Sulfur-containing polyamine polymer as well as preparation method and application thereof

Abstract

The invention discloses a sulfur-containing polyamine polymer as well as a preparation method and application thereof, and belongs to the technical field of polymer material synthesis. The sulfur-containing polyamine polymer is prepared by taking 3-methylene azetidine hydrochloride as a reaction monomer and carrying out cross-linking reaction on the reaction monomer and elemental sulfur or a mixture of elemental sulfur and 1, 3-bis (1-methyl vinyl) benzene in a sodium hydroxide aqueous solution. The sulfur-containing polyamine polymer prepared by the preparation method disclosed by the invention simultaneously contains amido (a polar group endows the material with adhesive force) and a dynamic reversible polysulfide bond (endows the material with repeatable processability); the preparation method does not need a catalyst, conditions are mild, only washing and drying are needed in post-treatment, operation is easy and convenient, and a product is easy to purify. The sulfur-containing polyamine polymer has a remarkable application effect in the field of wood bonding, the bonding strength is larger than 2 MPa, the requirement for the shearing strength of an indoor wood adhesive is met, and the sulfur-containing polyamine polymer can be recycled and has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and particularly relates to a sulfur-containing polyamine high polymer and a preparation method and application thereof. BACKGROUND

[0002] Polyamine high polymer is a kind of polymer rich in amine groups (including primary amine, secondary amine and tertiary amine) in the molecular chain, and polyethyleneimine (PEI) is the most representative variety in the material.

[0003] With the high reactivity and strong polarity of amine groups, polyamine high polymer can form a firm chemical bond with the surface of various substrates such as epoxy resin, wood and paper, and therefore has been widely used in the fields of wood bonding, paper and cellulose substrate compounding, pressure-sensitive adhesive preparation, etc., and exhibits excellent bonding performance.

[0004] However, the synthesis path of traditional polyamine materials has significant limitations, which is difficult to meet the current green and multifunctional industrial needs: 1) harsh synthesis conditions: the current mainstream preparation methods (such as ethyleneimine ring-opening polymerization and allylamine polymerization) need to be carried out in a strict waterless and oxygenless environment, and high-activity metal catalysts (such as alkyl aluminum compounds) or strong acids such as perchloric acid are needed, which not only puts high requirements on the sealing and corrosion resistance of production equipment, but also greatly increases the production cost, and the residual metal catalyst and the use of strong acid also bring safety hazards. 2) Poor monomer safety: the monomers such as ethyleneimine and allylamine used in the above synthesis route have high toxicity and high volatility, which can easily harm the health of operators during storage, transportation and reaction, and there is a risk of environmental leakage. 3) Complex functional modification: the polyamine products prepared by traditional methods have single function, and if sulfur elements or other functional groups are introduced to expand the performance, post-modification process must be used (such as sulfur-based modification using carbon disulfide (CS2)). Such post-modification process not only has low reaction efficiency and needs to be carried out in a strong alkaline environment (harsh conditions), but also easily generates by-products and industrial waste, causing secondary pollution.

[0005] Developing a method for directly preparing multifunctional polyamine materials in one step has become a technical bottleneck that needs to be broken through in the field of polyamine high polymers. In recent years, the use of chemical by-product elemental sulfur (S8) as a monomer to participate in polymer synthesis (such as “reverse vulcanization reaction”) has provided a green and low-cost new path for the polymer industry. However, in the existing technology, how to efficiently and controllably introduce elemental sulfur into the polyamine molecular skeleton to construct functional sulfur-containing polyamine high polymers with sulfur and nitrogen synergistic effect through one-step method still faces great challenges.

[0006] Therefore, developing a method for directly preparing a sulfur-containing polyamine high polymer in one step with simple and easily available raw materials, mild synthesis conditions and without catalysts, and applying it to the field of adhesives can not only fill the gap in the prior art and have important scientific significance, but also meet the needs of the industry for green and high-performance adhesive materials, and has broad industrial application prospects. SUMMARY

[0007] To solve the above technical problems, the application provides a sulfur-containing polyamine high polymer and a preparation method and application thereof.

[0008] To achieve the above object, the application provides the following technical scheme.

[0009] The application provides a sulfur-containing polyamine high polymer, and its structural formula is as follows:

[0010]

[0011] n is 0 or 1, the sulfur-containing polyamine high polymer of the application contains amino groups and polysulfide bonds, the polysulfide bond contains an integer greater than or equal to 0, and preferably x is an integer of 0-6.

[0012] Further, the structural formula of the sulfur-containing polyamine high polymer is as shown in formula I or formula II.

[0013]

[0014] Formula I Formula II

[0015] x is an integer of 0-6.

[0016] The application further provides a preparation method of the above-mentioned sulfur-containing polyamine high polymer, comprising the following steps: mixing 3-methyleneazetidine hydrochloride ( ) and elemental sulfur, and performing a crosslinking reaction in a sodium hydroxide aqueous solution to obtain a sulfur-containing polyamine high polymer as shown in formula I.

[0017] Or, mixing 3-methyleneazetidine hydrochloride, elemental sulfur and 1,3-di(1-methylvinyl)benzene ( ) and performing a crosslinking reaction in a sodium hydroxide aqueous solution to obtain a sulfur-containing polyamine high polymer as shown in formula II.

[0018] Further, the preparation method of 3-methyleneazetidine hydrochloride is as follows: removing the BOC protecting group of 1-BOC-3-methyleneazetidine ( ) by using an ethanol solution of hydrochloric acid, and removing the solvent to obtain 3-methyleneazetidine hydrochloride.​

[0019] Further, the molar ratio of 3-methyleneazetidine hydrochloride to sodium hydroxide in the aqueous sodium hydroxide solution is 1:1 when preparing the sulfur-containing polyamine polymer of Formula I or Formula II.

[0020] Further, the concentration of the aqueous sodium hydroxide solution is 8 mol / L.

[0021] Further, the molar ratio of 3-methyleneazetidine hydrochloride to elemental sulfur is 1:(3-5), for example, 1:3 or 1:5, when preparing the sulfur-containing polyamine polymer of Formula I.

[0022] Further, the molar ratio of 3-methyleneazetidine hydrochloride, elemental sulfur and 1,3-bis(1-methylethyl)benzene is (1-3):7:1, for example, 3:7:1 or 1:7:1, when preparing the sulfur-containing polyamine polymer of Formula II.

[0023] Further, the temperature of the cross-linking reaction is 100-160 ℃, and the time is 5-12 hours; preferably, the temperature of the cross-linking reaction is 120 ℃, and the time is 6 hours.

[0024] Further, after the cross-linking reaction, washing and vacuum drying are further included, and the temperature of the vacuum drying is 50 ℃.

[0025] Further, the washing is washing with deionized water three times.

[0026] The application further provides use of the above-mentioned sulfur-containing polyamine polymer in preparing an adhesive.

[0027] For example, the sulfur-containing polyamine polymer of the application can be used in the adhesion between wood, glass and metal plates (such as steel plates, aluminum plates and iron plates). When the sulfur-containing polyamine polymer of the application is used in the adhesion of wood, the adhesion strength is above 2 MPa, and the high adhesion performance is maintained after 3-5 cycles of use.

[0028] The primary amino group (-NH2) in the molecular chain of the sulfur-containing polyamine polymer of the application has strong polarity and nucleophilicity, and can have multiple actions with the main components of wood (cellulose, hemicellulose and lignin): 1) hydrogen bond combination: the nitrogen atom of the primary amino group forms a strong hydrogen bond with the hydrogen atom of the hydroxyl group (-OH) in wood, especially in the dense area of the hydroxyl group of cellulose, to form a dense hydrogen bond network, constituting the initial adhesion basis; 2) acid-base interaction: the primary amino group (alkaline) and the phenolic hydroxyl group (weakly acidic) of lignin in wood have an acid-base neutralization reaction, further enhancing the interfacial bonding force.

[0029] The polysulfide bond (-S xThe dynamic reversible characteristics of the polysulfide bond (x>=2) play a key role in the bonding process: 1) crosslinking network construction: the polysulfide bond can form a crosslinking structure through sulfur-sulfur bond exchange, so that the adhesive forms a three-dimensional network at the wood interface, and integrates the dispersed hydrogen bond and covalent bond action into the overall mechanical support; 2) interface wetting regulation: the moderate flexibility of the polysulfide bond makes the polymer chain more easily penetrate the micropores and cracks on the wood surface, thereby improving the wettability of the adhesive on the wood surface and expanding the effective contact area.

[0030] Compared with the prior art, the present application has the following advantages and technical effects:

[0031] (1) The present application successfully prepares a sulfur-containing polyamine polymer, which has a crosslinked network structure and contains both amino groups and polysulfide bonds, wherein the polysulfide bond has dynamic reversible characteristics, enabling the material to exhibit repeatable processing performance.

[0032] (2) The present application uses 3-methyleneazetidine hydrochloride, elemental sulfur and 1,3-bis(1-methylvinyl)benzene to prepare a crosslinked sulfur-containing polyamine polymer in a sodium hydroxide solution, which has mild conditions, does not require a catalyst, is simple to handle and easy to purify the product. BRIEF DESCRIPTION OF DRAWINGS

[0033] The accompanying drawings, which form a part of the present application, are used to provide further understanding of the present application, and serve as an aid in explaining the exemplary embodiments of the present application and their descriptions, and do not constitute an improper limitation on the present application. In the drawings:

[0034] Figure 1 X-ray diffraction spectrum of the sulfur-containing polyamine polymer (P1) prepared in Example 1 of the present application;

[0035] Figure 2 X-ray diffraction spectrum of the sulfur-containing polyamine polymer (P2) prepared in Example 2 of the present application;

[0036] Figure 3 X-ray diffraction spectrum of the sulfur-containing polyamine polymer (P3) prepared in Example 3 of the present application;

[0037] Figure 4 X-ray diffraction spectrum of the sulfur-containing polyamine polymer (P4) prepared in Example 4 of the present application;

[0038] Figure 5 Infrared spectrum of the sulfur-containing polyamine polymer (P1) prepared in Example 1 of the present application;

[0039] Figure 6 Infrared spectrum of the sulfur-containing polyamine polymer (P2) prepared in Example 2 of the present application;

[0040] Figure 7The infrared spectrum of the sulfur-containing polyamine polymer (P3) prepared in Example 3 of this invention;

[0041] Figure 8 The infrared spectrum of the sulfur-containing polyamine polymer (P4) prepared in Example 4 of this invention;

[0042] Figure 9 Thermogravimetric analysis diagram of sulfur-containing polyamine polymer (P1) prepared in Example 1 of this invention;

[0043] Figure 10 Thermogravimetric analysis diagram of sulfur-containing polyamine polymer (P2) prepared in Example 2 of this invention;

[0044] Figure 11 Thermogravimetric analysis diagram of sulfur-containing polyamine polymer (P3) prepared in Example 3 of this invention;

[0045] Figure 12 Thermogravimetric analysis diagram of sulfur-containing polyamine polymer (P4) prepared in Example 4 of this invention;

[0046] Figure 13 The stress-strain curve of the adhesive sample of sulfur-containing polyamine polymer (P1) prepared in Example 1 of the present invention;

[0047] Figure 14 The stress-strain curve of the adhesive sample of sulfur-containing polyamine polymer (P2) prepared in Example 2 of the present invention;

[0048] Figure 15 The stress-strain curve of the adhesive sample of sulfur-containing polyamine polymer (P3) prepared in Example 3 of the present invention;

[0049] Figure 16 This is a cycle diagram of the adhesive sample of sulfur-containing polyamine polymer (P4) prepared in Example 4 of the present invention after recycling and repeated adhesive tests 5 times. Detailed Implementation

[0050] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0051] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0052] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as those of ordinary skill in the art to which the application relates. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, the preferred methods and materials are described. All documents mentioned herein are incorporated by reference to disclose and describe in full the methods and / or materials which are described therein. In case of conflict, the content of the present specification will control.

[0053] Many modifications and variations of this application described in the specific embodiments of the application can be made by those skilled in the art without departing from the spirit or scope of the application. Other embodiments of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. The specification and examples given are exemplary only.

[0054] As used herein, the terms "comprise", "comprising", "include", "including", "have", "having" and the like are open-ended terms that are intended to mean "including but not limited to".

[0055] The embodiment of the present application provides a sulfur-containing polyamine polymer, which has the following structural formula:

[0056]

[0057] n is 0 or 1, and x is an integer greater than or equal to 0, preferably x is an integer from 0 to 6.

[0058] In the preferred embodiment of the present application, the sulfur-containing polyamine polymer has the structural formula as shown in Formula I or Formula II:

[0059] or

[0060] Formula I Formula II

[0061] x is an integer from 0 to 6.

[0062] The present application also provides a preparation method of the above-mentioned sulfur-containing polyamine polymer, which comprises the following steps: mixing 3-methyleneazetidine hydrochloride and elemental sulfur, and performing a cross-linking reaction in a sodium hydroxide aqueous solution to obtain a sulfur-containing polyamine polymer as shown in Formula I;

[0063] or, mixing 3-methyleneazetidine hydrochloride, elemental sulfur and 1,3-bis(1-methylethyl) benzene, and performing a cross-linking reaction in a sodium hydroxide aqueous solution to obtain a sulfur-containing polyamine polymer as shown in Formula II.

[0064] The preparation method of the sulphur-containing polyamine high polymer is relatively simple, controllable, and accurate in controlling key parameters in preparation, and the cross-linking degree and density of the cross-linking network can be flexibly controlled by adjusting the parameters, so that the chemical composition and mechanical properties of the material can be adjusted; the polysulfide structure in the product can form stable covalent cross-linking, so that the material exhibits repeatable adhesion.

[0065] In the preferred embodiments of the present application, when preparing the sulphur-containing polyamine high polymer shown in formula I or formula II, the molar ratio of 3-methyleneazetidine hydrochloride to sodium hydroxide in the aqueous sodium hydroxide solution is 1:1.

[0066] In the preferred embodiments of the present application, the concentration of the aqueous sodium hydroxide solution is 8 mol / L.

[0067] In the preferred embodiments of the present application, when preparing the sulphur-containing polyamine high polymer shown in formula I, the molar ratio of 3-methyleneazetidine hydrochloride to elemental sulfur is 1:(3-5), for example, 1:3 or 1:5.

[0068] In the preferred embodiments of the present application, when preparing the sulphur-containing polyamine high polymer shown in formula II, the molar ratio of 3-methyleneazetidine hydrochloride, elemental sulfur and 1,3-bis(1-methylethenyl)benzene is (1-3):7:1, for example, 3:7:1 or 1:7:1.

[0069] The present application optimizes the performance of the sulphur-containing polyamine high polymer by adjusting the ratio of elemental sulfur and 1,3-bis(1-methylethenyl)benzene, and the preparation of the sulphur-containing polyamine high polymer does not require a catalyst, the product is easy to purify, has good adhesion performance, and has a wide application prospect.

[0070] In the preferred embodiments of the present application, the temperature of the cross-linking reaction is 120℃, and the time is 5 hours.

[0071] In the preferred embodiments of the present application, after the cross-linking reaction, washing and vacuum drying are further included. The temperature of the exemplary vacuum drying is 50℃.

[0072] Exemplarily, the washing is washing with deionized water three times. The embodiments of the present application also provide the use of the above-mentioned sulphur-containing polyamine high polymer in preparing an adhesive.

[0073] The sulphur-containing polyamine high polymer prepared by the present application contains both amine groups (polar groups, which impart adhesion to the material) and dynamic reversible polysulfide bonds (which impart repeatable processing performance to the material); the preparation method does not require a catalyst, has mild conditions, and only requires washing and drying for post-treatment, which is simple to operate and easy to purify the product. The sulphur-containing polyamine high polymer has a remarkable application effect in the field of wood adhesion, with an adhesion strength greater than 2MPa, meeting the shear strength requirements of indoor wood adhesives, and can be recycled and used, which has a broad application prospect.

[0074] In a preferred embodiment of the present application, the preparation of 3-methyleneazetidine hydrochloride is as follows: removing the BOC protecting group of 1-BOC-3-methyleneazetidine with an ethanol solution of hydrochloric acid, and removing the solvent to obtain 3-methyleneazetidine hydrochloride.

[0075] In the following embodiment of the present application, the process of removing the BOC protecting group of 1-BOC-3-methyleneazetidine with an ethanol solution of hydrochloric acid, and removing the solvent to obtain 3-methyleneazetidine hydrochloride is as follows: adding 30 mmol of 1-BOC-3-methyleneazetidine, 40 mL of anhydrous ethanol and 60 mmol of hydrochloric acid into a reaction bottle, stirring at room temperature for 4 hours, removing most of the solvent by rotary evaporation after the reaction is completed, and vacuum drying to obtain a yellow solid, i.e. 3-methyleneazetidine hydrochloride. Unless otherwise specified, room temperature in the present application is 25±2℃.

[0076] Each raw material used in the embodiments of the present application is commercially available. As an example, 1-BOC-3-methyleneazetidine is purchased from Shanghai Bide Pharmaceutical Technology Co., Ltd.

[0077] It should be noted that the details not described in the present application are all conventional operating means in the art, and are not the focus of the present application.

[0078] The technical solutions of the present application are further described below through examples.

[0079] Example 1

[0080] Adding 3 mmol of 3-methyleneazetidine hydrochloride, 0.4 mL of an aqueous solution of sodium hydroxide with a concentration of 8 mol / L and 9 mmol of elemental sulfur into a reaction bottle, and reacting in an oil bath at 120℃ for 6 hours, after the reaction is completed, adding the obtained solid product into deionized water for ultrasonic washing, discarding the supernatant, repeating the washing for three times, and vacuum drying to obtain a solid, i.e. a sulfur-containing polyamine polymer (named as P1), the structural formula of which is , x is an integer from 0 to 6, and the sulfur content of P1 is 65.1% and the nitrogen content is 5.0% as measured by organic elemental analysis (OEA).

[0081] Example 2

[0082] 3 mmol of 3-methyleneazacyclobutane hydrochloride, 0.4 mL of 8 mol / L sodium hydroxide aqueous solution, and 15 mmol of elemental sulfur were added to a reaction flask and reacted in an oil bath at 120 °C for 6 hours. After the reaction, the resulting solid product was ultrasonically washed with deionized water, the supernatant was discarded, and the washing was repeated three times. The dried solid obtained after vacuum drying was the sulfur-containing polyamine polymer (named P2), and its structural formula is as follows: x is an integer from 0 to 6. P2 was characterized by organic elemental analysis and its sulfur content was found to be 75.6% and nitrogen content was 3.0%.

[0083] Example 3

[0084] 3 mmol of 3-methyleneazacyclobutane hydrochloride, 0.4 mL of 8 mol / L sodium hydroxide aqueous solution, 21 mmol of elemental sulfur, and 3 mmol of 1,3-bis(1-methylvinyl)benzene were placed in a reaction flask and reacted in an oil bath at 120 °C for 6 hours. After the reaction, the obtained solid product was added to deionized water and ultrasonically washed. The supernatant was discarded, and the washing was repeated three times. The dried solid obtained after vacuum drying was the sulfur-containing polyamine polymer (named P3), and its structural formula is as follows. x is an integer from 0 to 6. P3 was characterized by organic elemental analysis and its sulfur content was found to be 56.0% and nitrogen content was 1.2%.

[0085] Example 4

[0086] 3 mmol of 3-methyleneazacyclobutane hydrochloride, 0.4 mL of 8 mol / L sodium hydroxide aqueous solution, 7 mmol of elemental sulfur, and 1 mmol of 1,3-bis(1-methylvinyl)benzene were placed in a reaction flask and reacted in an oil bath at 120 °C for 6 hours. After the reaction, the obtained solid product was added to deionized water and ultrasonically washed. The supernatant was discarded, and the washing was repeated three times. The dried solid obtained after vacuum drying was the sulfur-containing polyamine polymer (named P4), and its structural formula is as follows: x is an integer from 0 to 6. P4 was characterized by organic elemental analysis and its sulfur content was found to be 47.8% and nitrogen content was 4.2%.

[0087] Example 5

[0088] The 3 mmol 3-methyleneazetidine hydrochloride, 0.4 mL of 8 mol / L sodium hydroxide aqueous solution, 7 mmol of elemental sulfur and 1 mmol of 1,3-di(1-methylvinyl)benzene were placed in a reaction bottle, and the reaction was carried out in an oil bath at 100 ℃ for 12 hours. After the reaction was completed, the obtained solid product was added to deionized water for ultrasonic washing, the supernatant was discarded, and the washing was repeated three times. After vacuum drying, the obtained dry solid was a sulfur-containing polyamine polymer (named P5), and its structural formula was: , x is an integer from 0 to 6. The P5 was characterized by organic elemental analysis, and the sulfur content was 47.2% and the nitrogen content was 4.5%.

[0089] Example 6

[0090] The 3 mmol 3-methyleneazetidine hydrochloride, 0.4 mL of 8 mol / L sodium hydroxide aqueous solution, 7 mmol of elemental sulfur and 1 mmol of 1,3-di(1-methylvinyl)benzene were placed in a reaction bottle, and the reaction was carried out in an oil bath at 160 ℃ for 5 hours. After the reaction was completed, the obtained solid product was added to deionized water for ultrasonic washing, the supernatant was discarded, and the washing was repeated three times. After vacuum drying, the obtained dry solid was a sulfur-containing polyamine polymer (named P6), and its structural formula was: , x is an integer from 0 to 6. The P6 was characterized by organic elemental analysis, and the sulfur content was 48.6% and the nitrogen content was 4.0%.

[0091] The test method of the bonding performance referred to the national standard GB / T 33333-2016, and the specific method was as follows:

[0092] S1, the sulfur-containing polyamine polymer was crushed by a pulverizer, and was uniformly laid on the surface of the bonding substrate (steel sheet or wood), and was fixed by a clamp;

[0093] S2, the fixed sample was placed in an oven, and was cured at 120 ℃ for 8 h;

[0094] S3, after the curing was completed, the sample was subjected to tensile test by a universal electronic testing machine;

[0095] S4, the sample after the tensile test could be recycled, and the steps S1-S3 were repeated to realize the repeated processing of the material.

[0096] The laying area of the above test sample was 375 mm 2 (15 mm * 25 mm), the tensile rate of the test was 30 mm / min, and all the stress-strain tensile tests were carried out at room temperature.

[0097] The adhesion properties of the sulfur-containing polyamine polymers (P1, P2, P3, P4) prepared in Examples 1-4 are shown in Table 1.

[0098] Table 1 Analysis of the adhesion properties of the sulfur-containing polyamine polymers

[0099]

[0100] As can be seen from Table 1, the maximum strain value of the sulfur-containing polyamine polymer (P4) prepared in Example 4 on wood is 0.43%, and the maximum stress value is 2.39 MPa.

[0101] Structural characterization:

[0102] 1. The X-ray diffraction spectrum of the sulfur-containing polyamine polymer (P1) prepared in Example 1 is shown in Figure 1 ; the infrared spectrum is shown in Figure 5 ; the thermal gravimetric analysis is shown in Figure 9 ; and the stress-strain is shown in Figure 13 .

[0103] As can be seen from Figure 1 , the sulfur-containing polyamine polymer (P1) does not have the absorption peak of elemental sulfur.

[0104] As can be seen from Figure 5 , the sulfur-containing polyamine polymer (P1) has a characteristic vibration peak of N-H above 3200 wavenumbers.

[0105] As can be seen from Figure 9 , the mass loss of the sulfur-containing polyamine polymer (P1) is 5% at a temperature of 181°C, i.e., the decomposition temperature is 181°C.

[0106] As can be seen from Figure 13 , the strength of the sulfur-containing polymer (P1) is 0.60 MPa, and the elongation at break is 0.048%.

[0107] 2. The X-ray diffraction spectrum of the sulfur-containing polymer (P2) prepared in Example 2 is shown in Figure 2 ; the infrared spectrum is shown in Figure 6 ; the thermal gravimetric analysis is shown in Figure 10 ; and the stress-strain is shown in Figure 14 .

[0108] As can be seen from Figure 2 , the sulfur-containing polyamine polymer (P2) does not have the absorption peak of elemental sulfur.

[0109] As can be seen from Figure 6 , the sulfur-containing polyamine polymer (P2) has a characteristic vibration peak of N-H above 3200 wavenumbers.

[0110] As can be seen from Figure 10It can be seen that the mass loss of the sulfur-containing polyamine macromolecule (P2) is 5%, and the temperature is 184°C, i.e. the decomposition temperature is 184°C.

[0111] From Figure 14 It can be seen that the strength of the sulfur-containing polymer (P1) is 0.75 MPa, and the elongation at break is 0.057%.

[0112] 3. The X-ray diffraction spectrum of the sulfur-containing polymer (P3) prepared in Example 3 is shown in Figure 3 ; the infrared spectrum is shown in Figure 7 ; the thermal gravimetric analysis is shown in Figure 11 ; and the stress-strain is shown in Figure 15 .

[0113] From Figure 3 It can be seen that the sulfur-containing polyamine macromolecule (P3) does not have the absorption peak of elemental sulfur.

[0114] From Figure 7 It can be seen that the sulfur-containing polyamine macromolecule (P3) has characteristic vibration peaks of N-H above 3200 wave numbers.

[0115] From Figure 11 It can be seen that the mass loss of the sulfur-containing polyamine macromolecule (P3) is 5%, and the temperature is 204°C, i.e. the decomposition temperature is 204°C.

[0116] From Figure 15 It can be seen that the strength of the sulfur-containing polymer (P3) is 0.89 MPa, and the elongation at break is 0.065%.

[0117] 4. The X-ray diffraction spectrum of the sulfur-containing polymer (P4) prepared in Example 4 is shown in Figure 4 ; the infrared spectrum is shown in Figure 8 ; and the thermal gravimetric analysis is shown in Figure 12 .

[0118] From Figure 4 It can be seen that the sulfur-containing polyamine macromolecule (P4) does not have the absorption peak of elemental sulfur.

[0119] From Figure 8 It can be seen that the sulfur-containing polyamine macromolecule (P4) has characteristic vibration peaks of N-H above 3200 wave numbers.

[0120] From Figure 12 It can be seen that the mass loss of the sulfur-containing polyamine macromolecule (P4) is 5%, and the temperature is 190°C, i.e. the decomposition temperature is 190°C.

[0121] From Figure 16 It can be seen that the maximum stress in the bonding process of the sulfur-containing polyamine macromolecule (P4) after being recycled and repeatedly subjected to the bonding test for 5 times can still reach 2.11 MPa.

[0122] The above merely provides the preferred embodiment of the present application, and the protection scope of the present application is not limited thereto, and any changes or substitutions easily conceived by those skilled in the art within the technical scope disclosed by the present application should be covered within the protection scope of the present application.

Claims

1. A sulfur-containing polyamine polymer, characterized by, The structural formula is as follows: n is 0 or 1, and x is an integer greater than or equal to 0.

2. The sulfur-containing polyamine polymer of claim 1, wherein, x is an integer of 0-6.

3. A process for the preparation of the sulphur-containing polyamine polymer according to any one of claims 1 to 2, characterized in that The method comprises the following steps: When n is 0, 3-methyleneazetidine hydrochloride is mixed with elemental sulfur, and a cross-linking reaction is carried out in a sodium hydroxide aqueous solution to prepare the sulfur-containing polyamine polymer. When n is 1, 3-methyleneazetidine hydrochloride, elemental sulfur and 1,3-bis(1-methylvinyl)benzene are mixed, and a cross-linking reaction is carried out in a sodium hydroxide aqueous solution to prepare the sulfur-containing polyamine polymer.

4. The method of claim 3, wherein the sulfur-containing polyamine polymer is prepared by the reaction of a polyamine compound and a sulfur compound in the presence of a base. When n is 0, the molar ratio of 3-methyleneazetidine hydrochloride to elemental sulfur is 1: (3-5).

5. The method of claim 3, wherein the sulfur-containing polyamine polymer is prepared by the reaction of a polyamine compound and a sulfur compound in the presence of a base. When n is 0 or 1, the molar ratio of 3-methyleneazetidine hydrochloride to sodium hydroxide in the sodium hydroxide aqueous solution is 1:

1.

6. The method of claim 5, wherein the sulfur-containing polyamine polymer is prepared by the reaction of a polyamine and a sulfur-containing compound. The concentration of the sodium hydroxide aqueous solution is 8 mol / L.

7. The method of claim 3, wherein the sulfur-containing polyamine polymer is prepared by the reaction of a polyamine compound and a sulfur compound in the presence of a base. When n is 1, the molar ratio of 3-methyleneazetidine hydrochloride, elemental sulfur and 1,3-bis(1-methylvinyl)benzene is (1-3) :7:

1.

8. The method of claim 7, wherein the sulfur-containing polyamine polymer is prepared by the reaction of a polyamine with a sulfur-containing compound. When n is 1, the molar ratio of 3-methyleneazetidine hydrochloride, elemental sulfur and 1,3-bis(1-methylvinyl)benzene is 3:7:1 or 1:7:

1.

9. The method of claim 3, wherein the sulfur-containing polyamine polymer is prepared by the reaction of a polyamine compound and a sulfur compound in the presence of a base. The temperature of the cross-linking reaction is 100-160 ℃, and the time is 5-12 hours.

10. Use of the sulfur-containing polyamine polymer according to any one of claims 1-2 in the preparation of an adhesive.

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