Non-isocyanate polyurethane and multi-component selective synthesis method thereof

Abstract

The invention discloses non-isocyanate polyurethane and a multi-component selective synthesis method of the non-isocyanate polyurethane. The synthesis method comprises the following steps: 1, mixing a polyamine compound and / or amino alcohol with non-substituted cyclic carbonate, and reacting at 0-100 DEG C to obtain polybasic primary alcohol containing carbamate; the polyamine compound contains at least two of amino groups and imino groups, and the amino alcohol contains at least one of primary alcohol hydroxyl groups and at least one of amino groups and imino groups; and 2, carrying out polymerization reaction on the carbamate-containing polybasic primary alcohol, a polybasic epoxy compound and a metal-free Lewis acid-base pair catalyst at 0-100 DEG C to obtain the non-isocyanate polyurethane. According to the preparation method, extremely abundant commercial polyamine, amino alcohol and non-substituted cyclic carbonate are taken as raw materials, the structure and performance of polyurethane can be accurately and flexibly regulated and controlled, and the preparation method is environment-friendly and sustainable.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer synthesis, and particularly relates to a non-isocyanate polyurethane and a multi-component selective synthesis method thereof. Background Art

[0002] A class of polymers containing carbamate groups (-NRCOO-) in the main chain structure is usually called polyurethane. It has excellent processing properties, mechanical properties, chemical stability and certain biocompatibility. It is one of the polymer materials with the largest output and the widest application. It is widely used in clothing, electronics, medical and construction fields. The methods for synthesizing polyurethane are mainly divided into two categories: isocyanate method and non-isocyanate method. The isocyanate method uses polyether / polyester diol or other polyols and di / triisocyanate as raw materials, and obtains polyurethane by gradual polymerization under the action of appropriate catalysts. This method is simple, efficient, and has a high degree of commercialization of raw materials. It is the main method for industrial production of polyurethane. This method has significant disadvantages such as high pollution of raw material isocyanate and its production process, and poor stability of isocyanate. Therefore, the development of green and environmentally friendly alternative synthesis methods is an important development direction in the field of polyurethane today.

[0003] The non-isocyanate method mainly synthesizes polyurethane through ester exchange or cyclic carbonate ring-opening reaction, avoiding the use of isocyanate, which meets the development needs of green chemistry. The former refers to the synthesis of polymers containing carbamate in the main chain through ester exchange reaction of small molecule diols and dibasic carbamates. A large number of small molecule byproducts are generated during the reaction of this method, and the atom economy is poor. It usually requires high temperature, vacuum and appropriate catalysts to improve the reaction efficiency and yield. The cyclic carbonate ring-opening method constructs a polyurethane structure by stepwise (ring-opening) polymerization of di / polyamines and di / polycyclic carbonates. This method has good atom economy and high reaction efficiency, and does not require a catalyst; however, there is a lack of mature commercial di / polycyclic carbonate monomer raw materials, and it is difficult to synthesize high-purity di / polycyclic carbonates, so it has not yet been applied in large-scale industry.

[0004] On the other hand, functionalized polyurethane is an important development direction and research content in the field of polymer synthesis. Highly polar or highly chemically active functional groups can give polyurethane unique physical and chemical properties and abundant post-modification or coupling sites, greatly expanding the adaptability and application range of polyurethane. In particular, hydroxyl groups, as polar functional groups with relatively moderate chemical activity, can be introduced as side groups to obtain hydroxyl-functionalized polyurethanes, thereby improving the hydrophilicity and biocompatibility of related materials (especially biomedical materials). However, hydroxyl-functionalized polyurethanes with linear structures cannot be obtained by traditional isocyanate methods. The literature "Sheng, X.; Ren, G.; Chen X.; et al,.Quantitative synthesis of bis (cyclic carbonate)s by iron catalyst for non-isocyanate polyurethane synthesis. Green Chemistry, 2015, 17, 373-379" obtains linear polyhydroxy polyurethanes by stepwise polymerization of diamines and dicyclic carbonates. However, this synthesis method has the following limitations: (1) As mentioned above, there is a lack of mature commercial polycarbonate monomer raw materials; (2) It is difficult and costly to synthesize high-purity di / polycarbonates; (3) Since the reaction between amino groups and substituted cyclic carbonates is not regioselective, the repeating units of the step-by-step polymerization product contain both randomly distributed primary and secondary hydroxyl groups, which is not conducive to batch stability of performance and post-modification reactions. Therefore, it is of great significance to establish a new method for the synthesis of functional non-isocyanate polyurethanes.

[0005] Unsubstituted cyclic carbonates are an important class of chemical products, among which ethylene carbonate is a highly polar organic solvent and electrolyte additive that can be obtained through the cycloaddition reaction of carbon dioxide and ethylene oxide. It is an important intermediate and platform compound for the high-value utilization of carbon dioxide. Both polyamines and amino alcohols are basic chemical raw materials, which are cheap, easy to obtain, and highly commercialized. They are widely used as basic modules to construct small molecules or polymer compounds; and many can be obtained through biomass conversion, which has renewable and sustainable characteristics. Di / ternary epoxy compounds are important raw materials for the epoxy resin industry. They are simple to synthesize, the raw materials are easy to obtain, and the structure is rich. There are many mature commercial products that are widely used to construct three-dimensional epoxy resin materials; many of the initial raw materials for synthesizing di / ternary epoxy compounds also have biomass sources. In theory, the reaction of diamines or difunctional amino alcohols with cyclic carbonates can obtain dihydric primary alcohols containing carbamates, and the step-by-step polymerization of the dihydric alcohols and di / ternary epoxy compounds can obtain (linear or branched) polyhydroxy functionalized polyurethanes. However, in the existing methods, the catalytic system is not selective for the reaction between the primary alcohol, carbamate in the raw material and the secondary alcohol produced during the reaction and the epoxy group. All three can undergo ring-opening reaction with the epoxy group, so the system is prone to uncontrolled excessive branching, hyperbranching, and even cross-linking, and it is impossible to obtain a polymer with a clear and uniform structure and good processing properties. It can be seen that the key to using this reaction for polyurethane synthesis lies in the selectivity of the catalytic system to avoid excessive branching or cross-linking. Therefore, it is of great significance to establish a simple, efficient, practical, inclusive and scalable method for synthesizing non-isocyanate polyurethane. Summary of the invention

[0006] In order to solve the shortcomings and deficiencies of the existing synthesis technology, the object of the present invention is to provide a non-isocyanate polyurethane and a multi-component selective synthesis method thereof.

[0007] The method first obtains a di / trivalent primary alcohol containing a carbamate group by reacting a di / trivalent amine and / or an amino alcohol with a non-substituted cyclic carbonate, then gradually polymerizes a di / trivalent epoxy compound and the aforementioned di / trivalent primary alcohol in a metal-free Lewis acid-base catalytic system, and utilizes a highly chemically selective ring-opening reaction between the primary alcohol hydroxyl group and the epoxy group to achieve the synthesis of a novel non-isocyanate polyurethane. In the step-by-step polymerization process, the NH group in the carbamate and the newly formed secondary alcohol hydroxyl group after the epoxy ring opening will not participate in the ring-opening reaction of the epoxy group, so there is no need to perform tedious operations such as protection and deprotection of the carbamate and the side hydroxyl group, the synthesis path is very simple, and the structure and composition of the obtained polymer are clear; and the monomer source is wide and the structure is rich, which greatly expands the structure and performance of the non-isocyanate polyurethane and provides a new synthesis method platform to meet different application requirements.

[0008] The cyclic carbonate of the present invention reacts only with amino groups and imino groups, and the hydroxyl groups remain inert; the synergistic catalytic effect of the metal-free Lewis acid-base pair ensures that the epoxy group reacts only with the primary hydroxyl groups, and the carbamate groups in the monomer and the secondary hydroxyl groups in the polymer remain inert; the dual chemical selectivity ensures that the generated polymer has a uniform chain structure and a controllable topological structure.

[0009] The purpose of the present invention is achieved by at least one of the following technical solutions.

[0010] A multi-component selective synthesis method of non-isocyanate polyurethane comprises the following steps:

[0011] The first step is to mix a polyamine compound and / or an amino alcohol with a non-substituted cyclic carbonate and react them at 0-100° C. to obtain a polyvalent primary alcohol containing carbamate; the polyamine compound contains at least two of an amino group and an imino group, and the amino alcohol contains at least one of a primary alcohol hydroxyl group and at least one of an amino group and an imino group;

[0012] In the second step, the polyol containing carbamate, the polyepoxide and the metal-free Lewis acid-base catalyst are polymerized at 0-100° C. to obtain non-isocyanate polyurethane.

[0013] Further, the polyamine compound includes at least one of a diamine compound and a triamine compound;

[0014] Further, the polycyclic epoxy compound includes at least one of a binary epoxy compound and a ternary epoxy compound;

[0015] The reactants may be only the above-mentioned diamine (or difunctional amino alcohol) and diepoxide to obtain linear polyurethane; or a certain amount of triamine (or trifunctional amino alcohol) or triepoxide may be added to obtain branched or crosslinked polyurethane.

[0016] Preferably, the molar ratio of the diamine to the triamine is 1:(0.01-100), and the molar ratio of the diepoxide to the triepoxide is 1:(0.01-100).

[0017] Further, the metal-free Lewis acid-base catalyst is composed of an organic base and an alkyl boron;

[0018] Preferably, the molar ratio of the epoxy group, the organic base and the alkyl boron in the polycyclic epoxy compound is 1:(0.005-2):(0.005-5).

[0019] Preferably, the organic base includes tertiary amines (DABCO, PMDETA, ME 6TREN, sparteine), amidines (DBN, DBU), guanidines (TBD, MTBD, TMG, PMG), triaminophosphine (HMTP, HETP, TMAP, TIPAP), phosphazene bases (BEMP, t BnP 1 , t BnP 2 , EtP 2 , t BnP 4 ), lithium / sodium / potassium / cesium tert-butoxide, lithium / sodium / potassium / cesium / ammonium pivalate, ionic compounds containing thiourea, urea, and carbamate (R 2 , R 3 , R 4 , R 5 R is independently selected from H, phenyl, tolyl, benzyl, cycloalkyl with 3-8 carbon atoms, chain alkyl with 1-20 carbon atoms, chain alkyl with 1-8 carbon atoms of borane substituent, heterocyclic group with 3-20 carbon atoms, heteroaryl with 5-20 carbon atoms; 5 directly connected to any carbon atom on the ring, and the value of L is 0 or 1; 6 ~R 13 Each of them is independently selected from an alkyl group with 1 to 8 carbon atoms and a benzyl group; Z is selected from at least one of N and P. The specific structural formula is as follows:

[0020]

[0021] Preferably, the alkyl boron includes B-isopinocampheyl-9-borabicyclo[3.3.1]nonane (S-Alphine-Borane), tri-sec-butylborane (T s BuB), triisopropylborane (T i At least one of PrB), trimethylborane (TMB), tri(straight-chain) alkylborane (TAB) having 2 to 8 alkyl carbon atoms, diethylmethoxyborane (MOEB) and trimethyl borate (TMBO). The specific structural formula is as follows:

[0022]

[0023] Furthermore, the polyamine compound includes (1) ethylenediamine or an alkyl diamine having 3 to 18 carbon atoms, (2) 1,3-diamino-2-hydroxypropane, (3) 2-methyl-1,3-propylenediamine or 2-phenyl-1,3-propylenediamine, (4) m-phenylenediamine, (5) neopentyldiamine, (6) 1,4-butynediamine, (7) 1,4-butenediamine, (8) perfluoroalkyl dimethylamine having 1 to 17 carbon atoms, (9) 2-methyl-1,4-butanediamine, (10) 3,6-disulfide Hetero-1,8-octanediamine, (11) 1,4-cyclohexanediamine, (12) 4,4'-diaminodicyclohexylmethane, (13) 2,2'-(ethylenedioxy)bis(ethylamine), (14) 1,3-cyclohexanedimethylamine, (15) diethylenetriamine and at least one of the N-alkyl, benzyl and allyl derivatives (the alkyl group is a straight or branched alkyl group having 1 to 18 carbon atoms) of the aforementioned di / triamines; the polyamine compound contains two of the aforementioned polyamine compounds in a molar ratio of 1:(1 to 100). The structural formula of the corresponding amine is as follows:

[0024]

[0025] Furthermore, the amino alcohol includes (1) aminoethanol or a primary amino alcohol having 3 to 18 carbon atoms, (2) 2-amino-1-propanol, (3) 2-amino-3-methylbutanol, (4) 2-amino-4-methylpentan-1-ol, (5) phenylglycinol, (6) phenylalaninol, (7) 2-amino-2-cyclohexylethanol, (8) threonine alcohol, (9) 3-amino-1-butanol, (10) 3-amino-4-methyl-1-pentanol. Alcohol, (11) 2-amino-3-methylpentan-1-ol, (12) tert-leucine alcohol, (13) 4-(aminomethyl)benzyl alcohol, (14) 2-aminobutane-1,4-diol and (15) lysine alcohol and at least one of the N-alkyl, benzyl and allyl derivatives (the alkyl group is a straight-chain or branched alkyl group having 1 to 18 carbon atoms) of the aforementioned amino alcohols; the amino alcohol contains two of the aforementioned amino alcohols in a molar ratio of 1:(1 to 100). The specific structural formula of the corresponding amino alcohol is as follows:

[0026]

[0027] Furthermore, the non-substituted cyclic carbonate comprises at least one of (1) ethylene carbonate, (2) 1,3-dioxane-2-one and (3) 1,3-dioxepan-2-one. The non-substituted cyclic carbonate contains two of the aforementioned non-substituted cyclic carbonates in a molar ratio of 1:(1-100).

[0028] The specific structural formula is as follows:

[0029]

[0030] Furthermore, the polycyclic epoxy compound includes (1) a linear alkyl terminal dioxirane having an alkyl carbon number of 1 to 20, (2) ethylene glycol diglycidyl ether or an alkyl glycol diglycidyl ether having a carbon number of 3 to 20, (3) polyethylene glycol diglycidyl ether, (4) neopentyl glycol diglycidyl ether, (5) 1,2-cyclohexanediol diglycidyl ether, (6) resorcinol diglycidyl ether, (7) a linear alkyl terminal dicarboxylic acid diglycidyl ester having an alkyl carbon number of 0 to 20, (8) 1,2- At least one of cyclohexanedicarboxylic acid diglycidyl ester, (9) 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, (10) hydantoin epoxy resin, (11) bisphenol A propoxy acid diglycidyl ether, (12) bisphenol A diglycidyl ether, (13) 1,3-bis(3-glycidyl ether propyl)tetramethyldisiloxane, (14) 1,3,5-triglycidyl-S-triazinetrione; the polycyclic epoxy compound contains two of the aforementioned polycyclic epoxy compounds in a molar ratio of 1:(1 to 100). The specific structural formula is as follows:

[0031]

[0032] Furthermore, the molar ratio of the total amount of amino groups and imino groups in the polyamine compound and / or amino alcohol to the carbonate in the unsubstituted cyclic carbonate is 1:(1-1.5);

[0033] Furthermore, the molar ratio of the epoxy group in the polycyclic epoxy compound to the primary alcohol hydroxyl group in the polycyclic primary alcohol containing carbamate is 1:(1-1.2).

[0034] Further, in the first step, the reaction is carried out in bulk or in an organic solvent;

[0035] Preferably, the organic solvent is a mixture of one or more of dichloromethane, chloroform, benzene, toluene, tetrahydrofuran, dioxane, 2-methyltetrahydrofuran, n-hexane, cyclohexane, tert-butanol, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, γ-butyrolactone, β-butyrolactone, γ-valerolactone, 1,1,3,3-tetramethylurea, tetraethyl urea, and tetrabutyl urea; the organic solvent contains two of the aforementioned organic solvents in a volume ratio of 1:(1-100).

[0036] Further, in the second step, the polymerization reaction is carried out in bulk or in an organic solvent;

[0037] Preferably, the organic solvent is a mixture of one or more of tert-butyl alcohol, isopropanol, benzene, toluene, tetrahydrofuran, dioxane, 2-methyltetrahydrofuran, n-hexane, cyclohexane, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, γ-butyrolactone, β-butyrolactone, γ-valerolactone, 1,1,3,3-tetramethylurea, tetraethylurea, and tetrabutylurea. The organic solvent contains two of the aforementioned organic solvents in a volume ratio of 1:(1-100).

[0038] In the first step, the polyamine compound and the amino alcohol can be used alone or in combination; further, the polyamine compound and the amino alcohol are used in combination, and the molar ratio of the polyamine compound to the amino alcohol is 1:(0.01-100).

[0039] Furthermore, in the first step, the initial total concentration of the polyamine compound and / or amino alcohol is 0.1-10 mol / L, and the initial concentration of the unsubstituted cyclic carbonate is 0.1-10 mol / L;

[0040] Furthermore, in the second step, the initial concentration of the polycyclic epoxy compound is 0.5-10 mol / L, and the initial concentration of the polycyclic primary alcohol containing carbamate is 0.5-10 mol / L.

[0041] Further, in the first step, the reaction is carried out in air or an inert atmosphere;

[0042] Further, in the first step, the reaction is carried out at room temperature;

[0043] Furthermore, in the first step, the reaction time is 1 to 24 hours;

[0044] Further, in the second step, the reaction is carried out in air or an inert atmosphere;

[0045] Furthermore, in a further step, the polymerization reaction is carried out at room temperature;

[0046] Furthermore, in the second step, the polymerization reaction time is 5 to 120 hours.

[0047] The two-step reaction is carried out continuously in the same reactor, and the polyol containing carbamate does not need to be separated and purified, or the polyol containing carbamate is separated and purified before the second step (stepwise polymerization) reaction.

[0048] The non-isocyanate polyurethane synthesized by the above-mentioned synthesis method.

[0049] In the synthesis method of the present invention, the synergistic catalytic effect of the metal-free Lewis acid-base pair enables the di- / tri-epoxy compound and the di- / tri-amine or amino alcohol modified by the cyclic carbonate to undergo a gentle and efficient stepwise polymerization reaction at room temperature; at the same time, due to the unique selectivity of the catalyst, the primary alcohol hydroxyl group attacks the epoxy group to open its ring at a rate much higher than that of the carbamate and the side-group secondary alcohol hydroxyl group, successfully avoiding the main chain carbamate and the side hydroxyl group from participating in the ring-opening reaction of the epoxy, achieving complete retention of the side hydroxyl group, thereby achieving efficient and highly selective synthesis of non-isocyanate polyurethane.

[0050] The invention establishes a novel non-isocyanate polyurethane and a synthesis method thereof, which has remarkable simplicity, economy and practicability, and has a wide source of monomer raw materials, diverse structures, rich and easily adjustable main chain structures, hydroxyl density and polymer properties.

[0051] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0052] (1) The present invention uses for the first time di- / tri-primary alcohols and di- / tri-epoxy compounds containing carbamate groups generated by the reaction of di- / tri-amines or amino alcohols and non-substituted cyclic carbonates as monomers. In such a multi-proton system, the synergistic mechanism of metal-free Lewis acids and bases on catalysts is used to achieve acid reversal of NH and OH groups, establish a chemically selective stepwise polymerization reaction, and realize a new one-pot continuous synthesis of non-isocyanate polyurethane. Compared with the traditional isocyanate method, this method does not require the use of toxic and harmful isocyanates, has a wide variety of monomers, and can obtain a richer polymer structure. In addition, the molecule contains a large number of hydroxyl groups, which improves the hydrophilicity and biocompatibility of the polymer. It is expected to become an excellent "substitute" for conventional polyurethane and be applied in the fields of biomedicine, daily chemical industry, etc.

[0053] (2) The present invention can directly use three monomer raw materials (di / triamine or amino alcohol, non-substituted cyclic carbonate and di / tri-epoxy compound) for the synthesis of non-isocyanate polyurethane. Compared with the harsher synthesis conditions (high vacuum, high temperature) of non-isocyanate polyurethane by ester exchange method, the reaction conditions involved in the present invention are very mild and can be carried out under normal pressure. The reaction temperature is room temperature or slightly higher than room temperature. It is atom-economical and no small molecule by-products are generated. There is no need to remove small molecule by-products (such as water, alcohol, etc.) during the reaction.

[0054] (3) The three raw material monomers used in the present invention have extremely rich structures, high-purity products with a high degree of commercialization, and are mostly biomass renewable resources, so non-isocyanate polyurethanes with rich structures and properties and high adjustability can be synthesized very economically and greenly, and the overall environmental friendliness and sustainability of the method can be further improved. However, the existing non-isocyanate polyurethane synthesis methods based on di / polycyclic carbonates lack high-purity commercial di / polycyclic carbonate raw materials, and can only use di / polyamines and almost no amino alcohols, so the polymer structure and performance are very limited.

[0055] (4) In the product provided by the present invention, the side hydroxyl group is highly modifiable and can be converted into other groups or polymers through mature organic or polymerization reactions, or undergo coupling reactions with other substances. Compared with traditional polyurethanes, it has the advantage of further enriching the structure and properties of polyurethanes through post-modification methods and broadening the application range of polyurethanes.

[0056] (5) The raw materials used in the method provided by the present invention are all solid or high-boiling-point liquids, so the reaction conditions are mild and the operation process is highly safe, which is suitable for large-scale, industrial production.

[0057] (6) The high efficiency of the catalytic system in the present invention enables the step-wise polymerization reaction of di / triamine or amino alcohol modified with cyclic carbonate and di / tri-epoxide to be carried out under mild conditions with low catalyst dosage, which is significantly more economical, simple and energy-saving than the traditional isocyanate method and the existing non-isocyanate method.

[0058] (7) The raw materials and catalysts used in the present invention do not contain metal ions and are non-toxic, harmless and environmentally friendly. Therefore, the non-isocyanate polyurethane material obtained by the method provided by the present invention is more suitable for applications in the fields of energy, microelectronics, biomedicine, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1a The stepwise polymerization product (non-isocyanate polyurethane) of 1,8-octanediamine, ethylene carbonate and 1,4-butanediol diglycidyl ether in Example 1 1 H NMR spectra;

[0060] Figure 1b SEC chart of the stepwise polymerization product (non-isocyanate polyurethane) of 1,8-octanediamine, ethylene carbonate and 1,4-butanediol diglycidyl ether in Example 1;

[0061] Figure 2a The stepwise polymerization product (non-isocyanate polyurethane) of 1,10-decanediamine, ethylene carbonate and 1,4-butanediol diglycidyl ether in Example 5 1 H NMR spectra;

[0062] Figure 2b SEC chart of the stepwise polymerization product (non-isocyanate polyurethane) of 1,10-decanediamine, ethylene carbonate and 1,4-butanediol diglycidyl ether in Example 5;

[0063] Figure 3a The stepwise polymerization product (non-isocyanate polyurethane) of 1,8-diamino-3,6-dioxaoctane, ethylene carbonate and 1,4-butanediol diglycidyl ether in Example 6 1 H NMR spectra;

[0064] Figure 3b SEC chart of the step-wise polymerization product (non-isocyanate polyurethane) of 1,8-diamino-3,6-dioxaoctane, ethylene carbonate and 1,4-butanediol diglycidyl ether in Example 6;

[0065] Figure 4a The stepwise polymerization product (non-isocyanate polyurethane) of Example 13, m-phenylenediamine, ethylene carbonate and 1,4-butanediol diglycidyl ether 1 H NMR spectra;

[0066] Figure 4b This is the SEC chart of the step-wise polymerization product (non-isocyanate polyurethane) of Example 13 m-xylylenediamine, ethylene carbonate and 1,4-butanediol diglycidyl ether. DETAILED DESCRIPTION

[0067] The specific implementation modes of the present invention are described in detail below in conjunction with examples, but the implementation modes of the present invention are not limited thereto.

[0068] The reaction degree of the epoxy groups in the di- / tertiary epoxy compounds and the structural characteristics of the resulting polymers in the following examples were measured by a Bruker AV400 liquid nuclear magnetic resonance spectrometer ( 1 H NMR) was measured, and the solvent was deuterated dimethyl sulfoxide. The molecular weight and dispersity of the obtained polymer were measured by size exclusion chromatography (SEC), and the instrument used an Agilent 1260infinity II pump and a PLgel 5μm mixed-C chromatographic column, with N,N-dimethylformamide (DMF) as the mobile phase, a column temperature of 50°C, and a flow rate of 1mL / min; a series of polymethyl methacrylate standard samples were used as calibration curves. The parts used in the following examples and proportions are all molar parts. As an example, the molar parts can be mol, mmol, etc., or any other amount commonly used in the art.

[0069] Example 1

[0070] In this example, 1,8-octanediamine and ethylene carbonate are reacted in the absence of a catalyst to generate a diol containing carbamate, and 1,4-butanediol diglycidyl ether and the aforementioned reaction product are gradually polymerized in a solution at room temperature using a metal-free Lewis acid-base pair as a catalyst to prepare a non-isocyanate polyurethane based on 1,8-octanediamine, ethylene carbonate and 1,4-butanediol diglycidyl ether by a one-pot method. The specific operation is as follows:

[0071] In an air atmosphere, 1 part (4.24 mmol) of 1,8-octanediamine, 2.1 parts (8.9 mmol) of ethylene carbonate and 0.5 mL of chloroform were added to a dried glass reactor in sequence, stirred and mixed thoroughly, and reacted at 50°C for 8 hours. In the first 2 hours, the state of the solution did not change significantly; after 6 hours of reaction, a white precipitate was precipitated in the reaction system. After the reaction was completed, chloroform was removed under vacuum conditions. Thereafter, 0.94 parts (4 mmol) of 1,4-butanediol diglycidyl ether, 0.03 parts (0.12 mmol) of triethylborane, and 0.01 (0.04 mmol) of phosphazene base were added to the reaction bottle under nitrogen conditions. t BnP 2 and 0.7mL tert-butyl alcohol (the initial concentration of diepoxy monomer is 1mol / L). Stir and mix evenly, seal the glass reactor and react at room temperature for 72h, and add methanol to terminate the reaction after the reaction. In the first 24h, the solution viscosity changes little; after 36h of reaction, the solution viscosity increases significantly in a few hours, which conforms to the characteristics of linear step-by-step polymerization, that is, the reaction degree of the group is high in the early stage of the reaction, but the molecular weight does not change significantly; in the later stage of the reaction, the reaction degree of the group changes slightly but the molecular weight changes significantly. In this embodiment, the molar ratio of 1,4-butanediol diglycidyl ether, 1,8-octanediamine, ethylene carbonate, organic base and alkyl boron is 1:1.06:2.23:0.01:0.03. After the polymerization is completed, ether is added for reverse precipitation three to four times to remove the catalyst, and the resulting product is a light yellow solid. Collect the precipitate and vacuum dry it.

[0072] H NMR spectrum of non-isocyanate polyurethane prepared by stepwise polymerization of 1,8-octanediamine, ethylene carbonate and 1,4-butanediol diglycidyl ether ( 1 H NMR) and SEC test results are shown in Figure 1a , Figure 1b The purified product 1 The H NMR spectrum fully shows that the polymer is a linear polymer. In addition, 1The characteristic signal peaks (i.e., ether bonds formed by the secondary alcoholic hydroxyl groups) that may be formed by the secondary alcoholic hydroxyl groups continuing to participate in the ring-opening reaction of the epoxy group were not observed in HNMR. This indicates that under this catalytic system, the difference in the reactivity of the primary alcoholic hydroxyl groups and the secondary alcoholic hydroxyl groups is amplified, so that the primary alcoholic hydroxyl groups react with the epoxy group preferentially over the secondary alcoholic hydroxyl groups, and the latter has no chance to participate in the reaction when the former exists, so the secondary alcoholic hydroxyl groups of the side groups are completely retained, which can ensure that the product structure has a high degree of uniformity. 1 H NMR showed that the reaction degree (conversion rate) of the epoxy groups was greater than 99%. The molecular weight of the obtained polyurethane was 81.8 kg / mol as measured by SEC, and the dispersion degree was 2.65.

[0073] The structure of non-isocyanate polyurethane is shown below:

[0074]

[0075] Example 2

[0076] In this example, the Lewis acid-base ratio was adjusted by adding 0.03 parts (0.12 mmol) of phosphazene base t BnP 2 and 0.9 parts (0.36 mmol) of triethylborane, the rest was the same as in Example 1, and the polymerization time was gradually shortened to 48 h. 1 H NMR shows that the reaction degree of the epoxy group can reach more than 99%. In this embodiment, the molar ratio of 1,4-butanediol diglycidyl ether, 1,8-octanediamine, ethylene carbonate, organic base and alkyl boron is 1:1.06:2.23:0.03:0.09. The molecular weight of the obtained polyurethane measured by SEC is 85.4kg / mol, and the dispersity is 2.87.

[0077] Example 3

[0078] In this example, the Lewis acid-base ratio is changed, 0.15 parts (0.6 mmol) of triethylborane is added, and the rest is the same as in Example 1, and the polymerization time is gradually shortened to 48 h. 1 H NMR shows that the reaction degree of the epoxy group can reach more than 99%. In this embodiment, the molar ratio of 1,4-butanediol diglycidyl ether, 1,8-octanediamine, ethylene carbonate, organic base and alkyl boron is 1:1.06:2.23:0.01:0.15. The molecular weight of the obtained polyurethane measured by SEC is 83.3 kg / mol, and the dispersity is 2.54.

[0079] Example 4

[0080] In this example, the di / triamine structure is changed, and 1,8-octanediamine is replaced by 1,5-pentanediamine with a shorter carbon chain. The rest is the same as in Example 3. 1H NMR shows that the reaction degree of the epoxy group can reach more than 99%. In this embodiment, the molar ratio of 1,4-butanediol diglycidyl ether, 1,5-pentanediamine, ethylene carbonate, organic base and alkyl boron is 1:1.06:2.23:0.01:0.15. The molecular weight of the obtained polyurethane measured by SEC is 79.3kg / mol, and the dispersity is 2.55.

[0081] The structure of non-isocyanate polyurethane is shown below:

[0082]

[0083] Example 5

[0084] In this example, the di / triamine structure is changed, and 1,8-octanediamine is replaced by 1,10-decanediamine having a longer carbon chain. The rest is consistent with Example 3. 1 H NMR shows that the reaction degree of epoxy groups can reach more than 99%. In this embodiment, the molar ratio of 1,4-butanediol diglycidyl ether, 1,10-decanediamine, ethylene carbonate, organic base and alkyl boron is 1:1.06:2.23:0.01:0.15. The obtained polyurethane purified product 1 H NMR and SEC images are shown in Figure 2a and Figure 2b The molecular weight of the obtained polyurethane was measured by SEC to be 86.9 kg / mol, and the dispersion degree was 2.91.

[0085] The structure of non-isocyanate polyurethane is shown below:

[0086]

[0087] Example 6

[0088] In this example, the di / triamine structure is changed, and 1,8-octanediamine is replaced by 1,8-diamino-3,6-dioxaoctane having the same atomic number but containing oxygen atoms, and the rest is consistent with Example 3. 1 H NMR ( Figure 3a ) shows that the reaction degree of epoxy groups can reach more than 99%. In this embodiment, the molar ratio of 1,4-butanediol diglycidyl ether, 2,2'-(ethylenedioxy)bis(ethylamine), ethylene carbonate, organic base and alkyl boron is 1:1.06:2.23:0.01:0.15. The molecular weight of the obtained polyurethane is determined by SEC( Figure 3b ) was measured to be 81.1 kg / mol, and the dispersion degree was 2.83.

[0089] The structure of non-isocyanate polyurethane is shown below:

[0090]

[0091] Example 7

[0092] In this example, the di / triamine structure is changed, and 1,8-octanediamine is replaced by 4,4'-diaminodicyclohexylmethane containing a cyclohexyl structure. The rest is the same as in Example 3. 1 H NMR shows that the reaction degree of epoxy groups can reach more than 99%. In this embodiment, the molar ratio of 1,4-butanediol diglycidyl ether, 4,4'-diaminodicyclohexylmethane, ethylene carbonate, organic base and alkyl boron is 1:1.06:2.23:0.01:0.15. The molecular weight of the obtained polyurethane measured by SEC is 76.4kg / mol, and the dispersity is 2.61.

[0093] The structure of non-isocyanate polyurethane is shown below:

[0094]

[0095] Example 7

[0096] In this example, the tert-butyl alcohol solvent in Example 1 was replaced with toluene solvent, and the rest was the same as in Example 1. The reaction was carried out at room temperature for 40 hours, and the crude product 1 H NMR showed that the reaction degree of epoxy groups could reach more than 99%. The molecular weight of the obtained polyurethane was measured by SEC to be 82.2 kg / mol, and the dispersion degree was 2.76.

[0097] Example 8

[0098] In this example, the tert-butyl alcohol solvent in Example 1 was replaced with dimethyl sulfoxide solvent, and the rest was the same as in Example 1. The reaction was carried out at room temperature for 63 hours, and the crude product 1 H NMR showed that the reaction degree of epoxy groups could reach more than 99%. The molecular weight of the obtained polyurethane was 83.9 kg / mol and the dispersion degree was 2.88 as measured by SEC.

[0099] Example 9

[0100] In this embodiment, the tert-butyl alcohol solvent in Example 1 was replaced with 1,1,3,3-tetramethylurea solvent, and the rest was the same as in Example 1. The reaction was carried out at room temperature for 74 hours, and the crude product 1 The reaction degree of epoxy groups measured by H NMR was more than 99%. The molecular weight of the obtained polyurethane was 77.9 kg / mol and the dispersion was 2.53 as measured by SEC.

[0101] Example 10

[0102] In this embodiment, the tert-butyl alcohol solvent in Example 1 was replaced with tetrahydrofuran solvent, and the rest was the same as in Example 1. The reaction was carried out at room temperature for 74 hours, and the crude product 1The reaction degree of epoxy groups measured by H NMR was more than 99%. The molecular weight of the obtained polyurethane was 87.1 kg / mol and the dispersion was 2.99 as measured by SEC.

[0103] Embodiment 11

[0104] In this embodiment, a Lewis acid-base pair is used as a catalyst to carry out the stepwise polymerization of bisphenol A diglycidyl ether and a diol obtained by the reaction of neopentyl diamine and ethylene carbonate, and a polyhydroxyl special polyurethane based on bisphenol A diglycidyl ether, neopentyl diamine and ethylene carbonate is prepared by a one-pot method. The specific operation is as follows:

[0105] Under air atmosphere, 1 part (4.24 mmol) of neopentyl diamine and 2.1 parts (8.9 mmol) of ethylene carbonate were fully stirred and mixed in a dried glass reactor, and reacted at 50°C for 8 hours. As the reaction proceeded, the viscosity of the reaction system gradually increased. After the reaction was completed, 0.94 parts (4 mmol) of bisphenol A diglycidyl ether, 0.15 parts (0.6 mmol) of triisopropyl borane, and 0.01 (0.04 mmol) of phosphazene base were added to the reaction bottle under nitrogen conditions. t BnP 2 and 0.7mL tetrahydrofuran (the initial concentration of diepoxy monomer is 1mol / L). Stir and mix evenly, seal the glass reactor and react at room temperature for 72h, and add methanol to terminate the reaction after the reaction is completed. In this embodiment, the molar ratio of bisphenol A diglycidyl ether, neopentyl diamine, ethylene carbonate, organic base and alkyl boron is 1:1.06:2.23:0.01:0.15. After the polymerization is completed, ether is added for reverse precipitation three to four times to remove the catalyst, and the resulting product is a light yellow solid. Collect the precipitate and vacuum dry it. 1 The reaction degree of epoxy groups measured by H NMR was more than 99%. The molecular weight of the obtained polyurethane was 88.6 kg / mol and the dispersion was 3.02 as measured by SEC.

[0106] The structure of non-isocyanate polyurethane is shown below:

[0107]

[0108] Example 12

[0109] In this embodiment, a Lewis acid-base pair is used as a catalyst to carry out the stepwise polymerization of 1,3-bis(3-glycidyloxypropyl)tetramethyldisiloxane and a diol obtained by the reaction of 1,3-cyclohexanedimethylamine and ethylene carbonate, and a non-isocyanate polyurethane containing two silicon-oxygen bonds in each repeating unit structure on the main chain is prepared by a one-pot method.

[0110] The specific operations are as follows:

[0111] Under an air atmosphere, 1 part (4.24 mmol) of 1,3-cyclohexanedimethanamine and 2.1 parts (8.9 mmol) of ethylene carbonate were thoroughly stirred and mixed in a dried glass reactor, and the reaction was carried out at 50 °C for 8 h. As the reaction proceeded, the viscosity of the reaction system gradually increased. After the reaction was completed, under nitrogen conditions, 0.94 part (4 mmol) of 1,3-bis(3-glycidyletheroxypropyl)tetramethyldisiloxane, 0.15 part (0.6 mmol) of triisopropylborane, and 0.01 part (0.04 mmol) of phosphazene base were added to the reaction flask. t BuP 2 and 0.7 mL of tetrahydrofuran (the initial concentration of the diepoxy monomer was 1 mol / L). The mixture was stirred and mixed evenly, the glass reactor was sealed and reacted at room temperature for 72 h. After the reaction was completed, methanol was added to terminate the reaction. In this example, the molar ratio of 1,3-bis(3-glycidyletheroxypropyl)tetramethyldisiloxane, 1,3-cyclohexanedimethanamine, ethylene carbonate, organic base, and alkylborane was 1:1.06:2.23:0.01:0.15. After the polymerization was completed, ether was added for reverse precipitation three to four times to remove the catalyst, and the obtained product was a pale yellow solid. The precipitate was collected and dried under vacuum to obtain the product. 1 The reaction degree of the epoxy group measured by 1H NMR reached more than 99%. The molecular weight of the obtained polyurethane was measured by SEC to be 88.6 kg / mol, and the dispersity was 2.57.

[0112] Due to the large bond angle, high bond energy, and partial ionic bond properties of the silicon-oxygen bond, polysiloxanes are endowed with excellent properties different from those of carbon-chain polymers, which makes silicone products widely used in aerospace, national defense, automobiles, construction, textiles, medical treatment, and other fields. Introducing a silicon-oxygen bond from the 1,3-bis(3-glycidyletheroxypropyl)tetramethyldisiloxane monomer into the main chain of non-isocyanate polyurethane can improve the high gas permeability, low surface energy, high and low temperature resistance, corrosion resistance, low dielectric, and other characteristics of non-isocyanate polyurethane materials.

[0113] The structure of non-isocyanate polyurethane is as follows:

[0114]

[0115] Example 13

[0116] In this example, a stepwise polymerization of 1,4-butanediol diglycidyl ether and a diol obtained from the reaction of m-xylenediamine and ethylene carbonate was carried out using a Lewis acid-base pair as a catalyst to prepare non-isocyanate polyurethane by a one-pot method. The specific operation is as follows:

[0117] Under air atmosphere, 1 part (4.24 mmol) of m-phenylenediamine and 2.1 parts (8.9 mmol) of ethylene carbonate were fully stirred and mixed in a dried glass reactor, and reacted at 50°C for 8 hours. As the reaction proceeded, the viscosity of the reaction system gradually increased. After the reaction was completed, 0.94 parts (4 mmol) of 1,4-butanediol diglycidyl ether, 0.15 parts (0.6 mmol) of triisopropylborane, and 0.01 (0.04 mmol) of phosphazene base were added to the reaction bottle under nitrogen conditions. t BnP 2 and 0.7mL tetrahydrofuran (the initial concentration of diepoxy monomer is 1mol / L). Stir and mix evenly, seal the glass reactor and react at room temperature for 72h, and add methanol to terminate the reaction after the reaction. In this embodiment, the molar ratio of 1,4-butanediol diglycidyl ether, m-phenylenediamine, ethylene carbonate, organic base and alkyl boron is 1:1.06:2.23:0.01:0.15. After the polymerization is completed, ether is added for reverse precipitation three to four times to remove the catalyst, and the resulting product is a light yellow solid. Collect the precipitate and vacuum dry it. 1 H NMR ( Figure 4a ) The reaction degree of epoxy groups can reach more than 99%. The molecular weight of the obtained polyurethane is determined by SEC ( Figure 4b ) was measured to be 97.6 kg / mol, and the dispersion degree was 3.11.

[0118] The structure of non-isocyanate polyurethane is shown below:

[0119]

[0120] Embodiment 14

[0121] In this embodiment, a Lewis acid-base pair is used as a catalyst to carry out the stepwise polymerization of resorcinol diglycidyl ether and a diol obtained by the reaction of isophorone diamine and ethylene carbonate, and a non-isocyanate polyurethane having a structure similar to that of a conventional polyurethane based on isophorone diisocyanate is prepared in one pot. The specific operation is as follows:

[0122] Under air atmosphere, 1 part (4.24 mmol) of isophorone diamine and 2.1 parts (8.9 mmol) of ethylene carbonate were fully stirred and mixed in a dried glass reactor, and reacted at 50°C for 8 hours. As the reaction proceeded, the viscosity of the reaction system gradually increased. After the reaction was completed, 0.94 parts (4 mmol) of resorcinol diglycidyl ether, 0.15 parts (0.6 mmol) of triisopropylborane, and 0.01 (0.04 mmol) of phosphazene base were added to the reaction bottle under nitrogen conditions. t BnP 2and 0.7mL tetrahydrofuran (the initial concentration of diepoxy monomer is 1mol / L). Stir and mix evenly, seal the glass reactor and react at room temperature for 72h, and add methanol to terminate the reaction after the reaction. In this embodiment, the molar ratio of 1,4-butanediol diglycidyl ether, isophorone diamine, ethylene carbonate, organic base and alkyl boron is 1:1.06:2.23:0.01:0.15. After the polymerization is completed, ether is added for reverse precipitation three to four times to remove the catalyst, and the resulting product is a light yellow solid. Collect the precipitate and vacuum dry it. 1 The reaction degree of epoxy groups measured by H NMR was more than 99%. The molecular weight of the obtained polyurethane was 89.1 kg / mol and the dispersion was 2.88 as measured by SEC.

[0123] The structure of non-isocyanate polyurethane is shown below:

[0124]

[0125] Embodiment 15

[0126] In this example, a Lewis acid-base pair is used as a catalyst to carry out the stepwise polymerization of hydantoin epoxy resin and diols obtained by the reaction of 1,4-cyclohexanediamine and ethylene carbonate, and a functional non-isocyanate polyurethane containing a five-membered nitrogen heterocycle and a double bond in the main chain is prepared in a one-pot method. The specific operation is as follows:

[0127] Under air atmosphere, 1 part (4.24 mmol) of 1,4-cyclohexanediamine and 2.1 parts (8.9 mmol) of ethylene carbonate were fully stirred and mixed in a dried glass reactor, and reacted at 50°C for 8 hours. As the reaction proceeded, the viscosity of the reaction system gradually increased. After the reaction was completed, 0.94 parts (4 mmol) of hydantoin epoxy resin, 0.15 parts (0.6 mmol) of triisopropylborane, and 0.01 (0.04 mmol) of phosphazene base were added to the reaction bottle under nitrogen conditions. t BnP 2 and 0.7mL tetrahydrofuran (the initial concentration of diepoxy monomer is 1mol / L). Stir and mix evenly, seal the glass reactor and react at room temperature for 72h, and add methanol to terminate the reaction after the reaction is completed. In this embodiment, the molar ratio of hydantoin epoxy resin, 1,4-cyclohexanediamine, ethylene carbonate, organic base and alkyl boron is 1:1.06:2.23:0.01:0.15. After the polymerization is completed, ether is added for reverse precipitation three to four times to remove the catalyst, and the resulting product is a light yellow solid. Collect the precipitate and vacuum dry it. 1 The reaction degree of epoxy groups measured by H NMR was more than 99%. The molecular weight of the obtained polyurethane was 95.6 kg / mol and the dispersion was 3.31 as measured by SEC.

[0128] The structure of non-isocyanate polyurethane is shown below:

[0129]

[0130] Example 16

[0131] In this example, the phosphazene base in Example 1 t BnP 2 The tertiary amine DABCO was used, and the rest was the same as in Example 1. The reaction was carried out at room temperature for 70 hours. 1 The reaction degree of epoxy groups measured by H NMR was more than 99%. The molecular weight of the obtained polyurethane was 92.6 kg / mol and the dispersion was 3.48 as measured by SEC.

[0132] Embodiment 17

[0133] In this example, the phosphazene base in Example 1 t BnP 2 Replaced with triaminophosphine HMTP, the rest is the same as Example 1. Reacted at room temperature for 72h, 1 The reaction degree of epoxy groups measured by H NMR was more than 99%. The molecular weight of the obtained polyurethane was 96.8 kg / mol and the dispersion was 3.11 as measured by SEC.

[0134] Embodiment 18

[0135] In this embodiment, a Lewis acid-base pair is used as a catalyst to carry out the stepwise polymerization of 1,4-butanediol diglycidyl ether and a diol obtained by the reaction of ethanolamine and ethylene carbonate to prepare a non-isocyanate polyurethane in one pot. The specific operation is as follows:

[0136] Under air atmosphere, 1 part (4.24 mmol) of ethanolamine and 1.1 parts (4.58 mmol) of ethylene carbonate were fully stirred and mixed in a dried glass reactor, and reacted at 50°C for 8 hours. As the reaction proceeded, the viscosity of the reaction system gradually increased. After the reaction was completed, 0.94 parts (4 mmol) of 1,4-butanediol diglycidyl ether, 0.15 parts (0.6 mmol) of triethylborane, and 0.01 parts (0.04 mmol) of phosphazene base were added to the reaction bottle under nitrogen conditions. t BnP 2and 0.7mL tetrahydrofuran (the initial concentration of diepoxy monomer is 1mol / L). Stir and mix evenly, seal the glass reactor and react at room temperature for 72h, and add methanol to terminate the reaction after the reaction. In this embodiment, the molar ratio of 1,4-butanediol diglycidyl ether, ethanolamine, ethylene carbonate, organic base and alkyl boron is 1:1.06:1.17:0.01:0.15. After the polymerization is completed, ether is added for reverse precipitation three to four times to remove the catalyst, and the resulting product is a light yellow solid. Collect the precipitate and vacuum dry it. 1 The reaction degree of epoxy groups measured by H NMR was more than 99%. The molecular weight of the obtained polyurethane was 103.6 kg / mol and the dispersion was 3.19 as measured by SEC.

[0137] The structure of non-isocyanate polyurethane is shown below:

[0138]

[0139] Embodiment 19

[0140] In this embodiment, a Lewis acid-base pair is used as a catalyst to carry out the stepwise polymerization of 1,4-butanediol diglycidyl ether and a diol obtained by the reaction of 2-amino-1-propanol and ethylene carbonate to prepare a non-isocyanate polyurethane in one pot. The specific operation is as follows:

[0141] Under air atmosphere, 1 part (4.24 mmol) of 2-amino-1-propanol and 1.1 parts (4.58 mmol) of ethylene carbonate were fully stirred and mixed in a dried glass reactor, and reacted at 50°C for 8 hours. As the reaction proceeded, the viscosity of the reaction system gradually increased. After the reaction was completed, 0.94 parts (4 mmol) of 1,4-butanediol diglycidyl ether, 0.15 parts (0.6 mmol) of triethylborane, and 0.01 (0.04 mmol) of phosphazene base were added to the reaction bottle under nitrogen conditions. t BnP 2 and 0.7mL tetrahydrofuran (the initial concentration of diepoxy monomer is 1mol / L). Stir and mix evenly, seal the glass reactor and react at room temperature for 72h, and add methanol to terminate the reaction after the reaction. In this embodiment, the molar ratio of 1,4-butanediol diglycidyl ether, 2-amino-1-propanol, ethylene carbonate, organic base and alkyl boron is 1:1.06:1.17:0.01:0.15. After the polymerization is completed, ether is added for reverse precipitation three to four times to remove the catalyst, and the resulting product is a light yellow solid. Collect the precipitate and vacuum dry it. 1 The reaction degree of epoxy groups measured by H NMR was more than 99%. The molecular weight of the obtained polyurethane was 101.9 kg / mol and the dispersion was 3.45 as measured by SEC.

[0142] The structure of non-isocyanate polyurethane is shown below:

[0143]

[0144] Embodiment 20

[0145] In this example, the structure of the non-substituted cyclic carbonate is changed, ethylene carbonate is replaced by 1,3-dioxane-2-one, and the rest is the same as in Example 3. 1 H NMR shows that the reaction degree of the epoxy group can reach more than 99%. In this embodiment, the molar ratio of 1,4-butanediol diglycidyl ether, 1,8-octanediamine, 1,3-dioxane-2-one, organic base and alkyl boron is 1:1.06:2.23:0.01:0.15. The molecular weight of the obtained polyurethane measured by SEC is 56.9kg / mol, and the dispersity is 2.23.

[0146] The structure of non-isocyanate polyurethane is shown below:

[0147]

[0148] Embodiment 21

[0149] This example changes the monomer structure, replaces 1,4-butanediol diglycidyl ether with 1,4-butanediol diglycidyl ether and 1,3,5-triglycidyl-S-triazinetrione, and prepares a cross-linked non-isocyanate polyurethane by a one-pot method. The specific operation is as follows:

[0150] Under air atmosphere, 1 part (4.24 mmol) of 1,8-octanediamine and 2.1 parts (8.9 mmol) of ethylene carbonate were fully stirred and mixed in a dried glass reactor, and reacted at 50°C for 8 hours. As the reaction proceeded, the viscosity of the reaction system gradually increased. After the reaction was completed, 0.9 parts (3.8 mmol) of 1,4-butanediol diglycidyl ether, 0.15 parts (0.6 mmol) of triethylborane, and 0.01 (0.04 mmol) of phosphazene base were added to the reaction bottle under nitrogen conditions. t BnP 2and 0.7mL tetrahydrofuran (the initial concentration of diepoxy monomer is 1mol / L). Stir and mix evenly, seal the glass reactor and react at room temperature for 72h. After the reaction is completed, add 0.05 parts (0.2mmol) of 1,3,5-triglycidyl-S-triazinetrione, seal the glass reactor and react at room temperature for 24h to obtain a cross-linked non-isocyanate polyurethane. In this embodiment, the molar ratio of 1,4-butanediol diglycidyl ether, 1,3,5-triglycidyl-S-triazinetrione, 1,8-octanediamine, ethylene carbonate, organic base and alkyl boron is 0.96:0.04:1.06:2.23:0.01:0.15. After the polymerization is completed, the product is immersed in methanol for 24h to remove the catalyst, and the resulting product is a light yellow solid.

[0151] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A multi-component selective synthesis method of non-isocyanate polyurethane, characterized in that: The steps include: The first step is to mix a polyamine compound and / or an amino alcohol with a non-substituted cyclic carbonate and react them at 0-100° C. to obtain a polyvalent primary alcohol containing carbamate; the polyamine compound contains at least two of an amino group and an imino group, and the amino alcohol contains at least one of a primary alcohol hydroxyl group and at least one of an amino group and an imino group; In the second step, the polyol containing carbamate, the polyepoxide and the metal-free Lewis acid-base catalyst are polymerized at 0-100° C. to obtain non-isocyanate polyurethane.

2. The multi-component selective synthesis method of non-isocyanate polyurethane according to claim 1, characterized in that: The polyamine compound includes at least one of a diamine compound and a triamine compound; The polycyclic epoxy compound comprises at least one of a binary epoxy compound and a ternary epoxy compound; The metal-free Lewis acid-base catalyst is composed of an organic base and an alkyl boron; the molar ratio of the epoxy group, the organic base and the alkyl boron in the polycyclic epoxy compound is 1:(0.005-2):(0.005-5).

3. A non-isocyanate polyurethane and a multi-component selective synthesis method thereof according to claim 2, characterized in that: The organic base includes at least one of tertiary amines, amidines, guanidines, triaminophosphines, phosphazene bases, lithium / sodium / potassium / cesium tert-butoxide, lithium / sodium / potassium / cesium / ammonium pivalate, ionic compounds containing thiourea, urea, and carbamates; The alkyl boron includes at least one of B-isopinocampheyl-9-borabicyclo[3.3.1]nonane, tri-sec-butylborane, triisopropylborane, trimethylborane, tri(straight-chain) alkylborane having 2 to 8 alkyl carbon atoms, diethylmethoxyborane and trimethyl borate.

4. The multi-component selective synthesis method of non-isocyanate polyurethane according to claim 1, characterized in that: The polyamine compound includes ethylenediamine, alkyl diamine with 3 to 18 carbon atoms, 1,3-diamino-2-hydroxypropane, 2-methyl-1,3-propylenediamine or 2-phenyl-1,3-propylenediamine, m-xylenediamine, neopentyldiamine, 1,4-butynediamine, 1,4-butenediamine, perfluoroalkyldimethylamine with 1 to 17 carbon atoms, 2-methyl-1,4-butanediamine, 3,6-dithia-1,8-octanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, 2,2'-(ethylenedioxy)bis(ethylamine), 1,3-cyclohexanedimethylamine, diethylenetriamine and at least one of N-alkyl, benzyl and allyl derivatives of the above amine compounds; The amino alcohols include aminoethanol, primary amino alcohols with 3 to 18 carbon atoms, 2-amino-1-propanol, 2-amino-3-methylbutanol, 2-amino-4-methylpentan-1-ol, phenylglycinol, phenylalaninol, 2-amino-2-cyclohexylethanol, threonine alcohol, 3-amino-n-butanol, 3-amino-4-methyl-1-pentanol, 2-amino-3-methylpentan-1-ol, tert-leucinol, 4-(aminomethyl)benzyl alcohol, 2-aminobutane-1,4-diol and lysine alcohol and at least one of the N-alkyl, benzyl and allyl derivatives of the above amino alcohols; The unsubstituted cyclic carbonate includes at least one of ethylene carbonate, 1,3-dioxane-2-one and 1,3-dioxepan-2-one.

5. The multi-component selective synthesis method of non-isocyanate polyurethane according to claim 1, characterized in that: The polycyclic epoxy compound includes at least one of a linear alkyl terminal dioxirane having an alkyl carbon number of 1 to 20, ethylene glycol diglycidyl ether, an alkyl glycol diglycidyl ether having a carbon number of 3 to 20, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether, resorcinol diglycidyl ether, a linear alkyl terminal dicarboxylic acid diglycidyl ester having an alkyl carbon number of 0 to 20, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, hydantoin epoxy resin, bisphenol A propoxy acid diglycidyl ether, bisphenol A diglycidyl ether, 1,3-bis(3-glycidyl ether propyl)tetramethyldisiloxane, and 1,3,5-triglycidyl-S-triazinetrione.

6. The non-isocyanate polyurethane and the multi-component selective synthesis method thereof according to claim 1, characterized in that: The molar ratio of the total amount of amino groups and imino groups in the polyamine compound and / or amino alcohol to the carbonate in the unsubstituted cyclic carbonate is 1:(1-1.5); The molar ratio of the epoxy group in the polycyclic epoxy compound to the primary alcohol hydroxyl group in the polycyclic primary alcohol containing carbamate is 1:(1-1.2).

7. A non-isocyanate polyurethane and a multi-component selective synthesis method thereof according to claim 1, characterized in that: In the first step, the reaction is carried out in bulk or in an organic solvent; the organic solvent is a mixture of one or more of dichloromethane, chloroform, benzene, toluene, tetrahydrofuran, dioxane, 2-methyltetrahydrofuran, n-hexane, cyclohexane, tert-butanol, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, γ-butyrolactone, β-butyrolactone, γ-valerolactone, 1,1,3,3-tetramethylurea, tetraethylurea, and tetrabutylurea; In the second step, the polymerization reaction is carried out in bulk or in an organic solvent; the organic solvent is a mixture of one or more of tert-butyl alcohol, isopropyl alcohol, benzene, toluene, tetrahydrofuran, dioxane, 2-methyltetrahydrofuran, n-hexane, cyclohexane, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, γ-butyrolactone, β-butyrolactone, γ-valerolactone, 1,1,3,3-tetramethylurea, tetraethyl urea, and tetrabutyl urea.

8. The multi-component selective synthesis method of non-isocyanate polyurethane according to claim 1, characterized in that: In the first step, a polyamine compound and an amino alcohol are mixed and used, and the molar ratio of the polyamine compound to the amino alcohol is 1:(0.01-100); In the first step, the initial total concentration of the polyamine compound and / or amino alcohol is 0.1-10 mol / L, and the initial concentration of the unsubstituted cyclic carbonate is 0.1-10 mol / L; In the second step, the initial concentration of the polycyclic epoxy compound is 0.5-10 mol / L, and the initial concentration of the polycyclic primary alcohol containing carbamate is 0.5-10 mol / L.

9. The multi-component selective synthesis method of non-isocyanate polyurethane according to any one of claims 1 to 8, characterized in that: In the first step, the reaction is carried out in air or an inert atmosphere; In the first step, the reaction time is 1 to 24 hours; In the second step, the reaction is carried out in air or an inert atmosphere; In the second step, the polymerization reaction time is 5 to 120 hours; The two-step reaction is continuously carried out in the same reactor, and the polyol containing carbamate does not need to be separated and purified, or the polyol containing carbamate is separated and purified before the second step reaction.

10. The non-isocyanate polyurethane synthesized by the synthesis method according to any one of claims 1 to 9.

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