CN116589740B

CN116589740B - Polymer polyol composition for preparing polyurethane rigid foam with excellent heat insulation performance

Info

Publication number: CN116589740B
Application number: CN202310861201.XA
Authority: CN
Inventors: 刘鹿; 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: 2023-07-14
Filing date: 2023-07-14
Publication date: 2023-09-22
Anticipated expiration: 2043-07-14
Also published as: CN116589740A

Abstract

A foaming polyether composition comprising an organic alcohol amine carbonate blowing agent and a polyether polyol, comprising; (I) 100 parts by weight of a polymer polyol comprising: 1) 45-65 wt% sorbitol starting polyether polyol; 2) 15-25 wt% aromatic polyester polyol; 3) 15-25 wt% pentaerythritol starting polyether polyol; 4) 3-7. 7 wt% toluene diamine starting polyether polyol; (II) 3.5-20 parts by weight of a catalyst, a foam stabilizer and a flame retardant; (III) 6-20 parts by weight of ethanol isopropanolamine and triisopropanolamine carbonate (AC) as foaming agents. The composition is used for preparing polyurethane rigid foam with very fine cells and excellent heat insulation performance.

Description

Polymer polyol composition for preparing polyurethane rigid foam with excellent heat insulation performance

Technical Field

The invention relates to a polymer polyol composition (white material) for foaming, which comprises a novel organic alcohol amine carbonate foaming agent and polyether polyol, and is used for preparing polyurethane rigid foam with fine foam holes and excellent heat insulation performance by reacting with isocyanate, in particular to preparing spray-type polyurethane rigid foam.

Background

The polyurethane rigid foam material is a high-quality heat-insulating material and is widely applied to industries such as refrigerators, freezers, water heaters, cold chain heat preservation and the like. Currently, in the fields of building outer wall spraying and pipeline winding spraying, the requirements of people on energy conservation and carbon reduction are higher and higher, so that the selection of the environment-friendly foaming agent for preparing the polyurethane heat insulation material in the field is also stricter and stricter.

In general, polyurethane rigid foams formed by spraying are prepared by mixing and spraying a polymer polyol composition (white stock) containing a polymer polyol of a polyether polyol and an aromatic polyester polyol (e.g., polyethylene phthalate polyol) and/or a toluenediamine polyether polyol as main raw materials with a polyisocyanate (black stock) and by reacting and curing, and contain an auxiliary agent such as a foaming agent, a catalyst and a foam stabilizer.

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

Currently, in the case of using a composite blowing agent containing a large amount of water, for example, in a blowing agent composed of water and cyclopentane or in a blowing agent composed of water and a hydrofluorocarbon type physical blowing agent, if the amount of water used is large, the polyurethane foam formed has a high open cell content, its size is unstable (shrinkage and deformation are liable to occur), and its heat insulating property is lowered.

In addition, in the spraying process of polyurethane foam, a white material (polymer polyol component a) and a black material (isocyanate component B) are usually mixed by an applicator and then sprayed (via a spray gun) on the surface of a substrate (e.g., a steel plate, a steel pipe, or a concrete structure such as a wall). In general, the polyurethane rigid foam is produced as a heat insulating material layer by spray foaming in a spray manner of 2 to 3cm per layer and a total thickness of 20 to 30cm, and molding and curing the foam. If higher activity or CO is used ₂ Higher content of hydrates of amine salts of carbonic acid alcohols as components of foaming agents for polyurethane foamsSpraying, it has been found that the foam rises too quickly in the early stages of the foaming reaction, the wet foam expands and rises rapidly, the skin of the foam skinns and cures rapidly, but the bond strength between the substrate and the foam or between two adjacent foam layers decreases (due to shrinkage of the foam), thus ultimately leading to (subsequent) polyurethane coatings sprayed on the substrate or on the cured polyurethane foam coating often cracking or peeling off from the substrate or from the cured polyurethane foam layer.

In addition, aqueous alcohol amines (e.g., carbonates of primary amine type alcohol amines such as ethanolamine, and carbonates of certain secondary amine type glycol amines such as di (diethanolamine) carbonate salts, etc.) are used in the prior art as foaming agents, and these alcohol amines have a large influence on the urethanization reaction between a polymer polyol composition (white stock) containing an amine catalyst and a polyisocyanate (black stock), and in particular, certain amine foaming agents influence the catalytic action of the amine catalyst, for example, cause excessive early reaction speed and insufficient post curing reaction, influence the strength of the foam, and cause dimensional instability (high open cell content, easy shrinkage and deformation) of the foam. In addition, when aqueous alcohol amine (e.g., triethanolamine hydrate) is used as a blowing agent in the preparation of spray-type polyurethane rigid foams having a relatively large thickness, a "core burn" phenomenon occurs in the interior of the foam due to a relatively high reaction rate and rapid heat release during spraying, which may reduce the heat insulating properties of the foam, and even cause the foam to crack from the substrate to form cracks or to crack between two adjacent foam layers to form cracks.

In addition, US2622099A, US4169856A, US2051486A, GB448373A, GB710861A, GB1387573A, GB642950A, GB760215A, GB655580a and CA1003358A disclose isopropanolamine, ethanolamine or butanolamine prepared by reacting aqueous ammonia with propylene oxide or ethylene oxide.

CN107663157a and CN103435499a disclose a process for producing ethanol diisopropanolamine from the reaction of ethanolamine with propylene oxide, but no product is disclosed as being useful in PU blowing agents.

CN114805902a discloses a chemically-physically combined type alcohol carbonate salt foaming agent composition for use in the preparation of cast polyurethane rigid foam, which comprises: 1) High water content and low bicarbonate content alcohol 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) 67-90wt% of a di (C2-C9 alcohol amine) carbonate salt; b) 10-33wt% water; c) 0-20wt% of C2-C9 alcohol amine.

CN109422913a discloses a blowing agent comprising a polyamine salt and a propanolamine salt and the use for polyurethane refrigerator and freezer foam materials.

CN109422903a discloses a blowing agent comprising a secondary amine salt and a propanolamine salt and the use for polyurethane refrigerator and freezer foam materials.

The foaming agents disclosed in the above-mentioned documents CN114805902A, CN109422913a and CN109422903a are used for casting foaming, but the use effect in spray polyurethane foaming is poor or unusable.

When using the prior art CO-containing ₂ And aqueous alcohol Amine Compositions (AC) and existing combination polyethers (polymer polyol compositions) are often subject to problems when spray foaming, especially when spraying foams onto the surface of cold metal and concrete substrates in cold winter: the initial adhesion strength between the sprayed PU foam layer and a substrate (e.g., steel, such as steel or steel pipe) or concrete substrate is low, the sprayed wet foam often peels off and falls off the substrate at normal spraying speeds, and the bond strength after the foam cures is low, and peeling occurs between the foam and the substrate after the foam cures.

Disclosure of Invention

In order to solve the technical problems existing in the prior art, the present inventors have first provided an aqueous alcohol amine composition (AC, alkanolamine composition) (or referred to as an aqueous alcohol amine mixture or an alcohol amine hydrate) comprising ethanol isopropanolamine and triisopropanolamine for polyurethane foam spraying, characterized in that It has lower alkalinity and reactivity with isocyanate, lower CO ₂ Content and higher flowability. Wherein a portion of the alcohol amine is reacted with CO ₂ And water to form carbonates, i.e., wherein the alcohol amine is partially salified. This alcohol Amine Composition (AC) is used alone as a blowing agent in polyurethane foam spraying to produce a polyurethane rigid foam. In addition, the foaming agent of the present application can delay the gel time of polyurethane foam and allow the curing time to be shortened. For example, when using conventional alcohol amines (e.g., diisopropanolamine carbonate or diethanolamine carbonate) as the blowing agent, the spray foam typically has a gel time of 50 to 60 seconds, however, when using the CO-containing compositions of the present application ₂ And aqueous alcohol Amine Compositions (AC), the gel time of the spray foam is typically 70 to 90 seconds.

Next, the present inventors have provided a polymer polyol composition for foaming, i.e., a white material for polyurethane foaming, for use in the preparation of a rigid polyurethane foam. By selecting specific polymer polyols with the CO-containing compositions of the application as blowing agents ₂ In combination with the aqueous alcohol Amine Composition (AC), the initial adhesion strength (the wet foam sprayed does not fall off the substrate at the usual spraying speeds) and the cure strength (no peeling occurs between the foam and the substrate after the foam cures) between the sprayed PU foam layer and the substrate (e.g. steel, such as steel or steel pipe) or concrete substrate. The above problems encountered when spraying foam onto the surface of metal and concrete substrates, especially at low temperatures in winter, are overcome.

According to a first aspect of the present invention there is provided a polymer polyol composition (white stock) for foaming comprising a novel organic alcohol amine carbonate blowing agent and a polyether polyol for use in the reaction with isocyanate to produce polyurethane rigid foams having very fine cells and excellent thermal insulation properties, especially for use in the production of spray polyurethane rigid foams.

More specifically, the present invention provides a polymer polyol composition for foaming (i.e., a white material for polyurethane foaming) for producing a polyurethane rigid foam excellent in heat insulating properties, comprising:

(I) 100 parts by weight of a polymer polyol comprising: 1) 45-65wt% (preferably 47-63wt%, more preferably 50-60wt%, e.g., 52, 54, 55, 56, 58 wt%) of a sorbitol-initiated polyether polyol (preferably a sorbitol-initiated polyoxypropylene polyol) having a hydroxyl value in the range of 340-520 mgKOH/g (preferably 350-490 mgKOH/g, such as 360, 370, 380, 400, 450, 470, 500); 2) 15-25wt% (preferably 17-23wt%, e.g., 18, 20, 22 wt%) of an aromatic polyester polyol having a hydroxyl value in the range of 210-550 mgKOH/g (preferably 220-500 mgKOH/g, more preferably 220-470mgKOH/g, such as 225, 230, 240, 250, 300, 350, 400, 450); 3) 15-25wt% (preferably 17-23wt%, e.g., 18, 20, 22 wt%) of a pentaerythritol-initiated polyether polyol (preferably a pentaerythritol-initiated polyoxypropylene polyol) having a hydroxyl value in the range of 290-500 mgKOH/g (preferably 300-470 mgKOH/g, more preferably 305-450 mgKOH/g, such as 310, 320, 330, 360, 400, 410, 440); 4) 3-7wt% (preferably 4-6 wt%, e.g., 5 wt%) of a toluenediamine-initiated polyether polyol (preferably toluenediamine-initiated polyoxypropylene polyol) having a hydroxyl number in the range of 350-580 mgKOH/g (preferably 360-550 mgKOH/g, such as 365, 370, 380, 400, 450, 500 or 530); wherein the weight percent is based on the sum of the percentages of the total of components 1) -4) (i.e., components 1) -4) is 100%);

(II) 3.5 to 20 parts by weight (preferably 4 to 18 parts by weight, such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 parts by weight) of an auxiliary agent comprising a catalyst, a foam stabilizer and optionally a flame retardant; for example, the adjuvant comprises 0.5 to 2.5 parts by weight (e.g., 1 or 1.5 or 2 parts by weight) of a catalyst, 1 to 4 parts by weight (e.g., 1.5, 2, 2.5, 3 or 3.5 parts by weight) of a foam stabilizer, and optionally (preferably 0 to 18 parts by weight, more preferably 0 to 16 parts by weight, such as 4, 5, 6, 8, 10, 15, 17 parts by weight) of a flame retardant, based on 100 parts by weight of the polymer polyol;

(III) 6 to 20 parts by weight (preferably 7 to 18 parts by weight, more preferably 8 to 16 parts by weight, preferably 9 to 14 parts by weight, such as 10, 11, 12, 15, 17, 19 parts by weight) of a CO-containing agent as a foaming agent ₂ And aqueous alcohol amine compositionAn AC); the alcohol Amine Composition (AC) comprises or consists essentially of:

(1) Ethanol isopropanolamine (A1);

(2) Triisopropanolamine (A2); and

(3) Water;

wherein the molar ratio of triisopropanolamine (A2) to ethanolisopanolamine (A1) is (0.2-6), preferably (0.25-5.5), 1, preferably (0.3-5), 1, preferably (0.4-4.5), 1, preferably (0.5-4), preferably (0.6-3.8), 1, preferably (0.7-3.7), preferably (0.8-3.6), 1, preferably (1.0-3.5), 1, preferably (1.1-3.3), preferably (1.5-3), 1, preferably (1.7-2.8), preferably (2.0-2.6), 1, preferably (2.2-2.4).

Wherein the water content is 5-38wt%, preferably 7-35wt%, preferably 8-33wt%, preferably 9-31wt%, preferably 10-30wt%, preferably 12-28wt%, preferably 13-26wt%, preferably 15-25wt%, preferably 16-24wt%, preferably 17-23wt%, based on the total weight of the alcohol Amine Composition (AC);

(A1) The total content of + (A2) + water is 90-100wt%, preferably 92-100%, preferably 94-100%, preferably 95-100%, preferably 96-100%, preferably 97-100%, preferably 98-100%, preferably 99-100%, such as 99.5 or 99.8% or 99.9%, based on the total weight of the alcohol Amine Composition (AC);

wherein a portion of the alcohol amine in the alcohol Amine Composition (AC) is replaced with CO ₂ Neutralization to give (final) alcohol Amine Composition (AC) CO ₂ The content of (3) is 1-7. 7 wt%, preferably 1.2-6.5 wt%, preferably 1.5-6.0 wt%, preferably 1.8-5.7 wt%, preferably 2-5.5 wt%, preferably 2.5-5.0 wt%, such as 3, 4 or 4.5 wt.%, based on the total weight of the (final) alcohol Amine Composition (AC).

In general, the alcohol Amine Composition (AC) comprises or consists essentially of the following components:

(1) Ethanol isopropanolamine (A1);

(2) Triisopropanolamine (A2);

(3) Water;

（4）CO ₂ ；

(5) Optionally (i.e., optionally) a C2-C6 alcohol amine (A3) other than (A1) and (A2) (e.g., ethanolamine, isopropanolamine, diethanolamine, diisopropanolamine),

Wherein (A1) + (A2) +water+CO ₂ The total content of + (A3) is (about) 100wt%, based on the total weight of the alcohol Amine Composition (AC).

That is, the alcohol Amine Composition (AC) further comprises (4) CO ₂ And (5) optionally a C2-C6 alcohol amine (A3) other than (A1) and (A2) (e.g., ethanolamine, isopropanolamine, diethanolamine, diisopropanolamine).

As described above, when the total content of (A1) + (A2) +water is 90 to 100wt%, CO ₂ And optionally the content of C2-C6-alcohol amines (A3) other than (A1) and (A2) is the balance, i.e.0 to 10 wt.% (e.g.CO ₂ The content of (C) is 0-7wt% or 1-7wt% or 0-6wt% or 1-6wt% or 2-5wt%. The A3 content may be 0-3wt% or 0-4wt% or 0-6wt% or 0-9wt% or 0-10wt% or 4-9wt% or 5-8 wt%.

When the total content of (A1) + (A2) +water is 93 to 100wt%, CO ₂ And optionally the content of C2-C6-alcohol amines (A3) other than (A1) and (A2) is the balance, i.e.0 to 7 wt.% (e.g.CO ₂ The content of (C) is 0-7wt% or 1-6wt% or 2-5wt%. The A3 content may be 0-7wt% or 0-6wt% or 1-6wt% or 2-5wt%, or 0-5wt% or 1-4 wt%.

When the total content of (A1) + (A2) +water is 94 to 100wt%, CO ₂ And optionally the content of C2-C6 alcohol amines (A3) other than (A1) and (A2) is the balance, i.e.0 to 6 wt.% (e.g.CO ₂ The content of (C) is 0-6wt% or 1-6wt% or 2-5wt%. The A3 content may be 0-6wt% or 0-5wt% or 1-4 wt%).

When the total content of (A1) + (A2) +water is 95-100wt%, CO ₂ And optionally the content of C2-C6-alcohol amines (A3) other than (A1) and (A2) is the balance, i.e.0 to 5 wt.% (e.g.CO ₂ The content of (C) is 0-5wt% or 1-5wt% or 2-4wt%. The A3 content is 0-5wt% or 0-4wt% or 1-3 wt%).

And so on. For example, when the total content of (A1) + (A2) +water is 96 to 100wt%, CO ₂ And optionally the content of C2-C6-alcohol amines (A3) other than (A1) and (A2) is the balance, i.e.0 to 4 wt.% (e.g.CO ₂ The content of (C) is 0-4wt% or 1-4wt% or 2-3wt%. A3 content is 0-4wt% or 0-3wt% or 1-2 wt%). For example, when the total content of (A1) + (A2) +water is 97 to 100wt%, CO ₂ And optionally the content of C2-C6-alcohol amines (A3) other than (A1) and (A2) is the balance, i.e.0 to 3 wt.% (e.g.CO ₂ The content of (C) is 0-3wt% or 1-3wt%. The A3 content is 0-3wt% or 0-2 wt%.

The C2-C6 alcohol amines (A3) other than (A1) and (A2) are ethanolamine, isopropanolamine, diethanolamine and/or diisopropanolamine; preferably, diethanolamine and/or diisopropanolamine.

Preferably, the aromatic polyester polyol is polyethylene phthalate glycol, polyethylene phthalate glycol and/or polyethylene phthalate/diethylene glycol.

Preferably, the CO is contained at an ambient temperature of 25 DEG C ₂ And the aqueous alcohol Amine Composition (AC) is in the form of a homogeneous liquid having 200 to 1000 centipoise (25 ℃), preferably 250 to 900 centipoise (e.g., 300, 400, 500, 600, 700, 800 centipoise).

Preferably, the alcohol Amine Composition (AC) is prepared by the following preparation method:

1) Preparation of alcohol Amine Composition (AC): mixing ethanol isopropanolamine, triisopropanolamine and water to obtain an alcohol Amine Composition (AC); wherein triisopropanolamine (A2) and ethanolisolamine (A1) are used in such an amount that the molar ratio of triisopropanolamine (A2) to ethanolisolamine (A1) in the resulting composition (AC) is (0.2-6): 1, preferably (0.25-5.5): 1, preferably (0.3-5): 1, preferably (0.4-4.5): 1, preferably (0.5-4): 1, preferably (0.6-3.8): 1, preferably (0.7-3.7): 1, preferably (0.8-3.6): 1, preferably (1.0-3.5): 1, preferably (1.1-3.3): 1, preferably (1.7-2.8): 1, preferably (2.0-2.6): 1, preferably (2.2-2.4): 1, thereby obtaining the composition (AC).

Wherein the amount of water is such that the water content in the (final) resulting alcohol Amine Composition (AC) is 5 to 38wt%, preferably 7 to 35wt%, preferably 8 to 33wt%, preferably 9 to 31wt%, preferably 10 to 30wt%, preferably 12 to 28wt%, preferably 13 to 26wt%, preferably 15 to 25wt%, preferably 16 to 24wt%, preferably 17 to 23wt%, based on the total weight of the (final) alcohol Amine Composition (AC);

Preferably, the total content of (A1) + (A2) +water in the (final) resulting alcohol Amine Composition (AC) is 90 to 100wt%, preferably 92 to 100%, preferably 94 to 100%, preferably 95 to 100%, preferably 96 to 100%, preferably 97 to 100%, preferably 98 to 100%, preferably 99 to 100%, such as 99.5%, 99.8%, 99.9%, based on the total weight of the (final) alcohol Amine Composition (AC);

2) CO is introduced into the alcohol Amine Composition (AC) obtained ₂ Gas so as to partially neutralize the alcohol amine compound in the composition (AC) to obtain a catalyst composition containing CO ₂ And an aqueous (final) alcohol Amine Composition (AC);

wherein CO ₂ The amount of (C) is such that CO in the (final) alcohol Amine Composition (AC) ₂ Is 1-6 wt%, preferably 1.2-5.5 wt%, preferably 1.5-5.0 wt%, preferably 1.8-4.7 wt%, preferably 2-4.5 wt%, preferably 2.5-4.0 wt%, such as 3 or 3.5 wt%, based on the total weight of the (final) alcohol Amine Composition (AC).

For the alcohol Amine Composition (AC) obtained in the present invention, when the molar ratio of triisopropanolamine (A2) to ethanolisopanolamine (A1) is in the range of (0.2-6): 1 and CO in the alcohol Amine Composition (AC) ₂ At levels in the range of 1-6 wt%, these conditions ensure that the alcohol Amine Composition (AC) does not crystallize, set and have a viscosity that is not too high at higher ambient temperatures (e.g., 30-40 ℃) and, thus, can be used as a blowing agent to prepare rigid polyurethane foams by spraying in summer or at higher ambient temperatures. When the proportion of triisopropanolamine is too high, the alcohol Amine Composition (AC) tends to crystallize and solidify. When the proportion of triisopropanolamine is low, meaning that the amount of ethanolisopanolamine is increased, the Alkanolamine Composition (AC) has a higher catalytic action and an effect of improving the reactivity, resulting in unstable foaming reaction.

Preferably, for the alcohol Amine Composition (AC) described above, the alcohol Amine Composition (AC) contains CO ₂ Is not higher than 7. 7 wt% (more preferably not higher than 6.5. 6.5 wt%, still more preferably not higher than 6 wt%). If CO in an alcohol Amine Composition (AC) ₂ Higher than 7 wt%, resulting in rapid expansion of the wet foam sprayed onto the (stainless steel or concrete) substrate or onto the cured foam layer and falling off the substrate; in addition, this may lead to sprayingThe coated, cured polyurethane foam layer often cracks from the substrate to form a crack or between two adjacent foam layers to form a crack.

The inventors of the present application have found that the aqueous-alcoholic-Amine Composition (AC) of the present application is a low viscosity liquid at ambient temperature (e.g. 30-40 ℃) probably because the asymmetric structure of the ethanolisolamine has a certain doping effect on triisopropanolamine, slightly reducing the association and crystallization tendency of triisopropanolamine. Generally, the viscosity or dynamic viscosity (30 ℃) of the aqueous alcohol Amine Composition (AC) is from 200 to 900 centipoise (mPas), preferably from 220 to 800, more preferably from 240 to 700, more preferably from 250 to 600 centipoise, for example 280, 300, 400, 500, 650, 750, or 850 centipoise.

Typically, the alcohol amine is CO ₂ The pH of the partially neutralized alcohol Amine Composition (AC) is in the range of 8 to 13.5, preferably 8 to 12, preferably 8.5 to 11.5, more preferably 9 to 11, preferably 9.1 to 10.5, preferably 9.2 to 10.

In fact, the aqueous-alcoholic Amine Composition (AC) of the present application comprises an alcoholic amine carbonate+water+free alcohol amine, and therefore it is a low viscosity composite blowing agent.

In the present application, "optional" means with or without (0).

In addition, the inventors of the present application have unexpectedly found that the above aqueous alcohol Amine Composition (AC) of the present application has good miscibility (or compatibility) in dry white materials formed from (I) polymer polyol and (II), which, when mixed, are capable of forming transparent, homogeneous and low viscosity white materials (i.e., polymer polyol compositions for foaming used in the preparation of polyurethane rigid foams).

The alcohol Amine Composition (AC) is directly used as a foaming agent for preparing polyurethane rigid foam, and is especially suitable for spraying the polyurethane foam.

The application also relates to the use of the above-described alcohol Amine Composition (AC) as a blowing agent for the preparation of (spray-type) rigid polyurethane foams, in particular as a blowing agent for the spraying of polyurethane rigid foams.

That is, the present invention also relates to the use of the (spray) foaming polymer polyol composition described above for the reaction with a polyisocyanate to prepare a spray rigid polyurethane foam.

The alcohol Amine Composition (AC) of the present invention can be used in combination with a small amount of a hydrofluorocarbon physical blowing agent (F2) having a boiling point in the range of 15 to 41 ℃. Preferably, the physical blowing agent (F1) is one or more (e.g., a combination of two or three or four or five) selected from HCFC-141b, HFC-245fa, HFC-365mfc, LBA and hexafluorobutene.

The thermal conductivity lambda (w/m.k, 20 ℃) of the spray polyurethane rigid foam of the invention is generally below 0.02250, preferably below 0.02240, more preferably below 0.02235, more preferably below 0.02230, more preferably below 0.02220, more preferably below 0.02210.

The compressive strength of the spray polyurethane rigid foam of the invention (in the direction perpendicular to the substrate, for example when the density of the foam is about 35 Kg/cm ³ In this case) is 240 to 285 (KPa), preferably 245 to 270 (KPa), preferably 250 to 267 (KPa), preferably 255 to 265 (KPa).

THE ADVANTAGES OF THE PRESENT INVENTION

1. The alcohol Amine Composition (AC) of the invention is not crystallized, not solidified and not too high in viscosity at higher ambient temperature (30-40 ℃ for example), and particularly, the raw materials of ethanol isopropanolamine and triisopropanolamine are easy to obtain, have lower cost and are suitable for construction in summer.

2. In the alcohol Amine Composition (AC) of the present invention, only a portion of the alcohol amine is CO ₂ Neutralization, in addition, by selecting particular polymer polyols 1) to 4), it is thus possible to avoid the use of the prior art with higher CO during the spraying of the foam ₂ The following phenomena are frequently encountered with alcohol amine compositions in amounts as blowing agents and other relatively reactive polyether polyol compositions: if the more reactive polyether polyol composition is used in greater amounts and a higher CO is used ₂ The blowing agent composition (or alcohol amine composition) in the amount which is too fast to react with the higher CO in the early stages of the foaming reaction (the reaction system has not gelled sufficiently) in the spraying operation ₂ The blowing agent composition (or alcohol amine composition) is heated to rapidly release a significant amount of CO ₂ The gas causes the wet foam sprayed onto the (stainless steel or concrete) substrate or onto the cured foam layer to expand rapidly and fall off the substrate, and in addition, the cured foam has a high brittleness and thus undergoes slight shrinkage and deformation, resulting in cracking between the cured foam material and the substrate or between adjacent two cured foam layers to form cracks. These problems are particularly pronounced in cold winter spraying.

3. Under the condition that a special foaming agent alcohol Amine Composition (AC) is used, the sorbitol-initiated polyether polyol (preferably sorbitol-initiated polyoxypropylene polyol) and the pentaerythritol-initiated polyether polyol (preferably pentaerythritol-initiated polyoxypropylene polyol) have good compatibility with a chemical foaming Agent (AC), have proper hydroxyl values, are favorable for forming very fine (small in cell size and very uniform in cell size) cells, and can remarkably improve the heat insulation performance of PU rigid foam.

4. Compared with ethylenediamine-initiated polyether polyol, the toluenediamine-initiated polyether polyol (preferably toluenediamine-initiated polyoxypropylene polyol) has lower activity and proper hydroxyl value (lower viscosity), and the chemical foaming agent AC has the effect of improving the reactivity, so that the use of the toluenediamine-initiated polyether polyol and the use of the polyester polyol with lower viscosity and lower activity can effectively reduce the reactivity of the whole material and improve the dimensional stability and the bonding strength of foam.

Drawings

Fig. 1 is an SEM photograph of the foam of example 1.

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

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

Fig. 4 is an SEM photograph of the foam of comparative example 1.

Fig. 5 is a photograph of a cross section of the foam of comparative example 1.

Fig. 6 is an SEM photograph of the foam of example 4.

Reference numerals: 1: cracks between the foam and the substrate (cement board); 2: a crack between two adjacent foam layers; 3: a substrate (cement board).

Detailed Description

The technical scheme of the present invention is further described in detail by the following examples, but the present invention is not limited to these examples.

The devices used in the examples are all devices commonly used in the art and commercially available in the market unless otherwise specified.

The measuring method of the alcohol amine content comprises the following steps: in the examples, gas chromatography may be used for the measurement of the content of various alcohol amines (e.g., ethanolisopanolamine or triisopropanolamine) in the aqueous alcohol amine mixture (AC) (or aqueous alcohol amine composition or alcohol amine hydrate). Wherein the gas chromatograph is equipped with a hydrogen Flame Ionization Detector (FID), and the mass concentration of the alcohol amine compound is about 10 mg/mL, which is a standard solution. Gas chromatography conditions: HP-5 capillary chromatography column (30 m X0.32 mm i.d.X0.25 μm,5% phenyl methyl-siloxane); the column temperature is programmed, the initial temperature is 80 ℃, the temperature is kept for 3 min, then the temperature is increased to 250 ℃ at the speed of 25 ℃/min, and the temperature is kept for 5 min; the temperature of the sample inlet is 250 ℃; the detector temperature is 260 ℃; the carrier gas is high-purity nitrogen, and the flow rate is 1.5 mL/min; the fuel gas is hydrogen with the flow rate of 30 mL/min; the fuel gas is air, and the flow rate is 300 mL/min; the tail blowing is nitrogen, and the flow rate is 25 mL/min; the sample injection mode is split sample injection, and the split ratio is as follows: 30:1; the sample loading was 1. Mu.L.

In the present application, the usual polyether polyols (polyoxypropylene polyols) and (aromatic) polyester polyols used for the preparation of polyurethane foams or for use in foaming compositions are selected from the following classes: polyether polyols (polyoxypropylene polyols), for example, polyether polyol 8310 (sucrose starter polyoxypropylene polyol, hydroxyl number 310) and polyether polyol 4110 (sucrose starter polyoxypropylene polyol), polyether polyol 8038 (sorbitol starter polyoxypropylene polyol, hydroxyl number 380) from optimized chemical company, polyether 450 (sorbitol starter polyoxypropylene polyol, hydroxyl number 450) from Nanjing red company, MN500 (glycerin starter polyoxypropylene polyol) and SA460 (sorbitol starter polyoxypropylene polyol), SU380 (sucrose starter oxypropylene polyol) and SA380 (sorbitol starter polyoxypropylene polyol), viscosity of polyethylene glycol 450 (TamgE) and polyethylene glycol 450 g (hydroxyl number 400 mg/mgKOH) from Shandong blue star, 15 mg/2000 g, 15 mg/2000 g, and viscosity 400 mg/g of polyethylene diamine, 13 mg/2000 g YD403 (ethylenediamine initiator polyoxypropylene polyol, hydroxyl value 770.+ -.40 mg KOH/g), YD460 (toluenediamine type polyoxypropylene polyol) and YD-4110 (polyether polyol, hydroxyl value 460 mg KOH/g), and SD7100 (toluenediamine type polyoxypropylene polyol) of Shanghai Dong chemical Co., ltd; and (aromatic) polyester polyols, for example, XCPA220-1 (aromatic polyester polyol, hydroxyl value 220 mg KOH/g) of Asahi chemical Co., ltd., nanjing Jinling Setapan chemical Co., ltd., polyester polyol PS4051, PS4027 or PS3152 of Nanjing Sedan chemical Co., ltd., polyester polyol CF6320 (hydroxyl value 320 mgKOH/g) of Jiangsu Fu New material Co., ltd., CF6245, CF6200, CF6300 and CF6255, and polyester polyol DM2003 of Beijing Oriental Meter chemical Co., ltd.

The usual catalysts are selected from: 33LV (a-33): dipropylene glycol solution of 33% triethylenediamine, N, N-dimethylethanolamine, N, N-dimethylbenzylamine, dipropylene glycol solution of 70% 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-pentamethyldiethylenetriamine), PC-41 (tris (dimethylaminopropyl) hexahydrotriazine), triethanolamine, JXP-508, JXP-509, TMR-2 (2-hydroxy-N, N, N-trimethyl-1-propylamine, U.S. aerochemical), TMR-3, TMR-4, dabco 2040 (winning chemistry). Commonly used silicone oil type foam stabilizers or silane surfactants: b8525 and B8408 of YingchangDe Guest (China) investment Co., ltd., AK-158, AK-8805, AK-8812, AK-8809, AK-8818 and AK-8860 of Jiangsu Meishan chemical Co., ltd., DC8545, DC1990, DC5188, DC6070, DC3042 and DC3201 of gas and chemicals Co., ltd., and silicone oil 8841 of Shanghai Mahao chemical technology Co., ltd. Non-silane surfactants: LK-221 and LK-443 of gas and chemicals Inc. Flame retardants are commonly used: flame retardants TCPP (Jiangsu Jack chemical Co., ltd.), TCPP (Qingdao Union beautification Co., ltd.), TCEP, DMMP, ammonium chloride, aluminum hydroxide powder, DM1201, DM1301, tetrabromophthalic anhydride diol.

CO is described below ₂ The aerated process produces an alkanolamine carbonate chemical blowing agent (i.e., an alkanolamine carbonate salt hydrate).

The water content of the salt of carbonic acid amine hydrate measured by the karl fischer method = the amount of free water in the hydrate + the amount of water produced by decomposition of the carbonate and optionally bicarbonate. Thus, the content of free water (wt%) in the alkanolamine salt chemical blowing agent (F1) (i.e., the ethanolamine salt hydrate) = (the water content of the ethanolamine salt hydrate measured by the karl fischer method) - (the amount of water produced by decomposition of the carbonate and optionally bicarbonate). For example, the water content in the alcohol Amine Composition (AC) described in the present application refers to the water content measured by the karl fischer method.

The test method of various parameters of the rigid polyurethane foam is carried out by referring to the following Chinese national standard GB:

detecting items	Reference standard
		Density (kg/m) ³ ）	GB/T6343-2009
Compressive Strength (KPa) (Z direction/X direction/Y direction)	GB/T8813-2008
		Coefficient of thermal conductivity (w/m.k, 22.5 ℃ C.)	GB/T3399-1982
Closed porosity (%)	GB/T10799-2008
		Water absorption (%)	GB/T8810-2005
Dimensional stability (70 ℃ C.,%)	GB/T8811-2008
		Dimensional stability (-20 ℃ C.,%)	GB/T8811-2008

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

Viscosity refers to the kinetic viscosity "centipoise (cP)" at 30 ℃.

Preparation example

A first part: preparation of alcohol amine

1) Adding 36.6 kg ethanolamine (molecular weight 61, 600 mol) and 16.7 kg deionized water into a high-pressure reaction kettle, stirring for dissolution, sealing the reactor, controlling the temperature between 60 ℃ and 95 ℃ under continuous stirring, controlling the pressure not higher than 0.3MPa, adding 34.8 kg propylene oxide (molecular weight 58, 600 mol, the mol ratio of propylene oxide to ethanolamine is 1:1) into the reactor in batches, controlling the temperature for reaction for 3 hours after the addition, and then cooling to 40 ℃. Then, 88 kg of the reaction product (alcohol amine hydrate AA1 a) was discharged from the reactor, and the product was sampled to have a content of ethanol isopropanolamine of 599.7 mol and a content of ethanol diisopropanolamine of 0.3 mol in the alcohol amine hydrate AA1a as measured by gas chromatography. Its viscosity (30 ℃) was 283 centipoise. The water content in the alcohol amine hydrate AA1a was 18.9. 18.9 wt%. ph=12.43.

A second part: compounding

2) From the reaction product of 88 kg (alcohol amine hydrate AA1 a), 4 batches of 20kg each were taken. For each batch, 20kg of the reaction product (alcohol amine hydrate AA1a,136.3mol of ethanol isopropanolamine) was charged into an autoclave, followed by addition of commercially available triisopropanolamine (molecular weight 191.3, purity 99wt%, water content 1%, hubei North scion, inc., N0168) and water, and compounding in the molar ratio and water content as in table 1 below, to obtain four batches of alcohol amine compositions AC (AA 1b-AA1 e).

In addition, the remaining 8kg of the reaction product (alcohol amine hydrate AA1 a) was charged into the autoclave, and then commercially available triisopropanolamine (molecular weight 191.3, purity 99wt%, water content 1wt%, hubei nana technology co., N0168), water and diisopropanolamine (molecular weight 133.189, purity 99wt%, water content 1wt%, south-jing constant chemical co., ltd.) were added and compounded in accordance with the molar ratio and water content in table 1 below to obtain a fifth batch of alcohol amine composition AC (AA 1 f).

Table 1: molar ratio of triisopropanolamine to ethanolisolamine

Alcohol amine hydrate No	Molar ratio of triisopropanolamine to ethanolisolamine	Water content wt%
			Alcohol amine composition AA1b	4 : 1	16.0
Alcohol amine composition AA1c	1 : 1	16.0
			Alcohol amine composition AA1d	0.25 : 1	16.0
Alcohol amine composition AA1e (comparative)	0.25 : 1	16.0
			Alcohol amine composition AA1f	1:1:0.1 (molar ratio of triisopropanolamine, ethanolisopanolamine and diisopropanolamine)	16.0

Third section: CO ₂ Neutralization and salification

Four batches of alcohol amine hydrate AA1b-AA1e and a fifth batch of alcohol amine composition AA1f obtained by compounding are respectively added into a high-pressure reaction kettle, and the mixture is controlled from CO ₂ Storing CO output from steel cylinders ₂ Under the condition that the pressure of the gas is not higher than 0.3MPa, respectively starting to introduce carbon dioxide gas into alcohol amine hydrates AA1b-AA1e and AA1f, controlling the temperature between 40 ℃ and 50 ℃ and controlling the temperature to react for 3 hours, Cooling to below 40deg.C, releasing pressure, adding small amount of water to make water content in the alcohol amine carbonate composition reach about 18 wt%, slowly stirring for 30 min, and discharging product to obtain alcohol amine carbonate compositions AA2b-AA2f (or called alcohol amine carbonate compositions 1-5). CO ₂ The content is shown in Table 2.

Table 2: CO in an alcohol carbonate salt composition ₂ Content of

Alcohol amine composition No	Molar ratio of triisopropanolamine to ethanolisolamine	Water content, wt%	CO ₂ Content by weight percent	Viscosity (centipoise/30 ℃ C.)
					Alcohol carbonate salt composition 1 (AA2b）	4 : 1	18	3.5	663
Alcohol carbonate salt composition 2 (AA2c）	1 : 1	18	4.0	626
					Alcohol carbonate salt composition 3 (AA2d）	0.25 : 1	18	5.0	675
Alcohol carbonate salt composition 4 (AA 2 e) (comparison)	0.25 : 1	18	7.5	989
					Alcohol carbonate salt composition 5 （AA2f）	1:1:0.1 (triisopropanolamine, ethanol isopropyl) Molar ratio of alcohol amine to diisopropanolamine	18	3.9	631

Along with CO ₂ The alcohol amine composition AC has a viscosity which increases rapidly with a content of more than 5%. When CO ₂ At lower levels (e.g., below 4 wt%), the level of triisopropanolamine primarily affects the viscosity of the alkanolamine carbonate composition AC, while when CO ₂ At a content of more than 5%, CO ₂ The content of (2) has a large influence on the viscosity of the alkanolamine carbonate composition AC.

Application examples

Example 1

1. Raw materials of white material component (190 kg): 55 kg polyether polyol 8038 (sorbitol initiator, hydroxyl value 380 mg KOH/g, available from Kagaku chemical Co., ltd.), 20 kg aromatic polyester polyol XCPA220-1 (hydroxyl value 220 mg KOH/g, available from Asahi Kagaku chemical Co., ltd.), 20 kg pentaerythritol-initiated polyoxypropylene polyol (TAE 305, hydroxyl value 300mg KOH/g, available from Shanghai high-bridge petrochemical Co., ltd.), 5 kg toluenediamine-initiated polyoxypropylene polyol, respectively, were weighed out Ether polyol YD401P (hydroxyl value 400 mgKOH/g, hebei Adam chemical Co., ltd.), 1 kg catalyst TMR-2 (air chemical Co., ltd.), 0.1 kg catalyst Dabco2040 (Yingzhang chemical Co., ltd.), 2 kg foam stabilizer DC3201 (gas and chemical Co., ltd.), 15 parts by weight of flame retardant TCPP (Jiangsu-Acer chemical Co., ltd.), and the alcohol amine carbonate composition 1 (AA 2 b) in the preparation example of 10 kg (wherein the molar ratio of triol amine A2 (triisopropanolamine) to diol amine A1 (ethanolic isopropanolamine) was 4:1, and CO ₂ Content 3.5 wt%).

2. The weighed polyether polyol 8038, aromatic polyester polyol XCPA220-1, polyether polyol TAE 305, toluenediamine starting polyether polyol 401P, catalysts TMR-2 and Dabco2040, foam stabilizer DC3201, flame retardant TCPP, and alcohol carbonate salt composition 1 (AA 2 b) were sequentially added to a reaction vessel, and stirred slowly (180 rpm) at room temperature for 1-2 hours to completely and uniformly mix them, thereby obtaining a uniform, transparent mixture (i.e., white material component).

3. The black material component was polymethylphenylpolyisocyanate (PM 200, wanhua chemistry) in an amount of 130, 130 kg.

4. The white and black components were sprayed onto an upstanding cementitious panel (substrate) at 30 ℃ by a solid rake (GRACO) coater a-25 at ambient temperature of 30 ℃. According to the thickness of 2-3cm of each layer of foam, the total thickness of the foam is 20cm, the spraying foaming is carried out in a spraying mode, and the phenomenon that wet foam falls off in the form of a sheet or block with a larger size is not observed in the spraying process. After foam formation and curing, polyurethane rigid foams were produced, and the performance parameters of the foam products produced are shown in Table 3. The cured foam was free from peeling of the foam from the substrate.

SEM photographs of the samples of the foam are shown in fig. 1. The cells of the foam are very fine, i.e. the size of the cells is small and the size of the cells is very uniform. The average diameter of the cells is 211 μm.

Example 2

Example 1 was repeated except that the same amount of the alkanolamine carbonate composition 2 (AA 2 c) of the preparation example (wherein triisopropanolamine A2 was used with ethanolThe molar ratio of isopropanolamine A1 is 1:1, CO ₂ Content 4.0. 4.0 wt%) instead of the alcohol carbonate salt composition 1 (AA 2 b), a polyurethane rigid foam was produced. SEM photographs of the foam are shown in fig. 2. The cell size is very uniform. The average diameter of the cells was 208 μm. Wherein, the phenomenon that wet foam falls off in the form of a sheet or block with larger size is not observed in the spraying process, and the phenomenon that the solidified foam is delaminated between adjacent foam layers is not observed.

Example 3

Example 1 was repeated except that the same amount of the alkanolamine carbonate composition 3 (AA 2 d) of the preparation example was used (wherein the molar ratio of triisopropanolamine A2 to ethanolisopanolamine A1 was 0.25:1, and CO ₂ 5.0. 5.0 wt%) instead of the alcohol carbonate salt composition 1 (AA 2 b), a polyurethane rigid foam was produced. SEM photographs of the foam are shown in fig. 3. The average diameter of the cells was 216 μm. Wherein, the phenomenon that wet foam falls off in the form of a sheet or block with larger size is not observed in the spraying process, and the phenomenon that the solidified foam is delaminated between adjacent foam layers is not observed.

Comparative example 1

Procedure example 1 was repeated except that the more reactive ethylenediamine starting polyether polyol YD403 was used in place of the toluenediamine starting polyether polyol YD401P, while the same amount of the alkanolamine salt composition 4 (AA 2 e) of the preparation example was used (wherein the molar ratio of triisopropanolamine A2 to ethanolisolamine A1 was 0.25:1, and CO ₂ Content 7.5. 7.5 wt%) instead of the alkanolamine carbonate composition 1 (AA 2 b).

1. Raw materials of white material component (190 kg): 55 kg polyether polyol 8038 (sorbitol initiator, hydroxyl value 380 mg KOH/g, available from Kagaku chemical Co., ltd.), 20 kg aromatic polyester polyol XCPA220-1 (hydroxyl value 220 mg KOH/g, available from Asahi Kagaku chemical Co., ltd.), 20 kg pentaerythritol-initiated polyoxypropylene polyol (TAE 305, hydroxyl value 300mg KOH/g, available from Shanghai high-bridge petrochemical Co., ltd.), 5 kg ethylenediamine-initiated polyether polyol YD403 (ethylenediamine initiator polyoxypropylene polyol, hydroxyl value 770.+ -.40 mg KOH/g, available from Hebei Adenode chemical Co., ltd.) were weighed separately) 1. 1 kg catalyst TMR-2 (air chemical Co., ltd.), 0.1. 0.1 kg catalyst Dabco2040 (Yingchang chemical Co., ltd.), 2. 2 kg foam stabilizer DC3201 (gas and chemical Co., ltd.), 15 parts by weight of flame retardant TCPP (Jiangsu-Jack chemical Co., ltd.), 10 kg preparation example of the alcohol amine carbonate composition 4 (AA 2 e) (wherein the molar ratio of triisopropanolamine A2 to ethanolisolamine A1 was 0.25:1, and CO ₂ Content 7.5 wt%).

2. The weighed polyether polyol 8038, aromatic polyester polyol XCPA220-1, polyether polyol TAE 305, ethylenediamine starting polyether polyol YD403, catalysts TMR-2 and Dabco2040, foam stabilizer DC3201, flame retardant TCPP, and alcohol carbonate salt composition 4 (AA 2 e) were added in this order to a reaction vessel, and stirred slowly (180 rpm) at room temperature for 1-2 hours to thoroughly and uniformly mix them, thereby obtaining a uniform, transparent mixture (i.e., white material component).

4. The white and black components were sprayed onto an upstanding cementitious panel (substrate) at 30 ℃ by a solid rake (GRACO) coater a-25 at ambient temperature of 30 ℃. Spraying and foaming according to the thickness of 2-3cm of each layer of foam, wherein the total thickness of the foam is 20cm, and observing the phenomenon that wet foam falls off in the form of blocks with larger size in the spraying process. After foam formation and curing, polyurethane rigid foams were produced, and the performance parameters of the foam products produced are shown in Table 3. SEM photographs of the samples of the foam are shown in fig. 4.

The cured polyurethane foam on the cement board (substrate) was cut with a power saw and the cross section was observed to find delamination between adjacent two foam layers to form a crack, as shown in fig. 5.

The results of comparative example 1 show that when a more reactive polyether polyol (e.g., ethylenediamine-initiated polyether polyol) is used and a higher CO is present ₂ At the content of the alkanolamine carbonate composition, the phenomenon that the wet foam falls off in the form of a large-sized lump was observed during spraying, and for the cured foam, delamination was found between adjacent foam layersAs shown by reference numerals 1 and 2 in fig. 5).

Example 4

Example 1 was repeated except that the same amount of the alkanolamine carbonate composition 5 (AA 2 f) of the preparation example was used (wherein the molar ratio of triisopropanolamine, ethanolisopanolamine and diisopropanolamine was 1:1:0.1, CO ₂ 3.9. 3.9 wt%) instead of the alcohol carbonate salt composition 1 (AA 2 b), a polyurethane rigid foam was produced. SEM photographs of the foam are shown in fig. 6. The cell size is relatively uniform. Wherein, the phenomenon that wet foam falls off in the form of a sheet or block with larger size is not observed in the spraying process, and the phenomenon that the solidified foam is delaminated between adjacent foam layers is not observed.

TABLE 3 foam performance parameters

Examples	Wet foam drop during spraying	Foam cracking	Whether or not the cell size is uniform	Average cell diameter [ mu ] m	Density kg/m ³	Compressive strength KPa	Coefficient of thermal conductivity (w/m.k, 22.5 ℃ C.)	Closed porosity, percent
									Ex.1	Without any means for	Without any means for	Very uniform	211	44.5	332	0.02201	95.8
Ex.2	Without any means for	Without any means for	Very uniform	208	43.8	315	0.02187	95.3
									Ex.3	Without any means for	Without any means for	Very uniform	216	41.3	303	0.02206	94.9
Comparative example 1	Has the following components	Has the following components	Slightly uniform	236	40.2	295	0.02224	88.7
									Ex.4	Without any means for	Without any means for	Uniformity of	218	44.1	306	0.02209	94.5

Note that: compressive strength is measured in the Z direction (direction perpendicular to the substrate) for a foam specimen, and "crack" refers to the cracking of a cured foam from a substrate to form a crack or between two adjacent foam layers to form a crack. By "slightly uniform" is meant that the cell size is moderately uniform.

As can be seen from Table 3 above, the present invention has a suitable CO ₂ The alcohol Amine Composition (AC) is used as a chemical foaming agent in combination with a specific polymer polyol composition, so that wet foam does not fall off during spraying, and the prepared polyurethane rigid foam material has excellent overall performance and excellent heat insulation performance.

Claims

1. A polymer polyol composition for use in the preparation of polyurethane rigid foams comprising:

(I) 100 parts by weight of a polymer polyol comprising: 1) 45-65wt% of a sorbitol-initiated polyether polyol having a hydroxyl value in the range of 340-520 mgKOH/g; 2) 15-25wt% of an aromatic polyester polyol having a hydroxyl value in the range of 210-550 mgKOH/g; 3) 15-25wt% of a pentaerythritol starting polyether polyol having a hydroxyl number in the range of 290-500 mgKOH/g; 4) 3-7. 7 wt% of a toluenediamine starting polyether polyol having a hydroxyl value in the range of 350-580 mgKOH/g; wherein the weight percentages are based on the total amount of components 1) to 4);

(II) 3.5-20 parts by weight of an auxiliary agent comprising a catalyst, a foam stabilizer and optionally a flame retardant;

(III) 6-20 parts by weight of a CO-containing component as a foaming agent ₂ And an aqueous alcohol Amine Composition (AC);

the alcohol Amine Composition (AC) comprises or consists of the following components:

(1) Ethanol isopropanolamine (A1);

(2) Triisopropanolamine (A2); and

(3) Water;

wherein the molar ratio of triisopropanolamine (A2) to ethanolisopanolamine (A1) is (0.2-6): 1;

wherein the water content is 5-38wt%, based on the total weight of the alcohol Amine Composition (AC);

(A1) The total content of + (A2) +water is 90-100wt%, based on the total weight of the alcohol Amine Composition (AC);

at an ambient temperature of 25 ℃, contains CO ₂ And the aqueous alcohol Amine Composition (AC) is in the form of a homogeneous liquid having 250 to 900 centipoise;

wherein a portion of the alcohol amine in the alcohol Amine Composition (AC) is replaced with CO ₂ Neutralization to give CO in the alcohol Amine Composition (AC) ₂ Is 1-5 wt% based on the total weight of the alcohol Amine Composition (AC).

2. The polymer polyol composition of claim 1, wherein:

the polymer polyol includes: 1) 50-60wt% of a sorbitol-initiated polyether polyol having a hydroxyl value in the range of 340-520 mgKOH/g; 2) 17-23wt% of an aromatic polyester polyol having a hydroxyl value in the range of 210-550 mgKOH/g; 3) 17-23wt% of a pentaerythritol starting polyether polyol having a hydroxyl number in the range of 290-500 mgKOH/g; 4) 4-6wt% of a toluenediamine-initiated polyether polyol having a hydroxyl number in the range of 350-580 mgKOH/g; wherein the weight percentages are based on the total amount of components 1) to 4); and/or

(II) the auxiliary agent comprises 0.5-2.5 parts by weight of catalyst, 1-4 parts by weight of foam stabilizer and 0-18 parts by weight of flame retardant,

the sum of the three is 3.5 to 20 parts by weight based on 100 parts by weight of the polymer polyol; and/or

In the alcohol Amine Composition (AC), the water content is 7 to 35wt%; and/or

Part of the alcohol amine in the alcohol Amine Composition (AC) is replaced by CO ₂ Neutralization to give CO in the alcohol Amine Composition (AC) ₂ The content of (2) is 1.2-5.0 wt%; and/or

The aromatic polyester polyol is polyethylene phthalate glycol, polyethylene phthalate glycol and/or polyethylene phthalate/diethylene glycol; and/or

(A1) The total content of + (A2) +water is 92-100 wt.%, based on the total weight of the alcohol Amine Composition (AC).

3. The polymer polyol composition according to claim 1 or 2, wherein:

1) The hydroxyl number of the sorbitol-initiated polyether polyol is in the range of 350-490 mgKOH/g; 2) The hydroxyl value of the aromatic polyester polyol is in the range of 220 to 500 mgKOH/g; 3) The hydroxyl value of the pentaerythritol initial polyether polyol is in the range of 300-470 mgKOH/g; 4) The hydroxyl value of the toluenediamine starting polyether polyol is in the range of 360-550 mgKOH/g; and/or

(II) the auxiliary agent comprises 1-2 parts by weight of catalyst, 1.5-3 parts by weight of foam stabilizer and 0-15 parts by weight of flame retardant, wherein the sum of the weight of the catalyst, the foam stabilizer and the flame retardant is 3.5-20 parts by weight; and/or

In the alcohol Amine Composition (AC), the water content is 8 to 33wt%; and/or

Part of the alcohol amine in the alcohol Amine Composition (AC) is replaced by CO ₂ Neutralization to give CO in the alcohol Amine Composition (AC) ₂ The content of (2) is 1.5-5.0 wt%; and/or

CO-containing as a blowing agent ₂ And the aqueous alcohol Amine Composition (AC) is used in an amount of 7 to 18 parts by weight based on 100 parts by weight of the polymer polyol; and/or

The molar ratio of triisopropanolamine (A2) to ethanolisopanolamine (A1) is (0.25-5.5): 1; and/or

(A1) The total content of + (A2) +water is 94-100 wt.%, based on the total weight of the alcohol Amine Composition (AC).

4. The polymer polyol composition of claim 3, wherein:

in the alcohol Amine Composition (AC), the water content is 10 to 30 wt%; and/or

Part of the alcohol amine in the alcohol Amine Composition (AC) is replaced by CO ₂ Neutralization to give CO in the alcohol Amine Composition (AC) ₂ The content of (2) is 1.8-5.0 wt%; and/or

CO-containing as a blowing agent ₂ And the aqueous alcohol Amine Composition (AC) is used in an amount of 8 to 16 parts by weight; and/or

The mole ratio of triisopropanolamine (A2) to ethanolisopanolamine (A1) is (0.3-5): 1; and/or

(A1) The total content of + (A2) +water is 95-100 wt.%, based on the total weight of the alcohol Amine Composition (AC).

5. The polymer polyol composition of claim 4, wherein:

in the alcohol Amine Composition (AC), the water content is 12-28 wt%; and/or

Part of the alcohol amine in the alcohol Amine Composition (AC) is replaced by CO ₂ Neutralization to give CO in the alcohol Amine Composition (AC) ₂ The content of (2.0-5.0) wt%; and/or

CO-containing as a blowing agent ₂ And the aqueous alcohol Amine Composition (AC) is used in an amount of 9 to 14 parts by weight; and/or

The molar ratio of triisopropanolamine (A2) to ethanolisopanolamine (A1) is (0.4-4.5): 1; and/or

(A1) The total content of + (A2) +water is 96-100 wt.%, based on the total weight of the alcohol Amine Composition (AC).

6. The polymer polyol composition of claim 5, wherein:

in the alcohol Amine Composition (AC), the water content is 15-25 wt%; and/or

Part of the alcohol amine in the alcohol Amine Composition (AC) is replaced by CO ₂ Neutralization to give CO in the alcohol Amine Composition (AC) ₂ The content of (2.5-5.0) wt%; and/or

The mole ratio of triisopropanolamine (A2) to ethanolisopanolamine (A1) is (0.5-4): 1; and/or

(A1) The total content of + (A2) +water is 97-100 wt.%, based on the total weight of the alcohol Amine Composition (AC).

7. The polymer polyol composition of claim 6, wherein:

The molar ratio of triisopropanolamine (A2) to ethanolisopanolamine (A1) is (0.6-3.8): 1.

8. The polymer polyol composition of claim 7, wherein:

the molar ratio of triisopropanolamine (A2) to ethanolisopanolamine (A1) is (0.7-3.7): 1.

9. The polymer polyol composition of claim 8, wherein:

the molar ratio of triisopropanolamine (A2) to ethanolisopanolamine (A1) is (0.8-3.6): 1.

10. Use of the polymer polyol composition according to any of claims 1-9 for the preparation of spray-on rigid polyurethane foams by reaction with polyisocyanates.