Polyimine and polyamine containing alkyl main chain and preparation method of polyimine and polyamine

Abstract

The invention discloses polyimine and polyamine containing an alkyl main chain and a preparation method of the polyimine and the polyamine, and belongs to the technical field of synthesis of high polymer materials. The preparation method comprises the following steps: firstly, reacting N, N '-diboryl diamine generated after boronizing alkyl diamine with organic dialdehyde under proper conditions to synthesize polyimine containing an alkyl main chain; and secondly, carrying out hydrogenation reduction reaction on the polyimine containing the alkyl main chain prepared in the first step under proper conditions to obtain polyamine. The method is used for solving the technical problems that an existing polyamine synthesis technology is limited by toxic monomers (such as ethyleneimine) and an alkyl-containing main chain structure cannot be synthesized by a traditional process, so that industrialization is difficult and varieties are scarce.

Description

Technical Field

[0001] The present invention belongs to the technical field of the synthesis of polymer materials, and particularly relates to a polyimine and a polyamine containing an alkyl main chain and a preparation method thereof. Background Art

[0002] Polyamines are a class of high molecular polymers containing multiple repeating amino (-NH) structural units. Polyamines have structural diversity, and by regulating the functional groups of their main chains and side chains, they have become indispensable materials in many industrial processes. For example, polyamines can be used as flocculants for water treatment to effectively remove suspended particles in water; in a certain oil extraction application case, polyamines can be used as mud stabilizers to help improve drilling efficiency and reduce costs; polyamines can be used in the paper manufacturing process as strengthening agents to increase the dry and wet strength of paper.

[0003] Currently, two examples of polyamine epichlorohydrin-dimethylamine copolymers and polyethyleneimine are known. Epichlorohydrin-dimethylamine copolymer (Dimethylamine-epichlorohydrin copolymer, Figure 1 ) is an important class of polyamine polymers with a CAS number of 39660-17-8. This polymer can be used as a water treatment flocculant for drinking water, sewage purification, and oilfield wastewater treatment, and has the characteristics of fast coagulation speed, good effect, and environmental friendliness. Due to its high molecular weight and strong adsorption bridging ability, it is widely used in industrial wastewater treatment. In addition, due to its high-efficiency flocculation effect and environmental protection characteristics, this polymer is also widely used in fields such as oilfield wastewater treatment, demonstrating its diverse application values. Polyethyleneimine (Polyethyleneimine, PEI, Figure 1 ) also known as polyaziridine, with a CAS number of 9002-98-6, is a water-soluble polyamine polymer. Polyethyleneimine has high reactivity and can react with the hydroxyl groups in cellulose and crosslink and polymerize, making the paper have wet strength and having a dry strengthening effect. Polyethyleneimine can also be used in fiber modification, printing and dyeing auxiliaries, ion exchange resins, and coagulation and sedimentation (metal trapping, wastewater treatment), etc. In addition, under certain conditions, polyethyleneimine materials can absorb carbon dioxide in the air and permanently seal carbon dioxide in the polyethyleneimine solid material, or carbon dioxide can be extracted for other fields. This material can be reused. The unique multi-level amine structure of polyethyleneimine can effectively compress and encapsulate protein or gene drugs, and compress DNA strands into spherical, circular, or rod-shaped structures through non-covalent bond interactions, and is commonly used as a high molecular drug carrier.

[0004] Epichlorohydrin-dimethylamine copolymer is formed by the polycondensation of dimethylamine and epichlorohydrin under heating conditions; while polyethyleneimine is obtained by the polymerization reaction of ethyleneimine monomers, and the ethyleneimine used is a corrosive and toxic monomer, which is not friendly to humans and the environment.

[0005] In addition to the above two known polyamines, the types of polyamine polymers are very few, and there is currently no universal synthesis method. It is worth mentioning that the traditional acid-catalyzed dehydration polycondensation method is difficult to be used to synthesize polyimines with an alkyl main chain, difficult to scale up production and industrialization, and thus limits the synthesis of its reduction product polyamine.

[0006] In summary, the existing polyamine synthesis technology is limited by toxic monomers (such as ethyleneimine) and traditional process defects (such as the inability to synthesize structures with an alkyl main chain), resulting in difficulties in industrialization and scarcity of types. There is an urgent need to develop a universal green synthesis method. Summary of the Invention

[0007] To overcome the above-mentioned disadvantages of the prior art, the object of the present invention is to provide a polyimine and polyamine with an alkyl main chain and a preparation method thereof. The alkyl polyimine is synthesized by the deboronation polycondensation method of N,N'-bisboronated diamine and dialdehyde, and then the polyamine is obtained by reduction with sodium borohydride. Based on this, a series of alkyl polyamines can be synthesized in excellent yields to solve the technical problems that the existing polyamine synthesis technology is limited by toxic monomers (such as ethyleneimine) and the traditional process cannot synthesize structures with an alkyl main chain, resulting in difficulties in industrialization and scarcity of types.

[0008] To achieve the above object, the present invention adopts the following technical solutions: The present invention provides a preparation method of a polyimine with an alkyl main chain, comprising the following steps: Boronate the alkyl diamine with an organoborane to generate N,N'-bisboronated diamine; React N,N'-bisboronated diamine with an organic dialdehyde to obtain a polyimine with an alkyl main chain.

[0009] In one embodiment, the organoborane is pinacol borane or 9-borabicyclo[3.3.1]nonane; the alkyl diamine is any one of 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine; the organic dialdehyde is any one of terephthalaldehyde, 2,5-bis(octyloxy)terephthalaldehyde, 3-bromoisophthalaldehyde, 2,5-thiophenedialdehyde, 2-bromomalonaldehyde, 2-chloromalonaldehyde, 1,4-cyclohexanedialdehyde.

[0010] In one embodiment, the molar ratio of the alkyl diamine to the organoborane is 1:(2.0 - 3.0); the molar ratio of N,N'-bisboronated diamine to the organic dialdehyde is 1:(0.8 - 1.2).

[0011] In one embodiment, the process of borating an alkyl diamine with an organic borane to produce N,N'-bisboronated diamine is as follows: Under nitrogen protection, the alkyl diamine is added to organic solvent I and stirred at room temperature to obtain a reaction mixture; the organic borane and triethylamine are added to the above reaction mixture, and the reaction is carried out by stirring at a set temperature to obtain a crude product of N,N'-bisboronated diamine; the crude product of N,N'-bisboronated diamine is cooled to room temperature, and the organic solvent is removed by a diaphragm pump at room temperature to obtain N,N'-bisboronated diamine; The process of reacting the N,N'-bisboronated diamine with an organic dialdehyde to obtain a polyimine containing an alkyl main chain is as follows: Under nitrogen protection, the organic dialdehyde and organic solvent II are added to the N,N'-bisboronated diamine, and the reaction is carried out by stirring at room temperature. Then, the organic solvent is removed by a diaphragm pump at room temperature to obtain a polyimine containing an alkyl main chain.

[0012] In one embodiment, the molar concentration of the alkyl diamine in organic solvent I is 0.1 to 5.0 mol / L; the molar ratio of triethylamine to alkyl diamine is 1:(10 to 100); the molar concentration of the organic dialdehyde in organic solvent II is 0.1 to 5.0 mol / L; the set temperature is 60°C to 120°C; The organic solvent I is any one of toluene, m-xylene, tetrahydrofuran, and acetonitrile; the organic solvent II is any one of toluene, o-xylene, m-xylene, tetrahydrofuran, and 1,4-dioxane.

[0013] The present invention also provides a polyimine containing an alkyl main chain prepared by the above method for preparing a polyimine containing an alkyl main chain. The structural formula of the polyimine containing an alkyl main chain is shown as the following formula (1): (1) In formula (1), R1 represents an alkyl group containing at least 3 carbon atoms, R2 is an aryl group, a heteroaryl group, or an alkyl group; n is the degree of polymerization of the polyimine containing an alkyl main chain, which is an integer from 10 to 1000.

[0015] The present invention also provides a method for preparing a polyamine containing an alkyl main chain. Using the above polyimine containing an alkyl main chain, the method includes the following steps: Dissolve the polyimine containing an alkyl main chain in organic solvent III, and then add it to a methanol solution of a hydrogenation reducing agent. The reaction is carried out by stirring at a set low temperature. After the reaction is completed, water is added to the reaction mixture to quench the remaining hydrogenation reducing agent, and then liquid separation and extraction are carried out to collect the first organic phase; An aqueous solution of hydrochloric acid was added to the first organic phase, stirred at room temperature, separated by liquid-liquid extraction, and the aqueous phase suspension was collected. An aqueous solution of sodium hydroxide was added to the aqueous phase suspension and stirred at room temperature, then an extractant was added, followed by liquid-liquid extraction. The second organic phase was collected, and the extractant was removed at room temperature using a diaphragm pump to obtain a polyamine with an alkyl main chain.

[0016] In one embodiment, the hydrogenation reducing agent is any one of sodium borohydride, lithium aluminum hydride, and borane·tetrahydrofuran; the molar ratio of the monomer of the polyimine with an alkyl main chain to the hydrogenation reducing agent is 1:(10 - 20); the molar ratio of the monomer of the polyimine with an alkyl main chain to hydrochloric acid is 1:(10 - 20); the molar ratio of the monomer of the polyimine with an alkyl main chain to sodium hydroxide is 1:(10 - 20).

[0017] In one embodiment, the monomer molar concentration of the polyimine with an alkyl main chain in organic solvent III is 0.1 - 5.0 mol / L; the organic solvent III is any one of dichloromethane, chloroform, tetrahydrofuran, and 1,4-dioxane; the molar concentration of the methanol solution of the hydrogenation reducing agent is 1.0 - 10.0 mol / L; the set low temperature is 0°C to -30°C; the volume ratio of the first organic phase to the aqueous solution of hydrochloric acid is 1:(0.5 - 2); the molar concentration of hydrochloric acid in the aqueous solution of hydrochloric acid is 12 mol / L; the volume ratio of the aqueous phase suspension to the aqueous solution of sodium hydroxide is 1:(0.5 - 1.5); the molar concentration of sodium hydroxide in the aqueous solution of sodium hydroxide is 1 - 3 mol / L.

[0018] The present invention provides a polyamine with an alkyl main chain prepared by the above-mentioned method for preparing a polyamine with an alkyl main chain. The structural formula of the polyamine with an alkyl main chain is as shown in the following formula (2): (2) In formula (2), R1 represents an alkyl group containing at least 3 carbon atoms, R2 is an aryl group, a heteroaryl group, or an alkyl group; n is the degree of polymerization of the polyamine with an alkyl main chain, which is an integer from 10 to 1000.

[0020] Furthermore, the polyamine with an alkyl main chain is obtained by a hydrogenation reduction reaction of the above-mentioned polyimine with an alkyl main chain and a hydrogenation reducing agent.

[0021] Compared with the prior art, the present invention has the following beneficial effects: On the one hand, the present invention provides a method for preparing a polyimine containing an alkyl main chain. By pre-borating the alkyl diamine, the reactivity of the monomer is significantly enhanced, enabling it to efficiently polymerize with an organic dialdehyde through deboronation condensation to produce a polyimine product. Under this polymerization mechanism, the polymerization reaction can be carried out at room temperature without the addition of extra catalysts and additives, with high efficiency and easy scalability. In contrast, the un-borated alkyl diamine is difficult to polymerize with the dialdehyde to form an alkyl polyimine. And under acid-catalyzed conditions, the alkyl polyimine is prone to degradation and the polymer yield is low.

[0022] On the other hand, the present invention also provides a method for preparing a polyamine containing an alkyl main chain. This preparation method uses the above-mentioned polyimine containing an alkyl main chain as the raw material. Different from the traditional method of synthesizing polyethyleneimine which requires the use of toxic and corrosive monomers such as ethyleneimine, it has environmental pollution and harm to the human body. The method for reducing and hydrogenating based on alkyl polyimine disclosed in the present invention can obtain alkyl polyamine polymers with high yield and safety, which is friendly to the environment and the human body. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Schematic structural diagrams of two existing polyamine polymers, epichlorohydrin-dimethylamine copolymer and polyethyleneimine; Figure 2 Schematic reaction diagrams for synthesizing polyimine containing an alkyl main chain by deboronation polycondensation method and synthesizing the corresponding polyamine by reduction and hydrogenation method proposed by the present invention.

[0024] Figure 3 Schematic process diagram for the diboration of 1,3-propanediamine by reaction with pinacol borane and then the deboronation condensation reaction with terephthalaldehyde to produce polyimine 3a.

[0025] Figure 4 Schematic process diagram for the diboration of 1,4-butanediamine by reaction with pinacol borane and then the deboronation condensation reaction with terephthalaldehyde to produce polyimine 3b.

[0026] Figure 5 Schematic process diagram for the diboration of 1,5-pentanediamine by reaction with pinacol borane and then the deboronation condensation reaction with terephthalaldehyde to produce polyimine 3c.

[0027] Figure 6 Schematic process diagram for the diboration of 1,6-hexanediamine by reaction with pinacol borane and then the deboronation condensation reaction with terephthalaldehyde to produce polyimine 3d.

[0028] Figure 7 Schematic process diagram for the diboration of 1,8-octanediamine by reaction with pinacol borane and then the deboronation condensation reaction with terephthalaldehyde to produce polyimine 3e.

[0029] Figure 8 Schematic process diagram of the deborylation polycondensation of the N,N'-bisboronated diamine intermediate 2e formed by the diboration of 1,8-octanediamine with 2,5-bis(octyloxy)terephthalaldehyde to produce polyimine 3f.

[0030] Figure 9 Schematic process diagram of the deborylation polycondensation of the N,N'-bisboronated diamine intermediate 2e formed by the diboration of 1,8-octanediamine with 3-bromoisophthalaldehyde to produce polyimine 3g.

[0031] Figure 10 Schematic process diagram of the deborylation polycondensation of the N,N'-bisboronated diamine intermediate 2e formed by the diboration of 1,8-octanediamine with 2,5-thiophenedicarboxaldehyde to produce polyimine 3h.

[0032] Figure 11 Schematic process diagram of the deborylation polycondensation of the N,N'-bisboronated diamine intermediate 2d formed by the diboration of 1,6-hexanediamine with 2-bromomalonaldehyde to produce polyimine 3i.

[0033] Figure 12 Schematic process diagram of the deborylation polycondensation of the N,N'-bisboronated diamine intermediate 2e formed by the diboration of 1,8-octanediamine with 2-chloromalonaldehyde to produce polyimine 3j.

[0034] Figure 13 Schematic process diagram of the deborylation polycondensation of the N,N'-bisboronated diamine intermediate 2e formed by the diboration of 1,8-octanediamine with 1,4-cyclohexanedicarboxaldehyde to produce polyimine 3k.

[0035] Figure 14 Schematic process diagram of the reaction of polyimine 3a containing a 1,3-propanediamine main chain with sodium borohydride to produce the corresponding polyamine 4a.

[0036] Figure 15 Schematic process diagram of the reaction of polyimine 3b containing a 1,4-butanediamine main chain with sodium borohydride to produce the corresponding polyamine 4b.

[0037] Figure 16 Schematic process diagram of the reaction of polyimine 3c containing a 1,5-pentanediamine main chain with sodium borohydride to produce the corresponding polyamine 4c.

[0038] Figure 17 Schematic process diagram of the reaction of polyimine 3d containing a 1,6-hexanediamine main chain with sodium borohydride to produce the corresponding polyamine 4d. Specific embodiments

[0039] To enable those skilled in the art to understand the features and effects of the present invention, the following provides a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein shall have the ordinary meanings understood by those skilled in the art regarding the present invention. In case of conflicts, the definitions in this specification shall prevail.

[0040] In this article, for the sake of concise description, not all possible combinations of all technical features in each embodiment or example are described. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each embodiment or example can be combined arbitrarily, and all possible combinations should be considered as the scope described in this specification.

[0041] This embodiment discloses a synthesis process of a polyimine and a polyamine containing an alkyl main chain. The synthesis scheme of the process includes two aspects of steps. The first aspect is the preparation method of the polyimine, and the second aspect is the preparation method of the polyamine. In the first aspect, the N,N'-bis(boron-based) diamine generated after the alkyl diamine is borated reacts with an organic dialdehyde under appropriate conditions to synthesize a polyimine containing an alkyl main chain. In the second aspect, the polyimine containing an alkyl main chain obtained in the first aspect undergoes a hydrogenation reduction reaction under appropriate conditions to obtain a polyamine.

[0042] Among them, the preparation method of the polyimine containing an alkyl main chain is as follows. The N,N'-bis(boron-based) diamine generated after the alkyl diamine is borated reacts with an organic dialdehyde under appropriate conditions to obtain a crude polyimine product. Then, the crude polyimine product is filtered and washed at room temperature, and then impurities are removed through Soxhlet extraction and drying operations, and a purified polyimine product is collected.

[0043] Specifically, the preparation method of the above-mentioned polyimine containing an alkyl main chain includes the following steps: S1: Under nitrogen protection, add the alkyl diamine to an appropriate organic solvent I and stir at room temperature to obtain a reaction mixture. S2: Add the organoborane and triethylamine to the reaction mixture in S1 and stir at a set temperature for reaction. After the reaction is completed, a crude N,N'-bis(boron-based) diamine product is obtained. S3: Cool the crude N,N'-bis(boron-based) diamine product to room temperature and use a diaphragm pump to pump out the organic solvent at room temperature to obtain an N,N'-bis(boron-based) diamine intermediate. S4: Under nitrogen protection, add the organic dialdehyde and organic solvent II to the N,N'-bis(boron-based) diamine intermediate in S3 and stir at room temperature for reaction. S5: After the reaction is completed, use a diaphragm pump to pump out the organic solvent at room temperature and collect the crude polyimine product. S6: The polyimide crude product is washed with a suitable organic solvent and then dried to obtain the polyimide product.

[0044] In S1, the alkylenediamine can be: 1,3 - propanediamine, 1,4 - butanediamine, 1,5 - pentanediamine, 1,6 - hexanediamine, 1,8 - octanediamine.

[0045] In S1, the organic solvent I can be: toluene, m - xylene, tetrahydrofuran, acetonitrile, and acetonitrile is preferably selected. Among them, the molar concentration of the alkylenediamine in the organic solvent I is 0.1 - 5.0 mol / L, and in the examples of the present invention, the molar concentration of the alkylenediamine in the organic solvent I is preferably 0.5 mol / L.

[0046] In S2, the organoborane can be pinacolborane, 9 - borabicyclo[3.3.1]nonane, and pinacolborane is preferably selected. Among them, the molar ratio of the alkylenediamine to the organoborane is 1:(2.0 - 3.0), and in the examples of the present invention, the molar ratio of the alkylenediamine to the organoborane is preferably 1:2.4. Under the condition of excessive organoborane, the reaction can proceed normally; the molar ratio of triethylamine to the alkylenediamine is 1:(10 - 100), and in the examples of the present invention, the molar ratio of triethylamine to the alkylenediamine is preferably 1:10.

[0047] In S2, the set temperature can be 60°C - 120°C, and 60°C, 80°C, 100°C, 120°C are preferably selected. In the examples of the present invention, 80°C is preferably selected.

[0048] In S4, the organic dialdehyde can be: terephthalaldehyde, 2,5 - bis(octyloxy)terephthalaldehyde, 3 - bromoisophthalaldehyde, 2,5 - thiophenedialdehyde, 2 - bromomalonaldehyde, 2 - chloromalonaldehyde, 1,4 - cyclohexanedialdehyde. In S4, the organic solvent II can be toluene, o - xylene, m - xylene, tetrahydrofuran, 1,4 - dioxane, and m - xylene is preferably selected. Among them, the molar ratio of N,N'-bis(boron - based)diamine to the organic dialdehyde is 1:(0.8 - 1.2), and in the examples of the present invention, the molar ratio of N,N'-bis(boron - based)diamine to the organic dialdehyde is preferably 1:1; the molar concentration of the organic dialdehyde in the organic solvent II is 0.1 - 5.0 mol / L, and in the examples of the present invention, the molar concentration of the organic dialdehyde in the organic solvent II is preferably 0.1 mol / L.

[0049] In S6, the solvent for washing the reaction mixture is preferably methanol, m - xylene or dichloromethane.

[0050] The present invention also provides a polyimide with an alkyl main chain prepared by the above - mentioned preparation method. The structural formula of the polyimide with an alkyl main chain is shown as the following formula (1): (1) In formula (1), R1 represents an alkyl group containing at least 3 carbon atoms, R2 is an aryl group, a heteroaryl group or an alkyl group; n is the degree of polymerization of the polyimine with an alkyl group-containing main chain, which is an integer from 10 to 1000.

[0052] Further, in formula (1), R1 represents an alkyl group containing 3 to 8 carbon atoms, R2 is an aryl group, a heteroaryl group or an alkyl group; n is the degree of polymerization of the polyimine with an alkyl group-containing main chain, which is an integer from 10 to 1000.

[0053] Further, in formula (1), R1 represents a linear alkyl group containing 3 to 8 carbon atoms, R2 is a phenyl group, a substituted phenyl group, a thiophenyl group, a linear alkyl group or a cyclic alkyl group; n is the degree of polymerization of the polyimine with an alkyl group-containing main chain, which is an integer from 10 to 1000.

[0054] Further, in formula (1), R1 can be independently selected from -CH2-CH2-CH2-, -CH2-(CH2)2-CH2-, -CH2-(CH2)3-CH2-, -CH2-(CH2)4-CH2- or -CH2-(CH2)6-CH2-; R2 is a substituent derived from an organic dialdehyde, and R2 is 1,4-phenyl-, 2,5-bis(octyloxy)-1,4-phenyl-, 3-bromo-1,5-phenyl-, 2,5-thiophenyl-, bromomethyl-, chloromethyl-, 1,4-cyclohexyl-; n is the degree of polymerization of the polyimine with an alkyl group-containing main chain, which is an integer from 10 to 1000.

[0055] Among them, the preparation method of the polyamine with an alkyl group-containing main chain is as follows. The polyimine with an alkyl group-containing main chain prepared by using the above S1~S6 is subjected to a hydrogenation reduction reaction under appropriate conditions to obtain a crude polyamine product, and then the crude polyamine product is subjected to extraction, washing and drying operations at room temperature to remove impurities, and the purified polyamine product is collected.

[0056] Specifically, it includes the following steps: S7: Dissolve the polyimine product with an alkyl group-containing main chain prepared by using the above S1~S6 in an appropriate organic solvent III, slowly add it to a methanol solution of a hydrogenation reducing agent, and stir at a set low temperature for reaction; S8: After the reaction is completed, add water to the reaction mixture to quench the remaining hydrogenation reducing agent, then separate the liquid and extract, and collect the first organic phase; S9: Add an aqueous solution of hydrochloric acid to the first organic phase, stir at room temperature, then separate the liquid and extract, and collect the aqueous phase suspension; S10: Add an aqueous solution of sodium hydroxide to the aqueous phase suspension, stir at room temperature, then add an extractant, separate the liquid and extract, and collect the second organic phase. The extractant is preferably dichloromethane; S11: Use a diaphragm pump to pump out the extractant at room temperature to obtain a polyamine product with an alkyl group-containing main chain.

[0057] In S7, the hydrogenation reducing agent can be sodium borohydride, lithium aluminum hydride, borane·tetrahydrofuran, and preferably sodium borohydride. In S7, the monomer molar concentration of the polyimine with an alkyl main chain in organic solvent III is 0.1 - 5.0 mol / L. In S7, the organic solvent III can be: dichloromethane, chloroform, tetrahydrofuran, 1,4-dioxane, and preferably dichloromethane. In S7, the low temperature is set to 0°C to -30°C, and the preferred low temperature reaction conditions can be 0°C, -10°C, -20°C, -30°C, and in the examples of the present invention, 0°C is preferred. In S7, the molar ratio of the monomer of the polyimine with an alkyl main chain to the hydrogenation reducing agent is 1:(10 - 20), and in the examples of the present invention, the molar ratio of the monomer of the polyimine with an alkyl main chain to the hydrogenation reducing agent is preferably 1:10. In the presence of an excessive hydrogenation reducing agent, the reaction can proceed normally. In S7, the molar concentration of the methanol solution of the hydrogenation reducing agent is 1.0 - 10.0 mol / L, and in the examples of the present invention, the molar concentration of the methanol solution of the hydrogenation reducing agent is preferably 1.0 mol / L.

[0058] In S9, the volume ratio of the first organic phase to the aqueous hydrochloric acid solution is 1:(0.5 - 2), and in the examples of the present invention, the volume ratio of the first organic phase to the aqueous hydrochloric acid solution is preferably 1:2; in the examples of the present invention, the molar concentration of hydrochloric acid in the aqueous hydrochloric acid solution is preferably 12 mol / L. In S9, the molar ratio of the monomer of the polyimine with an alkyl main chain to hydrochloric acid is 1:(10 - 20), and in the examples of the present invention, the molar ratio of the monomer of the polyimine with an alkyl main chain to hydrochloric acid is preferably 1:20. In the presence of an excessive amount of hydrochloric acid, the reaction can proceed normally.

[0059] In S10, the volume ratio of the aqueous suspension to the aqueous sodium hydroxide solution is 1:(0.5 - 1.5), and in the examples of the present invention, 1:1 is preferred; the molar concentration of sodium hydroxide in the aqueous sodium hydroxide solution is 1 - 3 mol / L, and in the examples of the present invention, 1 mol / L is preferred. In S10, the molar ratio of the monomer of the polyimine with an alkyl main chain to sodium hydroxide is 1:(10 - 20), and in the examples of the present invention, the molar ratio of the monomer of the polyimine with an alkyl main chain to sodium hydroxide is preferably 1:20. In the presence of an excessive amount of sodium hydroxide, the reaction can proceed normally.

[0060] The present invention also provides a polyamine with an alkyl main chain prepared by the above preparation method. This polyamine with an alkyl main chain is obtained by subjecting the above polyimine with an alkyl main chain to a hydrogenation reduction reaction with a hydrogenation reducing agent; The structural formula of this polyamine with an alkyl main chain is shown as the following formula (2): (2) In formula (2), R1 represents an alkyl group containing at least 3 carbon atoms, R2 is an aryl group, a heteroaryl group or an alkyl group; n is the degree of polymerization of the polyamine with an alkyl main chain, which is an integer from 10 to 1000.

[0062] Further, in formula (2), R1 represents an alkyl group containing 3 to 8 carbon atoms, R2 is an aryl group, a heteroaryl group or an alkyl group; n is the degree of polymerization of the polyamine with an alkyl main chain, which is an integer from 10 to 1000.

[0063] Further, in formula (2), R1 represents a linear alkyl group containing 3 to 8 carbon atoms, R2 is a phenyl group, a substituted phenyl group, a thiophenyl group, a linear alkyl group or a cyclic alkyl group; n is the degree of polymerization of the polyamine with an alkyl main chain, which is an integer from 10 to 1000.

[0064] Further, in formula (2), R1 can be independently selected from -CH2-CH2-CH2-, -CH2-(CH2)2-CH2-, -CH2-(CH2)3-CH2-, -CH2-(CH2)4-CH2- or -CH2-(CH2)6-CH2-; R2 is a substituent derived from an organic dialdehyde, and R2 is 1,4-phenyl-, 2,5-bis(octyloxy)-1,4-phenyl-, 3-bromo-1,5-phenyl-, 2,5-thiophenyl-, bromomethyl-, chloromethyl-, 1,4-cyclohexyl-; n is the degree of polymerization of the polyamine with an alkyl main chain, which is an integer from 10 to 1000.

[0065] Figure 1 Schematic diagrams of the structures of two commercially available polyamine polymer materials. Figure 2 Schematic diagram of the reactions for synthesizing polyimine by the deboronation polycondensation method and polyamine by the reduction hydrogenation method in the present invention. Figures 4 to 13 Schematic diagram of the examples of synthesizing polyimine with an alkyl main chain by the deboronation polycondensation reaction in Examples 1 to 11 of the present invention. From Figures 14 to 17 Schematic diagram of the examples of synthesizing the corresponding polyamine from polyimine with an alkyl main chain by the reduction hydrogenation method in Examples 12 to 15 of the present invention. Currently, it is difficult to obtain these polyimine and polyamine polymer materials with an alkyl main chain by traditional methods.

[0066] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0067] Conventional instruments and equipment in the art are used in the following examples. For the experimental methods without specific conditions noted in the following examples, they are generally carried out under conventional conditions or according to the conditions recommended by the manufacturer. Various raw materials are used in the following examples. Unless otherwise stated, commercially available products are used, and their specifications are conventional specifications in the art. In the specification of the present invention and the following examples, unless otherwise specified, "%" represents weight percentage, "parts" represents weight parts, and the ratio represents weight ratio.

[0068] Example 1 See Figure 3 This example discloses a polymerization process for synthesizing polyimine 3a by diboration of 1,3-propanediamine through reaction with pinacol borane followed by deboronation polycondensation reaction with terephthalaldehyde.

[0069] As Figure 3 shown, the specific synthesis steps of this example are as follows: S1. Under nitrogen protection, add 1,3-propanediamine (222 mg, 3 mmol) to acetonitrile (6 mL) and stir at room temperature; S2. Add pinacol borane (1.1 mL, 0.9 g, 7.2 mmol, 2.4 equiv.) and triethylamine (40 μL, 30 mg, 0.3 mmol, 10 mol%) to the reaction mixture in S1, and raise the temperature to 80 °C and stir for 18 hours; S3. After the reaction is completed, cool the reaction mixture to room temperature, and use a diaphragm pump to remove the organic solvent at room temperature to obtain the N,N'-bisboronated diamine intermediate 2a; S4. Under nitrogen protection, add N,N'-bisboronated diamine 2a (196 mg, 0.6 mmol, 1.0 equiv.) and terephthalaldehyde (81 mg, 0.6 mmol, 1.0 equiv.) to m-xylene (6 mL) and stir at room temperature for 18 hours; S5. After the reaction is completed, use a diaphragm pump to remove the organic solvent at room temperature and collect the reaction mixture; S6. Wash the reaction mixture with methanol and then dry to obtain the polyimine product 3a.

[0070] The polyimine product 3a obtained in this example is a white solid (96 mg), and the yield is 74%. The product was characterized by gel permeation chromatography, 1 H, 13 13C nuclear magnetic resonance, infrared spectroscopy and elemental analysis.

[0071] GPC (CHCl3, 35 °C): M n= 23.5 kDa, M w = 48.6 kDa, Ð = 2.07, DP n = 137. 1 1H NMR (400 MHz, CDCl3): δ 10.06 - 8.12 (m, 2H), 7.92 - 7.29 (m, 4H), 3.88 - 3.75 (m, 4H), 2.33 - 2.13 (m, 2H) ppm. 13 13C { 1 1H} NMR (101 MHz, CDCl3): δ 192.0, 160.9, 138.2, 130.1, 128.7, 128.4, 59.5, 32.1 ppm. IR (KBr, cm -1 -1): 3268 (w), 2925 (s), 2841 (s), 1698 (s), 1641 (s), 1605 (m), 1566 (m), 1449 (s), 1368 (s), 1343 (s), 1298 (s), 1216 (m), 1096 (m), 1049 (m), 1018 (m), 971 (s), 839 (s), 522 (m). Elem. Anal.: Calc. (%) for (C 11 H 12 N2) n : C 76.71, H 7.02, N 16.27; found: C 75.81, H 6.88, N 15.34. Example 2 See Figure 4 This example discloses a polymerization process for synthesizing polyimine 3b by diboration of 1,4 - butanediamine through reaction with pinacol borane and then deboronation polycondensation reaction with terephthalaldehyde.

[0072] As Figure 4 shown, the specific synthesis steps of this example are as follows: S1. Under nitrogen protection, add 1,4 - butanediamine (264 mg, 3 mmol) to acetonitrile (6 mL) and stir at room temperature; S2. Add pinacol borane (1.1 mL, 0.9 g, 7.2 mmol, 2.4 equiv.) and triethylamine (40 μL, 30 mg, 0.3 mmol, 10 mol%) to the reaction mixture in S1, and heat the mixture to 80 °C and stir for 18 h; S3. After the reaction is completed, cool the reaction mixture to room temperature, and remove the organic solvent at room temperature using a diaphragm pump to obtain the N,N'-bisboron diamine intermediate 2b; S4. Under nitrogen protection, add N,N'-bisboron diamine 2b (204 mg, 0.6 mmol, 1.0 equiv.) and terephthalaldehyde (81 mg, 0.6 mmol, 1.0 equiv.) to m-xylene (6 mL), and stir at room temperature for 18 h; S5. After the reaction is completed, remove the organic solvent at room temperature using a diaphragm pump, and collect the reaction mixture; S6. Wash the reaction mixture with methanol, and then dry it to obtain the polyimine product 3b.

[0073] The polyimine product 3b prepared in this example is a white solid (80 mg), and the yield is 71%. Gel permeation chromatography, 1 H, 13 13C nuclear magnetic resonance, infrared spectroscopy and elemental analysis were used to characterize the product.

[0074] GPC (CHCl3, 35 °C): M n = 21.2 kDa, M w = 41.2 kDa, Ð = 1.94, DP n = 114. 1 1H NMR (400 MHz, CDCl3): δ 10.4 - 8.23 (m, 2H), 8.06 - 7.68 (m, 4H), 3.72 - 3.49 (m, 4H), 1.81 - 1.72 (m, 4H) ppm. 13 13C { 1 1H} NMR (101 MHz, CDCl3): δ 192.0, 191.6, 160.2, 130.3, 130.1, 128.7, 128.4, 61.9, 28.8 ppm. IR (KBr, cm -1): 3264 (w), 3023 (w), 2932 (s), 2839 (s), 1700 (w), 1641(s), 1604 (m), 1567 (m), 1466 (m), 1442 (m), 1412 (s), 1374 (s), 1349 (s),1297 (s), 1204 (m), 1103 (w), 1049 (m), 1003 (s), 946 (s), 835 (s), 740 (w),579 (w), 524 (s). Elem. Anal.: Calc. (%) for (C 12 H 14 N2) n : C 77.38, H 7.58, N 15.04; found: C 76.35, H 7.02, N 14.01. Example 3 See Figure 5 This example discloses a polymerization process for synthesizing polyimine 3c by diboration of 1,5-pentanediamine through reaction with pinacol borane and then deboronation polycondensation reaction with terephthalaldehyde.

[0075] As Figure 5 shown, the specific synthesis steps of this example are as follows: S1. Under nitrogen protection, add 1,5-pentanediamine (306 mg, 3 mmol) to acetonitrile (6 mL), and stir at room temperature; S2. Add pinacol borane (1.1 mL, 0.9 g, 7.2 mmol, 2.4 equiv.) and triethylamine (40 μL, 30 mg, 0.3 mmol, 10 mol%) to the reaction mixture in S1, and heat to 80 °C and stir for 18 hours; S3. After the reaction is completed, cool the reaction mixture to room temperature, and use a diaphragm pump to remove the organic solvent at room temperature to obtain the N,N'-diboronic diamine intermediate 2c; S4. Under nitrogen protection, add N,N'-diboronic diamine 2c (213 mg, 0.6 mmol, 1.0 equiv.) and terephthalaldehyde (81 mg, 0.6 mmol, 1.0 equiv.) to m-xylene (6 mL), and stir at room temperature for 18 hours; S5. After the reaction is completed, use a diaphragm pump to remove the organic solvent at room temperature, and collect the reaction mixture; S6. Wash the reaction mixture with methanol, and then dry to obtain the polyimine product 3c.

[0076] The polyimide product 3c obtained in this example was a white solid (96 mg), with a yield of 79%. Gel permeation chromatography, 1 H, 13 13C nuclear magnetic resonance, infrared spectroscopy and elemental analysis were used to characterize the product.

[0077] GPC (CHCl3, 35 °C): M n = 17.7 kDa, M w = 47.7 kDa, Ð = 2.69, DP n = 88. 1 1H NMR (400 MHz, CDCl3): δ 10.05 - 8.19 (m, 2H), 7.90 - 7.50 (m, 4H), 3.66(m, 4H), 1.77 (m, 4H), 1.28 - 1.20 (m, 2H) ppm. 13 13C { 1 1H} NMR (101 MHz, CDCl3): δ 160.8, 137.9, 128.1, 60.2, 28.5, 22.6ppm. IR (KBr, cm -1 −1): 3269 (w), 3030 (m), 2932 (s), 2847 (s), 1923 (w), 1642(s), 1566 (m), 1507 (w), 1460 (s), 1436 (s), 1412 (s), 1371 (s), 1349 (s),1297 (s), 1216 (s), 1134 (s), 1093 (s), 10 48 (s), 1016 (s), 995 (s), 959 (s),832 (s), 732 (s), 527 (s), 470 (w). Elem. Anal.: Calc. (%) for (C 13 12 16 H n 16N2): C 77.96, H 8.05, N 13.99;found: C 76.72, H 7.30, N 13.64. Example 4 See Figure 6This example discloses a polymerization process for synthesizing polyimine 3d by diboration of 1,6-hexanediamine through reaction with pinacol borane followed by deboronation polycondensation reaction with terephthalaldehyde.

[0078] As Figure 6 shown, the specific synthesis steps of this example are as follows: S1. Under nitrogen protection, add 1,6-hexanediamine (348 mg, 3 mmol) to acetonitrile (6 mL) and stir at room temperature; S2. Add pinacol borane (1.1 mL, 0.9 g, 7.2 mmol, 2.4 equiv.) and triethylamine (40 μL, 30 mg, 0.3 mmol, 10 mol%) to the reaction mixture in S1, and heat to 80 °C and stir for 18 hours; S3. After the reaction is completed, cool the reaction mixture to room temperature, and use a diaphragm pump to remove the organic solvent at room temperature to obtain the N,N'-bisboronated diamine intermediate 2d; S4. Under nitrogen protection, add N,N'-bisboronated diamine 2d (222 mg, 0.6 mmol, 1.0 equiv.) and terephthalaldehyde (81 mg, 0.6 mmol, 1.0 equiv.) to m-xylene (6 mL) and stir at room temperature for 18 hours; S5. After the reaction is completed, use a diaphragm pump to remove the organic solvent at room temperature and collect the reaction mixture; S6. Wash the reaction mixture with methanol and then dry to obtain the polyimine product 3d.

[0079] The polyimine product 3d prepared in this example is a white solid (90 mg), and the yield is 70%. Gel permeation chromatography, 1 H, 13 13C nuclear magnetic resonance, infrared spectroscopy and elemental analysis were used to characterize the product.

[0080] GPC (CHCl3, 35 °C): M n Mw = 15.8 kDa, M w Mn = 34.2 kDa, Ð PDI = 2.16, DP n Mn = 74. 11H NMR (400 MHz, CDCl3): δ 10.05 - 8.20 (m, 2H), 7.92 - 7.52 (m, 4H), 3.63 - 3.60 (m, 4H), 1.72 (m, 4H), 1.42 (m, 4H) ppm. 13 13C { 1 1H} NMR (100 MHz, CDCl3): δ 160.4, 138.2, 128.3, 62.0, 61.7, 31.0, 30.8, 27.3, 27.1 ppm. IR (KBr, cm -1 ): 3266 (m), 3024 (s), 2930 (s), 2853 (s), 2269 (w), 1953 (w), 1827 (w), 1640 (s), 1566 (s), 1508 (m), 1465 (s), 1441 (s), 1413 (s), 1374 (s), 1350 (s), 1326 (s), 1297 (s), 1215 (s), 1165 (s), 1103 (s), 1056 (s), 1024 (s), 956 (s), 831 (s), 794 (m), 726 (s), 524 (s), 440 (s). Elem. Anal.: Calc. (%) for (C 14 H 18 N2) n : C 78.46, H 8.47, N 13.07; found: C 76.75, H 6.97, N 12.90. Example 5 See Figure 7 This example discloses a polymerization process for synthesizing polyimine 3e by diboration of 1,8 - octanediamine through reaction with pinacol borane followed by deboronation polycondensation reaction with terephthalaldehyde.

[0081] As Figure 7 shown, the specific synthesis steps of this example are as follows: S1. Under nitrogen protection, add 1,8 - octanediamine (432 mg, 3 mmol) to acetonitrile (6 mL) and stir at room temperature; S2. Add pinacolborane (1.1 mL, 0.9 g, 7.2 mmol, 2.4 equiv.) and triethylamine (40 μL, 30 mg, 0.3 mmol, 10 mol%) to the reaction mixture in S1, heat up to 80 °C and stir for 18 h; S3. After the reaction is completed, cool the reaction mixture to room temperature, and remove the organic solvent at room temperature using a diaphragm pump to obtain the N,N'-bisboron diamine intermediate 2e; S4. Under nitrogen protection, add N,N'-bisboron diamine 2e (0.6 mmol, 237 mg, 1.0 equiv.) and terephthalaldehyde (0.6 mmol, 81 mg, 1.0 equiv.) to m-xylene (6 mL), and stir at room temperature for 18 h; S5. After the reaction is completed, remove the organic solvent at room temperature using a diaphragm pump, and collect the reaction mixture; S6. Wash the reaction mixture with methanol, and then dry it to obtain the polyimine product 3e.

[0082] The polyimine product 3e prepared in this example is a white solid (122 mg), with a yield of 83%. Gel permeation chromatography, 1 H, 13 13C nuclear magnetic resonance, infrared spectroscopy and elemental analysis were used to characterize the product.

[0083] GPC (CHCl3, 35 °C): M n Mn = 16.4 kDa, M w Mw = 32.4 kDa, Ð Đ = 1.97, DP n Mn = 68. 1 1H NMR (400 MHz, CDCl3): δ 10.0 - 8.27 (m, 2H), 7.75 (m, 4H), 3.61 (m, 4H), 1.70 (m, 4H), 1.35 (m, 8H) ppm. 13 13C { 1 1H} NMR (100 MHz, CDCl3): δ 160.3, 138.2, 128.4, 62.1, 31.0, 29.5, 27.5 ppm. IR (KBr, cm -1): 3394 (w), 2923 (s), 2851 (m), 1640 (s), 1566 (w), 1465(m), 1436 (w), 1370 (m), 1343 (m), 1296 (m), 1216 (w), 1158 (w), 1103 (w),958 (m), 831 (s), 725 (w), 519 (m), 454 (w). Elem. Anal.: Calc. (%) for (C 16 H 22 N2) n : C 79.29, H 9.15, N 11.56;found: C 75.72, H 7.97, N 11.04. Example 6 See Figure 8 This example discloses a polymerization process for the deboronation polycondensation of N,N'-bisboronated diamine intermediate 2e generated from the diboration of 1,8-octanediamine and 2,5-bis(octyloxy)terephthalaldehyde.

[0084] As Figure 8 shown, the specific synthesis steps of this example are as follows: S1. Under nitrogen protection, N,N'-bisboronated diamine 2e (0.6 mmol, 237 mg, 1.0 equiv.) and 2,5-bis(octyloxy)terephthalaldehyde (0.6 mmol, 234 mg, 1.0 equiv.) were added to m-xylene (6 mL), and stirred at room temperature for 18 hours; S2. After the reaction was completed, the organic solvent was removed by a diaphragm pump at room temperature, and the reaction mixture was collected; S3. The reaction mixture was washed with methanol and then dried to obtain the polyimine product 3f.

[0085] The polyimine product 3f obtained in this example was a yellow solid (228 mg), with a yield of 76%. Gel permeation chromatography, 1 H, 13 C nuclear magnetic resonance, infrared spectroscopy and elemental analysis were used to characterize the product.

[0086] GPC (CHCl3, 35 ℃): M n = 14.1 kDa, M w = 35.6 kDa, Ð = 2.51, DP n = 28. 1 1H NMR (400 MHz, CDCl3): δ 10.48 - 8.64 (m, 2H), 7.57 - 7.34 (m, 2H), 4.04 - 4.00 (m, 4H), 3.63 - 3.60 (m, 4H), 1.80 - 1.77 (m, 4H), 1.70 (m, 4H), 1.45 (m, 4H), 1.37 - 1.28 (m, 24H), 0.89 - 0.86 (m, 6H) ppm. 13 13C { 1 1H} NMR (100 MHz, CDCl3): δ 189.8, 156.8, 156.3, 156.1, 152.8, 152.3, 131.7, 127.7, 126.5, 111.3, 110.7, 110.6, 69.3, 62.4, 32.0, 31.3, 31.1, 29.6, 29.5, 29.4, 29.3, 27.6, 26.2, 22.8, 14.3 ppm. IR (KBr, cm -1 -1): 2923 (s), 2853 (s), 1682 (w), 1630 (s), 1490 (s), 1466 (s), 1421 (s), 1378 (s), 1280 (s), 1202 (s), 1157 (m), 1126 (m), 1038 (s), 965 (m), 886 (m), 726 (s), 470 (m). Elem. Anal.: Calc. (%) for (C 32 48 54 H108 n N2O2): C 77.06, H 10.91, N 5.62; found: C 77.15, H 10.75, N 5.43. Example 7 See Figure 9 This example discloses a polymerization process of deboronation polycondensation of N,N'-bisboronated diamine intermediate 2e generated by diboration of 1,8-octanediamine and 3-bromoisophthalaldehyde.

[0087] As Figure 9 shown, the specific synthesis steps of this example are as follows: S1. Under nitrogen, add N,N'-bis(boryl)diamine 2e (0.6 mmol, 237 mg, 1.0 equiv.) and 3-bromoisophthalaldehyde (0.6 mmol, 129 mg, 1.0 equiv.) to m-xylene (6 mL) and stir at room temperature for 18 h. S2. After the reaction is completed, the organic solvent is removed by a diaphragm pump at room temperature and the reaction mixture is collected; S3. The reaction mixture was washed with methanol and then dried to obtain 3 g of polyimine product.

[0088] In this example, 3 g of polyimine product was obtained as a yellow oil (167 mg) with a yield of 86%. 1 H. 13 The products were characterized by C NMR, IR spectroscopy and elemental analysis.

[0089] GPC (CHCl3, 35 ℃): M n = 17.0 kDa, M w = 37.2 kDa, Ð = 2.20, DP n = 53. 1 H NMR (400 MHz, CDCl3): δ 9.99-8.22 (m, 2H), 8.14-7.90 (m, 3H), 3.66-3.49 (m, 4H), 1.70-1.67 (m, 4H), 1.34 (m, 8H) ppm. 13 C { 1 H} NMR (100 MHz, CDCl3): δ 190.5, 159.0, 158.8, 157.9, 139.3,138.7, 138.2, 136.1, 133.6, 132.5, 132.4, 132.3, 128.2, 126.8, 126.5, 123.9,123.4, 123.3, 61.9, 61.8, 61.4, 30.9, 30.5, 29.1, 27.4, 26.9 ppm. IR (KBr, cm -1): 2924 (s), 2849 (s), 2851 (s), 1704 (m), 1643 (s), 1566(s), 1436 (m), 1335 (s), 1257 (s), 1149 (m), 1100 (w), 1025 (m), 962 (s), 867(s), 679 (s). Elem. Anal.: Calc. (%) for (C 16 H 21 BrN2) n : C 59.82, H 6.59, N 8.72; found: C 58.39, H 6.35, N 8.27. Example 8 See Figure 10 This example discloses a polymerization process in which the N,N'-bisboronated diamine intermediate 2e generated by diboration of 1,8-octanediamine undergoes deborylation polycondensation with thiophene-2,5-dicarbaldehyde.

[0090] As Figure 10 shown, the specific synthesis steps of this example are as follows: S1. Under nitrogen protection, N,N'-bisboronated diamine 2e (0.6 mmol, 237 mg, 1.0 equiv.) and thiophene-2,5-dicarbaldehyde (0.6 mmol, 84 mg, 1.0 equiv.) were added to m-xylene (6 mL), and stirred at room temperature for 18 hours; S2. After the reaction was completed, the organic solvent was removed by a diaphragm pump at room temperature, and the reaction mixture was collected; S3. The reaction mixture was washed with methanol and then dried to obtain the polyimine product 3h.

[0091] The polyimine product 3h obtained in this example was a yellow solid (90 mg), with a yield of 60%, and the product was characterized by gel permeation chromatography, 1 H, 13 13C nuclear magnetic resonance, infrared spectroscopy and elemental analysis.

[0092] GPC (CHCl3, 35 ℃): M n Mn = 15.9 kDa, M w Mw = 40.1 kDa, Ð PDI = 2.52, DP n n = 64. 11H NMR (400 MHz, CDCl3): δ 9.91 - 8.27 (m, 2H), 7.22 - 7.19 (m, 2H), 3.57 - 3.54 (m, 4H), 1.65 (m, 4H), 1.32 - 1.30 (m, 8H) ppm. 13 13C { 1 1H} NMR (100 MHz, CDCl3): δ 183.4, 153.8, 145.0, 129.6, 61.6, 61.2, 30.9, 29.7, 29.4, 27.3, 27.1 ppm. IR (KBr, cm -1 -1): 2924 (s), 2852 (s), 1626 (s), 1465 (s), 1334 (m), 1233 (m), 1041 (w), 980 (w), 948 (w), 824 (m), 725 (w), 702 (m), 501 (m). Elem. Anal.: Calc. (%) for (C 14 12 20 H n 24 N2S): C 67.70, H 8.12, N 11.28, S 12.91; found: C 67.47, H 8.04, N 11.22, S 12.61. Example 9 See Figure 11 This example discloses a polymerization process of deboronation polycondensation of N,N'-bisboronated diamine intermediate 2d generated by diboration of 1,6 - hexanediamine with 2 - bromomalonaldehyde.

[0093] As Figure 11 shown, the specific synthesis steps of this example are as follows: S1. Under nitrogen protection, N,N'-bisboronated diamine 2d (0.6 mmol, 220 mg, 1.0 equiv.) and 2 - bromomalonaldehyde (0.6 mmol, 91 mg, 1.0 equiv.) were added to m - xylene (6 mL), and stirred at room temperature for 18 hours; S2. After the reaction was completed, the organic solvent was removed by a diaphragm pump at room temperature, and the reaction mixture was collected; S3. The reaction mixture was washed with dichloromethane and then dried to obtain the polyimine product 3i.

[0094] The polyimide product 3i obtained in this example is a yellow oil (90 mg), with a yield of 65%. Gel permeation chromatography, 1 H, 13 13C nuclear magnetic resonance, infrared spectroscopy and elemental analysis were used to characterize the product.

[0095] GPC (DMF, 35 °C): M n Mn = 15.3 kDa, M w Mw = 31.0 kDa, Ð Đ = 2.03, DP n n = 66. 1 1H NMR (400 MHz, methanol- d d4): δ 8.75 - 8.54 (m, 1H), 8.19 - 8.03 (m, 1H), 7.79 - 5.50 (m, 1H), 3.52 (m, 3H), 2.95 (m, 1H), 1.69 - 1.42 (m, 8H) ppm. 13 13C{ 1 1H} NMR (150 MHz, methanol- d d4): δ 181.1, 183.1, 163.8, 161.4, 159.4, 103.0, 96.0, 85.9, 50.7, 40.7, 31.7, 31.3, 31.2, 28.5, 27.0 ppm. IR (KBr, cm -1 −1): 3157 (m), 2929 (s), 2855 (s), 1598 (s), 1538 (s), 1444 (s), 1370 (s), 1331 (s), 1229 (s), 1169 (s), 1001 (m), 727 (w), 699 (m), 524 (m). Elem. Anal.: Calc. (%) for (C9H 15 BrN2) n : C 46.77, H 6.54, N 12.12; found: C 41.41, H 5.98, N 10.09. Example 10 See Figure 12This example discloses a polymerization process of deboronation polycondensation of N,N'-bis(boron-based) diamine intermediate 2e generated by diboration of 1,8-octanediamine with 2-chloromalonaldehyde.

[0096] As Figure 12 shown, the specific synthesis steps of this example are as follows: S1. Under nitrogen protection, N,N'-bis(boron-based) diamine 2e (0.6 mmol, 237 mg, 1.0 equiv.) and 2-chloromalonaldehyde (0.6 mmol, 63 mg, 1.0 equiv.) were added to m-xylene (6 mL), and stirred at room temperature for 18 hours; S2. After the reaction was completed, the organic solvent was removed by a diaphragm pump at room temperature, and the reaction mixture was collected; S3. The reaction mixture was washed with dichloromethane and then dried to obtain the polyimine product 3j.

[0097] The polyimine product 3j obtained in this example was a yellow oil (110 mg), with a yield of 85%. The product was characterized by gel permeation chromatography, 1 H, 13 13C nuclear magnetic resonance, infrared spectroscopy and elemental analysis.

[0098] GPC (DMF, 35 °C): M n Mn = 22.9 kDa, M w Mw = 44.5 kDa, Ð PDI = 1.94, DP n n = 107. 1 1H NMR (400 MHz, methanol- d d4): δ 8.62 - 8.06 (m, 2H), 7.95 - 7.67 (m, 1H), 3.46 (s, 3H), 2.83 (s, 1H), 1.66 (m, 4H), 1.37 (s, 8H) ppm. 13 13C { 1 1H} NMR (150 MHz, methanol- d d4): δ 183.3, 159.5, 159.0, 112.5, 97.7, 51.3, 50.6, 41.2, 31.4, 31.2, 31.0, 30.2, 30.1, 30.0, 29.6, 27.6, 27.5, 27.4, 27.3, 26.7, 25.0 ppm. IR (KBr, cm -1 ): 3499 (s), 2937 (s), 2861 (s), 1671 (s), 1550 (s), 1440(s), 1411 (s), 1384 (s), 1256 (s), 1096 (s), 1059 (s), 661 (m). Elem. Anal.: Calc. (%) for (C 11 H 19 ClN2) n : C 61.53, H 8.92, N 13.05; found: C 58.46, H 10.17, N 11.27. Example 11 See Figure 13 This example discloses a polymerization process of deboronation polycondensation of N,N'-bisboronated diamine intermediate 2e formed by diboration of 1,8-octanediamine and 2-chloromalonaldehyde.

[0099] As Figure 13 shown, the specific synthesis steps of this example are as follows: S1. Under nitrogen protection, add N,N'-bisboronated diamine 2e (0.6 mmol, 237 mg, 1.0 equiv.) and 1,4-cyclohexanedial (0.6 mmol, 84 mg, 1.0 equiv.) to m-xylene (6 mL), and stir at room temperature for 18 hours; S2. After the reaction is completed, remove the organic solvent at room temperature using a diaphragm pump, and collect the reaction mixture; S3. Wash the reaction mixture with methanol, and then dry to obtain the polyimine product 3k.

[0100] The polyimine product 3k prepared in this example is a white solid (80 mg), and the yield is 62%. Gel permeation chromatography, 1 H, 13 C nuclear magnetic resonance, infrared spectroscopy and elemental analysis were used to characterize the product.

[0101] GPC (CHCl3, 35 ℃): M n = 43.6 kDa, M w = 69.9 kDa, Ð = 1.60, DP n = 176. 11H NMR (400 MHz, CDCl3): δ 9.68 - 7.47 (m, 2H), 3.41 - 3.30 (m, 4H), 2.12(m, 2H), 1.91 (m, 4H), 1.57 - 1.54 (m, 4H), 1.30 - 1.12 (m, 12H) ppm. 13 13C { 1 1H} NMR (150 MHz, CDCl3): δ 167.7, 130.1, 61.6, 39.6, 36.1, 34.3,32.1, 29.9, 29.6, 29.5, 29.4, 27.4, 27.2, 26.0, 25.7, 25.5, 24.1, 22.8, 14.3ppm. IR (KBr, cm -1 −1): 3507 (s), 2933 (s), 2864 (s), 1675 (s), 1501 (s), 1442(s), 1409 (s), 1393 (s), 1258 (s), 1097 (s), 1064 (s), 657 (s). Elem. Anal.: Calc. (%) for (C 16 18 28 H n 36 Example 12 See Figure 14 This example discloses a synthetic process for synthesizing polyamine 4a by hydrogenation reduction of polyimine 3a containing a n - pentane main chain.

[0102] As Figure 14 shown, the specific synthesis steps of this example are as follows: S1. Dissolve polyimine 3a (172 mg, 1 mmol of the simplest repeating unit) in dichloromethane (10 mL), and slowly add it to a methanol solution (10 mL) of sodium borohydride (39� mg, 10.0 mmol, 10 equiv.) at 0 °C and stir for 12 hours; S2. After the reaction is completed, add water to the reaction mixture to quench the remaining sodium borohydride, then separate the layers and extract, and collect the organic phase; S3. Dilute concentrated hydrochloric acid (1.0 g, 20 equiv., 36% wt) in water (20 mL), then add it to the organic phase, stir at room temperature, then separate the layers, and collect the aqueous phase suspension; S4. Add an aqueous solution of sodium hydroxide (800 mg, 20 mmol, 20 equiv.) (20 mL) to the aqueous phase suspension, stir at room temperature, then add dichloromethane, separate the layers and extract, and collect the organic phase; S5. Remove the organic solvent at room temperature using a diaphragm pump to obtain polyamine 4a.

[0103] The polyamine product 4a obtained in this example was a white solid (155 mg), with a yield of 89%. Gel permeation chromatography, 1 H, 13 13C nuclear magnetic resonance, infrared spectroscopy and elemental analysis were used to characterize the product.

[0104] GPC (CHCl3, 35 °C): M n Mn = 20.1 kDa, M w Mw = 44.9 kDa, Ð Đ = 2.23, DP n n = 114. 1 1H NMR (400 MHz, CDCl3): δ 7.49 (s, 4H), 4.84 - 3.76 (s, 4H), 2.94 - 2.48 (m, 4H), 1.96 - 1.53 (m, 4H, C H 2+N H ) ppm. 13 13C { 1 1H} NMR (100 MHz, CDCl3): δ 140.8, 139.1, 138.0, 133.6, 129.6, 128.2, 127.0, 64.4, 60.2, 54.6, 53.9, 49.8, 48.0, 30.3, 24.3 ppm. IR (KBr, cm -1): 3286 (s), 2923 (s), 2819 (s), 2384 (m), 2314 (m), 1512(m), 1453 (s), 1420 (s), 1351 (m), 1170 (m), 1102 (s), 1049 (m), 1018 (m), 802 (s), 755 (s), 604 (m), 548 (m), 486 (m). Elem. Anal.: Calc. (%) for (C 11 H 16 N2) n : C 74.96, H 9.15, N 15.89; found: C 70.57, H 8.69, N 14.58. Example 13 See Figure 15 This example discloses a synthetic process for synthesizing polyamine 4b by hydrogenation reduction of polyimine 3b containing a n-pentane main chain.

[0105] As Figure 15 shown, the specific synthesis steps of this example are as follows: S1. Dissolve polyimine 3b (172 mg, 1 mmol simplest repeating unit) in dichloromethane (10 mL), and slowly add it to a methanol solution (10 mL) of sodium borohydride (390 mg, 10.0 mmol, 10 equiv.), and stir at 0 °C for 12 hours; S2. After the reaction is completed, add water to the reaction mixture to quench the remaining sodium borohydride, then separate the liquid and extract, and collect the organic phase; S3. Dilute concentrated hydrochloric acid (1.0 g, 20 equiv., 36% wt) in water (20 mL), then add it to the organic phase, stir at room temperature, then separate the liquid, and collect the aqueous phase suspension; S4. Add an aqueous solution (20 mL) of sodium hydroxide (800 mg, 20 mmol, 20 equiv.) to the aqueous phase suspension, stir at room temperature, then add dichloromethane, separate the liquid and extract, and collect the organic phase; S5. Use a diaphragm pump to remove the organic solvent at room temperature to obtain polyamine 4b.

[0106] The polyamine product 4b obtained in this example is a white solid (163 mg), the yield is 86%, and gel permeation chromatography, 1 H, 13 1H, 13C NMR, infrared spectroscopy and elemental analysis were used to characterize the product.

[0107] GPC (CHCl3, 35 °C): M n = 21.9 kDa, M w = 45.0 kDa, Ð = 2.05, DP n = 115. 1 1H NMR (400 MHz, CDCl3): δ 7.33 - 6.88 (m, 4H), 4.62 - 3.74 (m, 4H), 2.61(m, 4H), 1.53 - 1.26 (m, 6H, C H 2+N H ) ppm. 13 13C{ 1 1H} NMR (101 MHz, CDCl3): δ 139.2, 130.2, 128.8, 128.9, 127.2,53.9, 49.5, 28.0 ppm. IR (KBr, cm -1 ): 3294 (w), 3053 (m), 3016 (s), 2923 (s), 2861 (w), 2800(s), 2755 (s), 2383 (s), 2313 (s), 2269 (s), 1906 (m), 1512 (s), 1473 (s),1450 (s), 1419 (s), 1338 (s), 1258 (s), 1170 (s), 1127 (s), 1062 (s), 1034(s), 1018 (s), 979 (s), 925 (s), 814 (s), 787 (s), 598 (m), 485 (s). Elem. Anal.: Calc. (%) for (C 12 H 18 N2) n : C 75.74, H 9.53, N 14.72;found:C 71.94, H 8.72, N 13.22. Example 14 See Figure 16 This example discloses a synthesis process of polyamine 4c by hydrogenation reduction of polyimine 3c containing a n-pentane main chain.

[0108] AsFigure 16 As shown below, the specific synthesis steps of this example are as follows: S1. Dissolve polyimine 3c (200 mg, 1 mmol of the simplest repeating unit) in dichloromethane (10 mL), and slowly add it to a methanol solution (10 mL) of sodium borohydride (390 mg, 10.0 mmol, 10 equiv.). Stir at 0 °C for 12 hours; S2. After the reaction is completed, add water to the reaction mixture to quench the remaining sodium borohydride, then separate the layers and extract, and collect the organic phase; S3. Dilute concentrated hydrochloric acid (1.0 g, 20 equiv., 36% wt) in water (20 mL), then add it to the organic phase, stir at room temperature, and then separate the layers to collect the aqueous phase suspension; S4. Add an aqueous solution (20 mL) of sodium hydroxide (800 mg, 20 mmol, 20 equiv.) to the aqueous phase suspension, stir at room temperature, then add dichloromethane, separate the layers and extract, and collect the organic phase; S5. Use a diaphragm pump to remove the organic solvent at room temperature to obtain polyamine 4c.

[0109] The polyamine product 4c obtained in this example is a white solid (173 mg), and the yield is 85%. The product was characterized by gel permeation chromatography, 1 H, 13 13C nuclear magnetic resonance, infrared spectroscopy and elemental analysis.

[0110] GPC (CHCl3, 35 °C): M n Mw = 16.6 kDa, M w Mn = 41.5 kDa, Ð Đ = 2.50, DP n = 76. 1 1H NMR (400 MHz, CDCl3): δ 7.25 (s, 4H), 3.75 (s, 4H), 2.61 (m, 4H), 1.53 - 1.49 (m, 4H), 1.39 - 1.35 (m, 4H, C H 2+N H ) ppm. 13 13C { 1 1H} NMR (100 MHz, CDCl3): δ 139.3, 128.3, 54.0, 49.6, 30.2, 25.3 ppm. IR (KBr, cm -1 ): 3287 (m), 3014 (m), 2924 (s), 2853 (s), 2813 (s), 2383(m), 2313 (m), 1511 (m), 1451 (s), 1354 (m), 1304 (m), 1166 (s), 1106 (s),1018 (m), 802 (s), 732 (s), 607 (m), 478 (m). Elem. Anal.: Calc. (%) for (C 13 H 20 N2) n : C 76.42, H 9.87, N 13.71; found: C 73.45, H 9.29, N 12.98. Example 15 See Figure 17 This example discloses a synthesis process for synthesizing polyamine 4d by hydrogenation reduction of polyimine 3d containing a n-pentane main chain.

[0111] As Figure 17 shown, the specific synthesis steps of this example are as follows: S1. Dissolve polyimine 3d (214 mg, 1 mmol of the simplest repeating unit) in dichloromethane (10 mL), and slowly add it to a methanol solution (10 mL) of sodium borohydride (390 mg, 10.0 mmol, 10 equiv.). Stir at 0 °C for 12 hours; S2. After the reaction is completed, add water to the reaction mixture to quench the remaining sodium borohydride, then separate the layers and extract, and collect the organic phase; S3. Dilute concentrated hydrochloric acid (1.0 g, 20 equiv., 36% wt) in water (20 mL), then add it to the organic phase, stir at room temperature, and then separate the layers to collect the aqueous phase suspension; S4. Add an aqueous solution (20 mL) of sodium hydroxide (800 mg, 20 mmol, 20 equiv.) to the aqueous phase suspension, stir at room temperature, then add dichloromethane, separate the layers and extract, and collect the organic phase; S5. Use a diaphragm pump to remove the organic solvent at room temperature to obtain polyamine 4d.

[0112] The polyamine product 4d obtained in this example is a white solid (193 mg), and the yield is 90%. Using gel permeation chromatography, 1 H, 1313C NMR, IR spectroscopy and elemental analysis were used to characterize the product.

[0113] GPC (CHCl3, 35 °C): M n = 16.6 kDa, M w = 41.5 kDa, Ð = 2.50, DP n = 76. 1 1H NMR (400 MHz, CDCl3): δ 7.26 (s, 4H), 3.75 (s, 4H), 2.60 (m, 4H), 1.50 (m, 4H), 1.32 (m, 4H), 1.27 (m, 2H, N H ) ppm. 13 13C{ 1 1H} NMR (100 MHz, CDCl3): δ 139.3, 128.3, 54.0, 49.6, 32.3, 27.5 ppm. IR (KBr, cm -1 −1): 3695 (w), 3293 (w), 2922 (s), 2853 (s), 2800 (s), 1512 (s), 1449 (s), 1356 (s), 1318 (s), 1164 (m), 1125 (s), 1018 (s), 971 (s), 878 (s), 817 (s), 791 (s), 732 (s), 485 (s). Elem. Anal.: Calc. (%) for (C 14 12H 22 14N2) n : C 77.01, H 10.16, N 12.83; found: C 76.25, H 9.04, N 11.85. In summary, this embodiment discloses a series of polyimine and polyamine polymer materials containing an alkyl main chain and their preparation methods. By using the dehydrogenative borylation reaction of an alkyl diamine with pinacol borane to generate N,N'-bis(boronyl)alkyl diamine, and then carrying out a deborylation polycondensation reaction with an organic dialdehyde at room temperature, a polyimine crude product is synthesized with excellent yield. The polyimine crude product is filtered and washed at room temperature, and then impurities are removed through Soxhlet extraction and drying operations to collect the purified polyimine product. By using the reduction hydrogenation reaction of the polyimine on the imine group, a polyamine polymer material can be obtained. This method pre-borates the alkyl diamine, greatly improving the reactivity of the monomer, enabling it to undergo a deborylation polycondensation reaction with the organic dialdehyde. This polymerization reaction can be carried out at room temperature without the addition of extra catalysts and additives. The post-treatment and purification process of the polyimine and polyamine products containing an alkyl main chain is simple, with few impurities in the polymer, and it is easy to scale up production.

[0114] The above content is only for explaining the technical idea of the present invention and cannot be used to limit the protection scope of the present invention. Any modification made on the basis of the technical solution according to the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a polyimide with an alkyl main chain, characterized in that, It includes the following steps: Borylate the alkylenediamine with an organoborane to generate N,N'-bis(boryl)diamine; React N,N'-bis(boryl)diamine with an organic dialdehyde to obtain a polyimine with an alkyl main chain.

2. The preparation method of the polyimine containing an alkyl main chain according to claim 1, characterized in that, The organoborane is pinacolborane or 9-borabicyclo[3.3.1]nonane; the alkylenediamine is any one of 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine; the organic dialdehyde is any one of terephthalaldehyde, 2,5-bis(octyloxy)terephthalaldehyde, 3-bromoisophthalaldehyde, 2,5-thiophenedicarboxaldehyde, 2-bromomalonaldehyde, 2-chloromalonaldehyde, 1,4-cyclohexanedicarboxaldehyde.

3. The preparation method of the polyimine containing an alkyl main chain according to claim 1, characterized in that, The molar ratio of the alkylenediamine to the organoborane is 1:(2.0 - 3.0); the molar ratio of N,N'-bis(boryl)diamine to the organic dialdehyde is 1:(0.8 - 1.2).

4. The method for preparing a polyimine containing an alkyl main chain according to claim 3, characterized in that, The process of borylating the alkylenediamine with an organoborane to generate N,N'-bis(boryl)diamine is as follows: Under nitrogen protection, add the alkylenediamine to organic solvent I, stir at room temperature to obtain a reaction mixture; add the organoborane and triethylamine to the above reaction mixture, stir and react at a set temperature to obtain a crude product of N,N'-bis(boryl)diamine; cool the crude product of N,N'-bis(boryl)diamine to room temperature, and use a diaphragm pump to remove the organic solvent at room temperature to obtain N,N'-bis(boryl)diamine; The process of reacting N,N'-bis(boryl)diamine with an organic dialdehyde to obtain a polyimine with an alkyl main chain is as follows: Under nitrogen protection, add the organic dialdehyde and organic solvent II to N,N'-bis(boryl)diamine, stir at room temperature to react, and then use a diaphragm pump to remove the organic solvent at room temperature to obtain a polyimine with an alkyl main chain.

5. The preparation method of the polyimine containing an alkyl main chain according to claim 4, characterized in that, The molar concentration of the alkylenediamine in organic solvent I is 0.1 - 5.0 mol / L; the molar ratio of triethylamine to the alkylenediamine is 1:(10 - 100); the molar concentration of the organic dialdehyde in organic solvent II is 0.1 - 5.0 mol / L; the set temperature is 60°C - 120°C; The organic solvent I is any one of toluene, m-xylene, tetrahydrofuran, and acetonitrile; the organic solvent II is any one of toluene, o-xylene, m-xylene, tetrahydrofuran, and 1,4-dioxane.

6. A polyimine with an alkyl main chain prepared by the preparation method of the polyimine with an alkyl main chain described in any one of claims 1 to 5, characterized in that, The structural formula of the polyimine with an alkyl main chain is shown in the following formula (1): （1） In formula (1), R1 represents an alkyl group containing at least 3 carbon atoms, R2 is an aryl group, a heteroaryl group, or an alkyl group; n is the degree of polymerization of the polyimine with an alkyl main chain, which is an integer from 10 to 1000.

7. A method for preparing a polyamine containing an alkyl main chain, characterized in that, Using the polyimine with an alkyl main chain described in claim 6, it includes the following steps: Dissolve the polyimine with an alkyl main chain in organic solvent III, then add it to a methanol solution of a hydrogenation reducing agent, stir and react at a set low temperature. After the reaction, add water to the reaction mixture to quench the remaining hydrogenation reducing agent, and then perform liquid separation and extraction to collect the first organic phase; Add an aqueous solution of hydrochloric acid to the first organic phase, stir at room temperature, then perform liquid separation and extraction to collect the aqueous suspension; An aqueous sodium hydroxide solution was added to the aqueous suspension and stirred at room temperature. Then, an extractant was added, and liquid separation and extraction were carried out. The second organic phase was collected, and the extractant was removed at room temperature using a diaphragm pump to obtain a polyamine containing an alkyl main chain.

8. The method for preparing a polyamine containing an alkyl main chain according to claim 7, characterized in that, The hydrogenation reducing agent is any one of sodium borohydride, lithium aluminum hydride, and borane·tetrahydrofuran; the molar ratio of the monomer of the polyimine containing an alkyl main chain to the hydrogenation reducing agent is 1:(10 - 20); the molar ratio of the monomer of the polyimine containing an alkyl main chain to hydrochloric acid is 1:(10 - 20); the molar ratio of the monomer of the polyimine containing an alkyl main chain to sodium hydroxide is 1:(10 - 20).

9. The method for preparing a polyamine containing an alkyl main chain according to claim 7, characterized in that, The monomer molar concentration of the polyimine containing an alkyl main chain in organic solvent III is 0.1 - 5.0 mol / L; the organic solvent III is any one of dichloromethane, chloroform, tetrahydrofuran, and 1,4-dioxane; the molar concentration of the methanol solution of the hydrogenation reducing agent is 1.0 - 10.0 mol / L; the set low temperature is 0°C to -30°C; the volume ratio of the first organic phase to the aqueous hydrochloric acid solution is 1:(0.5 - 2); the molar concentration of hydrochloric acid in the aqueous hydrochloric acid solution is 12 mol / L; the volume ratio of the aqueous suspension to the aqueous sodium hydroxide solution is 1:(0.5 - 1.5); the molar concentration of sodium hydroxide in the aqueous sodium hydroxide solution is 1 - 3 mol / L.

10. A polyamine with an alkyl main chain prepared by the method for preparing a polyamine with an alkyl main chain according to any one of claims 7 to 9, characterized in that, The structural formula of the polyamine containing an alkyl main chain is shown in the following formula (2): （2） In formula (2), R1 represents an alkyl group containing at least 3 carbon atoms, R2 is an aryl group, a heteroaryl group, or an alkyl group; n is the degree of polymerization of the polyamine containing an alkyl main chain, which is an integer of 10 - 1000.

Images