CN116987259A - Multifunctional allylammonium crosslinking agent and preparation method thereof - Google Patents

Multifunctional allylammonium crosslinking agent and preparation method thereof Download PDF

Info

Publication number
CN116987259A
CN116987259A CN202310967481.2A CN202310967481A CN116987259A CN 116987259 A CN116987259 A CN 116987259A CN 202310967481 A CN202310967481 A CN 202310967481A CN 116987259 A CN116987259 A CN 116987259A
Authority
CN
China
Prior art keywords
multifunctional
allylammonium
general formula
selecting
radicals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310967481.2A
Other languages
Chinese (zh)
Inventor
马娟娟
邱越
刘才
高自菲
王政
张田林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Ocean University
Original Assignee
Jiangsu Ocean University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Ocean University filed Critical Jiangsu Ocean University
Priority to CN202310967481.2A priority Critical patent/CN116987259A/en
Publication of CN116987259A publication Critical patent/CN116987259A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32Polymers modified by chemical after-treatment
    • C08G65/329Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C08G65/33306Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32Polymers modified by chemical after-treatment
    • C08G65/329Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3344Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
    • C08G65/3346Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur having sulfur bound to carbon and oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32Polymers modified by chemical after-treatment
    • C08G65/329Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337Polymers modified by chemical after-treatment with organic compounds containing other elements

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention takes allylamine, acryloyloxy polyether sulfobetaine and bridging molecules as raw materials to prepare the multifunctional allylammonium cross-linking agent containing disulfobetaine plus quaternary ammonium cations or dicarboxybetaine plus quaternary ammonium cations, which not only can be used for the surface modification of various organic high polymer materials with high grafting efficiency, such as hydrophilicity, conductivity, antibacterial property, antifogging, antifouling property, anticoagulation property and the like, but also can be used as the cross-linking agent for preparing electroactive polyolefin materials to endow the polyolefin materials with hydrophilic, conductive or antibacterial functions.

Description

Multifunctional allylammonium crosslinking agent and preparation method thereof
Technical Field
The invention relates to a multifunctional allylammonium crosslinking agent and a preparation method thereof, in particular to a multifunctional allylammonium crosslinking agent containing disulfonic betaine and gemini quaternary ammonium cations or dicarboxylammonium betaine and gemini quaternary ammonium cations, gemini quaternary ammonium cations and a preparation method thereof, and belongs to the field of functional polymer materials.
Technical Field
The polymer materials such as polyester, polyethylene, polyvinyl chloride, polyurethane, polysilane and the like have excellent rebound, flexibility, wear resistance, chemical stability, no toxicity, no stimulation, no variation, biocompatibility and the like, and are suitable for manufacturing medical and sanitary instruments such as artificial organs, artificial skin, artificial blood vessels, bone adhesives, surgical sutures, medical dressings, interventional catheters, drug carriers, living goods and the like. However, the polymer materials have two major defects in the field of medical and health and need to be overcome. Firstly, the surface of the high polymer material is hydrophobic, which affects the water lubrication type contact between the high polymer material and human tissues or blood. Secondly, when the high molecular materials are placed on some human body parts for a long time, the proteins or bacteria are attached to the surfaces of the high molecular materials, and the high molecular materials grow to cause infection. Therefore, it is necessary to increase the hydrophilicity, antibacterial property, anticoagulation property, biocompatibility and the like of the polymer material surface in all directions. At present, the main method for modifying the surface of the polymer material is to bond three hydrophilic antibacterial substances such as polyethylene glycol, carboxyl betaine/sulfobetaine/phosphorylcholine or heparin on the surface of the polymer material.
The method for bonding three major hydrophilic antibacterial substances such as polyethylene glycol, carboxyl betaine/sulfobetaine/phosphorylcholine or heparin on the surface of the polymer material is various, wherein the most suitable method is that ethylene monomer carrying the hydrophilic antibacterial substances is grafted and polymerized on the surface of the polymer material. However, it has also been found that the problem of homo-polymerization of the vinyl monomer carrying the hydrophilic antibacterial substance on the surface of the polymer material is unavoidable, resulting in serious loss of the vinyl monomer raw material and complicated post-treatment. In order to improve the grafting efficiency of the vinyl monomer carrying the hydrophilic antibacterial substance on the surface of the polymer material, development of a technique and a method for improving the grafting efficiency of the surface of the polymer material have been desired. For example, WO 2008/022062,US 20150210627,CN 104086511,CN110204710,CN104086512,CN108385415,CN107574691,CN105218688,US10280148 discloses a batch of monoquaternary ammonium salts with multiple epoxy groups, polyquaternary ammonium salts with multiple epoxy groups or polyquaternary ammonium salts with multiple epoxy groups, which are used as cationic etherifying agents or modifying agents, for cationizing and crosslinking modifying materials such as cellulose fibers, starch or polyamide, and the like, so that the surface grafting reaction efficiency is greatly improved by 100%.
Based on the principle of molecular design, the present inventors created a multi-vinyl compound containing disulfobetaine+gemini quaternary ammonium cation, dicarboxybtaine+gemini quaternary ammonium cation or gemini quaternary ammonium cation+gemini quaternary ammonium cation in the molecular structure as a multi-functional allylammonium cross-linking agent by Michael addition reaction and nucleophilic substitution reaction based on the structural characteristics and functional applications of polyethylene glycol, sulfobetaine, carboxybetaine and quaternary ammonium salt and the modification requirements of the application field of the polymer materials. The invention provides the multifunctional allylammonium crosslinking agent, which is used for modifying the hydrophilicity, conductivity, antibacterial property, antifogging, antifouling property, anticoagulation property, biocompatibility and the like of the surface of a high polymer material based on a plurality of vinyl groups in a molecular structure to improve grafting efficiency; it can also be used as a functional cross-linking agent for preparing electroactive polyolefin materials, and endows the polyolefin materials with hydrophilicity, conductivity, antibacterial property and the like; the functional allylammonium crosslinking agent with different functional characteristics can be prepared by adjusting the length of the polyether chain, and the functional allylammonium crosslinking agent is suitable for the surface modification requirements of polymer materials in multiple fields. The multifunctional allylammonium crosslinking agent containing disulfo betaine and gemini quaternary ammonium cations, dicarboxy betaine and gemini quaternary ammonium cations or gemini quaternary ammonium cations and gemini quaternary ammonium cations has the advantages of novel structural design, simple preparation method and remarkable function modification effect.
Disclosure of Invention
The invention provides a multifunctional allylammonium crosslinking agent which is characterized by having a structure shown in a general formula (I) or a general formula (II):
wherein R in the general formula (I) or the general formula (II) is selected fromTaking C 1 ~C 18 Hydrocarbon radicals or radicalsR 1 Selecting H or CH 3 ,R 2 、R 3 C is selected respectively 1 ~C 18 Hydrocarbon group, n is selected from natural number between 0 and 2000, when Y is C 1 ~C 18 Hydrocarbon radicals or radicalsWhen X is 1 - And X 2 - Respectively select Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y selects-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is 1 - Selecting Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of, X 2 - Not selecting any, said->Refers to C 1 ~C 18 Hydrocarbylene or->
Wherein R is 4 C is selected respectively 1 ~C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000.
The invention provides a specific preparation method of a multifunctional allylammonium crosslinking agent containing disulfobetaine, gemini quaternary ammonium cations, dicarboxybtaine, gemini quaternary ammonium cations or gemini quaternary ammonium cations and gemini quaternary ammonium cations in a molecular structure, which comprises the following steps:
step one: preparation of allylamino polyether ammonium
Sequentially weighing a solvent and the acrylamide oxygen polyether ammonium with the general formula (III), adding the solvent and the acrylamide oxygen polyether ammonium with the general formula (III) into a reaction kettle, stirring and dissolving uniformly, controlling the temperature to be 0-100 ℃, adding diallylamine or N- (substituent) allylamine into the reaction kettle, and carrying out Michael addition reaction for 2-48 hours to prepare an allylamino polyether ammonium solution for later use;
wherein the acryloyloxy polyether ammonium has a structure shown in a general formula (III):
wherein R in the formula (III) 1 Selecting H or CH 3 ,R 2 And R is 3 C is selected respectively 1 ~C 18 Hydrocarbon group, when Y is C 1 ~C 18 Hydrocarbon radicals or radicalsWhen X is 2 - Selected from Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y selects-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is 2 - No selection is made. Wherein R is 4 C is selected respectively 1 ~C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000. Wherein the amount of the acryloyloxypolyether ammonium of the general formula (III) is 1.0 to 1.2 times of the molar amount of the diallylamine or the N- (substituent) allylamine.
The allylamine polyether ammonium has a structure shown in a general formula (IV) or a general formula (V):
wherein R in formula (IV) or formula (V) is C 1 ~C 18 Hydrocarbon radicals or radicalsR 1 Selecting H or CH 3 ,R 2 And R is 3 Respectively selectTaking C 1 ~C 18 Hydrocarbon group, when Y is C 1 ~C 18 Hydrocarbyl radicals or->When X is 2 - Selected from Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y selects-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is 2 - Any is not selected; wherein R is 4 C is selected respectively 1 ~C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000.
The substituent in the N- (substituent) allylamine refers to R, and the R is C 1 ~C 18 Hydrocarbon radicals or radicalsWherein R is 4 Selecting C 1 ~C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000.
The solvent is selected from one or more than two of water, methanol, ethanol, butanol, butanone, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, xylene, anisole, chlorobenzene, toluene, chloroform, carbon tetrachloride, 1, 2-dichloroethane, tetrahydrofuran, ethyl acetate, methyl acetate, butyl acetate, N-dimethylformamide, dimethyl sulfoxide or methylcyclohexane; the solvent is 50-500% of the total mass of diallylamine or N- (substituent) allylamine and the ammonium acryloyloxy polyether of the general formula (III).
Step two: preparation of multifunctional allylammonium crosslinking agent
Adding a bridge molecule and hydroquinone, N, into the allylamino polyether ammonium solution of the general formula (IV) or the allylamino polyether ammonium solution of the general formula (V) 2 Under the protection, the temperature is controlled to be 20-100 ℃, the stirring reaction is carried out for 2-20 hours, then the mixture is concentrated by rotary evaporation, the solid is separated out after the temperature is reduced, and the mixture is filtered, washed and dried to obtain the structure multifunctional shown in the general formula (I) or the general formula (II)Can be allylammonium type crosslinking agent.
Wherein the bridge molecule refers to a dialkylating agent having a structure of the formula (VI):
wherein saidSelected from C 1 ~C 18 Hydrocarbylene, -, and->One of, X 1 Refers to Cl, br, I or p-CH 3 C 6 H 4 SO 3 One of them. Wherein m is selected from natural numbers between 0 and 2000.
The dosage of the bridge molecule is 0.5 to 0.55 times of the mol weight of the diallyl amine or the N- (substituent) allylamine;
the dosage of the hydroquinone is 0.25-5% of the mass of the diallyl amine or the N- (substituent) allylamine.
The invention provides a multifunctional allylammonium crosslinking agent containing disulfo betaine and gemini quaternary ammonium cations, dicarboxybtaine and gemini quaternary ammonium cations or gemini quaternary ammonium cations and gemini quaternary ammonium cations, which has the following characteristics:
(1) the preparation method of the multifunctional allylammonium crosslinking agent belongs to classical organic chemical reaction, is simple and easy to operate, and has rich raw material sources and low cost; in addition, the main raw materials (including the acryloxypolyether ammonium) and the intermediates (including the intermediates in the general formula (IV) or the intermediates in the general formula (V)) used for preparing the multifunctional ethylene cross-linking agent have the chemical characteristics and the application functions of the grafting polymerization or copolymerization reaction of the target compounds.
(2) According to the application field and the use requirement of the high polymer material to be modified, the length of the polyether chain in the multifunctional allylammonium crosslinking agent structure can be adjusted, so that the hydrophilic modification of the multifunctional allylammonium crosslinking agent structure is mainly achieved, or the hydrophilic and biocompatible modification of the multifunctional allylammonium crosslinking agent structure is mainly achieved; secondly, the bridge molecular structure can be redesigned to obtain various combined effects of disulfo betaine, gemini quaternary ammonium cation, dicarboxybetaine, gemini quaternary ammonium cation or gemini quaternary ammonium cation and gemini quaternary ammonium cation, so as to meet the main purposes of antibacterial and hydrophilic modification, or the main purposes of antibacterial, hydrophilic and biocompatible modification, or the main purposes of biocompatibility, hydrophilic and antibacterial modification.
(3) More importantly, after the multifunctional allylammonium crosslinking agent is adopted to modify the high polymer material, the hydrophilic property, the antibacterial function and the like of the high polymer material after the surface modification are not reduced after severe conditions and environments are encountered in the use process.
(4) The multifunctional allylammonium crosslinking agent disclosed by the invention is soluble in water or alcohol solvents, so that the application process of the multifunctional allylammonium crosslinking agent does not generate toxic VOC.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The multifunctional allylammonium type crosslinking agent containing disulfobetaine + gemini quaternary ammonium cation, dicarboxybtaine + gemini quaternary ammonium cation or gemini quaternary ammonium cation + gemini quaternary ammonium cation and the preparation method provided by the present invention are further described by the following examples, and the purpose of the present invention is better understood. Therefore, the multifunctional allylammonium type crosslinking agents and the preparation methods thereof, which are not listed in the examples, should not be construed as limiting the scope of the present invention. Any improvement to the present invention falls into the act of infringing intellectual property.
EXAMPLE 1 preparation of multifunctional allylammonium Cross-linker of formula (I-1)
Adding 9.5 g of diallylamine into 80 g of absolute ethyl alcohol, stirring, slowly adding 55 g of methacryloxypolyether sulfobetaine of formula (V-1) at room temperature, continuously reacting for 24 hours after the addition of formula (V-1), adding 30 g of ethanol solution containing 9.0 g of p-dichlorobenzene and 0.15 g of hydroquinone into a reaction system, and adding N 2 Under the protection, the reaction temperature is raised to 70-80 ℃ again, stirring is carried out for 12 hours, then rotary evaporation concentration, cooling crystallization,Filtering, washing and drying to obtain the multifunctional allylammonium crosslinking agent of the formula (I-1) with the yield of 89.5%.
The unsaturation degree of the multifunctional allylammonium crosslinking agent shown in the formula (I-1) is 1.7755mol/Kg by adopting a GB/T12008.7-1992 method, and the unsaturation degree is basically consistent with a theoretical calculated value 1.7801mol/Kg, which shows that the structure of the multifunctional vinyl crosslinking agent shown in the formula (I-1) is consistent with the theoretical design.
EXAMPLE 2 preparation of multifunctional allylammonium Cross-linker of formula (I-2)
According to the method and the steps of example 1, the methacryloxypolyether sulfobetaine of the formula (V-1) is changed into the methacryloxypolyether sulfobetaine of the formula (V-2), the dichlorobenzene is changed into polyethylene glycol-200 bis-p-toluenesulfonate, and the multifunctional allylammonium crosslinking agent of the formula (I-2) is prepared, and the unsaturation degree of the multifunctional allylammonium crosslinking agent of the formula (I-2) is 0.7044mol/Kg by sampling analysis through a GB/T12008.7-1992 method and basically coincides with a theoretical calculation value of 0.7048mol/Kg, so that the structure of the multifunctional allylammonium crosslinking agent of the formula (I-2) accords with the theoretical design.
Example 3 preparation of multifunctional allylammonium Cross-linker of formula (II-1)
According to the method and procedure of example 1, diallylamine was changed to N-benzyl allylamine, the methacryloxypolyether sulfobetaine of formula (V-1) was changed to methacryloxypolyether sulfobetaine of formula (V-2), and p-dichlorobenzene was changed to polyethylene glycol-200 bis-p-toluenesulfonate to prepare a multifunctional allylammonium crosslinker of formula (II-1). The unsaturation degree of the multifunctional allylammonium crosslinking agent of the formula (II-1) is 0.3575mol/Kg by adopting a GB/T12008.7-1992 method, and the unsaturation degree is basically consistent with a theoretical calculated value 0.3587mol/Kg, which shows that the multifunctional allylammonium crosslinking agent of the formula (II-1) accords with the theoretical design.
EXAMPLE 4 preparation of multifunctional allylammonium Cross-linker of formula (II-2)
According to the method and the steps of example 1, diallyl amine is changed into omega-allylamino tetraglycol methyl ether, methacrylic acyloxy polyether sulfobetaine of the formula (V-1) is changed into methacrylic acyloxy polyether carboxyl betaine of the formula (V-3), and the multifunctional allyl ammonium cross-linking agent of the formula (II-2) is prepared, and the method of GB/T12008.7-1992 is adopted, wherein the unsaturation degree of the multifunctional allyl ammonium cross-linking agent of the formula (II-2) is 0.7601mol/Kg by sampling analysis and basically coincides with a theoretical calculated value 0.7591mol/Kg, so that the structure of the multifunctional allyl ammonium cross-linking agent of the formula (II-2) accords with the theoretical design.
EXAMPLE 5 preparation of multifunctional allylammonium Cross-linker of formula (III-1)
According to the method and procedure of example 1, the methacryloxy polyether sulfobetaine of formula (V-1) is changed to a methacryloxy polyether quaternary ammonium salt of formula (V-4) to produce a multifunctional allylammonium crosslinking agent of formula (III-1);
the unsaturation degree of the multifunctional allylammonium crosslinking agent shown in the formula (III-1) is 1.8065mol/Kg by adopting a GB/T12008.7-1992 method, and the unsaturation degree is basically consistent with a theoretical calculated value 1.8026mol/Kg, which shows that the structure of the multifunctional allylammonium crosslinking agent shown in the formula (III-1) is consistent with the theoretical design.
Example 6 Properties of multifunctional allylammonium Cross-linking Agents 1-5
The multifunctional allylammonium crosslinking agents in examples 1-5 can be dissolved in deionized water to prepare respective saturated aqueous solutions, 2mL of each concentration aqueous solution in examples 1-5 are mixed with 10mL of culture medium according to the dilution ratio of 1:2, 1:5, 1:10, 1:20, 1:50, 1:100 and 1:1000, 2 drops of pathogenic bacterial strain liquid are added, and after the mixture is fully mixed, the mixture is placed in a 37 ℃ incubator for culturing for 24 hours; the growth of pathogenic bacteria was observed, the Minimum Inhibitory Concentration (MIC) was calculated, and the test results are shown in table 1.
Table 1 results of bacteriostasis experiments

Claims (5)

1. The multifunctional allylammonium crosslinking agent is characterized by having a structure shown in a general formula (I) or a general formula (II):
wherein R in the general formula (I) or the general formula (II) is C 1 ~C 18 Hydrocarbon radicals or radicalsR 1 Selecting H or CH 3 ,R 2 And R is 3 C is selected respectively 1 ~C 18 Hydrocarbon group, n is selected from natural number between 0 and 2000, when Y is C 1 ~C 18 Hydrocarbon radicals or radicalsWhen X is 1 - And X 2 - Respectively select Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y selects-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is 1 - Selecting and removing Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of, X 2 - Not selecting any, said->Refers to C 1 ~C 18 Hydrocarbylene or->
Wherein R is 4 Selecting C 1 ~C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000.
2. A method for preparing a multifunctional allylammonium crosslinker, characterized in that the preparation method of the multifunctional allylammonium crosslinker is as follows:
step one: preparation of allylamino polyether ammonium
Sequentially weighing a solvent and the acryloyloxy polyether ammonium, adding the solvent and the acryloyloxy polyether ammonium into a reaction kettle, uniformly stirring and dissolving, controlling the temperature to be 0-100 ℃, adding diallyl amine or N- (substituent) allyl amine into the reaction kettle, and reacting for 2-48 hours to prepare an allylamino polyether ammonium solution for later use;
wherein the acryloyloxy polyether ammonium has a structure shown in a general formula (III):
wherein R in the formula (III) 1 Selecting H or CH 3 ,R 2 And R is 3 C is selected respectively 1 ~C 18 Hydrocarbon group, when Y is C 1 ~C 18 Hydrocarbon radicals or radicalsWhen X is 2 - Selected from Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y selects-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is 2 - Any is not selected;
wherein R is 4 Selecting C 1 ~C 18 A hydrocarbon group, m is selected from natural numbers between 0 and 2000;
the allylamine polyether ammonium has a structure shown in a general formula (IV) or a general formula (V):
wherein R in formula (IV) or formula (V) is C 1 ~C 18 Hydrocarbon radicals or radicalsR 1 Selecting H or CH 3 ,R 2 And R is 3 C is selected respectively 1 ~C 18 Hydrocarbon group, when Y is C 1 ~C 18 Hydrocarbyl radicals or->When X is 2 - Selecting Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y selects-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is 2 - Any is not selected;
wherein R is 4 Selecting C 1 ~C 18 A hydrocarbon group, m is selected from natural numbers between 0 and 2000;
the dosage of the acryloyloxy polyether ammonium is 1.0 to 1.2 times of the mol of diallyl amine or N- (substituent) allylamine;
step two: preparation of multifunctional allylammonium crosslinking agent
Adding a bridge molecule and hydroquinone, N, into the allylamino polyether ammonium solution of the general formula (IV) or the allylamino polyether ammonium solution of the general formula (V) 2 Under the protection, controlling the temperature to be 20-100 ℃, stirring and reacting for 2-20 hours, then concentrating by rotary evaporation, cooling and separating out solid, filtering, washing and drying to prepare the multifunctional allylammonium cross-linking agent with the structure shown in the general formula (I) or the general formula (II);
wherein the amount of the bridge molecule is 0.5 to 0.55 times the molar amount of the diallylamine or the N- (substituent) allylamine;
the dosage of the hydroquinone is 0.25-5% of the mass of the diallylamine.
3. A process for preparing a multifunctional allylammonium-type crosslinking agent as claimed in claim 2, wherein the substituent in the N- (substituent) allylamine is R, and R is C 1 ~C 18 Hydrocarbon radicals or radicals
Wherein R is 4 Selecting C 1 ~C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000.
4. A process for preparing a multifunctional allylic ammonium crosslinker according to claim 2, characterized in that the bridge molecule is referred to as a dialkylating agent having the structure of formula (vi):
wherein saidSelected from C 1 ~C 18 Hydrocarbylene, -, and->Wherein m is selected from natural numbers between 0 and 2000, X 1 Refers to Cl, br, I or p-CH 3 C 6 H 4 SO 3 One of the following;
wherein m is selected from natural numbers between 0 and 2000.
5. A method for preparing a multifunctional allylammonium-type crosslinking agent according to claim 2, characterized in that the solvent is selected from one or more of water, methanol, ethanol, butanol, butanone, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, xylene, anisole, chlorobenzene, toluene, chloroform, carbon tetrachloride, 1, 2-dichloroethane, tetrahydrofuran, ethyl acetate, methyl acetate, butyl acetate, N-dimethylformamide, dimethyl sulfoxide or methylcyclohexane; the solvent is 50-500% of the total mass of diallyl amine or N- (substituent) allyl amine and the acryloyloxy polyether ammonium in the general formula (III).
CN202310967481.2A 2023-08-03 2023-08-03 Multifunctional allylammonium crosslinking agent and preparation method thereof Pending CN116987259A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310967481.2A CN116987259A (en) 2023-08-03 2023-08-03 Multifunctional allylammonium crosslinking agent and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310967481.2A CN116987259A (en) 2023-08-03 2023-08-03 Multifunctional allylammonium crosslinking agent and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116987259A true CN116987259A (en) 2023-11-03

Family

ID=88526117

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310967481.2A Pending CN116987259A (en) 2023-08-03 2023-08-03 Multifunctional allylammonium crosslinking agent and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116987259A (en)

Similar Documents

Publication Publication Date Title
DE69126972T2 (en) USE OF AN ANTIBACTERIAL ACTIVE SUBSTANCE CONTAINING A POLYELECTROLYTE COMPLEX AND ANTIBACTERIAL MATERIAL
JP6709780B2 (en) Functional zwitterionic and mixed charge polymers, related hydrogels and methods of use thereof
Zhang et al. Platelet adhesive resistance of segmented polyurethane film surface-grafted with vinyl benzyl sulfo monomer of ammonium zwitterions
JP5587611B2 (en) Hydrophilic coating
O’Connor et al. The crosslinking of polysaccharides with polyamines and dextran–polyallylamine antibacterial hydrogels
CN110981999B (en) Antibacterial polymer and preparation method thereof
CN113968984B (en) Preparation method of safe and long-acting multifunctional wound dressing
Yang et al. Antimicrobial surfaces grafted random copolymers with REDV peptide beneficial for endothelialization
CN109810221B (en) Preparation method and application of betaine antibacterial agent
JP6195335B2 (en) Polymer compound, composition using the same, and medical device
CN115233333A (en) Antibacterial modified polyamide composite fiber and synthetic method thereof
CN110028614B (en) Antibacterial micro-nano gel and fiber with protein adsorption function and preparation method thereof
CN116987259A (en) Multifunctional allylammonium crosslinking agent and preparation method thereof
EP3111969B1 (en) Medical material and medical instrument using medical material
CN113134111A (en) Polyion liquid/polyurethane composite antibacterial film and preparation and application methods thereof
WO1995010523A1 (en) Alkoxysilane compound, surface treatment fluid and contact lens
CN115636884B (en) Preparation method of sodium hyaluronate derivative, cross-linked sodium hyaluronate and application
CN103131006B (en) A kind of graft copolymer, its preparation method and decorative material layer by layer
CN116987260A (en) Multifunctional diallylammonium monomer and preparation method thereof
KR20100093404A (en) Brush polyether-based polymers having a antibacterial function, preparation thereof and products comprising the polymer
WO2015170769A1 (en) Antibacterial polymer, production method therefor, and usage thereof
CN102219908A (en) Completely-biodegraded nanometer starch grafted poly glutamic acid benzyl ester
JP6886402B2 (en) Biodegradable injectable gel
CN117946287B (en) Preparation method and application of antibacterial amino acid-based cellulose polymer
CN105457091B (en) Polythene material of rhodium complex modification and preparation method thereof and purposes

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination