An organic adhesive with antibacterial function and its preparation method and application

Abstract

The present application belongs to the field of organic functional molecule synthesis and antibacterial hemostatic medical materials, and particularly relates to an organic adhesive with antibacterial function and a preparation method and application thereof. The organic adhesive is a guanidinium cation modified polysiloxane. The adhesive is prepared by introducing guanidinium cation groups into the polysiloxane structure based on molecular design and chemical synthesis. The adhesive exhibits excellent adhesion performance in various environments and can exhibit strong adhesion on substrates such as metals, glasses and biological epidermis. The adhesive can automatically debond according to the required time in a wet environment such as underwater, and can be immediately debonded using a mild solvent. The adhesive also has a significant bacteriostatic effect and rapid hemostatic ability, and is suitable for scenarios such as wound bacteriostatic hemostasis, wound tissue repair, wound care and on-demand debonding of wound adhesive or dressing.

Description

Technical Field

[0001] This invention belongs to the field of organic functional molecule synthesis and antibacterial and hemostatic medical materials, specifically relating to an organic adhesive with antibacterial function, its preparation method and application. Background Technology

[0002] In the field of antibacterial and hemostatic medical adhesives, statistics on bleeding-related deaths show that bleeding accounts for over 50% of combat casualties and 15%–25% of civilian deaths. Emergency medical adhesive dressings can effectively close wounds and stop bleeding, especially in environments with limited medical resources, such as in the field and on the battlefield. Medical adhesive dressings can quickly adhere and fix damaged wounds, minimizing the loss of tissue function and buying valuable time for subsequent treatment. Furthermore, the market demand for antibacterial and hemostatic functions is increasing.

[0003] In the field of on-demand bonding in medical applications, current commercial adhesives are typically single-use. Some medical adhesives have low detachment resistance, making it difficult to achieve tight adhesion underwater; others have high detachment resistance, which can cause secondary damage to the wound during detachment. The market demand for on-demand detachable medical adhesives is constantly increasing. There is an urgent need to develop medical adhesives that can bond and detach on demand.

[0004] In the field of on-demand debonding technology, adhesives capable of on-demand debonding are becoming increasingly important in many technological areas. DE19832629A1 describes an adhesive for on-demand debonding based on thermal or radiant energy; WO2010 / 128042A1, WO002 / 46260A1, and WO2010 / 002262A1 describe adhesives for heat-induced debonding; US2007 / 0142497A1 describes an adhesive for photothermal debonding; and WO2022 / 254267 describes an adhesive for electrical stimulation debonding. However, for wound adhesion in emergency situations, the implementation conditions for photoresponse and electrical response are demanding and uncontrollable, while thermal and mechanical responses can easily cause secondary damage to the wound. Therefore, for on-demand bonding technology, there is an urgent need to develop gentler on-demand bonding methods to adapt to the application scenarios of medical adhesives.

[0005] In the field of environmentally friendly and recyclable medical adhesives, developing recyclable medical adhesives remains a significant challenge. CN117402586A describes a highly chemically cross-linked silicone adhesive; such highly chemically cross-linked materials are insoluble, making environmentally friendly recycling difficult. Furthermore, the vast majority of used medical adhesives become medical waste, highlighting the urgent need to develop environmentally friendly and recyclable medical adhesives.

[0006] In summary, there is an urgent need to develop an adhesive that simultaneously possesses on-demand bonding, on-demand debonding, antibacterial and hemostatic properties, as well as recyclability. Summary of the Invention

[0007] To address the shortcomings and deficiencies of existing technologies, the primary objective of this invention is to provide an organic adhesive with antibacterial properties. This adhesive simultaneously possesses on-demand bonding, on-demand detachment, antibacterial and hemostatic functions, and is recyclable, making it applicable to emergency wound care needs.

[0008] Another object of the present invention is to provide a method for preparing the above-mentioned organic adhesive with antibacterial function.

[0009] Another object of the present invention is to provide the application of the above-mentioned organic adhesive with antibacterial function.

[0010] The objective of this invention is achieved through the following technical solution:

[0011] An antibacterial organic adhesive, wherein the organic adhesive is a cationic modified polysiloxane comprising the structure shown in formula (I), (II), (III), (IV) or (V):

[0012]

[0013] In the formula, X m+ The guanidine cationic group (guanidine, also known as guanidine, guanidine salt, or guanidineonium, is a group containing one carbon atom linked to three nitrogen atoms) is disposed at the end group and / or side chain of the polysiloxane (the above-mentioned cationic modified polysiloxane can be a linear polysiloxane or a cross-linked polysiloxane; the guanidine cationic group can specifically be disposed at the end group (formula (I)), side chain (formula (II)) or a combination thereof of the linear polysiloxane, or at the end group (formula (I)) and side chain (formulas (II) to (V) or a combination thereof) of the cross-linked polysiloxane); Y n- It is the anion of guanidine;

[0014] The number of repeating units in equations (II) to (V) is 1 to 1000; repeating units refer to the parts enclosed in parentheses; the values ​​of m and n are both 1 to 2;

[0015] R 1 R 2 and R 3 It can be a deletion group independently, or it can be –O–, –S–, –CO–O–, –O–CO–, or CO–NR. 7 –、–NR 7 –CO–、–O–CO–NR 7 –、–NR 7 –CO–O– or –NR 7 –CO–NR 7– or a divalent hydrocarbon group containing 1 to 60 carbon atoms, which may be –O–, –S–, –CO–O–, –O–CO–, or CO–NR. 7 –、–NR 7 –CO–、–O–CO–NR 7 –、–NR 7 –CO–O– or –NR 7 –CO–NR 7 – Intermittent; R 7 An alkyl group representing H or 1 to 20 carbon atoms can be interrupted by a group such as –O–, which means that the –O– group is adjacent to carbon atoms on both sides.

[0016] R 4 R 5 and R 6 It can be a missing group independently, or a hydrogen, aliphatic, aromatic, or fluorine-containing monovalent hydrocarbon group containing 1 to 60 carbon atoms, wherein the hydrocarbon group can be –O–, –S–, –CO–O–, –O–CO–, or CO–NR. 7 –、–NR 7 –CO–、–O–CO–NR 7 –、–NR 7 –CO–O– or –NR 7 –CO–NR 7 – Intermittent; R 7 An alkyl group representing H or 1 to 20 carbon atoms can be interrupted by a group such as –O–, which means that the –O– group is adjacent to carbon atoms on both sides.

[0017] In the formula, the asterisk (*) indicates the connection position with the polysiloxane unit in the polymer (adhesive), and the polysiloxane unit is selected from hydrocarbon siloxane, silicon-functional siloxane, carbon-functional siloxane or inactive modified siloxane; the single line “—” connected to the asterisk indicates covalent connection, including but not limited to single bond, double bond or other chemical bond connection methods, and other single lines are single bond connections.

[0018] Preferably, the percentage of monomer units containing the guanidine cationic group to the total number of monomer units is 0.1% to 50%. The term "ionic molar content" as used herein refers to the percentage of monomer units containing the cationic group to the total number of monomer units.

[0019] Preferably, the Y n– It can be chloride ions (-Cl) - ), bromide ions (-Br) - ), iodide ions (-I) - ), sulfonate (-SO3) – ), sulfate (-OSO3) 2- ), carboxylate (-PO3)2- ), phosphonate (-PO3) 2- ) or nitrate ions (-NO3) - )wait.

[0020] Preferably, the hydrocarbon-based siloxane: that is, all substituents on the silicon atoms are hydrocarbon groups, mainly including one or more of dimethylsiloxane, diethylsiloxane, or methylphenylsiloxane; the silicon-functionalized siloxane: that is, siloxanes in which functional groups (including Si-X bonds) are directly attached to some silicon atoms, mainly including one or more of hydrosiloxanes, hydroxysiloxanes, alkoxysiloxanes, acetoxysiloxanes, vinylsiloxanes, chlorine-terminated siloxanes, or amino-terminated siloxanes; the carbon-functionalized siloxane: that is, siloxanes in which functional groups (including Si-X bonds) are directly attached to some silicon atoms. The siloxanes containing Si-RX mainly include one or more of the following: aminoalkyl siloxanes, epoxyalkyl siloxanes, methacryloyloxyalkyl siloxanes, hydroxyalkyl siloxanes, thioalkyl siloxanes, hydroxyalkyl siloxanes, chlorinalkyl siloxanes, or cyanoalkyl siloxanes; the inactive modified siloxanes are siloxanes in which some silicon atoms are attached to inactive groups or polymeric segments, mainly including one or more of the following: polyether siloxanes, long-chain alkyl siloxanes, long-chain alkoxy siloxanes, fluoroalkyl siloxanes, and siloxanes whose main chain contains alkylene groups or cyclosilazane alkyl groups.

[0021] Preferably, the cationic modified polysiloxane is a linear polysiloxane or a lightly crosslinked polysiloxane. "Lightly crosslinked" means that the cationic modified polysiloxane, even with a three-dimensional crosslinked structure, can still dissolve or be uniformly dispersed in a solvent.

[0022] Preferably, the adhesive has a microphase separation structure. Microphase separation is a supramolecular structure, as demonstrated by X-ray scattering experiments at a scattering vector q (nm). -1 ) at 0.1nm -1 ~5nm -1 The presence of scattering peaks confirms this. The term "supramolecular interaction" in this paper refers to hydrogen bonding, electrostatic interactions, donor-acceptor interactions, dipole-dipole interactions, ion-pair interactions, van der Waals interactions, hydrophilic interactions, and combinations thereof. The term "microphase-separated structure" refers to the nanoscale phase regions formed by the aggregation of cationic groups, which can be scattered by the scattering vector q (nm) in X-ray scattering experiments. -1 ) at 0.1nm -1 ~5nm -1 This is confirmed by the presence of scattering peaks. In some embodiments, the adhesive has a microphase-separated structure.

[0023] This invention also provides a composition of an organic adhesive with antibacterial function, which is a copolymer and / or composite material prepared from a cationic modified polysiloxane containing the structure shown in formulas (I), (II), (III), (IV), or (V). The copolymer refers to a polymer (the adhesive) whose main chain, in addition to the polysiloxane, also copolymerizes other types of polymers and combinations thereof. The composite material refers to a material formed by physical or chemical compounding of the cationic modified polysiloxane with other organic substances, metals, inorganic substances, or mixtures thereof. In some embodiments, the adhesive is a cationic modified polysiloxane; in other embodiments, the adhesive is a physical composite material of the cationic modified polysiloxane.

[0024] Another object of the present invention is to provide a method for preparing the above-mentioned antibacterial organic adhesive, comprising the following steps:

[0025] (1) The amino-modified polysiloxane, guanidinizing agent and acid-binding agent are stirred at -20℃ to 160℃ for 0.1 to 120 hours with or without the addition of solvent;

[0026] (2) Stop stirring, dry the reaction solution directly or add it to a solvent to precipitate, wash and dry to obtain a viscous cationic modified polysiloxane.

[0027] The cationic modified polysiloxane obtained by this invention is a transparent, non-flowing gel-like sample after drying. In contrast, amino-containing polydimethylsiloxanes before the reaction conversion are generally free-flowing liquids. Therefore, the cationic structure incorporated into the polysiloxane significantly increases the material's viscosity, which is the main design principle for its use as an adhesive material.

[0028] Preferably, the amino-modified polysiloxane in step (1) contains at least one of an amino-terminal group, an amino-side group, or an amino T-type structure, for example, but not limited to a copolymer of (aminopropyl)-methylsiloxane and dimethylsiloxane, an amino-terminated polydimethylsiloxane or a copolymer of (aminopropyl)-methylsiloxane and dimethylsiloxane, or a copolymer of (aminoethylaminopropyl)-methylsiloxane and dimethylsiloxane (more preferably an amino-terminated polydimethylsiloxane or a copolymer of (aminopropyl)-methylsiloxane and dimethylsiloxane).

[0029] Preferably, the guanidinizing agent in step (1) includes, but is not limited to, pyrazole-1-formimide derivatives, and is preferably 1H-pyrazole-1-formamidine hydrochloride.

[0030] Preferably, the acid-binding agent in step (1) includes, but is not limited to, triethylamine and N,N-diisopropylethylamine.

[0031] Preferably, the solvent in step (1) includes at least one of polar solvents such as water, methanol, ethanol, acetonitrile, dimethylformamide, and dimethyl sulfoxide.

[0032] Preferably, the solvent in step (2) is at least one of the following solvents: acetone, acetonitrile, water, dichloromethane, diethyl ether, petroleum ether, etc.

[0033] Preferably, the cationic modified polysiloxane obtained in step (2) above can be either completely or partially converted from amino groups to guanidine groups. The sample with completely converted amino groups can be used directly, while the sample with partially converted amino groups can be used after thermal crosslinking in air at 60°C to 300°C.

[0034] The adhesive and / or its composition described in this invention simultaneously possess on-demand bonding, on-demand debonding, antibacterial and hemostatic functions, and are recyclable. They can be used to prepare medical dressings or medical tissue adhesive patches, etc. According to physical morphology, the adhesive and / or its composition can be prepared as solid products (e.g., elastomer products), liquid products (e.g., solution products or emulsion products), aerosol products (e.g., spray products), or any mixture thereof. According to function, the adhesive and / or its composition can be prepared as antibacterial products, antimicrobial products, bactericidal products, wound closure products, hemostatic products, tissue trauma hemostasis aids, tissue trauma repair products, tissue trauma antibacterial products, pharmaceutical products, or surgical products, etc. These can be applied to emergency wound care needs (e.g., bandaging, fixation, care, repair, and surgery) to achieve hemostasis and antibacterial effects, and can be debonded on demand during secondary wound treatment to protect the wound.

[0035] This invention provides a medical tissue dry adhesive patch, which is prepared from the above-mentioned antibacterial organic adhesive and / or its composition. Specifically, the present invention prepares the medical tissue dry adhesive patch by applying the above-mentioned adhesive and / or its composition between two films at a thickness of 0.02 mm to 2 cm. Preferably, the film can be any type or combination thereof, such as cloth-based, paper-based, metal, silicone, polymer film, or release film. The medical tissue dry adhesive patch is made into a tape or adhesive patch, and the tape / patch structure is cut into the required shape, which can be used in medical dressings (including applications in the preparation of tissue wound hemostatic aids, tissue wound closure products, tissue wound repair products, and tissue wound antibacterial products), facilitating adhesion and on-demand removal.

[0036] The present invention also provides a method for recycling adhesives, comprising the following steps:

[0037] a. Dissolving or dispersing the adhesive using a solvent; the solvent includes at least one of polar solvents such as water, methanol, ethanol, acetonitrile, dimethylformamide, and dimethyl sulfoxide;

[0038] b. Impurities are removed through extraction, centrifugation, or precipitation;

[0039] c. Drying yields reusable cationic modified polysiloxane adhesives.

[0040] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0041] 1. The antibacterial organic adhesive and / or its composition described in this invention have the advantage of on-demand bonding. "On-demand bonding" as used herein is defined as: (1) an adhesion sufficient to remain on a dry or wet surface for the required time; (2) an adhesion that can be achieved with pressure not exceeding that of a fingertip; typically tacky at room temperature. Bonding surfaces include, for example, metals, inorganic materials, polymers, biological epidermis, and biological tissues and organs. The antibacterial organic adhesive and / or its composition described in this invention can achieve an adhesion strength of 50 kPa or more to biological tissues. In one embodiment, the adhesive can be bonded to a dry surface. In one embodiment, the adhesive can be bonded to a wet surface. In one embodiment, the adhesive can be bonded to a biological surface.

[0042] 2. The antibacterial organic adhesives and / or compositions thereof described in this invention have the advantage of on-demand debonding. "On-demand debonding" as used herein is defined as: the complete debonding of the adhesive within the required time without peeling or other complex stimuli, achieved with the aid of a mild solvent; complete debonding refers to the absence of any peel strength or single lap shear strength.

[0043] One approach to on-demand debonding is that the aforementioned antibacterial organic adhesive and / or its composition can achieve rapid debonding with the assistance of a mild solvent. The mild solvent includes polar solvents such as water, methanol, ethanol, acetonitrile, dimethylformamide, and dimethyl sulfoxide, or any mixture thereof. For medical applications requiring urgent debonding, the ionic molar content of the on-demand debonding adhesive and / or its composition is preferably 1% to 50%, and the mild solvent is preferably a mixture of ethanol and water, including medical alcohol. In some embodiments, adhesives and / or their compositions with an ionic molar content of 2.8% to 22.1% can rapidly debond in methanol, dimethylformamide, ethanol, and medical alcohol. In some embodiments, adhesives and / or compositions thereof with an ionic molar content of 22.1% can rapidly detack in water or in an aqueous solution of ethanol with a volume fraction of ≥0%; adhesives and / or compositions thereof with an ionic molar content of 6.5%, 8.4%, and 8.4% can rapidly detack in an aqueous solution of ethanol with a volume fraction of ≥20%; and adhesives and / or compositions thereof with an ionic molar content of 2.8% and 3.8% can rapidly detack in an aqueous solution of ethanol with a volume fraction of ≥40%.

[0044] The second on-demand debonding method involves self-debonding in a mild solvent. The aforementioned antibacterial organic adhesives and / or their compositions can be gradually dissolved or dispersed in a mild solvent, achieving on-demand debonding according to the required time. They are gradually dissolved or dispersed in the mild solvent within the required time, achieving spontaneous on-demand debonding. For applications involving spontaneous debonding within the human body, the solvent is preferably water or an environment similar to blood and bodily fluids. In one embodiment, a cationic modified polysiloxane with an ionic molar content of 8.1% can self-debond after 10 days underwater. In another embodiment, a cationic modified polysiloxane with an ionic molar content of 22.1% can self-debond after 30 minutes underwater.

[0045] 3. The antibacterial organic adhesive and / or its composition described in this invention have the advantages of antibacterial and hemostatic properties and can be used as medical tissue adhesives. The medical tissue dry adhesive patch provided by this invention can be applied to rapid hemostasis, wound healing and repair, and wound antibacterial properties in moist physiological environments.

[0046] 4. The antibacterial organic adhesive and / or its composition described in this invention have the advantage of being recyclable. The adhesive, contaminated after adhesion to biological epidermis, can be dissolved or dispersed with the aid of a mild solvent. Impurities can be easily removed through one or a combination of operations such as extraction, centrifugation, and precipitation. Drying to remove the solvent allows for environmentally friendly recycling and reuse. Attached Figure Description

[0047] Figure 1 The results of single lap shear strength tests on different substrates under dry conditions for the adhesive prepared in Example 17;

[0048] Figure 2 The results of single lap shear strength tests on different substrates under dry conditions for the adhesive prepared in Example 18;

[0049] Figure 3 The test results show the change in single lap shear strength over time of the adhesive prepared in Example 17 on stainless steel under humid conditions.

[0050] Figure 4 This is a schematic diagram of the adhesive prepared in Example 17 after 10 days of humid conditions for on-demand debonding;

[0051] Figure 5 The test results show the change in single lap shear strength over time of the adhesive prepared in Example 18 on stainless steel under humid conditions.

[0052] Figure 6 A schematic diagram of the adhesive prepared in Example 18 after 30 minutes of humid conditions for on-demand debonding;

[0053] Figure 7 A photograph showing the effect of the adhesive prepared in Example 17 leaving no residue on the glass surface after wiping with medical alcohol;

[0054] Figure 8 This is a schematic diagram showing the rapid debonding of the adhesive prepared in Example 17 under the action of medical alcohol;

[0055] Figure 9 The adhesive prepared in Example 17 is shown in the single-lap shear strength test results and adhesion effect photos under complex wetting conditions on biological epidermis.

[0056] Figure 10 Diagram showing the diameter of the inhibition zone against Staphylococcus aureus by the adhesive prepared in Example 17;

[0057] Figure 11 Photographs showing the experimental results of the hemostatic effect of the adhesive prepared in Example 17 on the short tail wound of mice;

[0058] Figure 12 Photographs showing the experimental results of the hemostatic effect of the adhesive prepared in Example 17 on liver wounds in mice;

[0059] Figure 13 Photographs showing the recycling process of the adhesive prepared in Example 17. Detailed Implementation

[0060] To illustrate the present invention, the following embodiments are provided. These embodiments are for illustrative purposes only and are not intended to limit the scope of the appended claims. In the embodiments, the structures of the products and intermediates are confirmed by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy. The specific materials, amounts, conditions, and other details listed in the embodiments should not be construed as undue limitations on the invention. The embodiments can be implemented with appropriate modifications to the process parameters, but all similar substitutions and modifications will be apparent to those skilled in the art and are considered to be included in the invention. The invention has been described through preferred embodiments, and those skilled in the art will readily be able to modify or appropriately alter and combine the methods and applications described herein without departing from the content, spirit, and scope of the invention to implement and apply the technology of the invention.

[0061] Example 1:

[0062] Amino-terminated polydimethylsiloxane (average molecular weight approximately 850–900 g / mol, average repeating unit number m of dimethylsiloxane approximately 8–9, 5.00 g, 5.56 mmol, 11.45 mmol-NH₂), 1H-pyrazole-1-formamidine hydrochloride (1.68 g, 11.45 mmol), and N,N-diisopropylethylamine (1.48 g, 11.45 mmol) were added to a single-necked flask, followed by 5 mL of methanol as the reaction solvent. The ratio of amino groups in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and N,N-diisopropylethylamine was controlled at 1:1:1, and methanol was used as the solvent. The mixture was stirred at room temperature (25 °C) for 30 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 78%.

[0063] The adhesive structure is as follows:

[0064] 1 H NMR(ppm,500MHz,Methanol-d4):3.17(t,J=7.1Hz,-NH-CH2-CH2-CH2-Si,2H),1.68–1.58(m,-N H-CH2-CH2-CH2-Si,2H),0.66–0.58(m,-NH-CH2-CH2-CH2-Si,2H),0.16–0.04(m,Si-CH3,44H).

[0065] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0066] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 22.1%.

[0067] Example 2:

[0068] Amino-terminated polydimethylsiloxane (average molecular weight approximately 850–900 g / mol, average repeating unit m of dimethylsiloxane approximately 8–9, 5.00 g, 5.56 mmol, 11.45 mmol-NH₂), 1H-pyrazole-1-formamidine hydrochloride (3.36 g, 22.91 mmol), and N,N-diisopropylethylamine (4.44 g, 34.36 mmol) were added to a single-necked flask, followed by 5 mL of methanol as the reaction solvent. The ratio of the molar number of amino groups in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and N,N-diisopropylethylamine was controlled at 1:2:3, and methanol was used as the solvent. The mixture was stirred at room temperature (25 °C) for 30 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 82%.

[0069] The adhesive structure is as follows:

[0070] 1 H NMR(ppm,500MHz,Methanol-d4):3.17(t,J=7.1Hz,-NH-CH2-CH2-CH2-Si,2H),1.68–1.58(m,-N H-CH2-CH2-CH2-Si,2H),0.66–0.58(m,-NH-CH2-CH2-CH2-Si,2H),0.16–0.04(m,Si-CH3,44H).

[0071] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0072] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 22.1%.

[0073] Example 3:

[0074] Amino-terminated polydimethylsiloxane (average molecular weight approximately 850–900 g / mol, average repeating unit m of dimethylsiloxane approximately 8–9, 5.00 g, 5.56 mmol, 11.45 mmol-NH₂), 1H-pyrazole-1-formamidine hydrochloride (3.36 g, 22.91 mmol), and N,N-diisopropylethylamine (4.44 g, 34.36 mmol) were added to a single-necked flask, followed by 5 mL of methanol as the reaction solvent. The ratio of the molar number of amino groups in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and N,N-diisopropylethylamine was controlled at 1:2:3, and methanol was used as the solvent. The mixture was stirred at 60 °C for 5 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 85%.

[0075] The adhesive structure is as follows:

[0076] 1 H NMR(ppm,500MHz,Methanol-d4):3.17(t,J=7.1Hz,-NH-CH2-CH2-CH2-Si,2H),1.68–1.58(m,-N H-CH2-CH2-CH2-Si,2H),0.66–0.58(m,-NH-CH2-CH2-CH2-Si,2H),0.16–0.04(m,Si-CH3,44H).

[0077] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0078] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 22.1%.

[0079] Example 4:

[0080] Amino-terminated polydimethylsiloxane (average molecular weight approximately 850–900 g / mol, average repeating unit number m of dimethylsiloxane approximately 8–9, 5.00 g, 5.56 mmol, 11.45 mmol-NH₂), 1H-pyrazole-1-formamidine hydrochloride (3.36 g, 22.91 mmol), and N,N-diisopropylethylamine (4.44 g, 34.36 mmol) were added to a single-necked flask, followed by 5 mL of ethanol as the reaction solvent. The ratio of the molar number of amino groups in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and N,N-diisopropylethylamine was controlled at 1:2:3, with ethanol as the solvent. The mixture was stirred at room temperature (25 °C) for 5 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 83%.

[0081] The adhesive structure is as follows:

[0082] 1 H NMR(ppm,500MHz,Methanol-d4):3.17(t,J=7.1Hz,-NH-CH2-CH2-CH2-Si,2H),1.68–1.58(m,-N H-CH2-CH2-CH2-Si,2H),0.66–0.58(m,-NH-CH2-CH2-CH2-Si,2H),0.16–0.04(m,Si-CH3,44H).

[0083] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0084] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 22.1%.

[0085] Example 5:

[0086] Amino-terminated polydimethylsiloxane (average molecular weight approximately 850–900 g / mol, average repeating unit number m of dimethylsiloxane approximately 8–9, 5.00 g, 5.56 mmol, 11.45 mmol-NH₂), 1H-pyrazole-1-formamidine hydrochloride (3.36 g, 22.91 mmol), and N,N-diisopropylethylamine (4.44 g, 34.36 mmol) were added to a single-necked flask, followed by 5 mL of ethanol as the reaction solvent. The ratio of the molar number of amino groups in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and N,N-diisopropylethylamine was controlled at 1:2:3, and ethanol was used as the solvent. The mixture was stirred at 78 °C for 5 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the adhesive. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 88%.

[0087] The adhesive structure is as follows:

[0088] 1 H NMR(ppm,500MHz,Methanol-d4):3.17(t,J=7.1Hz,-NH-CH2-CH2-CH2-Si,2H),1.68–1.58(m,-N H-CH2-CH2-CH2-Si,2H),0.66–0.58(m,-NH-CH2-CH2-CH2-Si,2H),0.16–0.04(m,Si-CH3,44H).

[0089] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0090] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 22.1%.

[0091] Example 6:

[0092] Amino-terminated polydimethylsiloxane (average molecular weight approximately 850–900 g / mol, average repeating unit number m of dimethylsiloxane approximately 8–9, 5.00 g, 5.56 mmol, 11.45 mmol-NH₂), 1H-pyrazole-1-formamidine hydrochloride (3.36 g, 22.91 mmol), and triethylamine (3.48 g, 34.36 mmol) were added to a single-necked flask, followed by 5 mL of ethanol as the reaction solvent. The molar number of amino groups in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and triethylamine were controlled at 1:2:3, and ethanol was used as the solvent. The mixture was stirred at 25 °C for 30 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 86%.

[0093] The adhesive structure is as follows:

[0094] 1 H NMR(ppm,500MHz,Methanol-d4):3.17(t,J=7.1Hz,-NH-CH2-CH2-CH2-Si,2H),1.68–1.58(m,-N H-CH2-CH2-CH2-Si,2H),0.66–0.58(m,-NH-CH2-CH2-CH2-Si,2H),0.16–0.04(m,Si-CH3,44H).

[0095] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0096] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 22.1%.

[0097] Example 7:

[0098] Amino-terminated polydimethylsiloxane (average molecular weight approximately 5000 g / mol, average repeating unit number m of dimethylsiloxane approximately 64, 5.00 g, 1.0 mmol, 1.84 mmol-NH2), 1H-pyrazole-1-formamidine hydrochloride (0.54 g, 3.68 mmol), and N,N-diisopropylethylamine (0.71 g, 5.52 mmol) were added to a single-necked flask, followed by 5 mL of methanol as the reaction solvent. The ratio of the molar number of amino groups in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and N,N-diisopropylethylamine was controlled at 1:2:3, and methanol was used as the solvent. The mixture was stirred at room temperature (25 °C) for 30 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 91%.

[0099] The adhesive structure is as follows:

[0100] 1 H NMR(ppm,500MHz,Methanol-d4):3.16(t,J=7.1Hz,-NH-CH2-CH2-CH2-Si,2H),1.70–1.56(m,-NH -CH2-CH2-CH2-Si,2H),0.69–0.54(m,-NH-CH2-CH2-CH2-Si,2H),0.25–-0.04(m,Si-CH3,279H).

[0101] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0102] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 2.8%.

[0103] Example 8:

[0104] A polydimethylsiloxane with amino side groups (average molecular weight approximately 8000 g / mol, average repeating unit number m of dimethylsiloxane approximately 110–111, average repeating unit number n of guanidine-containing siloxane approximately 4–6, 5.00 g, 0.63 mmol, 2.48 mmol-NH2), 1H-pyrazole-1-formamidine hydrochloride (0.36 g, 2.48 mmol), and N,N-diisopropylethylamine (0.32 g, 2.48 mmol) were added to a single-necked flask, followed by 5 mL of methanol as the reaction solvent. The ratio of amino groups in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and N,N-diisopropylethylamine was controlled at 1:1:1, and methanol was used as the solvent. The mixture was stirred at room temperature (25 °C) for 30 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 85%.

[0105] The adhesive structure is as follows

[0106] 1 H NMR(ppm,500MHz,Methanol-d4):3.19–3.13(m,-NH-CH2-CH2-CH2-Si,2H),1.73–1.56(m,-NH- CH2-CH2-CH2-Si,2H),0.66–0.53(m,-NH-CH2-CH2-CH2-Si,2H),0.23–-0.02(m,Si-CH3,146H).

[0107] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0108] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 3.8%.

[0109] Example 9:

[0110] A polydimethylsiloxane with amino side groups (average molecular weight approximately 8000 g / mol, average repeating unit number m of dimethylsiloxane approximately 110–111, average repeating unit number h of guanidine-containing siloxane approximately 4–6, 5.00 g, 0.63 mmol, 2.48 mmol-NH2), 1H-pyrazole-1-formamidine hydrochloride (0.18 g, 1.24 mmol), and N,N-diisopropylethylamine (0.96 g, 7.44 mmol) were added to a single-necked flask, followed by 5 mL of methanol as the reaction solvent. The ratio of amino groups in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and N,N-diisopropylethylamine was controlled at 1:0.5:3, and methanol was used as the solvent. The mixture was stirred at room temperature (25 °C) for 30 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 88%.

[0111] The adhesive structure is as follows:

[0112] 1 H NMR(ppm,500MHz,Methanol-d4):3.19–3.13(m,-NH-CH2-CH2-CH2-Si,1H),2.69–2.59(m,NH2-CH2-CH2-CH2,1H),1.73–1.56(m,-NH-CH2-CH2-CH2-Si,1 H),1.50–1.38(m,NH2-CH2-CH2-CH2,1H),0.66–0.53(m,-NH-CH2-CH2-CH2-Si,1H),0.58–0.44(m,NH2-CH2-CH2-CH2,1H),0.23–-0.02(m,Si-CH3,146H).

[0113] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0114] 1 ¹H NMR and IR results indicate that the amino group has been partially converted into guanidine cations, with a molar content of 1.9%.

[0115] Example 10:

[0116] Amino-containing polydimethylsiloxane (average molecular weight approximately 8000 g / mol, average repeating unit number m of dimethylsiloxane approximately 110–111, average repeating unit number h of guanidine-containing siloxane approximately 4–6, 5.00 g, 0.63 mmol, 2.48 mmol-NH2), 1H-pyrazole-1-formamidine hydrochloride (0.29 g, 1.98 mmol), and N,N-diisopropylethylamine (0.96 g, 7.44 mmol) were added to a single-necked flask, followed by 5 mL of methanol as the reaction solvent. The ratio of the molar number of amino groups in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and N,N-diisopropylethylamine was controlled at 1:0.8:3, and methanol was used as the solvent. The mixture was stirred at 60 °C for 5 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 83%.

[0117] The adhesive structure is as follows

[0118] 1 H NMR(ppm,500MHz,Methanol-d4):3.19–3.13(m,-NH-CH2-CH2-CH2-Si,4H),2.82–2.50(m,NH2-CH2-CH2-CH2,1H),1.73–1.56(m,-NH-CH2-CH2-CH2-Si,4H ),1.65–1.40(m,2NH2-CH2-CH2-CH2,1H),0.66–0.53(m,-NH-CH2-CH2-CH2-Si,4H),0.63–0.41(m,NH2-CH2-CH2-CH2,1H),0.23–-0.02(m,Si-CH3,365H).

[0119] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0120] 1 ¹H NMR and IR results indicate that the amino group has been partially converted into guanidine cations, with a molar content of 3.0%.

[0121] Example 11:

[0122] The products of Examples 9 and 10 were heated in air at 300°C for 0.5 hours to allow the residual amino groups to undergo a crosslinking reaction. However, after crosslinking, the products remained soluble or dispersed in methanol or ethanol, and the crosslinked samples were still difficult-to-flow gel-like samples. The adhesive structure is as follows:

[0123]

[0124] Example 12:

[0125] A polydimethylsiloxane with amino side groups (average molecular weight approximately 8000 g / mol, average repeating unit number m of dimethylsiloxane approximately 110–111, average repeating unit number n of guanidine-containing siloxane approximately 4–6, 5.00 g, 0.63 mmol, 2.48 mmol-NH2), 1H-pyrazole-1-formamidine hydrochloride (0.73 g, 4.96 mmol), and N,N-diisopropylethylamine (0.96 g, 7.44 mmol) were added to a single-necked flask, followed by 5 mL of ethanol as the reaction solvent. The ratio of amino molars in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and N,N-diisopropylethylamine was controlled at 1:2:3, and ethanol was used as the solvent. The mixture was stirred at room temperature (25 °C) for 5 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the adhesive. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 86%.

[0126] 1 H NMR(ppm,500MHz,Methanol-d4):3.19–3.13(m,-NH-CH2-CH2-CH2-Si,2H),1.73–1.56(m,-NH- CH2-CH2-CH2-Si,2H),0.66–0.53(m,-NH-CH2-CH2-CH2-Si,2H),0.23–-0.02(m,Si-CH3,146H).

[0127] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0128] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 3.8%.

[0129] Example 13:

[0130] A polydimethylsiloxane with amino side groups (average molecular weight approximately 8000 g / mol, average repeating unit number m of dimethylsiloxane approximately 110–111, average repeating unit number n of guanidine-containing siloxane approximately 4–6, 5.00 g, 0.63 mmol, 2.48 mmol-NH2), 1H-pyrazole-1-formamidine hydrochloride (0.73 g, 4.96 mmol), and N,N-diisopropylethylamine (0.96 g, 7.44 mmol) were added to a single-necked flask, followed by 5 mL of ethanol as the reaction solvent. The ratio of amino molars in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and N,N-diisopropylethylamine was controlled at 1:2:3, and ethanol was used as the solvent. The mixture was stirred at 78 °C for 5 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the adhesive. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 92%.

[0131] The adhesive structure is as follows

[0132] 1 H NMR(ppm,500MHz,Methanol-d4):3.19–3.13(m,-NH-CH2-CH2-CH2-Si,2H),1.73–1.56(m,-NH- CH2-CH2-CH2-Si,2H),0.66–0.53(m,-NH-CH2-CH2-CH2-Si,2H),0.23–-0.02(m,Si-CH3,146H).

[0133] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0134] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 3.8%.

[0135] Example 14:

[0136] A polydimethylsiloxane with amino side groups (average molecular weight approximately 8000 g / mol, average repeating unit number m of dimethylsiloxane approximately 110–111, average repeating unit number n of guanidine-containing siloxane approximately 4–6, 5.00 g, 0.63 mmol, 2.48 mmol-NH2), 1H-pyrazole-1-formamidine hydrochloride (0.73 g, 4.96 mmol), and triethylamine (0.75 g, 7.44 mmol) were added to a single-necked flask, followed by the addition of 5 mL of ethanol as the reaction solvent. The ratio of the amino group in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and the triethylamine was controlled to be 1:2:3, and ethanol was used as the solvent. The mixture was stirred at 25 °C for 30 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 91%.

[0137] The adhesive structure is as follows

[0138] 1 H NMR(ppm,500MHz,Methanol-d4):3.19–3.13(m,-NH-CH2-CH2-CH2-Si,2H),1.73–1.56(m,-NH- CH2-CH2-CH2-Si,2H),0.66–0.53(m,-NH-CH2-CH2-CH2-Si,2H),0.23–-0.02(m,Si-CH3,146H).

[0139] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0140] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 3.8%.

[0141] Example 15:

[0142] A polydimethylsiloxane with amino side groups (average molecular weight approximately 2500 g / mol, average repeating unit number m of dimethylsiloxane approximately 21–31, average repeating unit number n of guanidine-containing siloxane approximately 2–4, 5.00 g, 2.0 mmol, 5.06 mmol-NH2), 1H-pyrazole-1-formamidine hydrochloride (1.48 g, 10.12 mmol), and N,N-diisopropylethylamine (1.96 g, 15.18 mmol) were added to a single-necked flask, followed by 5 mL of methanol as the reaction solvent. The ratio of amino groups in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and N,N-diisopropylethylamine was controlled at 1:2:3, and methanol was used as the solvent. The mixture was stirred at room temperature (25 °C) for 30 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 83%.

[0143] The adhesive structure is as follows

[0144] 1 H NMR(ppm,500MHz,Methanol-d4):3.17(t,J=7.1Hz,-NH-CH2-CH2-CH2-Si,2H),1.71–1.59(m,-N H-CH2-CH2-CH2-Si,2H),0.64–0.55(m,-NH-CH2-CH2-CH2-Si,2H),0.25–-0.07(m,Si-CH3,54H).

[0145] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0146] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 8.4%.

[0147] Example 16:

[0148] A polydimethylsiloxane with amino side groups (average molecular weight approximately 4500 g / mol, average repeating unit number m of dimethylsiloxane approximately 46–59, average repeating unit number n of guanidine-containing siloxane approximately 3–4, 5.00 g, 1.11 mmol, 4.11 mmol-NH2), 1H-pyrazole-1-formamidine hydrochloride (1.20 g, 8.22 mmol), and N,N-diisopropylethylamine (1.59 g, 12.32 mmol) were added to a single-necked flask, followed by 5 mL of methanol as the reaction solvent. The ratio of the amino group in the polydimethylsiloxane to the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride and N,N-diisopropylethylamine was controlled at 1:2:3, and methanol was used as the solvent. The mixture was stirred at room temperature (25 °C) for 30 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 86%.

[0149] The adhesive structure is as follows

[0150] 1 H NMR(ppm,500MHz,Methanol-d4):3.17(t,J=7.1Hz,-NH-CH2-CH2-CH2-Si,2H),1.74–1.55(m,-N H-CH2-CH2-CH2-Si,2H),0.71–0.54(m,-NH-CH2-CH2-CH2-Si,2H),0.33–-0.14(m,Si-CH3,98H).

[0151] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0152] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 6.5%.

[0153] Example 17:

[0154] A polydimethylsiloxane with amino side groups (average molecular weight approximately 500,000 g / mol, average repeating unit number m of dimethylsiloxane approximately 37–43, average repeating unit number n of guanidine-containing siloxane approximately 600–610, 5.00 g, 0.01 mmol, 1.04 mmol-NH2), 1H-pyrazole-1-formamidine hydrochloride (1.52 g, 10.39 mmol), and N,N-diisopropylethylamine (2.01 g, 15.58 mmol) were added to a single-necked flask, followed by 5 mL of methanol as the reaction solvent. The ratio of the amino group molars in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and the N,N-diisopropylethylamine was controlled at 1:2:3, and methanol was used as the solvent. The mixture was stirred at room temperature (25 °C) for 30 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample that was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly free-flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 86%.

[0155] The adhesive structure is as follows

[0156] 1 H NMR(ppm,500MHz,Methanol-d4):3.16(t,J=7.1Hz,-NH-CH2-CH2-CH2-Si,2H),1.76–1.56(m,-N H-CH2-CH2-CH2-Si,2H),0.70–0.49(m,-NH-CH2-CH2-CH2-Si,2H),0.30–-0.07(m,Si-CH3,60H).

[0157] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0158] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 8.1%.

[0159] Example 18:

[0160] A polydimethylsiloxane with amino side groups (average molecular weight approximately 200,000 g / mol, average repeating unit number m of dimethylsiloxane approximately 41–48, average repeating unit number n of guanidine-containing siloxane approximately 175–191, 5.00 g, 0.025 mmol, 13.11 mmol-NH2), 1H-pyrazole-1-formamidine hydrochloride (3.84 g, 26.21 mmol), and N,N-diisopropylethylamine (5.08 g, 39.32 mmol) were added to a single-necked flask, followed by 5 mL of methanol as the reaction solvent. The ratio of the amino group in the polydimethylsiloxane, the reaction equivalence of 1H-pyrazole-1-formamidine hydrochloride, and the N,N-diisopropylethylamine was controlled at 1:2:3, and methanol was used as the solvent. The mixture was stirred at room temperature (25 °C) for 30 minutes. After stirring was stopped, the reaction solution was added to 30 mL of acetonitrile to precipitate, yielding a viscous substance, i.e., the binder. The viscous substance was repeatedly washed three times with acetonitrile and dried to obtain a transparent, gel-like sample with an ion molar content of 22.1%, which was difficult to flow. In contrast, the amino-containing polydimethylsiloxane was a highly flowing liquid, demonstrating that the supramolecular structure of the guanidine cation increased the material's viscosity. The binder yield was 86%.

[0161] The adhesive structure is as follows

[0162] 1 H NMR(ppm,500MHz,Methanol-d4):3.26-3.11(t,J=7.1Hz,-NH-CH2-CH2-CH2-Si,2H),1.76–1.56(m, -NH-CH2-CH2-CH2-Si,2H),0.69–0.51(m,-NH-CH2-CH2-CH2-Si,2H),0.25–-0.07(m,Si-CH3,24H).

[0163] IR (cm) -1 ):2900,3350,3150,2960,1660,1260,1090-1020,800.

[0164] 1 ¹H NMR and IR results showed that the amino group had been completely converted into guanidine cations, with a molar content of 22.1%.

[0165] Example 19:

[0166] Small-angle X-ray scattering experiments on the guanidine-cation-containing polydimethylsiloxane (adhesive) prepared in Examples 1 to 18 all demonstrate that the scattering vector q (nm) -1 ) at 1nm -1 ~3nm -1Scattering peaks appear between them, while the corresponding scattering vector q (nm) of amino-containing polydimethylsiloxanes is... -1 ) at 1nm -1 ~3nm -1 No scattering peaks were observed between them, indicating that the supramolecular structure promotes microphase separation through ionic hydrogen bonding or electrostatic interactions.

[0167] Example 20:

[0168] A certain mass of silica powder was added to the adhesives prepared in Examples 1-18, and mechanically mixed until the mixture was uniform and no obvious particles were observed by the naked eye, thus obtaining a composite material adhesive. The mass of silica accounted for 5%, 10%, 20%, 30%, 40%, and 50% of the mass of the composite material adhesive.

[0169] Example 21:

[0170] A certain mass of clay flake powder was added to the adhesives prepared in Examples 1-18, and mechanically mixed until the mixture was uniform and no obvious particles were observed by the naked eye, thus obtaining a composite material adhesive. The different amounts of clay flakes added to the composite material adhesives accounted for 5%, 10%, 20%, 30%, 40%, and 50% of the mass of the composite material adhesive.

[0171] Performance testing:

[0172] 1. Take 100 mg of the adhesives or their composite adhesives with different ion molar contents prepared in Examples 1-18, 20, and 21, and soak them in 10 mL of different solvents. Stir and observe whether the adhesive can dissolve or disperse immediately, indicating that its main cohesive force has broken down and the adhesive has detached. The results are shown in Table 1:

[0173] Table 1 shows the results of whether the adhesives or their composite adhesives with different ion molar contents in Examples 1-18, 20, and 21 could rapidly detangle.

[0174]

[0175]

[0176] 2. The adhesives prepared in Examples 17 and 18 are applied to a thickness of 0.2 mm between a PET film and a PET release film, respectively, and then cut to form a transferable adhesive tape / patch structure. This tape can be used as an adhesive patch material in medical dressings, facilitating adhesion and on-demand removal.

[0177] 3. The adhesive prepared in Example 17 was applied in air to a thickness of 0.2 mm between two identical substrates (stainless steel sheet, copper sheet, and glass sheet) to create a single-lap test sample. Tensile testing was performed using a universal tensile testing machine. The single-lap shear strength, expressed in kPa, was obtained by dividing the maximum stress of the tensile curve by the initial joint area. This was used to evaluate the adhesion performance under dry conditions. The test was conducted at a constant temperature of 25°C. The results are as follows: Figure 1 As shown.

[0178] 4. The adhesive prepared in Example 18 was applied in air to a thickness of 0.2 mm between two identical substrates (stainless steel sheet, copper sheet, and glass sheet) to prepare a single-lap joint test sample. Tensile testing was performed using a universal tensile testing machine. The single-lap joint shear strength was obtained by dividing the maximum stress of the tensile curve by the initial joint area, with units of kPa. Adhesion performance under dry conditions was evaluated. The test was conducted at a constant temperature of 25°C, and the results are as follows: Figure 2 As shown.

[0179] 5. The adhesive prepared in Example 17 was applied underwater to two identical substrates (stainless steel sheets) to a thickness of 0.2 mm, forming a single-lap test sample. A tensile test was performed using a universal tensile testing machine. The single-lap shear strength was obtained by dividing the maximum stress of the tensile curve by the initial joint area, with units of kPa. The test was conducted at a constant temperature of 25°C to evaluate the attenuation of adhesion performance over time under wet conditions. The results are as follows: Figure 3 As shown in the diagram. Example 17 represents a type of adhesive with low ionic molar content (the percentage of ionic monomers in the total monomers is less than 15%), and a schematic diagram of the self-debonding results achieved underwater after 10 days is shown in the diagram. Figure 4 As shown in the figure. The results indicate that the material exhibits excellent adhesion under wet conditions and can be debonded as needed.

[0180] 6. The adhesive prepared in Example 18 was applied underwater to two identical substrates (stainless steel sheets) to a thickness of 0.2 mm, forming a single-lap test sample. Tensile testing was performed using a universal tensile testing machine. The single-lap shear strength was obtained by dividing the maximum stress of the tensile curve by the initial joint area, with units of kPa. The test was conducted at a constant temperature of 25°C to evaluate the attenuation of adhesion performance over time under wet conditions. The results are as follows: Figure 5 As shown. Example 18 represents a class of adhesives with high ionic molar content (the percentage of ionic monomers in the total monomers is greater than 15%), and a schematic diagram of the self-debonding result after 30 minutes underwater is shown. Figure 6 As shown in the figure. The results indicate that the material exhibits excellent adhesion under wet conditions and can be debonded as needed.

[0181] 7. The transferable adhesive tape / patch structure prepared according to the method described in Performance Test Experiment 2 of Example 17 was adhered to the glass surface by adhesive bonding. A photograph showing the adhesive being quickly removed with medical alcohol without leaving any residue is shown. Figure 7 As shown in the diagram. This illustrates how medical alcohol can quickly remove ionic adhesives. Figure 8 As shown.

[0182] 8. The adhesive prepared in Example 17 was applied underwater to two identical substrates (pigskin and sheepskin) to a thickness of 0.2 mm, forming a single-overlap test sample. Tensile testing was performed using a universal tensile testing machine. The single-overlap shear strength was obtained by dividing the maximum stress of the tensile curve by the initial joint area, with units of kPa. This evaluated the adhesion performance in the complex wetting environment of biological epidermis. The single-overlap shear strength was approximately 15–30 kPa. Adhesion photographs are shown below. Figure 9 As shown in the figure. The results indicate that the material exhibits excellent adhesion under complex wetting conditions on biological epidermis.

[0183] 9. Using Staphylococcus aureus as a Gram-positive bacterial model, the antibacterial ability of the adhesive prepared in Example 17 as a medical adhesive was evaluated. Inhibition zone experiments were conducted, demonstrating good antibacterial activity, such as... Figure 10 As shown.

[0184] 10. The adhesive prepared in Example 17, when used as a patch to treat a short-tailed wound in mice according to the method described in Performance Test Experiment 2, achieved a hemostasis time of 91 seconds, demonstrating good hemostatic function. Figure 11 The image shown is a photograph of the bleeding result from the short-tailed test.

[0185] 11. The adhesive from Example 17, when used to treat liver wounds in mice with adhesive patches prepared according to the method described in Performance Test Experiment 2, achieved a hemostasis time of 62 seconds, demonstrating good hemostatic function. Figure 12 The image shown is a photograph of the bleeding results from a liver wound experiment.

[0186] 12. The adhesive prepared in Example 17 was repeatedly bonded with pigskin 10 times. Dust impurities were added to simulate the condition of the adhesive after being contaminated by animal fat, hair, and dust. Since the material had no chemical cross-linking or a very low degree of chemical cross-linking, the contaminated adhesive was dissolved in methanol by stirring, allowed to stand, and the lower layer of fat was filtered out. Solid impurities were removed during filtration. Figure 13 As shown in the figure. The results indicate that the material remains recyclable even after use in polluted environments, which aligns with environmental protection and sustainability principles.

Claims

1. An organic adhesive with antibacterial function, characterized in that, The organic adhesive is a cation-modified polysiloxane comprising a structure represented by formula (I) or (II): In the formula, X m+ is a guanidinium cation group, the guanidinium cation group is arranged at an end group or / and a side chain of the polysiloxane; Y n- is an anion of the guanidinium cation group, and the values of m and n are both in the range of 1-2. The number of repeating units of formula (II) is 1-1000, and the repeating unit refers to the part enclosed in brackets; R 1 , R 2 independently a divalent aliphatic, aromatic, or fluorine-containing hydrocarbon group containing 1 to 60 carbon atoms; R 4 , R 5 is independently absent, or hydrogen; R 6 R is a group which is absent, or is hydrogen, an aliphatic, aromatic or fluorine-containing monovalent hydrocarbon group containing from 1 to 60 carbon atoms; In the formula, the asterisk indicates the connection position with the polysiloxane unit, and the polysiloxane unit is selected from at least one of a hydrocarbyl siloxane, a silicon-functional siloxane, a carbon-functional siloxane, or a non-reactive modified siloxane, and the single line indicates a single bond; The hydrocarbyl siloxane includes one or more of dimethylsiloxane, diethylsiloxane, or methylphenylsiloxane; The silicon-functional siloxane includes one or more of hydrogen-containing siloxane, hydroxyl siloxane, alkoxy siloxane, acetoxy siloxane, vinyl siloxane, chlorine-terminated siloxane, or amino-terminated siloxane; The carbon-functional siloxane includes one or more of amino-hydrocarbyl siloxane, epoxy-hydrocarbyl siloxane, methacryloxy-hydrocarbyl siloxane, hydroxy-hydrocarbyl siloxane, sulfur-hydrocarbyl siloxane, chloro-hydrocarbyl siloxane, or cyano-hydrocarbyl siloxane; The non-reactive modified siloxane includes one or more of polyether siloxane, long-chain alkyl siloxane, long-chain alkoxy siloxane, fluorinated hydrocarbyl siloxane, and siloxane with a main chain containing an alkylene group or a cyclosilazane group.

2. The organic binder according to claim 1, characterized in that The percentage of the number of monomer units of the guanidinium cation group to the total number of monomer units is 0.1%-50%.

3. The organic binder of claim 1, wherein The Y n– is one or more of a chloride, bromide, iodide, sulfonate, sulfate, carboxylate, phosphonate, or nitrate ion.

4. The organic binder of claim 1, wherein The organic adhesive has a microphase separation structure.

5. A composition of an organic binder having an antibacterial function, characterized by, It is a copolymer and / or composite material prepared from the organic adhesive of any one of claims 1-4.

6. The method of producing an organic adhesive having an antibacterial function according to any one of claims 1 to 4, characterized by, It comprises the following steps: (1) stirring the amino-modified polysiloxane, guanidination reagent, and acid-binding agent at -20°C-160°C for 0.1-120 hours with or without adding a solvent; (2) stopping stirring, directly drying the reaction solution or precipitating it in a solvent, washing, and drying to obtain a viscous cation-modified polysiloxane, which is the adhesive.

7. The production method according to claim 6, wherein The amino-modified polysiloxane in step (1) contains at least one of an amino end group, an amino side group, or an amino T-shaped structure; The guanidination reagent in step (1) includes a pyrazole-1-carboximidate derivative; The acid-binding agent in step (1) includes one or more of triethylamine and N,N-diisopropylethylamine; The solvent in step (1) includes at least one of water, methanol, ethanol, acetonitrile, dimethylformamide, and dimethyl sulfoxide; The solvent in step (2) is at least one of acetone, acetonitrile, water, dichloromethane, diethyl ether, and petroleum ether.

8. The preparation method according to claim 6, characterized in that, The amino-modified polysiloxane in step (1) includes at least one of a copolymer of (aminopropyl)-methylsiloxane and dimethylsiloxane, an amino-terminated polydimethylsiloxane, or a copolymer of (aminopropyl)-methylsiloxane and dimethylsiloxane, a copolymer of (aminoethylaminopropyl)-methylsiloxane and dimethylsiloxane; The cation-modified polysiloxane prepared in step (2) has all the amino groups converted to guanidino groups or some of the amino groups converted to guanidino groups; wherein the sample with all the amino groups converted to guanidino groups is used directly, and the sample with some of the amino groups converted to guanidino groups is used after heat crosslinking at 60°C-300°C in air.

9. Use of the organic adhesive having an antibacterial function according to any one of claims 1 to 4 and / or the composition of the organic adhesive having an antibacterial function according to claim 5 for the production of a medical dry adhesive patch or a medical dressing.

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