foams, and the energy consumption is large, and in order to reduce the thermal conductivity of foams, improve the thermal insulation performance of thermal insulation materials, and reduce the energy consumption, other physical blowing agents of hydrofluorocarbons are added, such as HCFC-141b (monofluorodichloroethane, molecular weight 116.95, boiling point 32 ℃), CFC-113 (trichlorotrifluoroethane, molecular weight 187.39, boiling point 47.7 ℃), CFC-11 (trichloromonofluoromethane, molecular weight 137.4), boiling point 23.8, HCFC-123 (trifluorodichloroethane, molecular weight 152.93, boiling point 27.85 HFC-245fa (molecular weight 134, boiling point 15.3 ℃), HFC-365mfc (molecular weight 148, boiling point 40.2 ℃), LBA (trans-1-chloro-3, 3, 3-trifluoropropene, molecular weight 130.5, boiling point 19 ℃), hexafluorobutene (molecular weight 164, boiling point 33 ℃), and the like. Certain chlorofluorocarbons are expensive. The production of these physical blowing agents of hydrofluorocarbons also produces chlorofluorocarbon-containing by-products which have an environmental impact.

US 6326412B 1 discloses ammonium carbamate as polyurethane blowing agent, wherein the viscosity of ammonium carbamate is up to 2200mpa.s (see column 6, lines 51-55 in column 6 of the description), which is in a viscous or semi-solid state.

At present, the heat insulation performance of polyurethane rigid foam materials used in the industries of refrigerators, freezers, water heaters, refrigerated vehicles (cold chain insulation) and the like is more and more important. In general, the Lance thermal conductivity of rigid polyurethane foams used in these industries is in the range of 19.00 to 20.00. lambda. (mW/m. multidot.K, 10 ℃ C.). If the thermal conductivity lambda 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, 18.00 or 17.95 (with 17.95-18.00 being the lowest limit value, it will become very difficult to continue to reduce this value), then each step brings about a huge economic benefit. For example, at least tens of millions of refrigerators and freezers are produced worldwide each year, and by using the improved rigid foam, a refrigerator or freezer saves 0.1-0.3 degrees of electricity per day and 36.5-109.5 degrees of electricity per year. The power savings are only dramatic in terms of the number of refrigerators and freezers produced annually throughout the world.

In the industrial production of rigid polyurethane foams in the refrigerator, freezer, water heater, refrigerator car (cold chain insulation) and other industries, a casting method using a spray gun is generally used in which a mixture for foaming (made by mixing white and black materials in a mixing chamber of a high-pressure casting machine) is injected into a mold through a single gate of the mold, the mixture for foaming (foaming material) undergoes a foaming reaction in the mold, is solidified, and is then released from the mold. For example, in a refrigerator production line, one refrigerator is off-line for 2 to 3 minutes on average, and therefore, the fluidity of the foaming mixture is very important, and it is required to be able to fill every corner of an irregular cavity of a mold in a short time, and to ensure that the foaming mixture is filled uniformly in the mold without leaving dead space. The foaming process in the industries of refrigerators, freezers, water heaters and the like is actually an on-line foaming process on an industrial production line.

Those skilled in the art believe that the thermal conductivity of the gas in the cells of the rigid polyurethane foam determines the thermal insulation properties of the foam, i.e., the lower the thermal conductivity of the gas in the cells, the better the thermal insulation properties of the foam. Accordingly, efforts have been made to develop novel fluorine-containing blowing agents having a lower thermal conductivity in the gaseous state.

Disclosure of Invention

The inventors of the present application found through many years of research that the microstructure of cells in the rigid polyurethane foam has a greater influence on the thermal insulation performance of the foam than the influence of the thermal conductivity of the gas in the cells on the thermal insulation performance of the rigid polyurethane foam. In these rigid polyurethane foams having excellent thermal insulation properties, the cell microstructure and the closed cell ratio in the rigid polyurethane foam mainly determine the thermal insulation properties of the foam.

The technical problem to be solved by the application is to improve the foaming process by optimizing the composition of the foaming composition, and further change the microstructure of the foam, so as to improve the heat insulation performance and the strength property of the produced rigid polyurethane foam.

In order to obtain a polyurethane rigid foam having a good cell microstructure, the inventors of the present application have studied a chemical-physical composite blowing agent consisting of a carbonate ethanolamine salt chemical blowing agent and a physical blowing agent.

The inventors of the present application found that, for a composite blowing agent consisting of a alkanolamine carbonate salt chemical blowing agent and a physical blowing agent, some influencing factors, such as the compatibility of the chemical blowing agent and the physical blowing agent, each or both in the form of a composite, with the polymer polyol as a white material, the activity of the chemical blowing agent and the boiling point of the physical blowing agent (which produces initial nucleation) (which influence the rise time or cream time of the foaming reaction), the content and type of alkanolamine (as a cross-linking agent), the content of water, etc., have a direct influence on the foaming reaction process.

The appropriate expansion rate and curing rate of the foamed mixture formed by mixing the white and black materials (i.e., the appropriate foaming rate, which includes rise time, stringiness time, and skinning time) primarily determine the cell microstructure during the foaming process. In addition, the content of water and the alcohol amine formed by the decomposition of the chemical blowing agent (the alcohol amine having a higher activity is used as a catalyst and a crosslinking agent first, and the water having a lower activity is used as a crosslinking agent or does not participate in the crosslinking reaction at the latter stage of the foaming reaction) determines the crosslinking strength of the inner walls of the cells and further affects the compressive strength and the deformation resistance of the foam. In addition, crosslinking of the cell walls helps prevent cell rupture and thus increases the rate of cell closure, which in turn increases the thermal insulation properties of the foam.

For polyurethane rigid foams (hereinafter referred to as "polyurethane rigid foams for refrigerators" or "PU foams for refrigerators" for short) used in the refrigerator, freezer, water heater, and cold chain insulation (refrigerator car) industries, which have high requirements in terms of thermal insulation properties, a suitable foaming speed is required in the industrial polyurethane foaming process in the production of refrigerators, freezers, water heaters, or refrigerator cars. Generally, in an on-line foaming process for industrial production, the foaming speed of the related art is as shown in the following table a:

table a: foaming speed for producing different types of foam

In general, polyisocyanates (e.g., polymethylene polyphenyl polyisocyanates, i.e., polymeric MDI) used to prepare polyurethane rigid foams are referred to as "black materials", while foaming polymer polyol compositions to which various auxiliaries (such as polyurethane catalysts, foam stabilizers, and optionally flame retardants, optionally chain extenders, and optionally crosslinkers) and blowing agents are added are referred to as "white materials". Of these, polymer polyol compositions for foaming to which various auxiliaries (such as polyurethane catalysts, foam stabilizers and optionally flame retardants, optionally chain extenders and optionally crosslinkers) have been added, but only without the addition of blowing agents, are referred to as "dry white". That is, "dry white" means: "white" without blowing agent, or a dry white for polyurethane foaming comprising polymer polyols and other auxiliaries besides blowing agent.

Typically, the polyurethane catalyst in the "dry white" or "white" includes a secondary amine type early catalyst (i.e., early catalyst) and a tertiary amine type late crosslinking catalyst (i.e., late catalyst).

The object of the present invention is to design specific blowing agent compositions for (pour-on) rigid polyurethane foams for refrigerators, freezers, water heaters (electric or solar water heaters) or refrigerated vehicles. In general, in a foaming reaction in a production line of a refrigerator, freezer, or refrigerator car, a mixture for foaming containing a black material and a white material is injected into a mold through a single injection port using a casting machine (or a high-pressure, medium-pressure, or low-pressure casting machine), the mixture for foaming has high fluidity and can uniformly fill the entire mold, and foaming is completed within a predetermined time (mold opening time or mold release time is generally about 180 seconds).

With respect to the ideal cell microstructure of the rigid polyurethane foam, it is meant a cell structure that is fine (or fine) and uniform in cell size. That is, on the one hand, the foam has a low density, on the other hand, the number of cells per unit volume is as large as possible (from the SEM photograph, the number of cells per unit area should be as large as possible), the average cell diameter is smaller, and the cell size is relatively uniform, and the closed cell ratio is high. At present, in the refrigerator and freezer industry, the foam density is generally 28-36Kg/m ³ (ii) a In the water heater industry, the foam density is generally 33-40Kg/m ³ . Generally, in the present application, when the density of the foam is in the range of 25 to 42Kg/m ³ In the range where the average cell diameter is in the range of 180-240 microns (preferably 190-230 microns, more preferably 195-220 microns), especially where the size of the cells is relatively uniform, such a cell microstructure is fine or desirable. That is, the greater the number of cells in a unit volume, the average cell diameter between 180 and 240 microns, the more uniform the cell diameter and the higher the closed cell fraction, the more desirable such a cell microstructure.

In this application, "optional" means with or without.

In the present application, the stated parts by weight are preferably (approximately) relative to 80 to 115 parts by weight (preferably 85 to 110 parts by weight, more preferably 90 to 100 parts by weight or 100-115 parts by weight) of a dry white for polyurethane foaming (shortly, dry white) comprising polymer polyols and further auxiliaries in addition to the blowing agent, or (approximately) relative to 80 to 115 parts by weight (preferably 85 to 110 parts by weight, more preferably 90 to 100 parts by weight or 100-115 parts by weight) of the total polymer polyols present in the dry white. The polymer polyols used in the dry white include polyether polyols (e.g., polyoxypropylene polyols) and/or polyester polyols (e.g., aromatic polyester polyols or PET polyols).

According to a first embodiment of the present invention, there is provided a high water content, low alcohol amine bicarbonate content, alkanolamine salt blowing agent composition (FC) for use in the preparation of cast polyurethane rigid foams, more particularly a carbonate alkanolamine salt blowing agent composition (FC) for use in the preparation of (cast) polyurethane rigid foams for use in refrigerators, freezers or refrigerated vehicles. In the casting foaming reaction in the production process of a refrigerator, freezer or refrigerator car, a mixture for foaming including a black material and a white material is injected into a mold through a (single) casting port, the mixture for foaming is uniformly filled in the entire cavity of the mold, and then the mold is opened or released over a period of about 180 seconds from the start of the injection. That is, the pre-, mid-and post-reactions were completed within 3 minutes.

Specifically, according to a first embodiment of the present invention, there is provided a high water content, low alcohol amine bicarbonate content, carbonate alkanolamine salt blowing agent composition (FC) for preparing polyurethane rigid foams, the FC comprising a high water content and low alcohol amine bicarbonate content carbonate alkanolamine salt chemical blowing agent (F1).

That is, the present invention provides a carbonate alkanolamine salt blowing agent composition (FC) for preparing polyurethane rigid foams, comprising the following components:

(1) a high water content of a carbonate alkanolamine salt chemical blowing agent (F1); and

(2) cyclopentane;

(3) optionally, a (hydrofluorocarbon) physical blowing agent (F2) having a boiling point in the range of 15 to 41 ℃, wherein the physical blowing agent (F2) is one or more (two or three) selected from HFC-245fa, HFC-365mfc, LBA and hexafluorobutene;

(4) optionally, water (F3);

wherein, the relative dosage (or mass ratio) of each component is as follows: the amount of water (F3) is 0 to 2 parts by weight, 0 to 1.5 parts by weight, more preferably 0 to 1 part by weight, further preferably 0 to 0.5 parts by weight, more preferably 0 to 0.1 parts by weight; the amount of the physical blowing agent (F2) is 0 to 7 parts by weight, preferably 0 to 6.5 parts by weight, preferably 0 to 6 parts by weight, preferably 0 to 5.5 parts by weight, preferably 0 to 5 parts by weight, more preferably 0 to 4.5 parts by weight, preferably 0 to 4 parts by weight, more preferably 0 to 3.5 parts by weight, more preferably 0 to 3 parts by weight, more preferably 0 to 2.5 parts by weight, most preferably 0 part by weight; the amount of chemical blowing agent (F1) is 1 to 10 parts by weight, preferably 1.2 to 9.5 parts by weight, preferably 1.3 to 9 parts by weight, preferably 1.4 to 8.5 parts by weight, preferably 1.5 to 8 parts by weight, preferably 2.8 to 8 parts by weight, preferably 3 to 8 parts by weight, preferably 3.5 to 7.5 parts by weight, preferably 4 to 7 parts by weight, preferably 4.5 to 6.5 parts by weight, preferably 5 to 6.5 parts by weight, more preferably 5 to 6 parts by weight, for example 5.5 parts by weight; and the amount of cyclopentane is 10 to 20 parts by weight, preferably 10.5 to 19.5 parts by weight, preferably 10.5 to 19 parts by weight, preferably 11 to 18.5 parts by weight, preferably 11.5 to 18 parts by weight, for example 12, 13, 14, 15, 16, 17 or 17.5 parts by weight.

Generally, the sum of the masses of water (F3) + physical blowing agent (F2) + chemical blowing agent (F1), preferably of water (F3) + chemical blowing agent (F1) (i.e. F2 is 0), more preferably of chemical blowing agent (F1) (i.e. F3 and F2 are 0), is: 4 to 10 parts by weight, preferably 4 to 9.5, 4 to 9, 4.5 to 8.5, for example 4.999 parts, 5 parts, 5.499 parts, 5.5 parts, 6, 7 or 8 parts. The amount of cyclopentane is 10 to 20 parts by weight, preferably 10.5 to 19.5, 11 to 19, 11.5 to 18.5, 12 to 18, 12 to 17.5, for example 13, 14, 15, 16 or 17. Preferably, the mass of the physical blowing agent (F2) is 0 part by weight. More preferably, the mass of water (F3) and the mass of physical blowing agent (F2) are both 0 part by weight.

In general, the ratio (or relative amount) of the sum of the masses of water (F3) + physical blowing agent (F2) + chemical blowing agent (F1) to the mass of cyclopentane, preferably the ratio (or relative amount) of the sum of the masses of water (F3) + chemical blowing agent (F1) (i.e. F2 is 0) to the mass of cyclopentane, more preferably the ratio (or relative amount) of the mass of chemical blowing agent (F1) (i.e. both F3 and F2 are 0) to the mass of cyclopentane is: (4-10 parts by weight) (10-20 parts by weight), preferably (4-9.5): 10-20), (4-9): 10-18), (4-9): 10-16), preferably (4.5-10): 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), more 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 (5.8-7.8): 11.5-18.8, preferably (5.9-7.6): 12-18.5, preferably (6-7): 13-18. Here, (4-10): (10-20) can also be expressed as (1-2.5): 2.5-5 parts by weight, and so on.

Generally, chemical blowing agents (F1) comprise the following ingredients (or components):

(A)67-90 wt% of a di (C2-C9 alcohol amine) carbonate salt; the amount is preferably 68-89.5 wt.%, more preferably 69-89 wt.%, 70-88.5 wt.%, 71-88 wt.%, 72-87.5 wt.%, 73-87 wt.%, e.g., 74, 75, 76, 78, 79, 80, 81, 82, 83, 84, 85, or 86 wt.%;

(B)10-33 wt% water; the water content is preferably from 10.5 to 32% by weight, preferably from 11 to 31% by weight, from 11.5 to 30% by weight, from 12 to 29% by weight, from 12.5 to 28% by weight, from 13 to 27% by weight, for example 14, 15, 16, 18, 19, 20, 21, 22, 23, 24, 25 or 26% by weight;

(C)0-20 wt% of (free) C2-C9 alcohol amine; the content is preferably 0.01 to 19 wt.%, preferably 0.02 to 18 wt.%, more preferably 0.03 to 17 wt.%, more preferably 0.04 to 16 wt.%, preferably 0.06 to 15 wt.%, for example 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 12, 13 or 14 wt.%;

and

(D)0-10 wt% of C2-C9 alcohol amine bicarbonate; the content is preferably 0 to 9 wt.%, preferably 0 to 8 wt.%, 0 to 7 wt.%, 0 to 6 wt.%, 0 to 5 wt.%, 0 to 4 wt.%, 0 to 3 wt.%, 0 to 2 wt.%, 0 to 1 wt.%, 0 to 0.5 wt.%, most preferably 0 wt.%;

the above percentages are based on the total weight of the chemical blowing agent (F1).

Generally, the sum of the weights of components (A), (B), (C) and (D) is from 90 to 100% by weight, preferably from 92 to 100% by weight, preferably from 93 to 100% by weight, preferably from 95 to 100% by weight, preferably from 98 to 100% by weight, preferably from 98.5 to 100% by weight, preferably from 99 to 100% by weight, preferably from 99.5 to 100% by weight, preferably from 99.8 to 100% by weight, more preferably 100% by weight, based on the total weight of the chemical blowing agent (F1).

In general, the total of the C2-C9 alcohol amines in the chemical blowing agent (F1) comprises or essentially comprises 70 to 100 mol%, preferably 72 to 100 mol%, preferably 75 to 100 mol%, preferably 77 to 100 mol%, preferably 80 to 100 mol%, preferably 82 to 100 mol%, preferably 85 to 100 mol%, preferably 87 to 100 mol%, preferably 90 to 100 mol%, preferably 92 to 100 mol%, preferably 95 to 100 mol%, preferably 97 to 100 mol%, preferably 98 to 100 mol%) of specific C4-C9 alcohol amines, the specific C4-C9 diol amines being (I) C4-C7 diol amines (Ia) having only hydroxyethyl groups, (II) C5-C9 diol amines (IIa) having hydroxyisopropyl groups or (III) a combination or mixture of component (I) alcohol amines (Ia) and component (II) alcohol amines (IIa), the mol% being based on the total molar amount of C2-C9 alkanolamines present in chemical blowing agent (F1) (or on the total molar amount of C2-C9 alkanolamines present in components (A), (C) and (D)), and (I) the C4-C7 dialamines (Ia) having only hydroxyethyl groups are one or more selected from the group consisting of diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine and N-propyldiethanolamine, and, (II) the C5-C9 dialolamine with hydroxyisopropyl group (IIa) is one or more selected from the group consisting of diisopropanolamine, ethanol isopropanolamine, N-methyl diisopropanolamine, N-ethyl diisopropanolamine, N-propyl diisopropanolamine, N-methyl ethanol isopropanolamine, N-ethyl ethanol isopropanolamine and N-propyl ethanol isopropanolamine.

In general, the pH of the chemical blowing agent (F1) is from 8.6 to 10.4, preferably from 8.8 to 10.2, preferably from 9 to 10.1, more preferably from 9.2 to 10, preferably from 9.3 to 9.7, more preferably from 9.4 to 9.6.

Preferably, when the blowing agent composition (FC) is used for the preparation of insulating foams for use at low temperatures, for example for the preparation of insulating foams for refrigerators or freezers, the sum of the masses of water (F3) + physical blowing agent (F2) + chemical blowing agent (F1) is (5.5 to 10 parts by weight, preferably 6 to 10 parts by weight, and the mass of cyclopentane is 10 to 20 parts by weight, preferably 12 to 18 parts by weight; alternatively, the ratio (or relative amounts) of the sum of the masses of water (F3) + physical blowing agent (F2) + chemical blowing agent (F1) to the mass of cyclopentane 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 chemical blowing agent (F1) is used in an amount of more than 5 parts by weight (e.g., 5 or 5.5 or 6 parts by weight) (in addition, for example, F2 or water (F3) is used in an amount of 0 to 1 part by weight) in order to give a foamed material (white plus black) having a high flowability, a foamed material having a suitable development time and stringiness time, the cell size of the resulting foam being relatively uniform, and a foam having a low product density (e.g., 28 to 36 Kg/m) ³ ) And simultaneously, the mechanical strength (the crosslinking density and the shrinkage deformation resistance of the cell wall) and the heat insulation performance of the obtained foam material are obviously improved.

Preferably, when the blowing agent composition (FC) is used for the preparation of insulating foams for use at higher temperatures, for example from 70 to 110 ℃, for the preparation of insulating foams for water heaters (electric water heaters or solar water heaters), the sum of the masses of water (F3) + physical blowing agent (F2) + chemical blowing agent (F1) is (4 to 10) parts by weight, preferably 4 to 9 parts by weight, preferably 4 to 8 parts by weight, preferably 5 to 7 parts by weight, preferably 5.5 to 6 parts by weight, the mass of cyclopentane is 10 to 20 parts by weight, preferably 12 to 18 parts by weight or 12 to 16 parts by weight; alternatively, the ratio (or relative amount) of the sum of the mass of water (F3) + physical blowing agent (F2) + chemical blowing agent (F1) to the mass of cyclopentane is (4-10 parts by weight) to (10-20 parts by weight), more preferably (4-9 parts by weight) to (12-18 parts by weight), and preferably (4-8 parts by weight) to (12-16 parts by weight). For example, the chemical blowing agent (F1) is used in an amount of 3 to 5.5 parts by weight (e.g., less than 5.5 or less than 5 parts by weight, such as 3 to 5.499 parts, or 4 parts by weight) (in addition, for example, F2 or water (F3) is used in an amount of 0 to 1 part by weight) so that the foam produced has a higher product density (e.g., about 40 Kg/m) ³ ) The foam material is suitable for playing a heat preservation effect at higher temperature (such as 70-110 ℃) and simultaneously reducing the production cost of the foam material.

The above-mentioned high-water content carbonate alkanolamine salt chemical foaming agent (F1) means a high-water content and low-alcohol amine bicarbonate content carbonate alkanolamine salt chemical foaming agent (F1). The term "N-propyl" as used herein includes N-N-propyl and N-isopropyl.

That is, the specific C4-C9 dialcohol amines are selected from one or more of (I) C4-C7 dialcohol amines (Ia) having only hydroxyethyl groups and (II) C5-C9 dialcohol amines (IIa) having hydroxyisopropyl groups. Preferably, the specific C4-C9 glycol amine is: (I) C4-C7 dialcohols (Ia) with only hydroxyethyl groups, or mixtures or combinations (III) of (I) alcamines (Ia) with (II) C5-C9 dialcohols (IIa) with hydroxyisopropyl groups.

Generally, when more than 0 wt% (e.g., more than 0.01 wt%) of free alcohol amine (e.g., C2-C9 alcohol amine or other alcohol amine) is present in chemical blowing agent (F1), alcohol amine bicarbonate is not present in chemical blowing agent (F1).

Preferably, the chemical foaming agent (F1) is prepared by introducing CO into a mixture of C2-C9 alcohol amine and water ₂ Gas neutralization method; preferably, the neutralization method comprises: introducing CO at a surface pressure of 0.09-0.4MPa (0.9-4atm, e.g. 0.09-0.35MPa or 0.1-0.3MPa) into a mixture of C2-C9 alcohol amine and water ₂ Until the gas is saturated, optionally, the above-mentioned C2-C9 alcohol amine (preferably, the above-mentioned specific C4-C9 diol amine, such as diethanolamine and/or diisopropanolamine) is further added to the resultant product so that the pH of the product is in the range of 8.6 to 10.4 (preferably 8.8 to 10.2, 9 to 10.1, preferably 9.2 to 10, preferably 9.2 to 9.7, preferably 9.4 to 9.6), to obtain a chemical blowing agent (F1); preferably, the amount of water in the mixture of C2-C9 alcohol amine and water is such that the (free) water content in the prepared chemical blowing agent (F1) is 10-33 wt.%, preferably 10.5-32 wt.%, preferably 11-31 wt.%, 11.5-30 wt.%, 12-29 wt.%, 12.5-28 wt.%, 13-27 wt.%, for example 14, 15, 16, 18, 19, 20, 21, 22, 23, 24, 25 or 26 wt.%. The above-mentioned C2-C9-ol amines described here comprise the above-mentioned specific C4-C9-diol amines, of which the specific C4-C9-diol amines and their composition (mol%) are as defined above. Preferably, CO is introduced into the mixture of C2-C9 alcohol amine and water ₂ The pressure of the gas should be chosen (generally based on the basicity of the alcohol amine C2-C9) to be sufficient to make the alcohol amine C2-C9 CO as stoichiometric as possible to form the di (C2-C9 alcohol) carbonate salt ₂ Neutralize but formMore than 10 wt% (e.g., 0-10 wt%, preferably 0-9 wt%, 0-8 wt%, 0-7 wt%, 0-6 wt%, 0-5 wt%, 0-4 wt%, 0-3 wt%, 0-2 wt%, 0-1 wt%, 0-0.5 wt%, most preferably 0 wt%) of C2-C9 alkanolamine bicarbonate, the wt% based on the weight of the formed chemical blowing agent (F1) (i.e., alkanolamine carbonate salt hydrate).

Introducing CO ₂ In the gas neutralization method, suitable CO is selected according to the alkalinity of different C2-C9 alcohol amines ₂ Pressure so that the C2-C9 alcohol amine is CO as close as possible to the stoichiometry of the formation of the di (C2-C9 alcohol amine) carbonate salt ₂ The content of C2-C9 alkylolamine bicarbonate in the neutralized and obtained chemical blowing agent (F1) is as low as possible, for example less than 10 wt.%, more preferably less than 8 wt.% or even less than 5 wt.%, CO ₂ The choice of pressure is readily accomplished by those skilled in the art. In addition, in order to prepare a chemical blowing agent (F1) which contains two or more types of alcohol amines of different basicity and in which the content of formed alcohol amine bicarbonates is low, it is possible to use different CO respectively ₂ Introducing CO into each alcohol amine under the pressure of gas ₂ Gas to produce carbonate (almost no alcohol amine bicarbonate) of each alcohol amine. The neutralization products of two or more kinds which are almost free of alkylol amine bicarbonates are then mixed in corresponding proportions to obtain a chemical blowing agent containing a plurality of alkylol amine carbonates and a smaller amount of alkylol amine bicarbonates (F1). In addition, for the introduction of CO ₂ In the case of a product with a higher amount of alkanolamine carbonate prepared from a more basic alkanolamine (e.g., (Ib) a secondary amine type C3-C5 monoalkanolamine with only hydroxyethyl groups, or (IIb) a secondary amine type C4-C6 monoalkanolamine with hydroxyisopropyl groups), it is possible to further add a weakly basic diamine to the product to convert the alkanolamine bicarbonate to the alkanolamine carbonate, thereby reducing the bicarbonate content of the product to about 0 wt.%, i.e., to form an alkanolamine mixture containing a more basic alkanolamine and a less basic alkanolamine, but this alkanolamine mixture is still not preferred because it contains a more basic alkanolamine (e.g., N-methylethanolamine) which has a higher onset time for the foaming reactionWith an effect.

First, the inventors have found experimentally that the small amount of unstable alkylol amine bicarbonate present in the blowing agent composition (FC) has a great influence on the blowing reaction, resulting in a reduced rise time in the blowing reaction (e.g., to 1-2 seconds). For example, a violent reaction occurs immediately after the white material is mixed with the black material due to the presence of bicarbonate, and the foam rapidly expands to run away. The reason for this may be that the alkylol amine bicarbonate is unstable (easily decomposed) and the reactivity is high. It is therefore important to control the content of the alkylol amine bicarbonate in the chemical blowing agent (F1) to less than 10 wt%, in particular less than 8 wt% or 5 wt%.

Secondly, with control of the bicarbonate content, further selection of various alcohol amines from the group of C2-C9 alcohol amines also enables further improvement of the properties of the blowing agent composition.

Preferably, the specific C4-C9 glycol amine is: (I) alcamines (Ia), or (III) a combination or mixture of alcamines (Ia) of component (I) and alcamines (IIa) of component (II); more preferably, the specific C4-C9 diol amine is (III) a combination or mixture consisting of components (I) an alcanolamine (Ia) and (II) an alcanolamine (IIa); thus, the molar ratio of the alkanolamines (Ia) of component (I) to the alkanolamines (IIa) of component (II) is 1 (0-2.5), preferably 1 (0.1-2), more preferably 1 (0.2-1.5), more preferably 1 (0.22-1.2), more preferably 1 (0.24-0.9), more preferably 1 (0.25-0.5), more preferably 1 (0.27-0.4), more preferably 1 (0.29-0.45), most preferably 3: 1. Preferably, in the combination or mixture of (III) consisting of the alkanolamines (Ia) and (II) of component (I) and (IIa), the mol% of component (I) is from 28 to 100 mol%, more preferably from 33 to 91 wt%, more preferably from 40 to 83 wt%, more preferably from 45 to 82 wt%, more preferably from 52 to 81 wt%, more preferably from 66 to 80 wt%, more preferably from 71 to 78 wt%, more preferably from 68 to 77 wt%, most preferably 75 mol%, based on the total molar amount of component (I) and component (II).

Generally, in the present application, the C2-C9 alcohol amines include (includes) specific C4-C9 dialkanolamines (e.g., C4-C9 dialkanolamines (Ia + IIa) having hydroxyethyl and/or hydroxyisopropyl groups, such as diethanolamine or diisopropanolamine), secondary amine type C3-C6 monoalkanolamine (e.g., secondary amine type C3-C6 monoalkanolamine (Ib + IIb) having hydroxyethyl or hydroxyisopropyl groups, such as N-methyl monoisopropanolamine or N-methyl ethanolamine) and optionally primary amine type C2-C9 monoalkanolamine and optionally tertiary amine type C4-C7 monoalkanolamine and optionally tertiary amine type C6-C9 triolamine.

In general, C4-C9 glycol amines (Ia + IIa) having hydroxyethyl and/or hydroxyisopropyl groups include (includes), such as diethanolamine, diisopropanolamine, ethanolisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, N-propyldiisopropanolamine, N-methylethanoisopropanolamine, N-ethylethanolisopropanolamine and N-propylethanolisopropanolamine.

Typically, secondary amine type C3-C6 monoalkanolamine (Ib + IIb) with hydroxyethyl or hydroxyisopropyl groups include (include) include, for example, N-methyl monoethanolamine, N-ethyl monoethanolamine, N-propyl monoethanolamine, N-methyl monoisopropanolamine, N-ethyl monoisopropanolamine and N-propyl monoisopropanolamine.

In general, the total C2-C9 alcohol amine in the chemical blowing agent (F1) may also comprise less than 30 mol%, for example from 0 to 30 mol%, preferably from 0 to 28 mol%, preferably from 0 to 25 mol%, preferably from 0 to 23 mol%, preferably from 0 to 20 mol%, preferably from 0 to 18 mol%, preferably from 0 to 15 mol%, preferably from 0 to 13 mol%, preferably from 0 to 10 mol%, preferably from 0 to 8 mol%, preferably from 0 to 5 mol%, preferably from 0 to 3 mol%, preferably from 0 to 2 mol%, of other C2-C9 alcohol amines in addition to the abovementioned specific C4-C9 diol amines. For example, these other C2-C9 alkanolamines are one or more selected from secondary amine type C3-C6 monoalkanolamine with hydroxyethyl or hydroxyisopropyl groups (Ib + IIb) (i.e., (Ib) secondary amine type C3-C5 monoalkanolamine with hydroxyethyl groups only and (IIb) secondary amine type C4-C6 monoalkanolamine with hydroxyisopropyl groups only); wherein, the secondary amine type C3-C5 monoethanolamine (Ib) having only hydroxyethyl groups is one or more selected from N-methyl monoethanolamine, N-ethyl monoethanolamine and N-propyl monoethanolamine; and, the secondary amine type C4-C6 monoalkanolamine (IIb) having only hydroxyisopropyl groups is one or more selected from N-methyl monoisopropanolamine, N-ethyl monoisopropanolamine and N-propyl monoisopropanolamine. Here, the mol% is based on the total molar amount of C2-C9 alkanolamines present in the chemical blowing agent (F1) (or on the total molar amount of C2-C9 alkanolamines present in components (A), (C) and (D)).

Generally, the specific C4-C9 dialolamine is one or two or more (preferably, two or more) selected from the group consisting of C4-C7 diethanolamines (which includes diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and N-propyldiethanolamine), C6-C9 diisopropanolamines (which includes diisopropanolamine, N-methyldiiropanolamine, N-ethyldiisopropanolamine, and N-propyldiisopropanolamine), and C5-C8 ethanolisopropanolamine (which includes ethanolisopropanolamine, N-methylethanolisopropanolamine, N-ethylethanolisopropanolamine, and N-propylethanolisopropanolamine); more preferably, the specific C4-C9 glycol amine is a mixture of (C4-C7 diethanolamines) and (C6-C9 diisopropanolamines and/or C5-C8 ethanolisopropanolamines), for example in a molar ratio according to 0.3-5:1 (preferably 0.7-4.5: 1); more preferably, the specific C4-C9 glycol amine is a mixture of (C4-C7 diethanolamines) and (C6-C9 diisopropanolamines and/or C5-C8 ethanolisopropanolamines) in a 1.5-4.5:1 molar ratio (preferably 1.8-4.2:1, more preferably 2-4:1, more preferably 2.3-3.7:1, more preferably 2.5-3.5:1, more preferably 2.7-3.3:1, more preferably 2.8-3.2:1, especially 3:1 molar ratio); more preferably, the specific C4-C9 glycol amine is a mixture of (diethanolamine) and (diisopropanolamine and/or ethanolisopropanolamine) in a molar ratio of 1.5-4.5:1, more preferably in a molar ratio of 1.8-4.2:1, more preferably 2-4:1, more preferably 2.3-3.7:1, more preferably 2.5-3.5:1, more preferably 2.7-3.3:1, more preferably 2.8-3.2:1, especially 3: 1.

Typically, the secondary amine type C3-C6 monoalkanolamine (Ib + IIb) is one or two or more selected from the group consisting of N-methyl monoethanolamine, N-methyl monoisopropanolamine, N-ethyl monoethanolamine, N-ethyl monoisopropanolamine, N-propyl monoethanolamine and N-propyl monoisopropanolamine.

In general, all of the C2-C9 alcohol amines in the chemical blowing agent (F1) may possibly include, in addition to the above-mentioned specific C4-C9 diol amines and secondary amine type C3-C6 mono-alcohol amines having hydroxyethyl or hydroxyisopropyl groups (i.e., (Ib) secondary amine type C3-C5 mono-alcohol amines having only hydroxyethyl groups and (IIb) secondary amine type C4-C6 mono-alcohol amines having only hydroxyisopropyl groups), other C2-C9 alcohol amines (simply referred to as "impurity alcohol amines IA"), for example, primary amine type C2-C9 mono-alcohol amines, tertiary amine type C4-C9 mono-alcohol amines (for example, N-dimethylethanolamine and N-dimethylisopropanolamine), tertiary amine type C6-C9 triol amines (for example, triethanolamine, triisopropanolamine), and the like. The content of such other alkanolamines (impurity alkanolamines IA) in chemical blowing agent (F1) should be as low as possible, generally from 0 to 30mol, preferably from 0 to 28 mol%, preferably from 0 to 25 mol%, preferably from 0 to 23 mol%, preferably from 0 to 20 mol%, preferably from 0 to 18 mol%, preferably from 0 to 15 mol%, preferably from 0 to 13 mol%, preferably from 0 to 10 mol%, preferably from 0 to 8 mol%, preferably from 0 to 5 mol%, preferably from 0 to 3 mol%, preferably from 0 to 2 mol%, based on the total molar amount of C2-C9 alkanolamines present in chemical blowing agent (F1) (or based on the total molar amount of C2-C9 alkanolamines present in components (A), (C) and (D)).

In addition, it is possible that the total C2-C9 alcohol amines in the chemical blowing agent (F1) include, in addition to the specific C4-C9 diol amines mentioned above, other alcohol amines: (Ib) secondary amine type C3-C5 monoalkanolamine with only hydroxyethyl groups, (IIb) secondary amine type C4-C6 monoalkanolamine with only hydroxyisopropyl groups, and the so-called "impurity alkanolamines IA" mentioned above; the total mol% of all these other alkanolamines is from 0 to 30 mol%, preferably from 0 to 28 mol%, preferably from 0 to 25 mol%, preferably from 0 to 23 mol%, preferably from 0 to 20 mol%, preferably from 0 to 18 mol%, preferably from 0 to 15 mol%, preferably from 0 to 13 mol%, preferably from 0 to 10 mol%, preferably from 0 to 8 mol%, preferably from 0 to 5 mol%, preferably from 0 to 3 mol%, preferably from 0 to 2 mol%, based on the total molar amount of C2-C9 alkanolamines present in the chemical blowing agent (F1) (or based on the total molar amount of C2-C9 alkanolamines present in components (A), (C) and (D)).

The parts by weight stated above are (approximately) relative to or based on 80 to 115 parts by weight (preferably 85 to 110 parts by weight, more preferably 85 to 100 or 90 to 100 parts by weight or 90 to 115 parts by weight or 100 parts by weight of 115 parts by weight, for example 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 102, 105, 107, 108, 110, 112, 113 or 114 parts by weight) of dry white polyurethane foam comprising polymer polyols and auxiliaries other than blowing agents. Wherein the other auxiliaries include polyurethane catalysts, foam stabilizers and optionally flame retardants, optionally chain extenders and optionally crosslinkers. The blowing agent composition (FC) is used for a foaming reaction by mixing with a white material and a polyisocyanate as a black material to prepare a rigid polyurethane foam. When the amount of chemical blowing agent (F1) was greater than 12 parts by weight and the amount of CP was correspondingly reduced, the viscosity of the resulting white mass increased significantly.

The physical blowing agents described herein (F2), namely HFC-245fa, HFC-365mfc, LBA and hexafluorobutene, are all hydrofluorocarbon physical blowing agents.

When the blowing agent composition (FC) does not comprise a physical blowing agent (F2), the chemical blowing agent (F1) and the cyclopentane are each contained in a separate container. In addition, when the blowing agent composition (FC) further comprises a physical blowing agent (F2), the chemical blowing agent (F1) is contained in a separate container, while the physical blowing agent (F2) and the cyclopentane are contained in separate containers or in the same container.

The blowing agent compositions (FC) of the present invention are used for the preparation of cast polyurethane rigid foams, more preferably for the preparation of cast polyurethane rigid foams in the production of refrigerators, freezers, water heaters or refrigerated vehicles.

In the present application, the amount of the chemical blowing agent (F1) is generally not less than 3 parts by weight, which enables the polyurethane rigid foam obtained to have good thermal insulation properties and strength properties.

If the chemical blowing agent (F1) is used in an amount of less than 3 parts by weight (e.g. 1 to 2.8 parts by weight), it is primarily used for the early nucleation of the foaming reaction, since CO is immediately produced when the white material is mixed with the black material ₂ A gas. The physical blowing agent is a foaming agent which generates bubbles by vaporization after the temperature of a foaming mixture is raised by using reaction heat, and the foaming and the expansion are delayed. The preliminary nucleation is advantageous in increasing the number of cells and improving the uniformity of cell size, and thus also contributes to improving the microstructure of the rigid polyurethane foam, thereby improving the thermal insulation properties of the foam to some extent. Of course, polyurethane rigid foams that are used in amounts greater than 3 parts by weight (i.e., 3 to 8 parts by weight) are more preferred in order to achieve a better balance of properties.

When water (F3) is present in the blowing agent composition (FC), this means that the production cost of the rigid foam is reduced by additionally using a small amount (up to 2 parts by weight) of water and correspondingly simultaneously reducing the amount of physical blowing agent, but this reduces the strength and the deformation resistance of the produced foam, and at the same time reduces the cell closing rate of the foam and the thermal insulation properties are reduced. Therefore, it is preferable that the amount of water (F3) should be reduced, more preferably to 0 parts by weight.

In addition, when the physical blowing agent (F2) is present in the blowing agent composition (FC), this means that the higher the amount of the physical blowing agent (F2) used, the production cost of the rigid foam is significantly increased and the strength properties of the rigid foam are reduced, but the thermal insulation properties of the produced foam are not significantly improved. Therefore, it is preferable that the amount of the physical blowing agent (F2) should be reduced, more preferably to 0 parts by weight. When the amount of the physical foaming agent (F2) is reduced, the amount of the chemical foaming agent (F1) is correspondingly increased so as to obtain a rigid foam having a prescribed foam density or equivalent foam density.

Preferably, the blowing agent composition (FC) comprises only component (1), the chemical blowing agent (F1), and component (2), cyclopentane, i.e., both component (2), the physical blowing agent (F2), and component (3), water (F3), are used in amounts of 0 parts by weight. Thus, the mass ratio (or relative amount) of the chemical blowing agent (F1) to cyclopentane is (4-10 parts by weight) to (10-20 parts by weight), preferably (4-9.5) to (10-20), (4-9) to (10-18), (4-9) to (10-16), preferably (4.5-10) to (10-20), (5-9.5) to (10-18), (5-9.5) to (10-16), (5-9) to (10-20), (5-9) to (10-18), (5-9) to (10-16), more preferably (5.5-9) to (10-20), (5.5-8.5) to (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 (5.8-7.8) (11.5-18.8), preferably (5.9-7.6) (12-18.5), preferably (6-7) (13-18), more preferably (6-7) (14-18), more preferably (6-7) (15-18), more preferably (6-7) (16-18).

In these cases, on the one hand, the production costs of rigid foams are significantly reduced, while, surprisingly, the rigid polyurethane foams formed have a very low thermal conductivity, i.e.Lance λ (mW/m.K, 10 ℃). This coefficient is referred to below as the thermal conductivity (λ).

In general, the blowing agent composition (FC) is used in an amount sufficient to produce a (cast) rigid polyurethane foam having a density of from 25 to 38Kg/cm, relative to or based on from 80 to 115 parts by weight (preferably from 85 to 110 parts by weight, preferably from 90 to 100 parts by weight, for example 100 parts by weight) of dry white matter ³ In the range of 26 to 37Kg/cm is preferred ³ Preferably 27 to 36.5Kg/cm ³ Preferably 28 to 36Kg/cm ³ Preferably 28.5 to 35.5Kg/cm ³ Preferably 29 to 35Kg/cm ³ E.g. 30, 31, 32, 33 or 34Kg/cm ³ 。

It is preferred in this application that the sum of the amounts of water of both the high water content carbonate alkanolamine salt chemical foaming agent (F1) of component (1) and the optional water (F3) of component (4) is 1 to 3.7 wt.% (preferably 1.1 to 3.5 wt.%, preferably 1.2 to 3.3 wt.%, preferably 1.25 to 3 wt.% or 1.3 to 2.5 wt.% or 1.4 to 2 wt.%, e.g. 1.5, 1.6, 1.7, 1.8 wt.%), (approximately) relative to or based on 100 parts by weight of dry white matter. An amount of water within this range enables the foaming composition to have desirable fluidity while ensuring excellent strength properties and heat insulating properties of the rigid foam produced.

The chemical blowing agent (F1) consists of components A), B), optionally C) and optionally D); preferably, the chemical blowing agent (F1) consists of components a), B) and optionally C) or consists of components a), B) and optionally D); more preferably, the chemical blowing agent (F1) consists of components A) and B).

According to a most preferred embodiment of the present invention, there is provided a blowing agent composition (FC) wherein: the specific C4-C9 glycol amine is a mixture of diethanolamine and diisopropanolamine in a molar ratio of 1 (0.15-3), preferably 1 (0.2-1.5), more preferably 1 (0.22-1.2), more preferably 1 (0.24-0.9), more preferably 1 (0.25-0.5), more preferably 1 (0.27-0.4), more preferably 1 (0.29-0.45). Preferably, the pH of the chemical blowing agent (F1) is 9.2 to 10, preferably 9.3 to 9.7, more preferably 9.4 to 9.6. More preferably, the content of component (D), C2-C9 alkylol amine bicarbonate, is 0-5 wt%, 0-4 wt%, 0-3 wt%, 0-2 wt%, 0-1 wt%, 0-0.5 wt%, most preferably 0 wt%. Polyurethane rigid foams (density) obtained using such blowing agent compositions (FC)At 25-38Kg/cm ³ Range) has a thermal conductivity lambda (mW/m.K, 10 ℃) of less than 18.30 or less than 18.20 or less than 18.10, even less than 18.05. The diisopropanolamine present in small amounts in the chemical blowing agent (F1) consisting of diethanolamine and diisopropanolamine serves as a compatibilizing or solubilizing action, and can increase the compatibility between the blowing agent composition (FC) and the polymer polyol in the dry white, can form a transparent, homogeneous white, and improves the microstructure and the closed cell content of the rigid polyurethane foam, and thus can reduce the thermal conductivity λ (mW/m.K, 10 ℃) of the foam to, for example, less than 18.05.

The invention provides a white material for polyurethane foaming, which comprises the following components: (1) a dry white for polyurethane foaming comprising polymer polyols and further auxiliaries in addition to blowing agents, wherein the further auxiliaries comprise polyurethane catalysts, foam stabilizers and optionally flame retardants, optionally chain extenders and optionally crosslinkers; and (2) the above-described alkanolamine carbonate salt blowing agent composition (FC).

Preferably, the polymer polyols in the dry white mass comprise 8-52 wt.% (preferably 9-50 wt.%, preferably 10-48 wt.%, preferably 12-47 wt.%, preferably 15-45 wt.%, preferably 16-40 wt.%, more preferably 18-35 wt.%) of aromatic/semi-aromatic polyester polyols (such as polyethylene phthalate, polyethylene isophthalate or polyethylene terephthalate) and/or toluene diamine polyoxypropylene polyols and 92-48 wt.% (preferably 91-50 wt.%, preferably 90-52 wt.%, preferably 88-53 wt.%, preferably 85-55 wt.%, preferably 84-60 wt.%, more preferably 82-65 wt.%) of (non-toluene diamine type or non-toluene diamine initiated) polyoxypropylene polyols, namely, a polyoxypropylene polyol other than a tolylenediamine polyoxypropylene polyol.

The present invention also provides a polyurethane foaming composition (or mixture) comprising:

(1) a polyisocyanate as a black material (preferably, polymethylene polyphenyl polyisocyanate or polymeric MDI);

(2) a dry white for polyurethane foaming comprising polymer polyols and other auxiliaries except for a foaming agent; and

(3) the above-described alkanolamine carbonate salt blowing agent composition (FC).

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 to 1.36:1, preferably 1.13 to 1.35:1, preferably 1.15 to 1.30:1, preferably 1.17 to 1.27:1, preferably 1.18 to 1.25:1, most preferably 1.2: 1.

Aromatic/semi-aromatic polyester polyols in the present application refer to aromatic polyester polyols and/or semi-aromatic polyester polyols, typically having low viscosities (25 ℃) (e.g., 3000-.

As for the polymer polyol in the dry white, 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.

Toluene diamine polyoxypropylene polyol refers to a toluene diamine initiated or initiated polyoxypropylene polyol.

Preferably, when aromatic/semi-aromatic polyester polyols are used, the amount of toluene diamine polyoxypropylene polyol used is reduced or eliminated.

On the one hand, diethanolamines (e.g. diethanolamine or N-methyldiethanolamine) have a relatively low viscosity, but they are slightly less compatible with dry white materials comprising polyoxypropylene polyol and small amounts of polyester polyol and/or tolylenediamine polyether polyol (white materials obtained by mixing dry white materials with a blowing agent containing diethanolamines under stirring followed by rapid defoaming by centrifugation, the materials being found to have a delamination phenomenon, i.e. a thinner layer of the material at the bottom), and the thermal insulation properties of the obtained rigid polyurethane foam are not optimal.

On the other hand, diisopropanolamines (such as diisopropanolamine, ethanol isopropanolamine, and N-methyl diisopropanolamine) and ethanol isopropanolamine have a relatively high viscosity (when mixing dry white materials with a blowing agent containing the diisopropanolamine to obtain white materials by hand stirring, it is obvious that stirring of the white materials is more difficult and the white materials have a higher viscosity), resulting in a less uniform mixing of the white materials with the black materials and a less than optimal thermal insulation performance of the polyurethane rigid foam obtained. However, it was unexpected that the use of these (diisopropanolamines and/or ethanolisopropanlamines) in combination with diethanolamines could significantly improve the compatibility between the blowing agent obtained and the dry white material, enable the formation of a homogeneous, transparent white material, in turn improve the microstructure of the foam produced and increase the closed cell content, bringing the thermal conductivity of the foam almost to the lowest limit (for example a lambda value as low as 18.10 or even lower than 18.02). The use of the two types of alcohol amines in combination may lead to a doping effect, which reduces the viscosity with respect to each other.

The invention also provides the use of the above-described carbonate alkanolamine salt blowing agent composition (FC) for formulating polyurethane foaming compositions.

The present invention also provides a method for preparing a polyurethane rigid foam, the method comprising: mixing and foaming a polymer polyol composition white comprising the above blowing agent composition (FC) with a polyisocyanate (preferably, polymethylene polyphenyl polyisocyanate or polymeric MDI) as a black material; preferably, casting foaming is performed using a casting machine.

The present invention also provides a rigid polyurethane foam obtained by the above-mentioned process for preparing a rigid polyurethane foam, wherein the rigid polyurethane foam has a density of 25 to 38Kg/cm ³ In the range of 26 to 37Kg/cm is preferred ³ Preferably 27 to 36.5Kg/cm ³ Preferably 28 to 36Kg/cm ³ Preferably 28.5 to 35.5Kg/cm ³ Preferably 29 to 35Kg/cm ³ E.g. 30, 31, 32, 33 or 34Kg/cm ³ 。

The rigid polyurethane foam has a Lance thermal conductivity lambda (mW/m.K, 10 ℃) of less than 18.50, preferably less than 18.40, more preferably less than 18.30, more preferably less than 18.20, more preferably less than 18.05.

The water and alcohol amine have stronger hydrogen bond action, which is larger than the chemical bond between alcohol amine and carbonate.

For the use of the blowing agent compositions (FC) in the production of rigid polyurethane foams in the refrigerator, freezer, water heater and refrigerator car industries, a further increase in the relative amount of cyclopentane in the blowing agent (FC) above 22 parts by weight leads to the formation of a two-phase system (phase separation) in the formulated white mass. Wherein the presence of oil droplets is found when the white mass is stirred and, in addition, delamination occurs on standing, which means that too much cyclopentane is freed from the water and polymer polyol constraints (or that the solubility of cyclopentane in the white mass is limited) and it no longer participates in the formation of the multi-complex. Thus, a homogeneous foaming system cannot be formed in the foaming reaction, the cell diameter in the resulting foam is particularly non-uniform (where oil droplets become vaporization centers, creating large or extra large pores at the oil droplet locations), the cell diameter is typically greater than 300 microns or even greater than 350 microns, and the thermal insulation properties of the foam are significantly reduced.

The phase separation phenomenon indicated that the physical blowing agent (F2) and the cyclopentane have good compatibility with the dry white and a clear and homogeneous white can be formed only when the content of the physical blowing agent (F2) and/or cyclopentane in the Foaming Composition (FC) is within a certain range.

The inventors have found through experiments that the use of such a dry white material can improve the compatibility or solubility of cyclopentane in the white material system and, at the same time, can also improve the compatibility of HFC-245fa, HFC-365mfc, LBA and hexafluorobutene in the white material system due to the presence of a portion of the polyester polyol containing benzene rings and the toluenediamine polyether polyol in the dry white material. However, since hexafluorobutene has a higher molecular weight, a higher density and a higher polarity, and the higher density affects the density distribution of hexafluorobutene in the white material, its compatibility in the white material system is inferior to that of HFC-245fa, HFC-365mfc and LBA in the white material, and therefore, in the present invention, the use of hexafluorobutene is not preferable.

In addition, in the refrigerator, freezer, water heater and refrigerator car industries, when the relative amount of cyclopentane in the foaming agent (FC) is further reduced to less than 8 parts by weight, this will result in a decrease in the flowability of the white material formed, the mold cannot be filled by pouring in a short time during the production of the refrigerator, and the releasability of the mold after foaming is also affected, resulting in a substantial decrease in the production efficiency of the refrigerator production line and a decrease in the thermal insulation performance of the refrigerator.

When the water content of the chemical blowing agent (F1) is less than 9% by weight or even less than 8% by weight or less than 7% by weight, this leads to an increase in the viscosity of the blowing agent formed, to a deterioration in the compatibility of the blowing agent in the white material, to the precipitation of alkanolamines as solids or viscous substances from the white material (due to the dehydration of the polyol), to an increase in the activity of the blowing agent, to a considerable reduction in the rise time of the foam during the foaming process in the refrigerator production (for example to 1 to 3 seconds), and to a too rapid and uncontrolled foaming.

The suitable rise time and flowability of the foaming mixture are very important for casting the foam in a mold in the field of refrigerators, freezers, water heaters or refrigerated vehicles, since the foaming mixture is injected via a single injection opening into the inner cavity of the mold, which has a complex structure. If the rise time is too short or the flowability is too poor, the foaming mixture foams and hardens in a region near the injection port in the mold, the foaming mixture cannot reach a further region, and therefore, the entire mold cavity cannot be uniformly filled, which results in too poor mold opening performance of the rigid foam and an uneven distribution of the overall density of the foam in the mold.

For example, in the production of polyurethane rigid foams on the production line of the refrigerator manufacturing industry, the opening time of the mold is often about 180 seconds, and therefore, the drawing time is also important.

In addition, when the water content of the chemical blowing agent (F1) is higher than 38% by weight or even higher than 40% by weight or higher than 45% by weight, more black material (polyisocyanate such as polymethylene polyphenyl polyisocyanate or polymeric MDI) will be consumed in the foaming reaction, more urea bonds will be generated in the foam, resulting in a decrease in dimensional stability and a decrease in closed cell ratio of the resulting foam to lower the thermal insulation performance of the foam.

When the pH of the chemical blowing agent (F1) is lower than 8.6, the chemical blowing agent (F1) has low activity and reduced alkalinity, and the blowing agent (F1) binds acidic CO ₂ The capability of gas is reduced, when the white material and the black material are stirred and mixed in the foaming process, the white material is slightly heated due to the reaction heat in the initial stage of reaction, so that CO is generated ₂ Escape rapidly from the foaming mixture, CO ₂ The gas does not sufficiently exert the foaming action, resulting in a reduction in the size of cells of the resulting foam.

In addition, when the pH of the chemical blowing agent (F1) is higher than 10.4 or even higher than 10.5, the chemical blowing agent (F1) is highly active and alkaline, meaning that more alkaline alcohol amine is present in the blowing agent (F1), and the excess presence of these alkaline alcohol amine rapidly exerts a precatalyst effect, resulting in a runaway rate of the blowing reaction (e.g., 1-3 seconds of rise time, rapid expansion and rise of the blowing reaction mass), and further, the precatalyst blowing reaction (chain growth reaction) is too fast, which also severely interferes with the late catalytic crosslinking effect of the tertiary amine catalyst, reducing the strength and the deformation resistance of the resulting foam.

The excess component (C) free C2-C9 alcohol amine (mainly comprising specific C4-C9 dialkanolamine (Ia + IIa) and optionally secondary amine type C3-C6 monoalkanolamine (Ib + IIb)) in the chemical blowing agent (F1) is used on the one hand for adjusting the pH value of the chemical blowing agent (F1) and reducing the content of the alkylol amine bicarbonate, on the other hand it is used as a pre-catalyst for adjusting the foaming speed (e.g. the rise time) in the foaming reaction and as a cross-linking agent, and component (C) C2-C9 alcohol amine (mainly comprising (Ia + IIa) and optionally (Ib + IIb)) is used together with water as a mid-late cross-linking agent in the foaming reaction for increasing the strength of the inner walls of the cells and thus increasing the strength and the deformation resistance of the foam.

More preferably, when the total of the C2-C9 alcohol amine in the chemical blowing agent (F1) consists of diethanolamine and diisopropanolamine in a molar ratio of 2.8-3.2:1 (especially 3:1), the foaming mixture obtained by mixing the white material and the black material, which has high fluidity and can uniformly fill the whole cavity of the mold, is caused to smoothly proceed at the optimum foaming speed (rise time and drawing time), and the Lance thermal conductivity (Lance) of the resulting rigid polyurethane foam is lower than 18.05 or 18.03, almost reaching the limit value of the thermal insulation performance, which represents a great improvement in the thermal insulation performance of the foam.

In addition, if the boiling point of the physical blowing agent (F2) is lower than 15 ℃ or higher than 41 ℃, it may affect smooth progress of the foaming process. In the present inventionIt is desirable to first generate CO by reacting a chemical blowing agent (F1) with a polyisocyanate ₂ The gas plays the role of nucleation and foaming in the early stage, and then the physical foaming agent and cyclopentane play the role of foaming in turn along with the rise of the temperature of the reaction mixture, which is beneficial to the smooth proceeding of the foaming process.

If the boiling point of the physical blowing agent (F2) is less than 15 ℃, the low-boiling blowing agent volatilizes and escapes immediately upon mixing the blowing agent composition (FC) with the dry white material, and in addition, the early foaming action causes the composition of the foaming reaction mixture to become uneven.

If the boiling point of the physical blowing agent (F2) is higher than 41 deg.C, the foaming action of the physical blowing agent (F2) is somewhat delayed, which affects the smooth progress of the foaming reaction, and in addition, when the foam is cooled to room temperature, the high-boiling physical blowing agent (F2) in the cell holes loses its supporting action on the cells due to condensation to become liquid, resulting in shrinkage and deformation of the foam in later use.

When the total C2-C9 alcohol amine in the chemical blowing agent (F1) comprises less than 70 mol% of a specific C4-C9 diol amine, this means that the so-called total C2-C9 alcohol amine comprises more other C2-C9 alcohol amines, for example, (Ib) secondary amine type C3-C5 mono-alcohol amines having only hydroxyethyl groups and (IIb) secondary amine type C4-C6 mono-alcohol amines having only hydroxyisopropyl groups, as well as the so-called "impurity alcohol amines IA" mentioned above.

Since the small-molecule primary amine type C2-C9 monoalcohol amine has higher basicity and higher reactivity, when a white material containing a large amount of small-molecule primary amine is mixed with a black material, the rise time of the foaming mixture is greatly shortened (e.g., 1-2 seconds), and the reaction is rapid, the foam expands rapidly, leading to a runaway foaming process, and the possibility of carrying out the foaming reaction at a smooth rate, adversely affecting the microstructure and closed cell ratio of the produced rigid foam. Thus, in the blowing agent composition (FC), the lower the content of primary amine type C2-C9 monoalkanolamine, the better.

In addition, tertiary amine type C4-C7 monoalcohols and tertiary amine type C6-C9 triolines have a catalytic action and likewise influence the rate of the blowing reaction. For example, the inventors have found that when the C2-C9 alcohol amine in the chemical blowing agent (F1) comprises a relatively large amount (e.g., greater than 40 mol%) of triethanolamine, this results in a "core burn" in the foam, i.e., the core of the foam appears dark yellow or burnt yellow.

According to the present invention, there is provided a rigid polyurethane foam obtained by the above-mentioned process, particularly when the rigid polyurethane foam has a density of 25 to 38Kg/cm ³ In this range, its Lance (Lance) thermal conductivity, λ (mW/m.K, 10 ℃) is less than 18.80, preferably less than 18.70, less than 18.60, less than 18.50 or less than 18.40, more preferably less than 18.30, 18.20, 18.10, 18.04.

The inventors of the present application have found through extensive experiments that the microstructure and the closed cell content of the rigid foam can be optimized by optimizing the composition of the blowing agent, so that the thermal conductivity of the rigid polyurethane foam can be desirably reduced even to the present limit value. When the density (core density, ASTM D1622-03) of the rigid polyurethane foam obtained by the present invention is 25 to 38Kg/cm ³ In the range of 26 to 37Kg/cm is preferred ³ Preferably 27 to 36.5Kg/cm ³ Preferably 28 to 36Kg/cm ³ Preferably 28.5 to 35.5Kg/cm ³ Preferably 29 to 35Kg/cm ³ When the average cell diameter is in the range of 170-230 [ mu ] m (preferably 180-220 [ mu ] m, more preferably 170-210), the thermal conductivity (Mw/m.k, 10 ℃) of the rigid polyurethane foam is generally 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.

THE ADVANTAGES OF THE PRESENT INVENTION

1. The inventors of the present application have found a detrimental effect of the alkylol amine bicarbonate in the preparation of rigid polyurethane casting foams, and thus have minimized the alkylol amine bicarbonate content of the chemical blowing agent (F1), for example by introducing CO into the alkylol amine ₂ Selecting proper CO for alcohol amines with different alkalities in gas neutralization reaction ₂ The pressure of the gas. In addition, the selection of the type and relative amount of the alcohol amine improves the performance of the foaming agent composition (such as the compatibility between the composition and the dry white material), so that the foaming mixture formed by mixing the black material and the white material has ideal fluidity to uniformly fill the whole mould and the foaming mixture has proper fluidityThe starting time and the wire drawing time are suitable for the production of the polyurethane rigid foam in a single-port pouring mode in the fields of refrigerators, freezers, water heaters and refrigerated trucks. The prepared foam has good mould opening performance.

2. The carbonate alkanolamine salt foaming agent composition (FC) of the (cast) polyurethane rigid foam of the present invention has good compatibility with dry white materials for foaming, can form a foaming system which is uniform and transparent and has good fluidity and can be used to obtain polyurethane rigid foam having good cell microstructure and closed cell ratio, particularly, when the polymer polyols in the dry white material comprise 10-52 wt% (preferably 15-45 wt%, more preferably 18-35 wt%) of an aromatic/semi-aromatic polyester polyol and/or a toluene diamine polyoxypropylene polyol and 90-48 wt% (i.e., the balance) (preferably 85-55 wt%, more preferably 82-65 wt%) of a polyoxypropylene polyol (e.g., a sucrose-initiated polyoxypropylene polyol, or a pentaerythritol-initiated polyoxypropylene polyol).

3. Preferably, the chemical blowing agent (F1) is prepared by introducing CO into a mixture of C2-C9 alcohol amine and water ₂ Gas neutralization, wherein the C2-C9 alcohol amine contains a major amount (70-100 mol%) of the specified C4-C9 glycol amine. Selection of suitable CO depends on the basicity of the particular C4-C9 glycol amine ₂ The pressure of the gas being sufficient to cause the alcohol amine to react with the CO ₂ The neutralization reaction is carried out in stoichiometric amounts to form carbonate, and CO on the other hand ₂ The pressure should not be so high that too much alkanolamine bicarbonate is formed. Suitable CO ₂ At a pressure such that the CO is introduced into a (saturated or nearly saturated) mixture of the alcohol amine and water ₂ The chemical blowing agent (F1) prepared by the method of neutralization of gas contains a small amount (0.1 to 20% by weight, preferably 0.1 to 14% by weight) of unneutralized C2-C9 alcohol amine (particularly specific C4-C9 diol amine), and therefore, the rigid foam formed by using the chemical blowing agent (F1) has very excellent thermal insulation properties.

4. The (casting type) polyurethane rigid foam carbonate alkanolamine salt foaming agent composition (FC) is matched with the industrial online foaming reaction process in the industries of refrigerators, freezers, water heaters and cold chain heat preservation (refrigerated trucks), the existing production line is not changed at all, the foaming reaction speed on the casting foaming production line is relatively stable, and the obtained foam material has excellent heat insulation performance and deformation resistance.

5. The blowing agents of the present invention have significant cost advantages over third and fourth generation fluorine-containing blowing agents.

6. Polymer polyols used in the refrigerator, freezer, water heater and refrigerator car (cold chain insulation) industry for making (pour-on) rigid polyurethane foams typically comprise 8-52% by weight of an aromatic polyester polyol and/or a toluene diamine polyether polyol and the balance a non-toluene diamine polyoxypropylene polyol, cyclopentane and a chemical blowing agent in such systems being able to form a homogeneous system that is transparent and has good flow properties, resulting in uniform foaming, fine cells and uniform cell size.

Drawings

FIGS. 1A and 1B are SEM photographs of the foam of example 1.

FIG. 2 is an SEM photograph of the foam of comparative example 1.

FIG. 3 is an SEM photograph of the foam of example 3.

Fig. 4 is an SEM photograph of the foam of comparative example 2.

FIG. 5 is an SEM photograph of the foam of example 4.

Fig. 6 is an SEM photograph of the foam of comparative example 3.

FIG. 7 is an SEM photograph of the foam of example 5.

FIGS. 8A, 8B and 8C are SEM photographs of the foam of example 6.

Fig. 9 is an SEM photograph of the foam of comparative example 4.

Fig. 10 is an SEM photograph of the foam of comparative example 6.

Fig. 11 and 12 are SEM photographs of two foams of example 8.

Detailed Description

The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to these examples.

The apparatuses used in the examples are those generally used in the art and commercially available on the market unless otherwise specified. For polyurethane rigid foams of different fields of application, correspondingly suitable foaming speeds are required. Generally, the foaming rates of the related art are shown in table a above.

For the foaming reaction in the production of refrigerators, freezers, water heaters or refrigerated vehicles, the rise time is generally 6 to 7 seconds and the stringing time is generally 30 to 45 seconds (preferably 35 to 40 seconds).

The present invention is directed to polyurethane rigid foams for applications in the refrigerator, freezer, water heater, cold chain insulation (refrigerator car) industry, and to specific blowing agent compositions.

In the present application, the usual polyether polyols (polyoxypropylene polyols) and (aromatic) polyester polyols used in the preparation of polyurethane foams or in the foaming compositions are selected from the following classes: polyether polyols (polyoxypropylene polyols), for example, polyether polyol 4110 (sucrose initiator polyoxypropylene polyol) of Binshi GROUP Co., Ltd. (BEFAR GROUP CO., LTD.), polyether 450 (sorbitol initiator polyoxypropylene polyol) of Nanjing Hongbaoli Co., Ltd.), MN500 (glycerin initiator polyoxypropylene polyol) and SA 460 (sorbitol initiator polyoxypropylene polyol) of Shandong Landong Dainig chemical Co., Ltd.), SA 460 (sorbitol initiator polyoxypropylene polyol), SU380 (sucrose initiator oxypropylene polyol) and SA380 (sorbitol initiator polyoxypropylene polyol), YD8260 (sucrose and diethylene glycol-initiated polyoxypropylene polyol), YD403 (ethylenediamine initiator polyoxypropylene polyol) and YD460 (tolylenediamine-type polyoxypropylene polyol) of Shandong Asian chemical GROUP Co., Ltd., and, SD7100 (tolylenediamine type polyoxypropylene polyol) of great chemical co., ltd, shanghai; (aromatic) polyester polyols, for example, PS4051, PS4027 or PS3152 from Nanjing Jinlingstainpu chemical Co., Ltd, the polyester polyols CF6320, CF6245, CF6200, CF6300 and CF6255 from Jiangsu Fusheng New materials Co., Ltd, and the polyester polyol DM2003 from Beijing Oriental Meilong chemical technology Co., Ltd.

The usual catalysts are selected from: 33LV (A-33): 33% dipropylene glycol solution of triethylene diamine, N, N-dimethylethanolamine, N, N-dimethylbenzylamine, 70% dipropylene glycol solution of bis (dimethylaminoethyl) ether, 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-propylamine formate), TMR-3, TMR-4. Commonly used silicone oil type foam stabilizers or silane surfactants: b8525 and B8408 of invested Inc. of Wingchuang Texaco (China), AK-158, AK-8805, AK-8812, AK-8809, AK 8818, and AK-8860 of Meissda chemical Co., Ltd, Jiangsu, DC8545, DC1990, DC5188, DC6070, DC3042, and DC3201 of gas and chemicals Co., Ltd, and silicone oil 8841 of Shanghai Maihao chemical technology Co., Ltd. Non-silane surfactants: gas and chemicals LK-221 and LK-443. Common flame retardants: TCPP, TCEP, DMMP, ammonium chloride, aluminum hydroxide powder, DM1201, DM1301, tetrabromophthalic anhydride diol.

CO is introduced below ₂ Aeration method a carbonate alkanolamine salt chemical blowing agent (F1) (CFA), carbonate alkanolamine salt hydrate in the following examples, was prepared.

The water content of the alkanolamine carbonate salt hydrate as 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 and bicarbonate. Therefore, the content (wt%) of free water in the carbonate alkanolamine salt chemical foaming agent (F1) (i.e., carbonate alkanolamine salt hydrate) is ═ water content of carbonate alkanolamine salt hydrate (measured by karl fischer method) - (amount of water produced by decomposition of the carbonate and bicarbonate salts).

Preparation of example 1

2744g (24mol) of mixture of diethanolamine (Mw 105.14) and diisopropanolamine (Mw 133.2) (the molar ratio of diethanolamine to diisopropanolamine is 3:1, 18mol:6mol) and 914g of water are mixed and added into a transparent quartz glass high-pressure reactor with 5 liters, the reactor is started to be stirred and sealed, then carbon dioxide is introduced into the reactor under continuous stirring and the temperature is controlled between 40 ℃ and 65 ℃,control of CO ₂ The surface pressure of the gas is not higher than 0.3MPa (namely the range of 0.28-0.3 MPa), the temperature is controlled for reaction for 10 hours, the temperature is reduced to below 40 ℃, the pressure is released, and the product is discharged. The alkanolamine carbonate hydrate 1 is obtained, which is referred to as "chemical blowing agent" (CFA) or as alkanolamine carbonate chemical blowing agent (F1). The carbonate ethanolamine salt hydrate 1 was measured by a pH meter (thunder magnet PHS-3C type, Shanghai Yidian Science Instrument co., Ltd.) to have a pH of 9.522, a water content of 21.12% (karl fischer method), a viscosity of 360 cps (25 ℃), and a decomposition temperature of 42 ℃ to 70 ℃. The alcohol amine-water mixture was determined to have absorbed about 514g (about 11.68mol) of CO by weight gain analysis ₂ (molecular weight 44). 0.544 mol (2.2666 mol%, based on the mol of the entire alcohol amine) of the alcohol amine was not neutralized. 11.7mol (210.6g) of water were involved in the neutralization reaction. The amount of free water in hydrate 1 was 703.76g (16.86%).

In addition, as a reference, the above procedure was repeated except that the molar ratio of diethanolamine to diisopropanolamine was changed to further obtain carbonate ethanolamine salt hydrates 1A, 1B and 1C:

carbonate ethanolamine salt hydrate No	1A	1	1B	1C
					Molar ratio of diethanolamine to diisopropanolamine	5:1	3:1	1:1	1:2

Preparation of example 2 (reference)

Mixing 3kg (40mol) of MMEA (methyl monoethanolamine) (molecular weight 75) and 1kg of water, adding the mixture into a 5L transparent quartz glass high-pressure reactor, starting stirring, sealing the reactor, then controlling the temperature to be between 40 and 65 ℃ under continuous stirring, introducing carbon dioxide into the reactor, controlling the pressure to be not higher than 0.1MPa (namely the range of 0.09 to 0.1 MPa), controlling the temperature for reaction for 10 hours, cooling to below 40 ℃, then releasing the pressure, and discharging the product. Thereby obtaining the carbonate ethanolamine salt hydrate 2 (CFA). The pH value is 9.972, the water content is 20.39% (Karl Fischer method), the viscosity is 286 centipoises (25 ℃), and the decomposition temperature is 42 ℃ -70 ℃. The alcohol amine-water mixture was determined to have absorbed about 913g (about 20.75mol) of CO by gravimetric analysis ₂ . A portion (about 1.5mol, in terms of mol% 3.75 mol%, based on the mol of the entire alcohol amine, or about 204g) of the alcohol amine bicarbonate (molecular weight 136) is formed in the mixture (hydrate 2), the latter being present in an amount by weight of about 4.2% by weight. 20.75 moles (373.5 grams) of water participated in the neutralization reaction. The amount of free water in hydrate 2 was 626.5g (12.75 wt%).

Although CO is introduced into the aqueous solution of methyl monoethanolamine ₂ CO control in gas processes ₂ The pressure of (a) is not higher than 0.1MPa, but still a small amount of unstable alkylolamine bicarbonate is formed, which indicates that the methylmonoethanolamine is highly basic.

Preparation of example 3

Adding 3.57kg (30mol) of N-methyldiethanolamine (molecular weight 119) and 1kg of water into a 5L transparent quartz glass high-pressure reactor, stirring for dissolving, sealing the reactor, then controlling the temperature to be between 40 and 65 ℃ under continuous stirring, introducing carbon dioxide into the reactor, controlling the pressure to be not higher than 0.3MPa (such as the range of 0.275 to 0.289 MPa), controlling the temperature for reaction for 10 hours, cooling to below 40 ℃, then releasing the pressure, and discharging the product to obtain the alkanolamine carbonate hydrate 3 (CFA). pH 9.53, water content 19.14% (Karl Fischer method), viscosity 641 centipoise (25 deg.C)) The decomposition temperature is 42-70 ℃. The alcohol amine-water mixture was determined to absorb about 640g (about 14.5mol) of CO by weight gain analysis ₂ . 29.09mol of the alcohol amine participated in the neutralization reaction, and in addition, about 0.91mol (3.03 mol%, based on the mol of the entire alcohol amine) of the alcohol amine was not neutralized. About 14.5mol (about 261g) of water participated in the neutralization reaction. The amount of free water in hydrate 3 was about 738g (14.4176%).

Preparation of example 4

Adding 3192g (24mol) of diisopropanolamine (with the molecular weight of 133.2) and 0.932kg of water into a 5L transparent quartz glass high-pressure reactor, stirring for dissolving, sealing the reactor, then controlling the temperature to be between 40 and 65 ℃ under continuous stirring, introducing carbon dioxide into the reactor, controlling the pressure to be not higher than 0.3MPa (such as the range of 0.29 to 0.3MPa), controlling the temperature for reaction for 10 hours, cooling to below 40 ℃, then releasing the pressure and discharging the product. Thereby obtaining the carbonate ethanolamine salt hydrate 4 (CFA). The pH value is 9.222, the water content is 20.12%, the viscosity is 1510 centipoises (25 ℃), and the decomposition temperature is 42-70 ℃. The alcohol amine-water mixture was determined to have absorbed about 510g (about 11.5909mol) of CO by weight gain analysis ₂ . 0.818mol of diisopropanolamine is not CO-coated ₂ And (4) neutralizing. 11.5909mol of water (208.636 g of water) take part in the neutralization reaction. 721.3638g (15.57 wt%) of free water in Compound 4.

The viscosity (1510 centipoise) of the product of example 4 was much higher compared to the viscosity (360 centipoise) of the product of example 1.

Preparation of example 5 (reference)

Preparation example 2 was repeated except that 213g (1.6mol) of diisopropanolamine and 120g of water were further added to the obtained alcohol amine hydrate 2, and the mixture was stirred to convert the alcohol amine bicarbonate therein to alcohol amine carbonate, to obtain alcohol amine hydrate 5 at pH 9.8512.

Preparation of example 6 (reference)

Mixing 3kg (40mol) monoisopropanolamine (molecular weight 75) and 1kg water, adding into a 5L transparent quartz glass high-pressure reactor, stirring, sealing the reactor, controlling the temperature to 40-65 deg.C under continuous stirring, introducing carbon dioxide into the reactor, and controlling the pressure not to exceedAnd (3) controlling the temperature to react for 10 hours under the pressure of more than 0.1MPa, cooling to below 40 ℃, releasing the pressure and releasing the product. Thereby obtaining the carbonate ethanolamine salt hydrate 6. The pH value is 9.970, the water content is 20.38% (Karl Fischer method), the viscosity is 290 centipoises (25 ℃), and the decomposition temperature is 42-70 ℃. The alcohol amine-water mixture was determined to have absorbed about 912g (about 20.73mol) of CO by weight gain analysis ₂ . Part of the alkanolamine bicarbonate is formed in the mixture.

Preparation of example 7 (reference)

Hydrate 6 of preparative example 6 (reference) and hydrate 4 of preparative example 4 were mixed in a 6.5:3.5 molar ratio of monoisopropanolamine to diisopropanolamine (mol% of monoalkanolamine is 65 mol%) to give hydrate 7A having a viscosity of about 1044 centipoise (25 ℃).

Hydrate 6 of preparative example 6 (reference) and hydrate 4 of preparative example 4 were mixed in a 1:1 molar ratio of monoisopropanolamine to diisopropanolamine (mol% of monoalkanolamine is 50 mol%) to obtain hydrate 7B having a viscosity of about 1182 centipoise (25 ℃).

Preparation of example 8

Hydrate 3 of preparative example 3 and hydrate 4 of preparative example 4 were mixed in a 3:1 molar ratio of N-methyldiethanolamine to diisopropanolamine to obtain hydrate 8 having a viscosity of about 915 cps (25 ℃).

Preparation of example 9

Hydrate 6 of preparative example 6 (reference) and hydrate 4 of preparative example 4 were mixed in a 0.36:1 molar ratio of monoisopropanolamine to diisopropanolamine (mol% of the monoalkanolamine is about 26 mol%) to obtain hydrate 9 having a viscosity of about 1255 centipoise (25 ℃).

Preparation of example 10

Hydrate 6 of preparative example 6 (reference) and hydrate 1 of preparative example 1 were mixed in a 0.36:1 molar ratio of monoisopropanolamine (ethanolamine + diisopropanolamine) (mole% of monoalkanolamine is about 26 mole%) to give hydrate 10 having a viscosity of about 532 centipoise (25 ℃).

Application examples

Example 1

1. The components used and the relative amounts:

foaming agent: 6 parts by weight of the alkanolamine carbonate hydrate 1(CFA) prepared from example 1 above and 18 parts by weight of cyclopentane as blowing agent.

Dry white materials: the composition consists of the following components: 40 parts by weight of polyether polyol SD-7100 (tolylenediamine polyoxypropylene polyol, produced by Shanghai Town Chemical Co., Ltd.), 20 parts by weight of polyether polyol SA-460 (sorbitol initiator polyoxypropylene polyol, produced by Zibonuli Chemical Co., Ltd.), 10 parts by weight of aromatic polyester polyol PS-4051(PET polyol, produced by Nanjing Jinling Spandex Chemical Co., Ltd.), 20 parts by weight of polyether polyol YD-8260 (polyoxypropylene polyol, produced by Hebei Asia Tokyo Chemical Co., Ltd., using sucrose and diethylene glycol as initiators), 10 parts by weight of polyether polyol YD-403 (ethylenediamine initiator polyoxypropylene polyol, produced by Hebei Asia Tokyo Chemical Co., Ltd.), 3 parts by weight of foam stabilizer 8841 (silicone oil, produced by Shanghai Meghai Chemical Co., Ltd.) (Co., Ltd.), a mixture thereof, 0.1 part by weight of N, N, N, N, N-pentamethyldiethylenetriamine (code No. PC-5, manufactured by winning U.S. Degussa, Ltd.), 0.5 part by weight of the amine catalyst BX-405 (manufactured by winning U.S. Degussa, Ltd.), and 1 part by weight of tris (dimethylaminopropyl) hexahydrotriazine (code No. PC-41, manufactured by winning U.S. Degussa, Ltd.).

Black materials: 156 parts of polyisocyanate MDI (PM200, Vantanhua chemical group Co., Ltd.) as a black material.

Observations on the transparency and compatibility of the white material: the above blowing agent and dry white were mixed under stirring to obtain a clear white, indicating a good compatibility between the blowing agent and the dry white (polymer polyol).

Observation of the delamination phenomenon: the white material obtained by mixing the dry white material and the whole of the foaming agent under stirring was then rapidly defoamed by centrifugation (speed 4500rpm, time of centrifugation 5 minutes), and then observed whether the material had a phenomenon of stratification (i.e. whether there was a thin layer of material at the bottom), with the result that: the white material was not found to delaminate after the defoaming treatment.

2. The foaming reaction process comprises the following steps:

cast foaming was carried out by a high pressure cast foaming machine (RSC16/16, Claus Ma-Fei, Germany) using the same formulation (or composition) as described above. Wherein, the foaming agent, the dry white material and the black material are input into a pouring foaming machine through respective material pipelines to be stirred and mixed, and then the mixed foaming material is poured into a semi-finished product mold by a spray gun to be foamed. The specific operation is as follows: firstly, setting the amount of a foaming material poured for the first time of a pouring machine to be about 200g, then pouring the foaming material with the set amount into a plastic bag by a spray gun for free foaming, measuring the rising time of the foaming material to be 6 seconds and the wire drawing time of a spray gun mouth to be 35 seconds, and then pouring the foaming material with the corresponding set amount into a Lanzhi mould for foaming according to the volume setting pouring material amount of the Lanzhi mould. And opening the mold (namely opening the inner and outer clamping molds) after 180 seconds. Samples of the foam were taken and used to analyze the microstructure and thermal insulation properties of the foam. From two batches of foam product, 2 foam samples were taken for SEM analysis. SEM photographs of the two samples are shown in fig. 1A and 1B.

As is clear from the SEM photographs, the number of cells per unit area is relatively large, the average cell diameter of the cells of the two foam samples is small (about 217 μm and about 210 μm) and the size of the cells is relatively uniform.

The elicitation time for the foaming process was measured to be 6 seconds and the drawing time was measured to be 35 seconds. The elicitation time and the drawing time are in good agreement with the time range on the industrial production line of the refrigerator, and therefore, the foam is suitable for the refrigerator.

Comparative example 1

Example 1 was repeated except that the amount of blowing agent (water + CP) was as shown in Table 1. The SEM photograph of the foam is shown in figure 2. The average cell diameter of the foam was about 346 microns.

Observations on the transparency and compatibility of the white material: the blowing agent (water + CP) and the dry white material were mixed under stirring to obtain a cloudy white material (with oil droplets), indicating poor compatibility between the blowing agent and the dry white material (polymer polyol).

The clouding phenomenon is attributed to the poor compatibility between the blowing agent (water + CP) without the alkanolamine or alcohol carbonate salt and the dry white material.

Example 2 (comparative)

1. The components used and the relative amounts:

foaming agent: 7 parts by weight of the alkanolamine carbonate hydrate 2(CFA) prepared from example 2 above and 18 parts by weight of Cyclopentane (CP) as blowing agent.

Dry white materials: the composition consists of the following components: 40 parts by weight of tolylenediamine polyether polyol SD-7100, 20 parts by weight of polyether polyol SA-460, 10 parts by weight of aromatic polyester polyol PS-4051, 20 parts by weight of polyether polyol YD-8260, 10 parts by weight of polyether polyol YD-403, 3 parts by weight of silicone oil type foam stabilizer 8841 (manufactured by Shanghai Mehao chemical science and technology Co., Ltd.), 0.1 part by weight of N, N, N, N, N-pentamethyldiethylenetriamine (code PC-5, manufactured by WingdTex. Ltd.), 0.5 part by weight of amine catalyst BX-405 (manufactured by WingTex. Co., Ltd.) and 1 part by weight of tris (dimethylaminopropyl) hexahydrotriazine (code PC-41, manufactured by WingTex. Ltd.).

Observations on the transparency and compatibility of the white material: the above blowing agent and dry white were mixed under stirring to obtain a slightly cloudy white, indicating a slightly lower compatibility between the blowing agent and the dry white (polymer polyol).

2. The foaming reaction process comprises the following steps:

cast foaming was carried out by a high pressure cast foaming machine (RSC16/16, Claus Ma-Fei, Germany) using the same formulation (or composition) as described above. Measuring the rising time of the foaming material to be 3 seconds and the wire drawing time of the spray gun mouth to be 27 seconds, and then setting the quantity of the pouring material according to the volume of the semi-finished product mold to pour the foaming material with the corresponding set quantity into the semi-finished product mold for foaming. And opening the mold (namely opening the inner and outer clamping molds) after 180 seconds. It was found that the foam was concentrated in the vicinity of the gate and that the far region of the mould cavity was free of foam, i.e. the foam did not fill the whole mould cavity. The density distribution of the foam in the mould is not uniform.

The above results indicate casting foam failure. The reason is that N-methyl monoethanolamine carbonate has strong basicity and reactivity, and the presence of a small amount of bicarbonate of primary amine has a serious influence on casting foaming, and thus, the early reaction of foaming process is too severe because the hydramine contains only N-methyl monoethanolamine hydrate 2.

Example 3

1. The components used and the relative amounts:

foaming agent: 3 parts by weight of the alkanolamine carbonate hydrate 3(CFA) prepared from example 3 above as blowing agent, 1.8 parts by weight of water, 3 parts by weight of HFC-245fa and 17 parts by weight of cyclopentane.

Dry white materials: the composition consists of the following components: 40 parts by weight of polyether polyol SD-7100, 20 parts by weight of polyether polyol SA-460, 10 parts by weight of polyester polyol PS-4051, 20 parts by weight of polyether polyol YD-8260, 10 parts by weight of polyether polyol YD-403, 3 parts by weight of foam stabilizer 8841 (manufactured by Shanghai Megao chemical science and technology Co., Ltd.), 0.1 part by weight of N, N, N, N, N-pentamethyldiethylenetriamine (code PC-5, manufactured by WingdTex. Ltd.), 0.5 part by weight of amine catalyst BX-405 (manufactured by WingTex. Ltd.) and 1 part by weight of tris (dimethylaminopropyl) hexahydrotriazine (code PC-41, manufactured by WingTex. Ltd.).

Black materials: 157 parts of polyisocyanate MDI (PM200, Tantawa chemical group, Ltd.) as a black material.

Observation of the delamination phenomenon: no delamination was observed after the white material was defoamed by centrifugation.

2. The foaming reaction process comprises the following steps:

the same foaming reaction procedure as in example 1 was repeated. The rise time of the foamed material was measured to be 6 seconds and the nozzle drawdown time was measured to be 35 seconds. An SEM photograph of the rigid foam is shown in fig. 3.

As is clear from the SEM photographs, the average cell diameter of the cells was small (about 228um, slightly larger than that of example 1) and the size of the cells was relatively uniform.

Comparing the results of example 1 with those of example 3, it can be found that: the use of diisopropanolamine in combination with diethanolamine improves the compatibility between the blowing agent composition and the dry white.

Comparative example 2

Example 3 was repeated except that the blowing agent (245fa + CP) was used in the amounts shown in Table 1. The SEM photograph of the foam is shown in figure 4. The cells of the foam are coarse and their size is not uniform.

Observations on the transparency and compatibility of the white material: the blowing agent (245fa + CP) and dry white were mixed under agitation to obtain a cloudy white (with oil droplets), indicating poor compatibility between the blowing agent and the dry white (polymer polyol).

The clouding phenomenon is attributed to the poor compatibility between the blowing agent without the carbonate alkanolamine salt (245fa + CP) and the dry white material.

Example 4

1. The components used and the relative amounts:

foaming agent: 3 parts by weight of the alkanolamine carbonate hydrate 4 prepared from example 4 above as a blowing agent, 1.8 parts by weight of water, 3 parts by weight of LBA and 17 parts by weight of CP (cyclopentane).

Observations on the transparency and compatibility of the white material: the above blowing agent and dry white were mixed under stirring to obtain a clear, homogeneous white, indicating a very good compatibility between the blowing agent and the dry white (polymer polyol).

2. The foaming reaction process comprises the following steps:

the same foaming reaction procedure as in example 1 was repeated. The rise time of the foamed material was measured to be 6 seconds and the nozzle drawdown time was measured to be 35 seconds. An SEM photograph of the rigid foam is shown in fig. 5.

As is clear from the SEM photograph, the average cell diameter of the cells is small (about 239um is slightly larger than that of example 1) and the size of the cells is relatively uniform.

The results of this example 4 show that the viscosity of the chemical blowing agent (F1) has the potential to affect the microstructure and properties of the foam.

Comparative example 3

Example 4 was repeated except that the blowing agent was (LBA + CP), wherein the amount of blowing agent (LBA + CP) was as shown in Table 1. The SEM photograph of the foam is shown in fig. 6. The cells of the foam are coarse and their size is not uniform.

Observations on the transparency and compatibility of the white material: the blowing agent (LBA + CP) and the dry white material were mixed under stirring to obtain a cloudy white material (oil droplets), indicating poor compatibility between the blowing agent and the dry white material (polymer polyol).

Example 5

Example 3 was repeated except that 3 parts by weight of the alkanolamine carbonate hydrate 1 in example 1 was used instead of 3 parts by weight of the alkanolamine carbonate hydrate 3. The SEM photograph of the resulting rigid foam is shown in FIG. 7.

As is clear from the SEM photograph, the average cell diameter of the cells is small (about 220um, slightly larger than that of example 1) and the size of the cells is relatively uniform.

Table 1-foaming composition and foam performance parameters comparison:

note 1: CFA in the table refers to a high-water content carbonic acid organic alcohol amine salt foaming agent; the lambda value (or K factor) was determined according to GB/T10295-. The "swell ratio (180 s)" in the table means a swell ratio measured after opening a mold for a Laminaria japonica from the time of starting pouring the material into the mold for a period of 180 seconds (3 minutes).

Note 2: lance die size was 1600 × 300 × 80 mm. The whole foam is divided into a left part and a right part (namely, the left side and the right side) on average by taking the long side as the direction, wherein each part is taken as a density point (density measuring point) every 20cm from the bottom to the top, the left side and the right side are taken as 16 density points in total, and the difference between the highest value and the lowest value of the density is taken as the density range. The average of the 16 density point densities is the average density.

As can be seen from the above table 1, when the organic alcohol amine carbonate hydrate with high water content and low alcohol amine bicarbonate content is used as a chemical foaming agent and is combined with cyclopentane, or the hydrate is combined with a hydrofluorocarbon physical foaming agent and cyclopentane, the prepared polyurethane foam material has excellent overall performance, low thermal conductivity and good thermal insulation performance. In particular, the rigid polyurethane foams obtained in examples 1 and 5 using the foaming composition comprising (diethanolamines + diisopropanolamines) have very excellent thermal insulation properties.

Example 6

Example 1 was repeated except that the same amounts of the alkanolamine carbonate salt hydrate 1A, 1B and 1C prepared in example 1 were used instead of the respective alkanolamine carbonate salt hydrate 1 prepared in example 1. Polyurethane rigid foams 6A-6C were obtained. Comparison was made with the foam of example 1.

TABLE 2 average cell diameter and thermal conductivity of rigid polyurethane foams (Lambda, Mw/m.k (10 ℃ C.))

From the comparison of the data in table 2, the foam of example 1 (wherein the molar ratio of diethanolamine to diisopropanolamine is 3:1) has the lowest thermal conductivity.

SEM photographs of foams 6A-6C are shown in FIG. 8A, FIG. 8B, and FIG. 8C. It can be seen that the molar ratio of diethanolamine to diisopropanolamine affects the average cell diameter of the foam and that the size of the average cell diameter has some effect on the thermal insulation performance at equivalent foam densities.

Comparative example 4

Example 1 was repeated except that the amount of cyclopentane (18 parts) was changed to 24 parts by weight of cyclopentane.

Observations on the transparency and compatibility of the white material: the blowing agent composition and dry white were mixed under agitation to give a cloudy white and clear oil droplets were found in the white indicating that cyclopentane had segregated from the white and phase separation had occurred. This indicates that the solubility of cyclopentane in the white material is limited.

The foaming reaction process comprises the following steps: the rise time of the foamed material was measured to be 7 seconds and the nozzle drawdown time to be 43 seconds.

The SEM photograph of the foam is shown in fig. 9. As is clear from the SEM photographs, the average cell diameter of the cells was large (about 330 μm) and the size of the cells was not uniform. In addition, a plurality of oversized cells can be seen in the SEM photograph. These very large cells may be formed during the foaming process by oil droplets (cyclopentane) as foaming centers.

Comparative example 5

Example 1 was repeated to conduct experiments 1a, 2a, 3a and 4a except that hydrate 5, hydrate 6, hydrate 7A and hydrate 7B of preparation example 5 (reference), preparation example 6 (reference) and preparation example 7 (reference) were respectively used in the same amounts in place of hydrate 1 in example 1 to conduct casting foaming to obtain rigid polyurethane foams 5, 6, 7A and 7B. Mainly aims at investigating the starting time and the drawing time of the foaming process.

TABLE 3 rise time and drawdown time of the foaming process

Experimental No	1a	2a	3a	4a
					Alcohol amine hydrate No	5	6	7A	7B
Rise time(s)	4	3	4.5	5
					Muzzle drawing time (second) (material temperature 22 ℃, ambient temperature 30 ℃)	31	28	30	33

In experiment 1a, the rise time and the stringiness time of experiment 1a using hydrate 6 (preparation example 6) having a reduced content of alkylolamine bicarbonate were respectively prolonged as compared with the rise time (3 seconds) and the stringiness time (27 seconds) in example 2 (comparative), but the requirement for pouring foaming in a refrigerator could not be satisfied.

Experiment 2a as in example 2 (comparative), the casting foam failed, indicating that the use of hydrate 6, which contains only primary amine (isopropanolamine), resulted in a blowing agent composition that was too basic and reactive. Primary amine bicarbonates have a severe effect on casting foaming.

The results of experiments 3a and 4a show that the rise time and the drawing time cannot meet the requirements of pouring foaming of a refrigerator when the mol% of primary amine (isopropanolamine) is higher than 30 mol%.

Example 7

Example 1 was repeated except that hydrate 8, hydrate 9 and hydrate 10 in preparative example 8, preparative example 9 and preparative example 10 were used in the same amounts, respectively, instead of hydrate 1 in example 1. Pouring and foaming to obtain rigid polyurethane foams 8, 9 and 10. Mainly aims at investigating the starting time and the drawing time of the foaming process.

TABLE 3 rise time and drawdown time of the foaming process

The results of experiment 1b show that N-methyldiethanolamine, instead of diethanolamine, gives almost the same results.

The results of experiments 2b and 3b show that the start time and the drawing time of the casting and foaming process can meet the requirements of the refrigerator casting and foaming when the mol% of the primary amine (isopropanolamine) is lower than 30 mol%.

Comparative example 6

Example 1 was repeated except that the white material contained only non-toluene diamine type polyether polyol, but not polyester polyol and toluene diamine type polyether polyol. Namely, the composition of the dried white material is as follows;

dry white materials: the composition consists of the following components: 40 parts by weight of polyether polyol SA-460 (sorbitol initiator), 30 parts by weight of polyether polyol YD-8260 (sucrose and diethylene glycol are used as initiators), 30 parts by weight of polyether polyol YD-403 (ethylenediamine initiator), 3 parts by weight of foam stabilizer 8841 (manufactured by Shanghai Megao chemical Co., Ltd.), 0.1 part by weight of N, N, N, N, N-pentamethyldiethylenetriamine (code PC-5, manufactured by Woodward chemical Co., Ltd., U.S.), 0.5 part by weight of amine catalyst BX-405 (manufactured by Woodward chemical Co., Ltd., U.S.), and 1 part by weight of tris (dimethylaminopropyl) hexahydrotriazine (code PC-41, manufactured by Woord chemical Co., Ltd., U.S.).

An SEM photograph of the formed foam is shown in fig. 10. There are coarse cells, resulting in a foam with a higher thermal conductivity. The foam had a lambda (Mw/m.k, 10 ℃ C.) of 18.95. Although the non-tolylenediamine-type polyoxypropylene polyol has good flowability, the compatibility between the cyclopentane-containing blowing agent composition of the present invention and a dry white (non-tolylenediamine-type polyoxypropylene polyol) that does not contain a polyester polyol or a tolylenediamine-type polyoxypropylene polyol is not so good.

Example 8

Example 3 was repeated to conduct experiments 1a and 2d except that in experiment 1d 1 part by weight of the alkanolamine carbonate hydrate 1 of example 1 was used as CFA (chemical blowing agent) and 5 parts by weight of 245fa and in addition in experiment 2d 2 parts by weight of the alkanolamine carbonate hydrate 1 of example 1 was used as CFA (chemical blowing agent) and 4 parts by weight of 245 fa.

The foam of experiment 1d had a lambda (Mw/m.k, 10 ℃ C.) of 18.59. The foam of experiment 2d had a lambda (Mw/m.k, 10 ℃ C.) of 18.52. SEM photographs of the rigid foams obtained in experiment 1d and experiment 2d are shown in fig. 11 and 12, respectively.

As can be seen from the SEM photographs, although the hydrates 1 are used in a lower amount (1 or 2 parts by weight), they can exert nucleation in the early stage of the foaming process, thus contributing to the improvement of uniformity of cells and the reduction of the average size of cells (compared to fig. 4 of comparative example 2 and fig. 6 of comparative example 3), and the thermal conductivity of the foam can be reduced to less than 18.60.

Example 9 foam for Water heaters

Example 1 was repeated except that CP was 12 parts by weight and CFA was 4 parts by weight. The product density of the resulting foam (i.e., the density of the foam product measured after opening the casting mold) was 40.5Kg/cm ³ And a thermal conductivity K factor (mW/m.K, 22.5 ℃) of 19.49.

Claims

1. A carbonate alkanolamine salt blowing agent composition (FC) for the preparation of polyurethane rigid foams comprising the following components:

(2) cyclopentane;

(3) optionally, a hydrofluorocarbon-based physical blowing agent (F2) having a boiling point in the range of 15 to 41 ℃, wherein the physical blowing agent (F2) is one or more (two or three) selected from HFC-245fa, HFC-365mfc, LBA and hexafluorobutene;

(4) optionally, water (F3);

wherein, the relative dosage of each component is as follows: the amount of water (F3) is 0 to 2 parts by weight, 0 to 1.5 parts by weight, more preferably 0 to 1 part by weight, further preferably 0 to 0.5 parts by weight, more preferably 0 to 0.1 parts by weight; the amount of the physical blowing agent (F2) is 0 to 7 parts by weight, preferably 0 to 6.5 parts by weight, preferably 0 to 6 parts by weight, preferably 0 to 5.5 parts by weight, preferably 0 to 5 parts by weight, more preferably 0 to 4.5 parts by weight, preferably 0 to 4 parts by weight, more preferably 0 to 3.5 parts by weight, more preferably 0 to 3 parts by weight, more preferably 0 to 2.5 parts by weight, most preferably 0 part by weight; the amount of the chemical blowing agent (F1) is 1 to 10 parts by weight, preferably 1.2 to 9.5 parts by weight, preferably 1.3 to 9 parts by weight, preferably 1.4 to 8.5 parts by weight, preferably 1.5 to 8 parts by weight, preferably 2.8 to 8 parts by weight, preferably 3 to 8 parts by weight, preferably 3.5 to 7.5 parts by weight, preferably 4 to 7 parts by weight, preferably 4.5 to 6.5 parts by weight, preferably 5 to 6.5 parts by weight, more preferably 5 to 6 parts by weight; and the amount of cyclopentane is 10 to 20 parts by weight, preferably 10.5 to 19.5 parts by weight, preferably 10.5 to 19 parts by weight, preferably 11 to 18.5 parts by weight, preferably 11.5 to 18 parts by weight;

and the ratio or relative amount of the sum of the mass of water (F3) + physical blowing agent (F2) + chemical blowing agent (F1) to the mass of cyclopentane is (4-10) to (10-20), preferably (4-9.5) to (10-20), (4-9) to (10-18), (4-9) to (10-16), preferably (4.5-10) to (10-20), (5-9.5) to (10-18), (5-9.5) to (10-16), (5-9) to (10-20), (5-9) to (10-18), (5-9) to (10-16), more preferably (5.5-9) to (10-20), (5.5-8.5): 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 (5.8-7.8): 11.5-18.8, preferably (5.9-7.6): 12-18.5, preferably (6-7): 13-18);

and

wherein the chemical foaming agent (F1) comprises the following components:

(A)67-90 wt% of a di (C2-C9 alcohol amine) carbonate salt; the content is preferably 68 to 89.5 wt%, more preferably 69 to 89 wt%, 70 to 88.5 wt%, 71 to 88 wt%, 72 to 87.5 wt%, 73 to 87 wt%;

(B)10-33 wt% water; the water content is preferably from 10.5 to 32% by weight, preferably from 11 to 31% by weight, from 11.5 to 30% by weight, from 12 to 29% by weight, from 12.5 to 28% by weight, from 13 to 27% by weight;

(C)0-20 wt% of C2-C9 alcohol amine; the content is preferably 0.01 to 19 wt%, preferably 0.02 to 18 wt%, more preferably 0.03 to 17 wt%, more preferably 0.04 to 16 wt%, preferably 0.06 to 15 wt%; e.g., 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 035, 04, 045, 05, 055, 06, 065, 07, 075, 0.8, 085, 09, 095, 1, 1.5, 2, 25, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 12, 13, or 14 wt%;

and

the above percentages being based on the total weight of chemical blowing agent (F1);

wherein the sum of the weights of components (A), (B), (C) and (D) is from 90 to 100% by weight, preferably from 92 to 100% by weight, preferably from 93 to 100% by weight, preferably from 95 to 100% by weight, preferably from 98 to 100% by weight, preferably from 98.5 to 100% by weight, preferably from 99 to 100% by weight, preferably from 99.5 to 100% by weight, preferably from 99.8 to 100% by weight, more preferably 100% by weight, based on the total weight of the chemical blowing agent (F1);

wherein the total amount of C2-C9 alcohol amines in the chemical blowing agent (F1) comprises or essentially comprises 70-100 mol%, preferably 72-100 mol%, preferably 75-100 mol%, preferably 77-100 mol%, preferably 80-100 mol%, preferably 82-100 mol%, preferably 85-100 mol%, preferably 87-100 mol%, preferably 90-100 mol%, preferably 92-100 mol%, preferably 95-100 mol%, preferably 97-100 mol%, preferably 98-100 mol%) of specific C4-C9 diol amines, which are (I) C4-C7 diol amines (Ia) with only hydroxyethyl groups, (II) C5-C5 diol amines (387) with hydroxyisopropyl groups or (III) a combination or mixture of (I) alcohol amines (Ia) and (II) alcohol amines (IIa), the mol% is based on the total molar amount of C2-C9 alkanolamines present in the chemical blowing agent (F1), and (I) C4-C7 dialolamine with only hydroxyethyl groups (Ia) is one or more selected from diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine and N-propyldiethanolamine, and (II) C5-C9 dialolamine with hydroxyisopropyl groups (IIa) is one or more selected from diisopropanolamine, ethanoldsopropanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, N-propyldiisopropanolamine, N-methylethanoldropanolamine, N-ethylethanolisopropanolamine and N-propylethanoldropanolamine;

and

wherein the chemical blowing agent (F1) has a pH of 8.6 to 10.4, preferably 8.8 to 10.2, preferably 9 to 10.1, more preferably 9.2 to 10, preferably 9.3 to 9.7, more preferably 9.4 to 9.6.

2. The blowing agent composition (FC) according to claim 1, characterized in that: relative to or on the basis of 80 to 115 parts by weight (preferably 85 to 110 parts by weight, preferably 90 to 100 parts by weight) of a dry white mass for polyurethane foaming comprising polymer polyols and further auxiliaries in addition to the blowing agent, including polyurethane catalysts, foam stabilizers and optionally flame retardants; wherein the blowing agent composition (FC) is used for a foaming reaction by mixing with a white material and a polyisocyanate as a black material to prepare a rigid polyurethane foam;

and/or

The total C2-C9 alcohol amine in the chemical blowing agent (F1) comprises or mainly comprises 90-100 mol% (preferably 92-100 mol%, preferably 95-100 mol%, preferably 97-100 mol%, preferably 98-100 mol%) of a specific C4-C9 diol amine, which is (I) a C4-C7 diol amine (Ia) having only hydroxyethyl groups, (II) a C5-C9 diol amine (IIa) having hydroxyisopropyl groups or (III) a combination or mixture consisting of component (I) alcohol amine (Ia) and component (II) alcohol amine (IIa);

and/or

Chemical blowing agent (F1) and cyclopentane are contained in separate containers when the blowing agent composition (FC) does not contain physical blowing agent (F2), or chemical blowing agent (F1) is contained in a separate container and physical blowing agent (F2) and cyclopentane are contained in separate containers or in the same container when the blowing agent composition (FC) further contains physical blowing agent (F2);

and/or

The blowing agent composition (FC) is used for the preparation of rigid cast polyurethane foams, more preferably for the preparation of rigid cast polyurethane foams during the production of refrigerators, freezers, water heaters or refrigerated vehicles;

and/or

The specific C4-C9 glycol amine is (I) an alcanolamine (Ia), or (III) a combination or mixture consisting of a component (I) alcolamine (Ia) and a component (II) alcolamine (IIa), wherein the molar ratio of component (I) alcolamine (Ia) to component (II) alcolamine (IIa) is 1 (0 to 2.5), preferably 1 (0.1 to 2), more preferably 1 (0.2 to 1.5), more preferably 1 (0.22 to 1.2), more preferably 1 (0.24 to 0.9), more preferably 1 (0.25 to 0.5), more preferably 1 (0.27 to 0.4), more preferably 1 (0.29 to 0.45), most preferably 3: 1;

and/or

The total amount of C2-C9 alcohol amine in the chemical blowing agent (F1) also comprises 0-30 mol%, preferably 0-28 mol%, preferably 0-25 mol%, preferably 0-23 mol%, preferably 0-20 mol%, preferably 0-18 mol%, preferably 0-15 mol%, preferably 0-13 mol%, preferably 0-10 mol%, preferably 0-8 mol%, preferably 0-5 mol%, preferably 0-3 mol%, preferably 0-2 mol% of other C2-C9 alcohol amines than the above-mentioned specific C4-C9 diol amines, these other C2-C9 alcohol amines being selected from one or more of (Ib) secondary amine type C3-C5 mono-ol amines having only hydroxyethyl groups and (IIb) secondary amine type C4-C6 mono-ol amines having only hydroxyisopropyl groups; wherein, the secondary amine type C3-C5 monoalkanolamine (Ib) having only hydroxyethyl groups is one or more selected from N-methylmonoethanolamine, N-ethylmonoethanolamine and N-propylmonoethanolamine; and, secondary amine type C4-C6 monoalcohols (IIb) having only hydroxyisopropyl groups are one or more selected from N-methyl monoisopropanolamine, N-ethyl monoisopropanolamine and N-propyl monoisopropanolamine; the mol% is based on the total molar amount of C2-C9 alkanolamines present in chemical blowing agent (F1) (or on the total molar amount of C2-C9 alkanolamines present in components (A), (C) and (D)).

3. The blowing agent composition (FC) according to claim 1 or 2, characterized in that:

wherein the blowing agent composition (FC) is used in an amount sufficient to produce a rigid polyurethane foam having a density of from 25 to 38Kg/cm, relative to or based on 80 to 115 parts by weight (preferably 85 to 110 parts by weight, more preferably 90 to 100 parts by weight) of dry white matter ³ In the range of 26 to 37Kg/cm is preferred ³ Preferably 27 to 36.5Kg/cm ³ Preferably 28 to 36Kg/cm ³ Preferably 28.5 to 35.5Kg/cm ³ Preferably 29 to 35Kg/cm ³ E.g. 30, 31, 32, 33 or 34Kg/cm ³ ；

And/or;

the sum of the water amounts of both the high water content carbonate alkanolamine salt chemical foaming agent (F1), component (1), and optionally water (F3), component (4), is 1.2 to 3.5 wt.% (preferably 1.25 to 3 wt.%), relative to or based on 100 parts by weight of dry white stock;

and/or;

the chemical blowing agent (F1) consists of components A), B), optionally C) and optionally D); preferably, the chemical blowing agent (F1) consists of components a), B) and optionally C) or consists of components a), B) and optionally D); more preferably, the chemical blowing agent (F1) consists of components A) and B);

and/or

The specific C4-C9 diol amines are (III) combinations or mixtures consisting of the components (I) alcoholamines (Ia) and (II) alcoholamines (IIa), and the molar ratio of the alcoholamines (Ia) to the alcoholamines (IIa) is 1 (0.2-1.5), more preferably 1 (0.22-1.2), more preferably 1 (0.24-0.9), more preferably 1 (0.25-0.5), more preferably 1 (0.27-0.4), more preferably 1 (0.29-0.45), most preferably 3: 1.

4. Blowing agent composition (FC) according to any of claims 1 to 3, wherein the chemical blowing agent (F1) is obtained by passing CO through a mixture of a C2-C9 alcohol amine and water ₂ Gas neutralization method; preferably, the neutralization method comprises: introducing CO with a surface pressure of 0.09-0.4MPa (preferably 0.09-0.35MPa or 0.1-0.3MPa) into a mixture of C2-C9 alcohol amine and water ₂ Until the gas is saturated, optionally, the above-mentioned C2-C9 alcohol amine (preferably, the above-mentioned specific C4-C9 diol amine, such as diethanolamine and/or diisopropanolamine) is further added to the resulting neutralized product so that the pH of the product is in the range of 8.8 to 10.2 (preferably 9 to 10.1, more preferably 9.2 to 10, preferably 9.2 to 9.7, more preferably 9.4 to 9.6), to obtain a chemical blowing agent (F1); preferably, the amount of water in the mixture of C2-C9 alcohol amine and water therein is such that the free water content in the prepared chemical blowing agent (F1) is 10-33 wt% water, preferably 10.5-32 wt%, preferably 11-31 wt%, 11.5-30 wt%, 12-29 wt%, 12.5-28 wt%, 13-27 wt%; preferably, CO is introduced into the mixture of C2-C9 alcohol amine and water ₂ The pressure of the gas should be selected to be sufficient to ensure that the C2-C9 alcohol amine is CO as close as possible to the stoichiometry of the formation of the di (C2-C9 alcohol amine) carbonate salt ₂ Neutralizing but forming no more than 10 wt% (e.g., 0-10 wt%, preferably 0-9 wt%, preferably 0-5 wt%, 0-4 wt%, 0-3 wt%) of a C2-C9 alkanolamine bicarbonate, the wt% based on the weight of the alkanolamine carbonate hydrate formed (F1);

preferably, for the preparation of bagsA chemical blowing agent (F1) containing two or more alcohol amines of different basicity and having a low content of formed alcohol amine bicarbonates, capable of blowing by reaction in respectively different CO ₂ Introducing CO into each alcohol amine under the pressure of gas ₂ Gas is used to prepare a carbonate ethanolamine salt containing almost no alkanolamine bicarbonate per each alkanolamine, and then two or more neutralization product carbonate ethanolamine salts containing almost no alkanolamine bicarbonate are mixed in corresponding proportions to obtain a chemical foaming agent containing a plurality of alkanolamine carbonates and a smaller amount of alkanolamine bicarbonate (F1).

5. Blowing agent composition (FC) according to any one of claims 1 to 4, wherein:

C4-C7 dialcohols amine (Ia) with only hydroxyethyl groups is one or more selected from diethanolamine and N-methyldiethanolamine, and C5-C9 dialcohols amine (IIa) with hydroxyl isopropyl groups is one or more selected from diisopropanolamine, ethanol isopropanolamine, N-methyl diisopropanolamine, N-ethyl diisopropanolamine, N-methyl ethanol isopropanolamine and N-ethyl ethanol isopropanolamine; more preferably, the C4-C7 dialolamine (Ia) having only hydroxyethyl groups is one or more selected from diethanolamine and N-methyldiethanolamine, and the C5-C9 dialolamine (IIa) having hydroxyisopropyl groups is one or more selected from diisopropanolamine, ethanolisopropanolamine, N-methyldiisopropanolamine and N-methylethanolisopropanolamine; more preferably, the C4-C7 dialolamine (Ia) having only hydroxyethyl groups is diethanolamine, and the C5-C9 dialolamine (IIa) having hydroxyisopropyl groups is diisopropanolamine;

and/or

The blowing agent composition (FC) comprises only component (1) chemical blowing agent (F1) and component (2) cyclopentane, i.e., component (2) physical blowing agent (F2) and component (3) water (F3) are both used in amounts of 0 parts by weight, and the ratio or relative amounts by mass of chemical blowing agent (F1) to cyclopentane are (4-10) to (10-20), preferably (4-9.5) to (10-20), (4-9) to (10-18), (4-9) to (10-16), preferably (4.5-10) to (10-20), (5-9.5) to (10-18), (5-9.5) to (10-16), (5-9) to (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): (10.5-19.5), (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 (5.8-7.8): (11.5-18.8), preferably (5.9-7.6): 12-18.5), preferably (6-7): 12-18.5), more preferably (6-7): 14-18), still more preferably (6-7): 15-18, still more preferably (6-7): 16-18.

6. Blowing agent composition (FC) according to any one of claims 1 to 5, wherein: the blowing agent composition (FC) is used for the preparation of a white mass for rigid polyurethane foams, preferably for the preparation of rigid cast polyurethane foams during the production of refrigerators, freezers, water heaters or refrigerated vehicles, by mixing with a dry white mass;

preferably, the polymer polyols in the dry white material comprise 8-52 wt.% (preferably 9-50 wt.%, preferably 10-48 wt.%, preferably 12-47 wt.%, preferably 15-45 wt.%, preferably 16-40 wt.%, more preferably 18-35 wt.%) of aromatic/semi-aromatic polyester polyols (e.g. polyethylene phthalate polyols, polyethylene isophthalate polyols or polyethylene terephthalate polyols) and/or toluene diamine polyoxypropylene polyols and 92-48 wt.% (preferably 91-50 wt.%, preferably 90-52 wt.%, preferably 88-53 wt.%, preferably 85-55 wt.%, preferably 84-60 wt.%, more preferably 82-65 wt.%) of (non-toluene diamine type or non-toluene diamine initiated) polyoxypropylene polyols.

7. The blowing agent composition (FC) according to any of claims 1 to 6, wherein: the specific C4-C9 glycol amine is a mixture of diethanolamine and diisopropanolamine in a molar ratio of 1 (0.1-2), preferably 1 (0.2-1.5), more preferably 1 (0.22-1.2), more preferably 1 (0.24-0.9), more preferably 1 (0.25-0.5), more preferably 1 (0.27-0.4), more preferably 1 (0.29-0.45).

8. An aqueous alkanolamine carbonate salt chemical blowing agent (F1) comprising the following ingredients:

(C)0-20 wt% of C2-C9 alcohol amine; the content is preferably 0.01 to 19 wt%, preferably 0.02 to 18 wt%, more preferably 0.03 to 17 wt%, more preferably 0.04 to 16 wt%, preferably 0.06 to 15 wt%; e.g., 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 12, 13, or 14 wt%;

and

9. A polyurethane foaming white material, comprising: (1) a dry white for polyurethane foaming comprising polymer polyols and further auxiliaries in addition to blowing agents, wherein the further auxiliaries comprise polyurethane catalysts, foam stabilizers and optionally flame retardants, optionally chain extenders and optionally crosslinkers; and

(2) a carbonate alkanolamine salt blowing agent composition (FC) as set forth in any one of claims 1-7;

preferably, the polymer polyols in the dry white mass comprise 8-52 wt.% (preferably 9-50 wt.%, preferably 10-48 wt.%, preferably 12-47 wt.%, preferably 15-45 wt.%, preferably 16-40 wt.%, more preferably 18-35 wt.%) of aromatic/semi-aromatic polyester polyols (such as polyethylene phthalate, polyethylene isophthalate or polyethylene terephthalate) and/or toluene diamine polyoxypropylene polyols and 92-48 wt.% (preferably 91-50 wt.%, preferably 90-52 wt.%, preferably 88-53 wt.%, preferably 85-55 wt.%, preferably 84-60 wt.%, more preferably 82-65 wt.%) of (non-toluene diamine type or non-toluene diamine initiated) polyoxypropylene polyols.

10. A polyurethane foaming composition comprising:

(2) a dry white for polyurethane foaming comprising polymer polyols and further auxiliaries in addition to blowing agents, wherein the further auxiliaries comprise polyurethane catalysts, foam stabilizers and optionally flame retardants, optionally chain extenders and optionally crosslinkers; and

(3) a carbonate alkanolamine salt blowing agent composition (FC) as set forth in any one of claims 1-7;

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 to 1.36:1, preferably 1.13 to 1.35:1, preferably 1.15 to 1.30:1, more preferably 1.17 to 1.27:1, more preferably 1.18 to 1.25:1, most preferably 1.2: 1;

11. A method for preparing a rigid polyurethane foam, the method comprising: mixing and foaming a polymer polyol composition white mass comprising a blowing agent composition (FC) according to any one of claims 1 to 7 with a polyisocyanate (preferably, polymethylene polyphenyl polyisocyanate or polymeric MDI) as black mass; preferably, casting foaming is performed using a casting machine;

12. The rigid polyurethane foam obtained by the process according to claim 11, wherein the rigid polyurethane foam has a density of 25 to 38Kg/cm ³ In the range of 26 to 37Kg/cm is preferred ³ Preferably 27 to 36.5Kg/cm ³ Preferably 28 to 36Kg/cm ³ Preferably 28.5 to 35.5Kg/cm ³ Preferably 29 to 35Kg/cm ³ E.g. 30, 31, 32, 33 or 34Kg/cm ³ ；

And/or the presence of a gas in the gas,

the Lance thermal conductivity lambda (mW/m.K, 10 ℃ C.) of the rigid polyurethane foam is less than 18.50, preferably less than 18.40, more preferably less than 18.30, more preferably less than 18.20, more preferably less than 18.05.