Liquid foaming mixture containing polyester polyol and carbon dioxide adduct

Abstract

The invention discloses a liquid foaming mixture, which consists of a CO2 adduct, a solvent and a macromolecular polyol, and the mass percentages of the three are as follows: 1-60% of the CO2 adduct, 1-97% of the solvent and 2-98% of the macromolecular polyol; the CO2 adduct consists of a grafted modified polyamine polymer and CO2, and the CO2 and the main chain of the polyamine polymer exist in the form of an adduct; the polyamine polymer is a polymer containing 4 or more amino groups in the molecular chain, and the molecular weight is greater than 140; the solvent is composed of alcohol, amine and / or alcoholamine with a carbon number of ≤8 and a total of hydroxyl and amino groups of 2-5; the macromolecular polyol refers to a polyester polyol containing an ester group in the main chain structure and a functionality of not less than 2 and / or a polycarbonate polyol containing a carbonate group in the main chain structure and a functionality of not less than 2.

Description

Technical Field

[0001] The invention relates to the technical field of foaming agents, in particular to a polymer solution foaming mixture capable of releasing carbon dioxide (CO2), and particularly to a polyurethane foaming mixture for a polyester system. Background Art

[0002] Polyurethane foam is widely used in sofas, mattresses, car seat cushions, refrigerators, pipes and building insulation. Generally speaking, the production of polyurethane foam often requires a large amount of foaming agents. Traditional foaming agents are low-boiling chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC) compounds, which contain chlorine atoms in their structure and will destroy the ozone layer. The foaming agents currently used include hydrofluorocarbon (HFC) compounds and fluorinated olefin (HFO) compounds that do not contain chlorine and do not destroy the ozone layer. However, the former has a strong greenhouse effect and is one of the culprits of global warming. The latter's decomposition products in the atmosphere contain trifluoroacetic acid (CF3COOH) and hydrofluoric acid (HF), which may cause acid pollution and damage the ecological environment. Common foaming agents also include alkane foaming agents (such as cyclopentane). The performance of this type of foaming agent is similar to that of HFO. Although it has a smaller impact on the environment, it has the risk of being flammable and explosive.

[0003] An adduct is formed by the reaction of a polyamine polymer and CO2, and the adduct can release CO2 when heated for polyurethane foaming. The advantage of this foaming agent is that CO2 can be fixed in the polyamine polymer at room temperature and can be mixed with polyurethane raw materials, overcoming the disadvantage that gaseous CO2 is difficult to store in the foaming raw materials. During the polyurethane foaming process, the foaming agent absorbs the heat of reaction and releases CO2 for foaming. This type of foaming agent is solid and difficult to disperse in the polyurethane raw materials. Chinese patent CN 103965470 A discloses a CO2 adduct foaming agent of hydrophobically modified polyethyleneimine, and the hydrophobic chain used is a polypropylene glycol chain or an alkyl chain. The hydrophobic modification improves the dispersibility of the foaming agent in the polyurethane raw materials to a certain extent. Chinese patent CN 112457520A uses a mixture of hydrophobically modified polyethyleneimine and polyether polyol, and then absorbs CO2 to generate a CO2 adduct foaming agent of hydrophobically modified polyethyleneimine in situ, and the foaming agent is present in the polyether polyol in the form of nanoparticles. This method greatly improves the dispersibility of the foaming agent, but also increases the viscosity of the foaming mixture, causing inconvenience in use; excessively high viscosity may hinder the growth of bubbles and even cause bubble rupture, leading to foaming failure.

[0004] In fact, traditional polyurethane foaming agents are all liquid, which can be easily mixed with other liquid raw materials for foaming. Existing CO2 adduct foaming agents are all solid, which is very inconvenient to use. The development of liquid CO2 adduct foaming agents can not only retain the environmentally friendly characteristics of CO2 adduct foaming agents, but also increase the convenience of construction.

[0005] At the same time, in the actual polyurethane foaming process, the raw materials other than isocyanate are usually formulated into a component, called white material, including macromolecular polyols, catalysts, foaming agents, and foaming agents. According to the requirements of the formula, flame retardants and some fillers and other additives may also be contained; isocyanate is a separate component, called black material. During the foaming process, the black and white materials are mixed through a mixing head and can be directly injected into the mold (molded foaming), or sprayed onto the substrate (spray foaming), or injected into an open container (box foaming) to complete the preparation of the foam material. In many cases, the ingredients and spraying are carried out in different places or even different companies. It is usually required that the white material has a certain storage time (usually 6 months). After the solid CO2 adduct foaming agent is dispersed in the white material, it is also easy to agglomerate, which is not conducive to the long-term storage of the white material. Summary of the invention

[0006] The inventors of the present invention have actively sought for solvents for the existing CO2 adduct foaming agents of polyamine polymers, which are inconvenient to use, in the hope of developing a liquid CO2 adduct foaming agent system. The foaming agent is a CO2 adduct, which contains zwitterions (hydrophilic structures) composed of alkylammonium cations and carbamate anions in its molecular structure, and it is difficult for general organic solvents to dissolve the foaming agent. Water can dissolve the CO2 adduct of polyamine polymers. However, water itself is also a foaming agent for polyurethane. Introducing too much water will cause a large number of urea bonds to be generated in the generated polymer structure, and the foam will become brittle. At the same time, the coexistence of water and the CO2 adduct foaming agent of polyamine polymers in a system will bring constraints to the foam formula design. For example, in order to obtain low-density foam, it is necessary to increase the amount of foaming agent; if there is water in the foaming agent, the amount of water will inevitably be increased, and the increase in water will increase the amount of isocyanate, making the foam brittle. In other words, it is difficult to prepare low-density and soft foam. In addition, in general, CO2 adduct foaming agents of polyamine polymers need to be hydrophobically modified (in order to improve the dispersibility of the foaming agent in the polyurethane raw material; at the same time, grafting modification will increase steric hindrance to avoid excessive reaction between the free amino groups formed after the polyamine polymer releases CO2 and isocyanate, which will lead to excessive cross-linking density of the foam and also cause the foam to become brittle). After hydrophobic modification, the solubility in water will decrease a lot. Therefore, it is not appropriate to use water alone as a solvent for CO2 adduct foaming agents of polyamine polymers.

[0007] The inventors carefully studied the molecular structure of the CO2 adduct of polyamine polymers and found that the alkyl ammonium cations and carbamate anions contained in the structure can form hydrogen bonds, so they actively explored the feasibility of using compounds containing hydroxyl and amino groups as solvents for the CO2 adduct of polyamine polymers. After a lot of exploration, it was found that alcohols, amines and / or alcoholamines with a carbon number of ≤8 and a total of hydroxyl and amino groups of 2 to 5 can dissolve the CO2 adduct of polyamine polymers. At the same time, the alcohols, amines and / or alcoholamines can also react with isocyanates, one of the raw materials of polyurethane, to become part of the polyurethane foam product. Therefore, the alcohols, amines and / or alcoholamines dissolve the CO2 adduct foaming agent of polyamine polymers (i.e., the CO2 adduct foaming agent of polyamine polymers) on the one hand, so that the foaming agent can be fully mixed with the liquid polyurethane raw material and play the role of a foaming agent in the foam preparation process; at the same time, the alcohols, amines and / or alcoholamines can also react with isocyanates to play the role of a chain extender and eventually become part of the foam material.

[0008] At the same time, when the inventors used a liquid foaming agent composed of a CO2 adduct of a polyamine polymer and a solvent, they found that the liquid foaming agent could form a uniform mixture in a polyester polyol (and / or polycarbonate) and could maintain a transparent homogeneous liquid state for a long time, thereby obtaining a long-term stable liquid polyester (polycarbonate) foaming system containing a CO2 adduct, which laid the foundation for the preparation of polyester and polycarbonate white material foaming systems containing a CO2 adduct.

[0009] One of the purposes of the present invention is to provide a liquid foaming mixture, characterized in that the foaming mixture is at least composed of a CO2 adduct, a solvent and a macromolecular polyol, and the mass percentages of the three are as follows: 1 to 60% of CO2 adduct, 1 to 97% of solvent, and 2 to 98% of macromolecular polyol, and the mass ratio of the CO2 adduct to the solvent does not exceed 70:30; the CO2 adduct is composed of a polyamine polymer and CO2, and CO2 and the polyamine polymer exist in the form of an adduct; or the CO2 adduct is composed of a grafted modified polyamine polymer and CO2, and CO2 and the main chain of the polyamine polymer exist in the form of an adduct; the polyamine polymer is a polymer containing 4 or more amine groups in the molecular chain, the atoms connected to the amine groups are carbon atoms, and its structure is at least one of straight chain, branched, and hyperbranched, and the molecular weight is greater than 140; the solvent is carbon The invention relates to an alcohol, amine and / or alcoholamine having an atomic number ≤8 and a total of 2 to 5 hydroxyl and amino groups; and the solvent is a reactive solvent, that is, the solvent can dissolve the CO2 adduct and react chemically with other substances in the foaming system to become a part of the foam; the macromolecular polyol refers to a polyester polyol containing an ester group in the main chain structure and a functionality of not less than 2 and / or a polycarbonate polyol containing a carbonate group in the main chain structure and a functionality of not less than 2; the polyester polyol includes but is not limited to polybutylene adipate, polyethylene adipate, polybutylene adipate glycol, polycaprolactone, polyhydroxybutylate, polyhydroxypentylate, polylactic acid, polyglycolic acid, and polylactic acid glycolic acid copolyester; the polycarbonate polyol includes but is not limited to polyhexamethylene carbonate diol, polyhexanediol pentanediol carbonate, and polybutylene carbonate hexanediol.

[0010] The liquid foaming mixture is actually in the homogeneous region of the ternary phase diagram of the CO2 adduct, the solvent and the macromolecular polyol. The mixture is a thermodynamically stable homogeneous substance and can exist for a long time. In actual use, other components of the foam formula, such as catalysts, foam leveling agents (usually these substances are also liquid and used in very small amounts), etc., can be mixed with the liquid foaming mixture to form a white material as needed, which can also exist stably for a long time.

[0011] In the actual white material system, polymer polyol is the main component. For the present invention, the white material system with a higher content of polyester or polycarbonate is more practical. Therefore, for the liquid foaming mixture provided by the present invention, the following component ratio is more practical, that is, the mass percentage of the CO2 adduct, solvent and macromolecular polyol is: CO2 adduct 1-25%, solvent 5-40%, macromolecular polyol 60-90%, and the mass ratio of CO2 adduct to solvent does not exceed 70:30.

[0012] The polyamine polymer includes but is not limited to at least one of polyethyleneimine, polypropyleneimine, polybutyleneimine, polyethyleneamine, and polyallylamine; the graft-modified polyamine polymer may be grafted with at least one of the following side chains:

[0013] (1) The side chain is polyethylene glycol, polypropylene oxide, polyoxybutylene or polytetrahydrofuran, and the degree of polymerization is at least 1;

[0014] (2) The side chain contains a hydrocarbon group having 1 to 22 carbon atoms.

[0015] Specifically, the grafted side chain can be a polyether oligomer such as polyethylene glycol, polypropylene oxide, polyoxybutylene and polytetrahydrofuran, containing at least one repeating unit, and the structure is exemplified as follows:

[0016]

[0017] Wherein m is at least 1, n is a positive integer from 1 to 4, and Q is a linking group between the grafted side chain and the main chain of the polyamine polymer. The linking group Q is a replaceable group, and the groups that can be selected are:

[0018]

[0019] The grafted side chain of the grafted polyamine polymer may also contain a hydrocarbon group with 1 to 22 carbon atoms and at least one unsaturated bond, and its structure is exemplified as follows:

[0020] C n H 2n-1 -M-,

[0021] Wherein n is an integer from 1 to 22, and M is a linking group between the hydrophobic side chain and the main chain of the polyamine polymer. The linking group M is a replaceable group. The linking group M is a replaceable group, and M can be directly a covalent bond or an amide bond, and can also be selected from the following groups:

[0022]

[0023] It should be pointed out that the linking groups Q and M between the above-mentioned grafted side chains and the main chain of the polyamine polymer are all replaceable groups, and those skilled in the art can also select other groups for replacement, which are not listed here one by one.

[0024] As for the specific preparation method of the above-mentioned grafted polyamine polymer, the glycidyl ether with grafted side chains and the polyamine polymer can be reacted in an ethanol solution to obtain a grafted modified polyamine polymer. The structure of the glycidyl ether with a hydrophobic chain is:

[0025] Wherein m is at least 1, n is a positive integer from 1 to 4, and the connecting group between the side chain and the main chain of the grafted polyamine polymer prepared by this method is Q1.

[0026] The grafted polyamine polymer can also be prepared by the following method: first, the alkoxy polyether oligomer is reacted with iodoacetic acid and 2-bromoisocyanate to obtain a halogenated hydrocarbon-terminated product, and the reaction is as follows (wherein m is at least 1, and n is a positive integer from 1 to 4):

[0027]

[0028]

[0029] The above reaction is based on an alkoxy polypropylene glycol oligomer as an example, wherein the repeating units may also be repeating units of polyethylene glycol, polyoxetane and polytetrahydrofuran.

[0030] Secondly, the above-mentioned halogenated hydrocarbon end-capping product is reacted with a polyamine polymer to remove the hydrogen halide to obtain N-substituted hydrophobic modified polyethyleneimine (the connecting group between the side chain and the main chain is Q2 or Q3).

[0031] The grafted polyamine polymer can also be prepared by reacting a bromide or iodide of an alkane with a polyamine polymer. The structure of the bromide or iodide can be:

[0032] C n H 2n+1 -Br, or C n H 2n+1 -I,

[0033] wherein n is an integer from 1 to 22. The linking group between the side chain and the main chain of the grafted polyamine polymer prepared by this method is a covalent bond.

[0034] The grafted polyamine polymer can also be prepared by reacting a saturated carboxylic acid or an unsaturated carboxylic acid with a polyamine polymer. The structure of the carboxylic acid can be:

[0035] R-COOH,

[0036] Wherein R is a hydrocarbon group having carbon atoms of 1 to 22. The connecting group between the side chain and the main chain of the grafted polyamine polymer prepared by this method is an amide bond.

[0037] All these reactions are known chemical reactions, and their specific preparation methods can refer to existing disclosed technologies, such as patent document CN 108355472 A.

[0038] In addition, in the preparation method of the grafted polyamine polymer provided by the present invention, the grafting degree of the grafted polyamine polymer is 1 to 45 mol% based on the N atoms of the polyamine polymer. Preferably, the grafting degree of the grafted polyamine polymer is 3 to 20 mol% based on the N atoms of the polyamine polymer. Generally, the greater the grafting degree of the grafted polyamine polymer, the more conducive it is to dissolve in the solvent. However, if the grafting rate is too large, the number of amino groups of the grafted polyamine polymer that react with CO2 will decrease, and the CO2 content in the grafted polyamine polymer CO2 adduct will decrease, thereby reducing the foaming ability.

[0039] Specifically, the solvent of the liquid foaming mixture of the present invention is at least one of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butylene glycol, pentanediol, glycerol, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, diethylene glycol, and diglycolamine; the butylene glycol is 1,4-butylene glycol or any isomer of 1,4-butylene glycol containing two hydroxyl groups, and the pentanediol is 1,5-pentanediol or any isomer of 1,5-pentanediol containing two hydroxyl groups. Among them, ethylene glycol, ethanolamine, diethanolamine and triethanolamine have good solubility. Ethylene glycol is relatively cheap and is often used as the preferred solvent.

[0040] When ethylene glycol is mixed with other small molecules containing hydroxyl groups and / or amino groups, it can also have a good dissolving effect. The other small molecules containing hydroxyl groups and / or amino groups are at least one of 1,2-propylene glycol, 1,3-propylene glycol, glycerol, butanediol, pentanediol, hexanediol, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, butanediamine, diethylene glycol, diglycolamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; the butanediol, pentanediol, and hexanediol are any isomers containing two hydroxyl groups of the corresponding diols; the butanediamine is any isomer containing two amino groups of 1,4-butanediamine or 1,4-butanediamine. When ethylene glycol is mixed with other small molecules containing hydroxyl groups and / or amino groups, the mass percentage of ethylene glycol is preferably not less than 50%.

[0041] It should be noted that the liquid foaming mixture of the present invention may also contain water, and the amount of water used does not exceed 40% of the mass of the solvent in the liquid foaming agent containing CO2 adduct. Water itself is also a chemical foaming agent for polyurethane materials, and water also has a certain dissolving effect. However, if the amount of water used is too large, it will be unfavorable for the dissolution of the CO2 adduct of the polyamine polymer grafted with hydrophobic links; at the same time, too much water will also cause the prepared foam to become brittle.

[0042] Another object of the present invention is to provide the use of the liquid foaming mixture for preparing polyurethane foam. Because the liquid foaming mixture contains polyester polycarbonate polyol, the liquid foaming mixture of the present invention is particularly suitable for making polyester-type and polycarbonate-type polyurethane foams. Of course, the liquid foaming mixture provided by the present invention can also be used as a raw material for polyether, polyester and / or polycarbonate polyurethane foam systems. Because the liquid foaming mixture provided by the present invention is a thermodynamically stable homogeneous system with long-term stability, it is particularly suitable for preparing polyester-type white materials or polycarbonate-type white materials.

[0043] Compared with the prior art, the present invention has the following positive effects:

[0044] 1. The liquid foaming mixture provided by the present invention is composed of a CO2 adduct of a polyamine polymer, a solvent and a polyester (polycarbonate) polyol, which solves the problem that the solid CO2 adduct of the polyamine polymer is difficult to disperse in the polyurethane raw material, and facilitates the application of the CO2 adduct of the polyamine polymer as an environmentally friendly foaming agent in polyurethane foam.

[0045] 2. The liquid foaming mixture provided by the present invention is a homogeneous system composed of CO2 adducts of polyamine polymers, solvents and polyester (polycarbonate) polyols, has long-term storage stability, and is particularly suitable for preparing white materials for polyester and polycarbonate polyurethane foams.

[0046] 3. The solvent of the liquid foaming mixture provided by the present invention contains hydroxyl and / or amino groups in its molecular structure, which can react with isocyanate to become a part of the foam structure, thereby preventing the solvent from becoming a volatile substance to pollute the environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Attached Figure 1 The chemical structural formula of the side chain raw material used in preparing the grafted polyamine polymer in Examples (1) to (21) of the preparation of the grafted polyamine polymer.

[0048] Attached Figure 2 Examples 2 (10% C4-PEI-CO2), 4 (10% C8-PEI-CO2), 11 (10% C 12 -PEI-CO2) used in the ternary phase diagram of CO2 adduct, solvent and macromolecular polyol. PEA is poly (ethylene glycol adipate) ester, in which the chain segment molar ratio of ethylene glycol and diethylene glycol is 1:1, the molecular weight is 1500, the functionality is 2, and the hydroxyl value is 76.2 mgKOH / g; EG is the solvent ethylene glycol. The straight line composed of dotted points in the figure is that the composition ratio of CO2 adduct and solvent is 70:30; the composition ratio of CO2 adduct and solvent in the area below the dotted straight line is less than 70:30. * is the three-composition used in Examples 2, 4, and 11 (located in the homogeneous region).

[0049] Attached Figure 3 The ternary phase diagram of CO2 adduct, solvent and macromolecular polyol used in Examples 1 (5% C8-PEI-CO2), 4 (10% C8-PEI-CO2) and 12 (15% C8-PEI-CO2). PEA is poly(ethylene glycol adipate) ester, in which the chain segment molar ratio of ethylene glycol and diethylene glycol is 1:1, the molecular weight is 1500, the functionality is 2, and the hydroxyl value is 76.2 mgKOH / g; EG is the solvent ethylene glycol. The straight line composed of dotted points in the figure indicates that the composition ratio of CO2 adduct and solvent is 70:30; the composition ratio of CO2 adduct and solvent in the area below the dotted straight line is less than 70:30. * is the three-component composition used in Examples 4 and 12 (located in the homogeneous region). The three-component ratio indicated by "+" corresponds to the composition of Example 1. DETAILED DESCRIPTION

[0050] In order to make the purpose, technical scheme and technical effect of the present invention clearer, the present invention is further described in detail below in conjunction with specific embodiments. It should be noted that all these embodiments are for further illustrating the present invention and shall not be construed as limiting the present invention. Some non-essential improvements and adjustments made by those skilled in the art to the present invention according to the above-mentioned content of the present invention still belong to the protection scope of the present invention.

[0051] Preparation Example of Grafted Polyamine Polymer

[0052] Before describing the specific embodiments, the preparation of the grafted polyamine polymer of the present invention is first described. The polyamine polymer of the present invention is a polymer containing amino groups in the molecular structure, including but not limited to polyethyleneimine (PEI), polypropyleneimine (PPI), polybutyleneimine (PBI), and its molecular structure is respectively 2, 3, 4 methylene groups between amino groups, and of course polyamine polymers with 5 or 6 methylene groups are also possible (these polyalkyleneamines can have linear, branched and hyperbranched structural changes), but the more methylene groups there are, the less amino group content that absorbs CO2, and the foaming ability of the foaming agent per unit mass is reduced. In addition, polyamine polymers containing primary amine groups such as polyethyleneamine (PEA) and polyallylamine (PAA) can also be used. Its structure is shown below:

[0053]

[0054] The polyamine polymer of the present invention may be grafted with side chains to increase the dispersibility of its CO2 adduct in the polyurethane raw material, and the side chains include but are not limited to at least one of the following:

[0055] (1) The side chain is polyethylene glycol, polypropylene oxide, polyoxybutylene or polytetrahydrofuran, and the degree of polymerization is at least 1;

[0056] (2) The side chain contains a hydrocarbon group having 1 to 22 carbon atoms;

[0057] The grafting degree of the grafted side chains can be varied as required, and can be varied between 1% and 45%.

[0058] Specifically, the structure of the synthesized grafted modified polyamine polymer is shown in Table 1. The theoretical grafting degree is calculated by the molar ratio of the amino groups grafted with side chains to all the amino groups on the main chain, and the actual grafting degree is calculated by the area ratio of the proton signals related to the side chains and the main chain in the nuclear magnetic resonance spectrum. It should be noted that the sample code in the table is composed of the codes of the side chain and the polyamine polymer, such as 5% C8-PEI, wherein 5% C8 means that the side chain is an alkyl chain containing 8 carbon atoms, 5% means the designed grafting degree of the side chain (i.e., the theoretical grafting degree), PEI means that the polyamine polymer is polyethyleneimine, and the source of the side chain is C8-EPO, and its structure is shown in Figure 1 The codes of other samples have similar meanings. Some samples have two grafted side chains, and the theoretical grafting degree and side chain code of each side chain are listed separately. The sources of all side chains are listed in Figure 1 The code names of polyamine polymers are: PEI polyethylene imine, PPI polypropylene imine, PBI polybutylene imine, PEA polyethylene amine, PAA polyallyl amine. Except for PEA and PAA, the other polyamine polymers have linear, branched or hyperbranched structural variations.

[0059] Table 1

[0060]

[0061]

[0062] The process conditions and steps of the preparation examples (1) to (16), (20) and (21) of the grafted polyamine polymer are as follows: the corresponding polyamine polymer is added to a reaction kettle, and ethanol is added to the reaction kettle to make the mass concentration of the polyamine polymer about 10%, the polyamine polymer is completely dissolved under stirring, and then the corresponding glycidyl ether compound (Table 1, side chain raw material) is added to make the theoretical grafting degree of the side chain conform to the value listed in Table 1, the reaction is stirred at 50°C for 15 hours, and then the ethanol is removed by rotary evaporation; first, 10 parts by volume of petroleum ether is added to the product after rotary evaporation to dissolve the product and unreacted glycidyl ether compounds, and then 1 / 3 of the volume of petroleum ether is added to distilled water to precipitate the grafted modified polyamine polymer; the precipitated polyamine polymer is then washed with petroleum ether for at least three times, and then the petroleum ether is removed by rotary evaporation and dried to constant weight to obtain the product.

[0063] The process conditions and steps of the preparation of the graft modified polyamine polymer raw material (17) are as follows: 1 mol of polyethyleneimine measured by the repeating unit of polyethyleneimine is dissolved in chloroform to a mass concentration of about 10%, and then 0.03 mol of C 17 H 33 -COOH( Figure 1 ) and N,N'-carbonyldiimidazole (CDI), the theoretical grafting rate is 3%. Then the reaction is stirred under reflux for 12 hours, extracted with saturated brine three times, the chloroform layer is taken, the solvent is removed by rotary evaporation at 50°C, and finally dried in an oven at 75°C to obtain a purified hydrophobic link grafted polyethyleneimine product 3% C 17 H 33 -PEI.

[0064] The process conditions and steps of the preparation example (18) of the graft modified polyamine polymer raw material are as follows: 1 mol of polyethyleneimine measured by the repeating unit of polyethyleneimine is dissolved in chloroform to a mass concentration of about 10%, and then 0.2 mol of C2H5-I( Figure 1 ), reflux for 3 hours, cool to room temperature, extract the reaction mixture three times with a 5% sodium hydroxide aqueous solution with an equal volume to chloroform, remove the water layer, wash with water until the pH value of the water layer is neutral, dry the organic layer with anhydrous sodium sulfate, and remove the solvent by vacuum rotary evaporation at 40°C to obtain the corresponding hydrophobic chain-modified polyethyleneimine 20% C2H5-PEI.

[0065] The process conditions and steps of the preparation example (19) of the grafted polyamine polymer raw material are as follows: 1 mol of polyethyleneimine measured on the basis of the repeating unit of polyethyleneimine is dissolved in chloroform to a mass concentration of about 10%, and then 0.45 mol of C4-Br (Table 1) is added, and the mixture is refluxed for 6 hours, cooled to room temperature, and the reaction mixture is extracted three times with a 5% aqueous sodium hydroxide solution having an equal volume to that of chloroform.

[0066] The aqueous layer was removed and washed with water until the pH value of the aqueous layer was neutral. The organic layer was dried with anhydrous sodium sulfate and the solvent was removed by vacuum rotary evaporation at 40° C. to obtain the corresponding hydrophobic chain-modified polyethyleneimine 45% C4-PEI.

[0067] It can be seen from Table 1 that the actual grafting degree of each product is very close to the theoretical grafting degree, indicating that the grafting reaction is very complete. The theoretical grafting degree is calculated by the ratio of the molar number of the side chain to the molar number of the main chain nitrogen atoms, and the actual grafting degree is calculated by the area ratio of the proton signals related to the side chain and the main chain in the nuclear magnetic resonance spectrum. It can be seen from Table 1 that the grafting degree of the hydrophobic chain of each product is between 1 and 45%.

[0068] Examples 1 to 37

[0069] In this group of examples, grafted polyamine polymers (see Table 1) are prepared into corresponding CO2 adducts, which are then dissolved in corresponding solvents and macromolecular polyols (see Table 2) to form a liquid foaming mixture. The preparation method of the CO2 adduct of the polyamine polymer is as follows: 1 mass part of the polyamine polymer (the source is listed in Table 2, and the numbers in brackets refer to the serial numbers in Table 1) is dissolved in ethanol to obtain a polyamine polymer solution with a mass concentration of 10%, which is placed in a sealed reactor, and 0.5MPa of CO2 is introduced to react for 5 hours to obtain a white precipitate, which is filtered to remove the solvent, and then vacuum dried at 40°C for 3 days, and then placed in a sealed reactor and 0.5MPa of CO2 is introduced to maintain pressure for 2 days to obtain the CO2 adduct of the polyamine polymer. According to thermogravimetric testing, the amount of CO2 absorbed by all CO2 adducts is greater than 95% of the theoretical absorption amount. The liquid foaming mixture is prepared using the CO2 adduct, solvent and macromolecular polyol as raw materials, as shown in Table 2. In Table 2, the structure of the CO2 adduct is the sample code of the polyamine polymer (from Table 1, as shown in the "Source" of Table 2) plus "-CO2". It should be pointed out that the polyamine polymers of Examples 33 to 37 have no grafted side chains, and their molecular weights are directly given after the polyamine polymer code, such as PEI 2500-CO2 in Example 33, the molecular weight of the polyamine polymer PEI is 2500; in addition, the structures of the polyamine polymers of Examples 33, 34 and 35 are branched, linear and branched, respectively. When a mixed solvent is used, the numbers after the name of each component represent the mass percentage of the component in the solvent. When two or more macromolecular polyols are used, the numbers after the polyol code represent the percentage of the component in the total mass of the macromolecular polyol. The "mass ratio of the three" in Table 2 refers to the mass ratio of the solvent, CO2 adduct and macromolecular polyol (the total mass is 100 parts).

[0070] The codes of the macromolecular polyols in Table 2 are as follows: PEA, poly (ethylene glycol adipate), wherein the chain segment molar ratio of ethylene glycol to diethylene glycol is 1:1, molecular weight 1500, functionality 2, hydroxyl value 76.2 mgKOH / g, from Zhejiang Huafeng New Materials Co., Ltd.; PNA, poly (neopentyl adipate), molecular weight 10000, hydroxyl value 9-13, from Qingdao Xinyutian Chemical Co., Ltd.; PEBA, poly (ethylene glycol adipate butanediol) Ester, molecular weight 4000, hydroxyl value 25-31, from Qingdao Xinyutian Chemical Co., Ltd.; PBA, poly (butylene adipate) ester, molecular weight 3500, hydroxyl value 27-34, from Germany Evonik; PCL, poly (caprolactone), molecular weight 300, functionality 3, hydroxyl value 560, from Hunan Juren Chemical New Materials Co., Ltd.; PHC, polyhexamethylene carbonate, molecular weight 2000, hydroxyl value, 53-58, from Jiangsu Chemical Research Institute.

[0071] In order to prepare a homogeneous liquid foaming mixture of solvent, CO2 adduct and macromolecular polyol, it is necessary to draw a ternary phase diagram of the three. The ternary phase diagram of ethylene glycol, 10% C8-PEI-CO2 and PEA is used as an example for explanation. Take a certain amount of ethylene glycol and polyester PEA in a ratio of 1:9, 1:7, 1:5, 1:3, 1:1, 2:1, 4:1, 8:1 to form a solution (the two can be mixed in any proportion to obtain a uniform transparent solution). Determine the maximum solubility mass of 10% C8-PEI-CO2 in the above solution. The test method of the maximum solubility mass is explained by taking the case of 10% C8-PEI-CO2 dissolved in ethylene glycol and PEA (1:9) as an example. Take 18g PEA and 2g ethylene glycol and add them to a three-necked bottle, place it in a 30°C constant temperature water bath for stirring, then add 0.2g of 10% C8-PEI-CO2 powder and stir for two hours, let it stand for 3 days, observe whether there are solid particles in the system, if not, then continue to add 0.2g of 10% C8-PEI-CO2 powder, repeat the operation until insoluble particles appear, and record the three ratios at this time; then reduce the amount of 10% C8-PEI-CO2 by 0.1g based on this insoluble point to see if it dissolves; continue to take the average value of the solute mass between the insoluble point and the closest dissolving point to see if the average amount can dissolve, until the absolute value of the difference between the mass of the insoluble point and the closest dissolving point is less than 2% of the nearest dissolving mass (i.e., the maximum error is 2%), and take the mass of the nearest dissolving point as the maximum dissolving mass. The same is true for other different side chain graft operations. Similarly, the maximum solubility of 10% C8-PEI-CO2 in each ethylene glycol / PEA mixed solution was measured, and the percentage contents of the three components at each maximum solubility were plotted on the ternary phase diagram ( Figure 2 and Figure 3 ), connect the points of the maximum dissolved components to obtain the ternary phase diagram, and the area under the curve is the homogeneous region.

[0072] Table 2

[0073]

[0074]

[0075] After drawing the ternary phase diagram, as long as the ratio of the three selected is within the homogeneous region, a uniform liquid foaming mixture can be obtained. Figure 2 and 3 The three ratios indicated by "*" correspond to the compositions of Examples 2, 4, 11 and 12; Figure 3 The three ratios indicated by the “+” correspond to the composition of Example 1.

[0076] Depend on Figure 2 and Figure 3From the ternary phase diagram, we can see that although the structure of CO2 adduct has changed, the phase diagram is not much different, especially when the content of PEA in macromolecular polyol is higher than 50%, the phase diagram almost overlaps and is very close to the line of 70:30 of CO2 adduct and solvent (the dotted straight line composed of points in the figure). When the types of solvent, CO2 adduct and macromolecular polyol are replaced as described in Table 2, the phase diagram obtained is also the same as Figure 3 Similarly. Because the solvent and the macromolecular polyol are miscible, the composition of the solvent and the macromolecular polyol can vary from 0 to 100%, and the CO2 adduct has a certain solubility, and the maximum mass concentration does not exceed 60%. The homogeneous region of all phase diagrams is below the line where the ratio of CO2 adduct to solvent is 70:30.

[0077] The compositions in Table 2 can all obtain homogeneous foaming mixtures, which can exist stably for a long time. From a practical point of view, foaming mixtures with high macromolecular polyol content are more practical, because in the white material system, macromolecular polyol is always a major component. Foaming mixtures with high macromolecular polyol content can be directly used for polyurethane foaming. Therefore, the practical mass percentage composition of CO2 adduct, solvent and macromolecular polyol is CO2 adduct 1-30%, solvent 5-40%, macromolecular polyol 60-90%, and the mass ratio of CO2 adduct and solvent does not exceed 70:30. Most of the embodiments in Table 2 are within the practical mass percentage composition range.

[0078] It should be pointed out that although butanediol, pentanediol, and hexanediol in Table 2 are straight-chain diols and butanediamine is a straight-chain diamine, it is also possible to use corresponding diols or diamines with branched chains instead.

[0079] Examples 20, 27, 32 and 34 also use water as a component of the solvent. A mixed solvent consisting of an organic solvent and water also has a relatively good effect. The amount of water used can reach 40% of the mass of the mixed solvent.

[0080] Application Examples 1-5

[0081] This application example selects liquid foaming mixtures (Examples 2, 4, 11 and 12) to prepare corresponding polyurethane foams, and the formula is shown in Table 3 (this formula is only used to illustrate the foaming effect of different foaming mixtures, and the foaming formula can be adjusted according to different purposes of use). The actual mass parts of ethylene glycol, CO2 adduct and PEA (poly(ethylene glycol adipate) ester) in Examples 2, 4, 11 and 12 are 1.5 parts, 0.5 parts and 11.33 parts (satisfying the mass ratio of the three of 11.25:3.75:85.0).

[0082] Table 3

[0083]

[0084] In Table 3, glycerol comes from Chengdu Changlian Chemical Reagent Co., Ltd.; stannous octoate and triethylenediamine come from Chengdu High-end Polymer Technology Co., Ltd.; foam leveler BL-8530 comes from Shanghai Maihao New Material Technology Co., Ltd.; PM-200 is polymethylene polyphenyl isocyanate, comes from Wanhua Chemical Group Co., Ltd., and has an NCO content of 30.5-32.0%. Example 2 in the table refers to Example 2 (see Table 2), and so on.

[0085] The foaming mixtures of Examples 2, 4, 11 and 12 were directly used to prepare foams, and the formulas were shown in Table 3. Comparative Example 1 (referred to as Comparative Example 1) directly used a mixture of PEA and ethylene glycol without CO2 adducts instead of the foaming mixture, and foamed by a trace amount of water in the raw materials. The foaming mixture and other white material components were mixed according to the formula ratio, mechanically stirred at 800 r / min for 30 seconds, and then the black material was added, and then mechanically stirred at 1800 r / min for 15 seconds, and the foam was allowed to grow naturally. When the top of the foam was no longer sticky, the foaming was completed to obtain a polyurethane foam.

[0086] Since the foaming mixture in Table 3 is in liquid state, it can be easily mixed with other components. The density of the foam prepared by Application Examples 1 to 4 is much lower than that of Control Sample 1, indicating that the foaming mixture does play a role in foaming. Application Example 5 adds 0.1 parts by mass of water as an additional foaming agent on the basis of Application Example 4. Since water consumes isocyanate, the amount of PM-200 is also increased accordingly. The density of Application Example 5 is further reduced, and the density is also lower than that of Control Sample 2 (Comparison 2) using only water as a foaming agent, indicating that water and the foaming mixture of Example 12 play a role in foaming together.

[0087] In Application Example 5, the foaming agent water is directly mixed with the foaming mixture of Example 12 to obtain a uniform foaming mixture. This shows that when the foaming mixture of the present invention is actually used, water can be added to the foaming mixture of the present invention, and the added water also acts as a foaming agent. Such a use method also belongs to the protection scope of the present invention.

[0088] It should be pointed out that the polyurethane foam formula listed in the present invention is only to verify that the liquid foaming mixture prepared by the present invention can be used for the preparation of polyurethane foam, and it should not be understood as limiting the scope of use of the foaming agent material and the foaming mixture prepared by the present invention. The formation process of polyurethane foam is an exothermic reaction, and the heat released is just used to release the carbon dioxide in the foaming mixture prepared by the present invention. Therefore, the foaming mixture prepared by the present invention can be used to prepare various polyurethane foams.

[0089] The above description is only an embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention shall be included in the scope of the claims of the present invention.

Claims

1. A liquid foaming mixture, characterized in that The foaming mixture is composed of at least a CO2 adduct, a solvent and a macromolecular polyol, and the mass percentage of the three is: 1-60% of the CO2 adduct, 1-97% of the solvent, and 2-98% of the macromolecular polyol, and the mass ratio of the CO2 adduct to the solvent does not exceed 70:30; The CO2 adduct is composed of a polyamine polymer and CO2, and CO2 and the polyamine polymer exist in the form of an adduct; or the CO2 adduct is composed of a grafted modified polyamine polymer and CO2, and CO2 and the main chain of the polyamine polymer exist in the form of an adduct; the polyamine polymer is a polymer containing 4 or more amine groups in the molecular chain, the atoms connected to the amine groups are carbon atoms, and the structure is at least one of linear, branched, and hyperbranched, and the molecular weight is greater than 500; The solvent is composed of alcohol, amine and / or alcoholamine with a carbon number of ≤8 and a total of hydroxyl and amino groups of 2 to 5; and is a reactive solvent, that is, the solvent can both dissolve the CO2 adduct and react chemically with other substances in the foaming system to become part of the foam; the solvent optionally contains water, and the water content does not exceed 40% of the total solvent mass; The macromolecular polyol refers to a polyester polyol having an ester group in the main chain structure and a functionality of not less than 2 and / or a polycarbonate polyol having a carbonate group in the main chain structure and a functionality of not less than 2; The liquid foaming mixture is a thermodynamically stable homogeneous substance.

2. The liquid foaming mixture according to claim 1, characterized in that The liquid foaming mixture consists of a CO2 adduct, a solvent and a macromolecular polyol, and the mass ratio of the CO2 adduct to the solvent is no more than 70:

30.

3. The liquid foaming mixture according to claim 1, characterized in that The solvent is at least one of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butylene glycol, pentanediol, glycerol, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, diethylene glycol, and diglycolamine; the butylene glycol is 1,4-butylene glycol or any isomer of 1,4-butylene glycol containing two hydroxyl groups; the pentanediol is 1,5-pentanediol or any isomer of 1,5-pentanediol containing two hydroxyl groups.

4. The liquid foaming mixture according to claim 1, characterized in that The solvent composition contains at least two components, component one is ethylene glycol, and component two is at least one of 1,2-propylene glycol, 1,3-propylene glycol, glycerol, butanediol, pentanediol, hexanediol, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, butanediamine, diethylene glycol, diglycolamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; the butanediol, pentanediol, and hexanediol are any isomers of the corresponding diols containing two hydroxyl groups; the butanediamine is any isomer of 1,4-butanediamine or 1,4-butanediamine containing two amino groups.

5. The liquid foaming mixture according to claim 4, characterized in that The mass fraction of ethylene glycol in the solvent is ≥50%.

6. The liquid foaming mixture according to claim 1, characterized in that The polyamine polymer is selected from polyethyleneimine, polypropyleneimine, polybutyleneimine, polyethyleneamine, and polyallylamine.

7. The liquid foaming mixture according to claim 6, characterized in that The polyamine polymer is polyethyleneimine.

8. The liquid foaming mixture according to claim 1, characterized in that The polyamine polymer contains side chains, and the side chains are at least one of the following: (1) The side chain is polyethylene glycol, polypropylene oxide, polyoxetane or polytetrahydrofuran or polysiloxane, and the degree of polymerization is at least 1; (2) The side chain contains a hydrocarbon group having 1 to 22 carbon atoms.

9. The liquid foaming mixture according to claim 8, characterized in that The polypropylene oxide contains , wherein m is an integer of 1 to 15, and n is an integer of 1 to 6; the hydrocarbon group is an alkyl group having 1 to 16 carbon atoms.

10. Use of the liquid foaming mixture according to any one of claims 1 to 9 for preparing polyurethane foam.

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