A polyurea foam and a method for its production

Abstract

The application discloses a kind of polyurea foam material and preparation method thereof.The polyurea foam is prepared by mixing component B and component A, the component B at least includes the CO2 adduct of terminal amino compound;The component A includes polyisocyanate compound;The functionality of terminal amino compound and polyisocyanate compound is at least 2.The terminal amino compound includes terminal primary amino compound, terminal secondary amino compound and end-modified terminal primary amino compound;The terminal primary amino compound includes terminal primary amino polyoxyethylene ether, terminal primary amino polypropylene ether and terminal primary amino polydimethylsiloxane.The polyurea foam material prepared by the application does not contain other auxiliary components except a small amount of foam stabilizer, and the foam purity is high.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer foam materials, and particularly relates to a polyurea foam material and a preparation method thereof. BACKGROUND

[0002] Polyurea is a substance generated by the reaction of isocyanate component (A component) and amino compound component (B component), and has very excellent physical and chemical properties such as medium resistance, aging resistance, wear resistance, fire resistance, etc. In the synthesis process, the gel reaction of isocyanate and amino compound is extremely rapid, so the polyurea is little affected by other components in the synthesis process, but at the same time, it also increases the difficulty of using a blowing agent to prepare polyurea foam. Water reacts with isocyanate to release CO2, which is the most commonly used chemical blowing agent for polyurethane. In polyurea materials, the reaction ratio of isocyanate and amino is hundreds to thousands of times faster than that of water, so in polyurea, water is difficult to participate in the reaction and foam. At the same time, because the reaction of isocyanate and amino is very fast, other physical blowing agents have not had time to gasify and foam before the polyurea has already solidified and formed. Therefore, it is difficult to prepare polyurea foam by traditional methods.

[0003] Patent document CN 105418881 B discloses a preparation method of polyurea foam material, which essentially adds expandable microspheres to the polyurea material, and the expandable microspheres are expanded at a temperature of 80-120℃ to realize foam preparation, but this method needs to be realized under vacuum conditions and at a very high temperature. Patent document CN 114015004 A slows down the reaction speed of amino compounds and isocyanate by introducing a large amount of chain extender (4,4'-bis-sec-butylaminodiphenyl methane) of steric hindered secondary amine type, and assists with a low-boiling-point fluorochlorocarbon physical blowing agent to prepare a shock-absorbing polyurea rigid foam material, but the fluorochlorocarbon physical blowing agent used in this method will destroy the ozone layer and cause greater environmental pollution. Patent document CN 114920975 A uses excess water as a blowing agent to greatly inhibit the gel reaction of amino compounds and isocyanate, prolongs the foaming time of the material, and thus increases the amount of gas required for foaming. This method can prepare a polyurea foam with smaller density but slower solidification and molding speed.

[0004] At present, the existing preparation methods of polyurea foam are not mature, and have problems such as harsh reaction conditions, greater environmental pollution, slow solidification and molding, etc., and are not suitable for large-scale industrial production. SUMMARY

[0005] The inventors of the present application hope to develop a new system for preparing polyurea foam in view of the immaturity of the existing polyurea foam preparation method. The inventors of the present application explore the reaction of different types of amino-terminated compounds with CO2 to form a new adduct (see reaction formula (1), R1 and R2 can be hydrogen atoms or organic groups), and react with polyisocyanate compounds to prepare polyurea foam. When the CO2 adduct of the amino-terminated compound is contacted with isocyanate, the reverse reaction of reaction formula (1) releases CO2 (participates in foaming), the obtained amino compound and isocyanate react (polyurea is generated), which promotes the chemical equilibrium to move to the left; at the same time, the reaction of amino compound and isocyanate releases heat to further promote the decomposition of the CO2 adduct of the amino-terminated compound. Therefore, when preparing polyurea using the CO2 adduct of the amino-terminated compound, the gelation reaction and the foaming reaction almost occur at the same time, and the matching of the foaming speed and the gelation speed during the reaction process can be achieved to achieve the purpose of polyurea foaming.

[0006]

[0007] The purpose of the present application is to provide a polyurea foam material preparation method, wherein the polyurea foam is prepared by mixing component B and component A, the component B comprises at least a CO2 adduct of an amino-terminated compound; and the component A comprises a polyisocyanate compound.

[0008] In the present application, the CO2 adduct of the amino-terminated compound in the component B is obtained by reacting an amino-terminated compound with CO2. The amino-terminated compound is not particularly limited, and only needs to comprise two or more amino groups, and is in a liquid state or is mixed with a liquid amine compound to be in a liquid state, including primary amino-terminated compounds, secondary amino-terminated compounds and capped modified primary amino-terminated compounds. The reason for choosing secondary amine-terminated compounds and capped modified primary amino-terminated compounds to prepare CO2 adducts is that such compounds have a large steric hindrance near the secondary amine reaction group, which can moderately reduce the gelation reaction speed with isocyanate. Compared with the CO2 adduct of the primary amino-terminated compound, the CO2 adduct of the amino-terminated compound containing secondary amine can better realize the material leveling during the preparation of polyurea foam, which is convenient for industrial spraying and casting use.

[0009] In the present application, the terminal primary amino compound used to prepare the CO2 adduct raw material can be a small molecule polyamine (such as ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, etc.); or can be an oligomer, which has no particular limitation on the molecular weight, and the polymerization degree thereof is greater than 2. From the practical point of view, because the CO2 adduct is absorbed by the amine group, in order to make the terminal primary amino compound absorb more CO2, the amino content of the terminal primary amino compound should be as high as possible, that is, the molecular weight of the selected terminal primary amino compound should be as low as possible; the terminal primary amino compound is preferably a terminal primary amino polyoxyethylene ether, a terminal primary amino polyoxypropylene ether and a terminal primary amino polydimethylsiloxane with a polymerization degree of 1 to 35. Of course, the molecular weight of the commercialized terminal primary amino compound can be up to 5000, and such a compound is also acceptable, but the CO2 content of the adduct obtained after absorbing CO2 is low (which can be as low as 1%), but it is also acceptable for making high-density foam.

[0010] In the present application, the terminal secondary amino compound used to prepare the CO2 adduct raw material can be selected from the secondary amine chain extender, which can be Unilink 4100 (4,4'-dialkylphenyldiamine), Unilink 4200 (4,4'-bis-sec-butylaminodiphenylmethane), Clearlink 1000 (4,4'-bis-sec-butylaminodicyclohexylmethane), Clearlink 3000 (3,3'-dimethyl-4,4'-bis-sec-butylamino-dicyclohexylmethane), Jefflink 754 (4,4'-bis-sec-pentylcyclohexanediamine), etc., and the terminal secondary amino compound can also be polyaspartic acid ester.

[0011] In the present application, the end-capped modified terminal primary amino compound used to prepare the CO2 adduct raw material is prepared from a terminal primary amino compound by end-capping modification, in order to make the end-capped modified terminal primary amino compound absorb more CO2, the amine group content of the terminal primary amino compound should be as high as possible, and the terminal primary amino compound is preferably a terminal primary amino polyoxyethylene ether, a terminal primary amino polyoxypropylene ether and a terminal primary amino polydimethylsiloxane with a polymerization degree of 1 to 35, the terminal primary amino group is combined with the end-capping chain by covalent bond, and the purpose of introducing the end-capping chain is to obtain an end-capped modified terminal primary amino compound containing a secondary amine group, and the type of the end-capping chain has little effect on the preparation of the CO2 adduct. Specifically, the end-capping chain includes but is not limited to at least one of the following cases:

[0012] (1) the end-capping chain contains at least one repeating unit of polyoxyethylene ether and / or polyoxypropylene ether;

[0013] (2) the end-capping chain contains a trimethylsilyl group;

[0014] (3) the end-capping chain has a hydrocarbon group with a carbon atom number of 1 to 12;

[0015] (4) the end-capped chain contains a fluorine-containing alkyl group having 1 to 12 carbon atoms;

[0016] The number of moles of the end-capped chain is 0 to 100% based on the N atoms in the primary amino compound.

[0017] In the above end-capped chain, if the number of carbon atoms of the hydrocarbon group is greater than 12, the hydrophobic association thereof is too strong, resulting in a too large viscosity of the obtained CO2 adduct, which is even in a solid state and is inconvenient to use.

[0018] In the present application, the number of moles of the end-capped chain is 0 to 100% based on the N atoms in the primary amino compound (i.e. the end-capping rate is 0 to 100%). If the end-capping rate exceeds 100%, i.e. part of the primary amino groups are changed into tertiary amines, the tertiary amines do not participate in the reaction of polyurea, and at the same time, the tertiary amines catalyze the reaction of polyurea, resulting in that the preparation of the foam is not well controlled.

[0019] Specifically, the end-capped chain of the end-capped modified primary amino compound can be a polyoxyethylene ether or a polyoxypropylene ether, and contains at least one repeating unit, and the structure is exemplified as follows:

[0020]

[0021] wherein m is at least 1, n is a positive integer of 1 to 4, and Q is a linking group between the amine group and the end-capping chain in the end-capped modified primary amino compound. The linking groups Q and T belong to replaceable groups, and the groups that can be selected are as follows:

[0022]

[0023] The end-capped chain of the end-capped modified primary amino compound can also contain a silane, and the structure can be as follows:

[0024]

[0025] T is a linking group between the amine group and the end-capping chain in the end-capped modified primary amino compound, and T can be as follows:

[0026]

[0027] The end-capped chain of the end-capped modified primary amino compound can also contain a hydrocarbon group having 1 to 12 carbon atoms, and contains at least one unsaturated bond, and the structure is exemplified as follows:

[0028] C n H 2n-1 -M-,

[0029] wherein n is an integer from 1 to 12, and M is a linking group between the amine group and the capping chain in the end primary amino compound. The linking group M belongs to replaceable groups, and M can be a covalent bond directly.

[0030] The capping chain in the above-mentioned end primary amino compound can further contain an alkyl group or a fluorine-containing alkyl group with a carbon atom number of 1 to 12, and the structure thereof is exemplified as follows:

[0031] C n H 2n+1-m F m -M-,

[0032] wherein n is an integer from 1 to 12, m is 0 or an integer from 1 to 25, and M is a linking group between the amine group and the capping chain in the end primary amino compound. The linking group M belongs to replaceable groups, and M can be a covalent bond directly or can be selected from the following groups:

[0033]

[0034] It should be noted that the linking groups Q, T and M between the amine group and the capping chain in the above-mentioned modified end amino compound all belong to replaceable groups, and other groups can also be selected by those skilled in the art to replace them, which will not be described herein.

[0035] As for the specific preparation method of the above-mentioned end primary amino compound, a glycidyl ether with a hydrophobic chain can be added dropwise into an end amino compound to obtain a modified end amino compound. The structure of the glycidyl ether is as follows:

[0036]

[0037] wherein m is at least 1, and n is a positive integer from 1 to 4. The linking group between the amine group and the capping chain in the end primary amino compound prepared by this method is Q1; the structure of the glycidyl ether with a hydrophobic chain can also be as follows:

[0038]

[0039] wherein n is an integer from 1 to 12, and m is 0 or an integer from 1 to 25. The linking group between the capping chain and the main chain in the end primary amino compound prepared by this method is M2.

[0040] An alkyl group with an epoxy group or a fluorine-containing alkyl group with an epoxy group and an end primary amino compound can also be reacted in an ethanol solution to obtain an end primary amino compound. The structure of the alkyl group with an epoxy group or the fluorine-containing alkyl group with an epoxy group can be as follows:

[0041]

[0042] wherein n is an integer from 1 to 12, and m is 0 or an integer from 1 to 25, and the linking group between the amine group and the end-capping chain of the end-capped modified primary amino compound prepared by this method is M1.

[0043] The end-capped modified primary amino compound can also be prepared by the following method: taking an alkoxy polypropylene glycol oligomer as an example, first reacting the alkoxy polyether oligomer with iodoacetic acid and 2-bromoethyl isocyanate respectively to obtain a halogenated hydrocarbon end-capped product, as shown in the following reaction (wherein m is at least 1, and n is a positive integer from 1 to 4):

[0044]

[0045] Secondly, reacting the halogenated hydrocarbon end-capped product with an end-amino compound to remove hydrogen halide, thereby obtaining an N-substituted end-capped modified primary amino compound (the linking group is Q2 or Q3).

[0046] The end-capped modified primary amino compound can also be prepared by reacting a bromide or iodide of an alkane or a fluorine-containing alkane with an end-amino compound. The structure of the bromide or iodide can be:

[0047] C n H 2n+1-m F m -Br,C n H 2n+1-m F m -I,

[0048] wherein n is an integer from 1 to 12, and m is 0 or an integer from 1 to 25. The linking group between the amine group and the end-capping chain of the end-capped modified primary amino compound prepared by this method is a covalent bond.

[0049] All these reactions are known chemical reactions, and the specific preparation method can refer to the existing published technologies, such as patent document CN 108355472 A.

[0050] In the present application, a foam stabilizer can also be added to the B component. Any existing foam stabilizer for polyurethane foam can be used, including polyoxypropylene-polyoxyethylene copolyether, polyoxyethylene-polysiloxane copolymer, polyoxypropylene-polysiloxane copolymer, or polyoxyethylene propylene-polysiloxane copolymer. In particular, when the amino group of the CO2 adduct of the end-amino compound is a secondary amine, the reaction is slow, and a foam stabilizer can be added to avoid the formation of large cells; when the amino group of the CO2 adduct of the end-amino compound is a primary amine, because the reaction is fast, the cells have not had time to merge, and the polyurea material has already solidified, so no foam stabilizer can be added.

[0051] In the present application, the B component can also contain the terminal amino compound itself, which can be obtained by mixing the prepared CO2 adduct of terminal amino compound and terminal amino compound; or when preparing the CO2 adduct of terminal amino compound, the amount of CO2 is insufficient, at this time the system will contain the CO2 adduct of terminal amino compound and the terminal amino compound itself, and the CO2 content in the system can be adjusted according to the density of the prepared polyurea foam.

[0052] In the present application, the B component can also contain a terminal amino chain extender, which includes at least one of ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexanediamine, Unilink 4100 (4,4'-dialkylphenyldiamine), Unilink 4200 (4,4'-bis-sec-butylaminodiphenylmethane), Clearlink 1000 (4,4'-bis-sec-butylaminodicyclohexylmethane), Clearlink 3000 (3,3'-dimethyl-4,4'-bis-sec-butylamino-dicyclohexylmethane), Jefflink 754 (4,4'-bis-sec-pentylcyclohexanediamine).

[0053] In the present application, because the polyurea system itself reacts very quickly, the catalyst is not a necessary component, and generally no catalyst needs to be added in the B component. Therefore, the polyurea foam material of the present application is relatively pure in principle.

[0054] In the present application, the polyisocyanate compound in the A component is not particularly limited and can be selected from existing isocyanates, and the A component can be selected from one or more of polymethylene polyphenyl polyisocyanate (PMDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), p-phenylene diisocyanate (PDI), butylene diisocyanate (BDI), naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), and prepolymers of the above isocyanates (such as prepolymers of MDI, prepolymers of HMDI, prepolymers of TDI), IPDI trimer, and HDI trimer.

[0055] In the present application, the polyurea foam can be prepared by the following method, which comprises the following steps:

[0056] (1) uniformly mix the formula amount of CO2 adduct of terminal amino compound and other components such as foam stabilizer to obtain the B component;

[0057] (2) set the appropriate material temperature, mix the B component and the A component by using a high-pressure sprayer, spray and foam, or pour into a container to foam and form.

[0058] Another object of the present application is to provide a polyurea foam prepared by the method, wherein the polyurea foam is prepared by mixing a B component and an A component, the B component comprising at least a CO2 adduct of an amino-terminated compound, and the A component comprising a polyisocyanate compound. The polyurea foam provided by the present application does not contain a catalyst, and optionally, does not contain a foam stabilizer. Therefore, the polyurea foam provided by the present application has high purity.

[0059] The present application has the following positive effects:

[0060] 1. The CO2 adduct of an amino-terminated compound prepared by the present application uses raw materials that are inexpensive and readily available, has high yield, simple preparation process, low toxicity and less pollution, and is easy to promote in industry.

[0061] 2. The CO2 adduct of an amino-terminated compound prepared by the present application releases heat when reacting with a polyisocyanate compound, and rapidly releases CO2 during the gel reaction, thereby achieving the purpose of polyurea foaming.

[0062] 3. The polyurea foam prepared by the present application using the reaction between the CO2 adduct of an amino-terminated compound and a polyisocyanate compound does not require additional catalysts and fluorine-containing chlorocarbon physical blowing agents, is environmentally friendly, and the prepared polyurea foam contains only a small amount of foam stabilizer and no other additives, thereby having high foam purity. BRIEF DESCRIPTION OF DRAWINGS

[0063] APPENDIX Figure 1 The structures and types of the primary amino-terminated compounds used as raw materials for preparing Examples (1) to (13) and 1 to 11 are shown in Table 1.

[0064] APPENDIX Figure 2 The structures and types of the blocking raw materials used for preparing Examples (1) to (13) are shown in Table 2.

[0065] APPENDIX Figure 3 The structures and types of the secondary amino-terminated compounds used for Examples 12 to 18 are shown in Table 3. DETAILED DESCRIPTION

[0066] In order to make the purpose, technical solutions and technical effects of the present application clearer, the present application will be further described in detail below in combination with specific examples. It should be noted that all these examples are for further illustrating the present application, and should not be understood as limiting the present application. Some non-essential improvements and adjustments to the present application made by those skilled in the art based on the above content of the present application still belong to the protection scope of the present application.

[0067] Blocking-modified primary amino-terminated compound raw material preparation examples (1) to (13)

[0068] The raw material preparation examples of the present application select end primary amino compounds to prepare end primary amino compounds with end capping modification. Specifically, the end primary amino compounds selected in the examples of the present application are ZE-123 (a di-end primary amino polyoxyethylene ether with a molecular weight of about 206); ZE-140 (a di-end primary amino polyoxyethylene ether with a molecular weight of about 382); ZD-123 (a di-end primary amino polyoxypropylene ether with a molecular weight of about 248); ZD-140 (a di-end primary amino polyoxypropylene ether with a molecular weight of about 480); Tech-2402 (1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane with a molecular weight of 248.5); Tech-2405 (a di-end primary amino polydimethylsiloxane with a molecular weight of about 500); and Tech-2410 (a di-end primary amino polydimethylsiloxane with a molecular weight of about 1000). The structures and types of the end primary amino compounds selected are shown in Table 1. Figure 1 .

[0069] The end primary amino compounds with end capping modification described in the present application have end primary amino groups connected to end capping chains, and the end capping chains are at least one of the following:

[0070] (1) the end capping chains contain at least one repeating unit of polyoxyethylene ether and / or polyoxypropylene ether;

[0071] (2) the end capping chains contain trimethylsilyl groups;

[0072] (3) the end capping chains have hydrocarbon groups with a carbon atom number of 1 to 12;

[0073] (4) the end capping chains contain fluorine-containing alkyl groups with a carbon atom number of 1 to 12;

[0074] The end capping rate can vary as needed, and the end capping rate is 0-100% based on the N atoms in the end amino compounds. The linking groups between the end capping chains and the amine groups of the end amino compounds are replaceable, such as Q, T, and M described in the specification. Specifically, in the examples, the end capping chains are derived from glycidyl ethers, brominated hydrocarbons, and iodinated hydrocarbons, and the structures are shown in Table 2. These structures are only for illustrating the present application, and those skilled in the art can select other end capping raw materials as long as the compounds can react with the primary amines in the end amino compounds to change the primary amines to secondary amines. Figure 2

[0075] ​Specifically, the synthesized end-capped modified primary amino compounds are shown in Table 1. In Table 1, the raw material ratio refers to the molar ratio of the primary amino compound and the end-capping raw material. It should be noted that when the primary amino group in the primary amino compound is modified by end-capping, the excess of the end-capping raw material should be avoided to generate tertiary amine, because the tertiary amine nitrogen atom does not have active hydrogen and cannot effectively react with carbon dioxide to generate stable carbamate, which is not conducive to the absorption of CO2. In addition, the tertiary amine will also catalyze the subsequent polyurea foaming, affecting the reaction process. Therefore, the molar ratio of the primary amino compound and the end-capping raw material should be greater than 1:2, and the ratio of the two is between 1:2 and 1:0.2. The theoretical end-capping rate is the molar percentage of the end-capped chain to all N atoms, and the actual end-capping rate is calculated by the area ratio of the proton signals near the end-capped chain and the amine group in the nuclear magnetic spectrum.

[0076] The process conditions and steps for preparing the end-capped modified primary amino compounds in Examples (1) to (7), (9), (11) to (12) in Table 1 are as follows: 1 mole of the primary amino compound is weighed, and then the corresponding amount of the end-capping raw material (glycidyl ether compound) is added dropwise into the primary amino compound. The reaction is stirred at 50 to 70°C for 8 to 14 hours to obtain the corresponding end-capped modified primary amino compound.

[0077] The process conditions and steps for preparing the end-capped modified primary amino compounds in Examples (8) and (13) in Table 1 are as follows: 1 mole of the primary amino compound is dissolved in chloroform to obtain a mass concentration of about 10%, and then the corresponding amount of C2F3-I is added for reflux reaction for 3 hours. The reaction mixture is cooled to room temperature, and then extracted with 5% sodium hydroxide aqueous solution three times. The water layer is removed, and then washed with water until the pH value of the water layer is neutral. The organic layer is dried with anhydrous sodium sulfate, and then the solvent is removed by vacuum rotary evaporation at 40°C to obtain the corresponding end-capped modified primary amino compound.

[0078] The process conditions and steps for preparing the end-capped modified primary amino compounds in Example (10) in Table 1 are as follows: 1 mole of the primary amino compound is dissolved in chloroform to obtain a mass concentration of about 10%, and then the corresponding amount of C4-Br is added for reflux reaction for 6 hours. The reaction mixture is cooled to room temperature, and then extracted with 5% sodium hydroxide aqueous solution three times. The water layer is removed, and then washed with water until the pH value of the water layer is neutral. The organic layer is dried with anhydrous sodium sulfate, and then the solvent is removed by vacuum rotary evaporation at 40°C to obtain the corresponding end-capped modified primary amino compound.

[0079] Table 1

[0080]

[0081] From Table 1, it can be seen that the actual end-capped chain rate of each product is very close to the theoretical end-capped rate, indicating that the reaction is very complete, and the end-capped rate of each product is between 0 and 100%. The raw material preparation examples of this group fully demonstrate that the end-capped raw material successfully modifies the primary amino compound.

[0082] Raw material preparation examples 1-31 of CO2 adducts of primary amino compounds

[0083] In this group of preparation examples, primary amino compounds, secondary amine compounds and end-capped modified primary amino compounds are selected to absorb CO2 to form adducts, as shown in Table 2. Specifically, the primary amino compounds selected in this group of examples include ZE-123 (a binary primary amino polyoxyethylene ether with a molecular weight of about 206); ZE-140 (a binary primary amino polyoxyethylene ether with a molecular weight of about 382); ZE-1200 (a binary primary amino polyoxyethylene ether with a molecular weight of about 1800); ZT-133 (a ternary primary amino polyoxyethylene ether with a molecular weight of about 363); ZD-123 (a binary primary amino polyoxypropylene ether with a molecular weight of about 248); ZD-140 (a binary primary amino polyoxypropylene ether with a molecular weight of about 480); ZD-1200 (a binary primary amino polyoxypropylene ether with a molecular weight of about 2000); ZT-143 (a ternary primary amino polyoxypropylene ether with a molecular weight of about 430); Tech-2402 (1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, with a molecular weight of 248.5); Tech-2405 (a binary primary amino polydimethylsiloxane with a molecular weight of about 500); and Tech-2410 (a binary primary amino polydimethylsiloxane with a molecular weight of about 1000). The secondary amine compounds selected include Unilink 4100 (4,4'-dialkylphenylenediamine); Unilink 4200 (4,4'-bis-sec-butylaminodiphenylmethane); Clearlink 1000 (4,4'-bis-sec-butylamino-dicyclohexylmethane); Clearlink 3000 (3,3'-dimethyl-4,4'-bis-sec-butylamino-dicyclohexylmethane); Jefflink 754 (4,4'-bis-sec-pentylcyclohexanediamine); Desmophen NH 1220 (polyaspartic ester); and Desmophen NH 1420 (polyaspartic ester). The end-capped modified primary amino compounds selected are obtained from the raw material preparation examples (1) to (13), as shown in Table 1. The structures and types of the primary amino compounds selected are shown in Figure 1 , and the structures and types of the secondary amino compounds selected are shown in Figure 3 .

[0084] It should be noted that the CO2 adducts of the terminal amino compounds in Table 2 are numbered by the end-capping rate, the terminal amino compound, the end-capping material and CO2, such as ZE-123-CO2, wherein ZE-123 is the specific model of the terminal primary amino compound, and CO2 represents the adduct formed by the reaction of the terminal primary amino compound with CO2; or 80% C4-ZE140-CO2, wherein 80% represents the theoretical end-capping rate of the end-capped terminal primary amino compound, C4 represents the alkyl chain with 4 carbon atoms as the end-capping chain, and ZE-140 is the specific model of the terminal primary amino compound. In Table 2, “Original (1)” is from “Raw Material Preparation Example (1)” in Table 1, and the others are in the same manner.

[0085] Table 2

[0086]

[0087] The preparation process and steps of the CO2 adducts of the terminal amino compounds in Table 2 are as follows: the terminal amino compound is placed in a high-pressure reaction kettle, and CO2 is added to make the saturation degree of CO2 between 50% and 100% (the specific value is shown in Table 2), so as to obtain each CO2 adduct.

[0088] The theoretical CO2 content in Table 2 is calculated according to the content of the amino group in the terminal amino compound, and each two amino groups absorb one molecule of CO2. The actual CO2 content is tested by the thermogravimetric method. All the CO2 adducts have obvious thermal weight loss between 40 and 100°C, which can be attributed to the release of CO2. The actual saturation degree of CO2 is the ratio of the actual CO2 content to the theoretical CO2 content. The terminal amino compound prepared in the present application can fully absorb CO2 to form the CO2 adduct.

[0089] Examples [1] to

[10]

[0090] In this application, the CO2 adducts of the terminal amino compounds are selected to prepare polyurea foams. First, the CO2 adducts of different types of terminal amino compounds in Table 2 are compounded to obtain a formula suitable for preparing polyurea foams. The specific compounding formula is shown in Table 3. In Table 3, “1” represents “Example 1” in Table 2, and the others are in the same manner. The values of each formula in Table 3 are mass parts.

[0091] Table 3

[0092]

[0093]

[0094] Example [1]

[0095] A preparation method of a polyurea foam is provided in the present embodiment, the polyurea foam is prepared from a B component and an A component, the preparation raw materials of the B component include the following components in parts by weight:

[0096] 100 parts of CO2 adduct of terminal amino compound;

[0097] The CO2 adduct of terminal amino compound in the B component is compounded according to Formula I in Table 3.

[0098] The A component is a mixture of diphenylmethane diisocyanate (MDI, NCO content is 33.5wt%), polymethylene polyphenyl polyisocyanate (PMDI, NCO content is 31wt%) and prepolymer of MDI (NCO content is 10wt%) compounded at a weight ratio of 1:1:1.

[0099] The volume ratio of the B component and the A component is 1:1.

[0100] The preparation method includes the following steps:

[0101] Example [2]

[0102] A preparation method of a polyurea foam is provided in the present embodiment, the polyurea foam is prepared from a B component and an A component, the preparation raw materials of the B component include the following components in parts by weight:

[0103] 100 parts of CO2 adduct of terminal amino compound;

[0104] 2 parts of chain extender butanediamine

[0105] The CO2 adduct of terminal amino compound in the B component is compounded according to Formula II in Table 3.

[0106] The A component is a mixture of toluene diisocyanate (TDI, NCO content is 35wt%) and prepolymer of TDI (NCO content is 15wt%) compounded at a weight ratio of 2:1.

[0107] The volume ratio of the B component and the A component is 1:1.1.

[0108] The preparation method includes the following steps:

[0109] (1) mixing the formula amount of CO2 adduct of terminal amino compound and foam stabilizer to obtain the B component;

[0110] (2) The high-pressure spraying machine two-component material pump is inserted into the B component and A component raw material barrels respectively, the power supply and air compressor are turned on, the raw material and pipeline heating temperature of the spraying machine is set to 45°C, the gas source pressure is 6.5 MPa, the mixed raw material is sprayed on the wall surface using a spray gun, and more than 3 layers of spraying are performed to obtain a polyurea foam material with a thickness of 5 cm.

[0111] Example [3]

[0112] In this embodiment, a preparation method of a polyurea foam material is provided, the polyurea foam is prepared from a B component and an A component, and the preparation raw material of the B component includes the following components in parts by weight:

[0113] 100 parts of a CO2 adduct of an amino-terminated compound;

[0114] 2 parts of a foam stabilizer;

[0115] The CO2 adduct of the amino-terminated compound in the B component is compounded according to Formula III in Table 3, and the foam stabilizer is a polyoxypropylene-ethylene oxide copolyether with a brand BL-9734M.

[0116] The A component is a mixture of p-phenylene diisocyanate (PDI, NCO content of 52 wt%) and hexamethylene diisocyanate (HDI, NCO content of 31.5 wt%) at a weight ratio of 1:5.

[0117] The volume ratio of the B component to the A component is 1:1.1.

[0118] The preparation method includes the following steps:

[0119] (1) The CO2 adduct of the amino-terminated compound and the foam stabilizer are mixed in a formula amount to obtain a B component;

[0120] (2) The high-pressure spraying machine two-component material pump is inserted into the B component and A component raw material barrels respectively, the power supply and air compressor are turned on, the raw material and pipeline heating temperature of the spraying machine is set to 45°C, the gas source pressure is 7.5 MPa, the mixed raw material is sprayed in a mold using a spray gun, and more than 3 layers of spraying are performed to obtain a polyurea foam material with a thickness of 5 cm.

[0121] Example [4]

[0122] In this embodiment, a preparation method of a polyurea foam material is provided, the polyurea foam is prepared from a B component and an A component, and the preparation raw material of the B component includes the following components in parts by weight:

[0123] 100 parts of a CO2 adduct of an amino-terminated compound;

[0124] 2 parts of a foam stabilizer;

[0125] The CO2 adduct of the terminal amino compound in the B component was compounded according to Formula IV in Table 3, and the foam stabilizer was a polyoxypropylene ethylene ether-silicone copolymer with a trade name of L-580.

[0126] The A component was a mixture of naphthalene diisocyanate (NDI, NCO content of 40 wt%) and hexamethylene diisocyanate (HDI, NCO content of 31.5 wt%) at a weight ratio of 1:5.

[0127] The volume ratio of the B component to the A component was 1.1:1.

[0128] The preparation method included the following steps:

[0129] (1) Mixing the formula amount of the CO2 adduct of the terminal amino compound and the foam stabilizer to obtain the B component;

[0130] (2) Plugging the two-component material pumps of the high-pressure spraying machine into the raw material barrels of the B component and the A component respectively, turning on the power and the air compressor, setting the raw material and pipeline heating temperature of the spraying machine to 45°C, the gas source pressure to 7.5 MPa, and spraying the mixed raw material into the mold using a spray gun to obtain a polyurea foam material with a thickness of 5 cm after spraying more than 3 layers.

[0131] Example [5]

[0132] The difference between this example and Example [4] was that the CO2 adduct of the terminal amino compound in the raw material B component was compounded according to Formula V in Table 3, and the A component was a mixture of butylene diisocyanate (BDI, NCO content of 33.58 wt%) and a prepolymer of MDI (NCO content of 10 wt%) at a weight ratio of 1:4.

[0133] Example [6]

[0134] The difference between this example and Example [4] was that the CO2 adduct of the terminal amino compound in the raw material B component was compounded according to Formula VI in Table 3, and the A component was a mixture of lysine diisocyanate (LDI, NCO content of 33 wt%) and a prepolymer of HMDI (NCO content of 10.2 wt%) at a weight ratio of 1:3.

[0135] Example [7]

[0136] The difference between this example and Example [4] was that the CO2 adduct of the terminal amino compound in the raw material B component was compounded according to Formula VII in Table 3, and the A component was a mixture of isophorone diisocyanate (IPDI, NCO content of 37.5 wt%) and an IPDI trimer (NCO content of 12 wt%) at a weight ratio of 1:3.

[0137] Example [8]

[0138] The difference between this example and Example [4] is that the CO2 adduct of the terminal amino compound in the raw material B component is compounded according to Formula VIII in Table 3, and the A component is a mixture of hexamethylene diisocyanate (HDI, NCO content 31.5 wt%) and HDI trimer (NCO content 10.6 wt%) compounded at a weight ratio of 1:2.

[0139] Example [9]

[0140] The difference between this example and Example [4] is that the CO2 adduct of the terminal amino compound in the raw material B component is compounded according to Formula IX in Table 3 (the CO2 saturation of the adduct used in Formula IX is all greater than 90%, so it can be considered that the B component only contains the CO2 adduct of the terminal amino compound), and the B component does not contain a foam stabilizer; and the A component is a mixture of toluene diisocyanate (TDI, NCO content 35 wt%) and a prepolymer of TDI (NCO content 15 wt%) compounded at a weight ratio of 1:5.

[0141] Example

[10]

[0142] The difference between this example and Example [4] is that the CO2 adduct of the terminal amino compound in the raw material B component is compounded according to Formula X in Table 3 (the CO2 saturation of the adduct used in Formula X is all greater than 90%, so it can be considered that the B component only contains the CO2 adduct of the terminal amino compound and a foam stabilizer), and the A component is a mixture of lysine diisocyanate (LDI, NCO content 33 wt%) and a prepolymer of HMDI (NCO content 10.2 wt%) compounded at a weight ratio of 2:5.

[0143] Table 4

[0144]

[0145] The foaming reaction parameters in the preparation of the polyurea foams of Examples [1] to

[10] were measured and are shown in Table 4. The emulsification time is the time when the polyurea foam material starts to rise, and the gel time is the time when the polyurea foam is not sticky. In Table 4, “[1]” means “Example [1]”, and so on. Since the amine group in the CO2 adduct of the terminal amino compound reacts quickly with the isocyanate, the higher the amine group content in the CO2 adduct (i.e. the amine value of the CO2 adduct of the terminal amino compound in Table 4), the faster the foaming reaction, i.e. the shorter the emulsification time and the gel time. At the same time, the higher the primary amine content, the faster the reaction, because the reaction rate of the primary amine with the isocyanate is higher than that of the secondary amine with the isocyanate. Therefore, the higher the primary amine content in the CO2 adduct of the terminal amino compound, the shorter the emulsification time and the gel time.

[0146] The performance of Examples [1] to

[10] was tested, and the test results (the data are the average values of 5 tests) are shown in Table 5. The change in the mechanical properties of the foams is normal. Generally, the greater the density, the higher the mechanical strength.

[0147] Table 5

[0148]

[0149] The above description is only examples of the present application and is not intended to limit the present application. The present application can be variously changed and modified by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.

Claims

1. A process for the preparation of a polyurea foam material, characterized in that, The polyurea foam is prepared by mixing a B component and an A component, the B component comprising at least a CO2 adduct of an amino-terminated compound and no catalyst, the A component comprising a polyisocyanate compound, the amino-terminated compound and the polyisocyanate compound having a functionality of at least 2.

2. The process for the preparation of a polyurea foam according to claim 1, characterized in that, The CO2 adduct of the amino-terminated compound in the B component is prepared by reacting an amino-terminated compound with CO2, the amino-terminated compound comprising at least one of a primary amino-terminated compound, a secondary amino-terminated compound, and a capped modified primary amino-terminated compound, the primary amino-terminated compound comprising at least one of a primary amino-terminated polyoxyethylene ether, a primary amino-terminated polyoxypropylene ether, and a primary amino-terminated polydimethylsiloxane, the secondary amino-terminated compound comprising at least one of an aromatic dibasic secondary amine chain extender, an aliphatic dibasic secondary amine chain extender, and a polyaspartic ester, the capped modified primary amino-terminated compound being prepared by capping modification of a primary amino-terminated compound selected from a primary amino-terminated polyoxyethylene ether, a primary amino-terminated polyoxypropylene ether, and a primary amino-terminated polydimethylsiloxane, the primary amino group being covalently bonded to a capping chain, the capping chain comprising at least one of: (1) the capping chain containing at least one repeating unit of a polyoxyethylene ether and / or a polyoxypropylene ether; (2) the capping chain containing a trimethylsilyl group; (3) the capping chain containing a hydrocarbon group having 1 to 12 carbon atoms; (4) the capping chain containing a fluorine-containing alkyl group having 1 to 12 carbon atoms; the number of moles of the capping chain being 0 to 100% based on the N atoms in the amino-terminated polyether.

3. The method of producing a polyurea foam according to claim 1, wherein The B component can further comprise a foam stabilizer selected from a polyoxypropylene-polyoxyethylene copolyether, a polyoxyethylene-polysiloxane copolymer, a polyoxypropylene-polysiloxane copolymer, or a polyoxyethylene propylene-polysiloxane copolymer.

4. The method of claim 1, wherein the polyurea foam is prepared by reacting the polyisocyanate with the polyamine in the presence of water. The B component can further comprise an amino-terminated chain extender, the amino-terminated chain extender comprising at least one of ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexanediamine, Unilink 4100 (4,4'-dialkylphenyldiamine), Unilink 4200 (4,4'-bis-sec-butylaminodiphenylmethane), Clearlink 1000 (4,4'-bis-sec-butylaminodicyclohexylmethane), Clearlink 3000 (3,3'-dimethyl-4,4'-bis-sec-butylamino-dicyclohexylmethane), Jefflink 754 (4,4'-bis-sec-pentylcyclohexanediamine).

5. The method of claim 1, wherein the polyurea foam is prepared by reacting the polyisocyanate with the polyamine in the presence of a blowing agent. The polyisocyanate compound in the A component is selected from one or more of dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), p-phenylene diisocyanate (PDI), butylene diisocyanate (BDI), naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), pentamethylene diisocyanate (PDI), and prepolymers of the foregoing, and can also be selected from one or more of polymethylene polyphenyl polyisocyanate (PMDI), IPDI trimer, and HDI trimer.

6. The method of claim 1, wherein the polyurea foam is prepared by reacting the polyisocyanate with the polyamine in the presence of a blowing agent. The terminal amino compound includes a terminal secondary amino compound, which includes an aromatic dibasic secondary amine chain extender and an aliphatic dibasic secondary amine chain extender; the aromatic dibasic secondary amine chain extender is selected from at least one of Unilink 4100 (4,4'-dialkylphenyldiamine) and Unilink 4200 (4,4'-bis-sec-butylaminodiphenylmethane), and the aliphatic dibasic secondary amine chain extender is selected from at least one of Clearlink 1000 (4,4'-bis-sec-butylaminodicyclohexylmethane), Clearlink 3000 (3,3'-dimethyl-4,4'-bis-sec-butylamino-dicyclohexylmethane), and Jefflink 754 (4,4'-bis-sec-pentylcyclohexanediamine).

7. A polyurea foam prepared according to the method of any one of claims 1 to 6, characterized in that, The polyurea foam material contains no other auxiliary components except for a small amount of foam stabilizer, and has high foam purity.

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