CN113429560A - Multifunctional polyquaternary ammonium salt and preparation method thereof - Google Patents
Multifunctional polyquaternary ammonium salt and preparation method thereof Download PDFInfo
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- CN113429560A CN113429560A CN202110786171.1A CN202110786171A CN113429560A CN 113429560 A CN113429560 A CN 113429560A CN 202110786171 A CN202110786171 A CN 202110786171A CN 113429560 A CN113429560 A CN 113429560A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a multifunctional polyquaternium and a preparation method thereof, wherein the preparation raw materials comprise organic diamine, acrylic ester and epoxy chloropropane, the preparation method is simple, the preparation raw materials are easy to obtain, the variety of the raw materials is few, and the process is safe and efficient. The multifunctional polyquaternium aqueous solution is clear and transparent, and the appearance color is light. Multifunctional polyquaternary ammonium salt both has a plurality of epoxy groups and chloropropyl, the hydrophilic and antibiotic function of polyquaternary ammonium cation, can be right natural macromolecular material carries out the cross-linking modification function, can also give antistatic function, surface activity effect, the soft function of natural macromolecular material.
Description
Technical Field
The invention relates to polyquaternium, in particular to multifunctional polyquaternium with side chains containing epoxy groups and polyether chains, belonging to the field of functional polymer materials.
Technical Field
N- (2, 3-epoxy chloropropyl) trimethyl ammonium chloride, N- (2, 3-epoxy chloropropyl) triethyl ammonium chloride, N- (2-hydroxy-3-chloropropyl) triethyl ammonium chloride or N- (2-hydroxy-3-chloropropyl) trimethyl ammonium chloride with similar functions are used as micromolecule cationic etherifying agents of natural polymer materials such as starch or cellulose, and quaternary ammonium cations are grafted on a main chain of the natural polymer through chemical reaction of active groups such as O-H or N-H on the natural polymer materials and epoxy groups (or chloropropyl under alkali catalysis). For example, the quaternary ammonium cationic starch is used for preparing quaternary ammonium cationic starch by starch grafting, water-soluble cellulose ether can be obtained by the action of the quaternary ammonium cationic starch and cellulose, cationic gelatin can be prepared by the action of the cationic cellulose ether and gelatin, and lignin quaternary ammonium salt can be obtained by the action of the cationic cellulose ether and lignin grafting, so that the performance defects of the natural high polymer material are overcome, and the application range and the application field of the natural high polymer material are widened. However, since the small-molecule cationic etherifying agent has a single active site (epoxy group or chloropropyl group) and is easily damaged by water and a catalyst, grafting efficiency on a natural polymer is low and waste of raw materials is serious, and development of a cationic etherifying agent or a modifying agent having high grafting efficiency has been desired. For example, WO 2008/022062, US 20150210627, CN 104086511, CN110204710, CN104086512, CN108385415, CN107574691, CN105218688, US10280148 and the like disclose a batch of mono-quaternary ammonium salt, multi-quaternary ammonium salt or multi-quaternary ammonium salt of multi-epoxy group, which are used as cationic etherifying agents or modifying agents to perform cationic modification and crosslinking modification on materials such as cellulose fibers, protein fibers, starch, wood, paper, polyamide and the like, and the grafting reaction efficiency is greatly improved to 100%. In addition, the polyepoxy polyquaternium is also a raw material for preparing a conductive polymer, a polymer electrolyte, a photoconductive material, or is used as a gel antibacterial agent, a surfactant, an antistatic agent or a softening agent. Therefore, the multifunctional polyquaternium which is wide in source of design and development raw materials, simple in preparation method, safe in technical process and multifunctional and contains epoxy groups and polyether chains in the molecular chain structure has practical significance.
Disclosure of Invention
The invention provides a multifunctional polyquaternium according to the function and practical application requirements of the cationic etherifying agent or the modifying agent, in particular to a multifunctional polyquaternium with a side chain containing an epoxy group and a polyether chain, which has a structure shown in a general formula (A) or a general formula (B):
wherein in the general formula (A) or (B)
Is selected from C2～C18Alkylene or
R1Is selected from H or CH3N is a natural number of 2 to 2000, R2Is selected from
Wherein m is a natural number of 1 to 2000, R3Is selected from C1～C18A hydrocarbon group of (1).
The invention provides a multifunctional polyquaternium with side chains containing epoxy groups and polyether chains, and the multifunctional polyquaternium can be prepared by adjusting R in a general formula (A) or (B)3The size of the hydrocarbon group or the m value can respectively endow the hydrocarbon group with the functions of hydrophilicity, hydrophobicity, antistatic property, softness and the like, thereby meeting the requirements of various production and living fields. And because the general formula (A) or (B) contains more than one epoxy group or chloropropyl, the grafting efficiency with the natural high polymer is favorably improved, the high-efficiency cationization modification of the natural high polymer, the crosslinking modification of the main chain of the natural high polymer and the multifunctional modification of the natural high polymer are realized, the characteristics, functions and purposes of the modified natural high polymer material are enriched, and the application range of the modified natural high polymer material is expanded.
The invention relates to a preparation method of a multifunctional polyquaternium, which comprises the following steps:
step one, preparation of polyquaternary ammonium salt with side chain containing polyether chain
Weighing organic diamine and an organic solvent in a reaction kettle, controlling the temperature of materials in the reaction kettle to be 0-90 ℃, adding acrylic ester and N into the reaction kettle under stirring2Reacting for 2-72 hours under protection to obtain a general formula (D) shown as a reaction formula (1); then, controlling the temperature of the materials in the reaction kettle to be 0-60 ℃, and continuously adding chloromethyl oxirane into the reaction kettle within 2-20 hours to prepare a general formula (E) shown as a reaction formula (2); and then, raising the temperature of the materials in the reaction kettle to 70-90 ℃, continuously reacting for 2-24 hours, and distilling to remove the organic solvent in the reaction kettle to obtain the polyquaternary ammonium salt with the structure shown as the general formula (F) or the general formula (G) and the side chain containing the polyether chain, as shown in the reaction formula (3) and the reaction formula (3').
Wherein the organic diamine has a structure represented by the general formula (C):
wherein in the general formula (C)
Is selected from C2～C18Alkylene or
M is selected from a natural number of 1-2000;
the organic solvent is selected from one or more than two of chloroform, tetrahydrofuran, 1, 4-dioxane, ethanol, propanol, isopropanol, N-butanol, isobutanol, tert-butanol, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide or N, N-dimethylacetamide, and the dosage of the organic solvent is 1-10 times of the total mass of the dosages of organic diamine, acrylate and chloromethyl oxirane;
the acrylate has a structure represented by the general formula (H):
wherein R in the general formula (H)1Is selected from H or CH3，R2Is selected from
Wherein m is a natural number of 1 to 2000, R3Is selected from C1～C18A hydrocarbon group of (a);
the molar ratio of the organic diamine to the acrylic ester to the chloromethyl oxirane is 1: 1.8-2.2: 2.0-2.5;
in the general formula (D), the general formula (E), the general formula (F) or the general formula (G)
Is selected from C2～C18Alkylene or
R1Is selected from H or CH3N is a natural number of 2 to 2000, R2Is selected from
Wherein m is a natural number of 1 to 2000, R3Is selected from C1～C18A hydrocarbon group of (1).
Step two, preparation of multifunctional polyquaternary ammonium salt
Dissolving the polyquaternium of the general formula (F) or (G) prepared in the step one in a solvent, preparing a saturated solution, putting the saturated solution into a reaction kettle, controlling the temperature of materials in the reaction kettle to 0-25 ℃ under stirring, adding epoxy chloropropane with the mass being 0.2-2 times of the total mass of the polyquaternium of the general formula (F) and the polyquaternium (G), stirring and reacting for 4-48 hours, and then performing rotary evaporation to remove the solvent and excessive epoxy chloropropane to prepare the multifunctional polyquaternium with the side chain containing epoxy groups and polyether chains and the structure shown in the general formula (A) or (B), wherein the multifunctional polyquaternium is shown in the reaction formula (4) or the reaction formula (4'):
wherein in the general formula (F), the general formula (G), the general formula (A) or the general formula (B)
Is selected from C2～C18Alkylene or
R1Is selected from H or CH3，R2Is selected from
n is a natural number of 2-2000; wherein m is a natural number of 1 to 2000, R3Is selected from C1～C18A hydrocarbyl group;
the solvent is one or more than two of water, epoxy chloropropane, chloroform, tetrahydrofuran, 1, 4-dioxane, methanol, ethanol, propanol, isopropanol, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide or N, N-dimethylacetamide;
compared with the prior art, the invention has the beneficial effects that:
(1) the multifunctional polyquaternary ammonium salt provided by the invention has the advantages of easily available preparation raw materials, few raw material ingredients, simple preparation method and safe and efficient process;
(2) the multifunctional polyquaternium aqueous solution provided by the invention is clear and transparent, and has light appearance color.
(3) The multifunctional polyquaternary ammonium salt provided by the invention has a plurality of epoxy groups or chloropropyl groups, and the cationic hydrophilic and antibacterial functions of the polyquaternary ammonium salt, can perform a cross-linking modification function on the natural polymer material, and can endow the natural polymer material with an antistatic function, a surface activity function and a softening function.
Detailed Description
The present invention provides a multifunctional polyquaternium having epoxy groups and polyether chains in its side chains and a method for preparing the same, which are further illustrated by the following examples, for the purpose of better understanding the present invention. Therefore, the multifunctional polyquaternium containing polyepoxy and polyether chains in the side chains and the preparation method which are not listed in the examples should not be construed as limiting the scope of the present invention.
EXAMPLE 1 preparation of multifunctional Polyquaternium (1)
Weighing 12 g of ethylenediamine and 300 g of chloroform, mixing in a reaction kettle, controlling the temperature of a feed liquid in the reaction kettle to be 15-25 ℃, slowly adding 200 g of methoxypolyethylene glycol-400 methacrylate, and continuously stirring for reaction for 6 hours after the materials are added; and then reducing the temperature of the material liquid in the reaction kettle to 5-10 ℃, dropwise adding 40 g of chloromethyl oxirane, after the material feeding is finished, increasing the temperature in the reaction kettle to 25-45 ℃, continuously stirring and reacting for 2 hours, increasing the temperature in the reaction kettle to 80-85 ℃, reacting for 2.5 hours, reducing the temperature of the material liquid in the reaction kettle to 5-10 ℃, adding 120 g of epichlorohydrin, keeping the temperature and stirring and reacting for 24 hours, and then performing rotary evaporation to remove chloroform and redundant epichlorohydrin to prepare 284 g of the multifunctional polyquaternium (1) in a faint yellow paste shape. According to the GB1677-1981 detection method, the epoxy value of the polyquaternium (1) is measured to be 18.03 percent, and the polyquaternium is easy to dissolve in water, methanol and ethanol, soluble in chloroform, tetrahydrofuran and 1, 4-dioxane, insoluble in cyclohexane, benzene and toluene, and extremely easy to deliquesce after being naturally placed.
EXAMPLE 2 preparation of multifunctional Polyquaternium (2)
The multifunctional polyquaternium (2) was prepared by replacing ethylenediamine with 1, 6-hexanediamine according to the preparation method and the procedure of example 1. According to the GB1677-1981 detection method, the epoxy value of the multifunctional polyquaternium (2) is measured to be 16.65 percent, and the multifunctional polyquaternium is easy to dissolve in water, methanol, ethanol, tetrahydrofuran and 1, 4-dioxane and is slightly soluble in cyclohexane, benzene and toluene.
EXAMPLE 3 preparation of multifunctional Polyquaternium (3)
According to the preparation method and the operation steps of the example 1, the multifunctional polyquaternium (3) can be prepared by changing ethylenediamine into 1, 6-hexanediamine and the methoxypolyethylene glycol-400 methacrylate into lauryloxypolyethylene glycol-400 methacrylate. According to the GB1677-1981 detection method, the epoxy value of the multifunctional polyquaternium (3) is measured to be 15.78 percent, the multifunctional polyquaternium is dissolved in water and then foamed, is dissolved in ethanol, tetrahydrofuran or 1, 4-dioxane solvent, is slightly dissolved in cyclohexane, benzene and toluene, and is naturally placed for absorbing moisture.
EXAMPLE 4 preparation of multifunctional Polyquaternium (4)
According to the preparation method and the operation steps of the example 1, the multifunctional polyquaternium (4) can be prepared by changing ethylenediamine into alpha, omega-double-terminal amino polyether-400 and changing methoxy polyethylene glycol-400 methacrylate into lauryl oxy polyethylene glycol-400 methacrylate. According to the GB1677-1981 detection method, the epoxy value of the multifunctional polyquaternium (4) is 8.72 percent, the multifunctional polyquaternium is dissolved in water, then foams, is dissolved in methanol, ethanol, tetrahydrofuran and 1, 4-dioxane, and is slightly soluble in cyclohexane, benzene and toluene.
Example 5 fungicidal Activity of multifunctional Polyquaternium (1-4)
According to the method of GB15979-2002, the multifunctional polyquaternary ammonium salt of the embodiment (1-4) is dissolved in deionized water, and bactericide solutions with the mass percentage concentration of 0.1% are respectively prepared, and the foaming performance and the antibacterial performance of staphylococcus aureus are tested, and the results are shown in Table 1.
TABLE 1 Properties of the multifunctional Polyquaternium in examples 1-4
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (6)
1. A multifunctional polyquaternium, in particular to a multifunctional polyquaternium with side chains containing epoxy groups and polyether chains, which has a structure shown in a general formula (A) or a general formula (B):
wherein in the general formula (A) or the general formula (B)
Is selected from C2～C18Alkylene or
R1Is selected from H or CH3N is a natural number of 2 to 2000, R2Is selected from
Wherein m is a natural number of 1 to 2000, R3Is selected from C1～C18A hydrocarbon group of (1).
2. The method for preparing a multifunctional polyquaternium according to claim 1, characterized by comprising the steps of: step one, preparing polyquaternary ammonium salt with a side chain containing a polyether chain:
weighing organic diamine and an organic solvent in a reaction kettle, controlling the temperature of materials in the reaction kettle to be 0-90 ℃, adding acrylic ester and N into the reaction kettle under stirring2Reacting for 2-72 hours under protection to obtain a general formula (D) shown as a reaction formula (1); then, controlling the temperature of the materials in the reaction kettle to be 0-60 ℃, and continuously adding chloromethyl oxirane into the reaction kettle within 2-20 hours to prepare a general formula (E) shown as a reaction formula (2); and then, increasing the temperature of the materials in the reaction kettle to 70-90 ℃, continuously reacting for 2-24 hours, and distilling to remove the organic solvent in the reaction kettle to obtain the poly-quaternary ammonium salt with the side chain containing the polyether chain and the structure shown in the general formula (F) or the general formula (G), as shown in the reaction formulas (3) and (3'):
wherein in the general formula (D), the general formula (E), the general formula (F) or the general formula (G)
Is selected from C2～C18Alkylene or
R1Is selected from H or CH3N is a natural number of 2 to 2000, R2Is selected from
Wherein m is a natural number of 1 to 2000, R3Is selected from C1～C18A hydrocarbon group of (a);
the molar ratio of the organic diamine to the acrylic ester to the chloromethyl oxirane is 1: 1.8-2.2: 2.0-2.5;
the dosage of the organic solvent is 1-10 times of the total mass of the dosages of the organic diamine, the acrylic ester and the chloromethyl oxirane;
step two, preparation of multifunctional polyquaternium:
dissolving the polyquaternium of the general formula (F) or (G) prepared in the step one in a solvent, preparing a saturated solution, putting the saturated solution into a reaction kettle, controlling the temperature of materials in the reaction kettle to 0-25 ℃ under stirring, adding epoxy chloropropane with the mass 0.2-2 times of the total mass of the polyquaternium of the general formula (F) and the general formula (G), stirring and reacting for 4-48 hours, and then performing rotary evaporation to remove the solvent and excessive epoxy chloropropane to prepare the multifunctional polyquaternium with the side chain containing epoxy groups and polyether chains and the structure shown in the general formula (A) or (B), wherein the multifunctional polyquaternium is shown in the reaction formula (4) or the reaction formula (4'):
wherein in the general formula (F), the general formula (G), the general formula (A) or the general formula (B)
Is selected from C2～C18Alkylene or
R1Is selected from H or CH3，R2Is selected from
n is a natural number of 2-2000; wherein m is a natural number of 1 to 2000, R3Is selected from C1～C18A hydrocarbyl group.
3. The method for preparing a multifunctional polyquaternium according to claim 2, wherein the organic diamine has a structure represented by the general formula (C):
wherein in the general formula (C)
Is selected from C2～C18Alkylene or
Wherein m is a natural number of 1 to 2000.
4. The method of claim 2, wherein the organic solvent is one or more selected from the group consisting of chloroform, tetrahydrofuran, 1, 4-dioxane, ethanol, propanol, isopropanol, N-butanol, isobutanol, t-butanol, N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.
5. The method for preparing a multifunctional polyquaternium according to claim 2, wherein the acrylate has a structure represented by the general formula (H):
wherein R in the general formula (H)1Is selected from H or CH3，R2Is selected from
Wherein m is a natural number of 1 to 2000, R3Is selected from C1～C18A hydrocarbon group of (1).
6. The method for preparing a multifunctional polyquaternium according to claim 2, wherein the solvent is one or more selected from the group consisting of water, epichlorohydrin, chloroform, tetrahydrofuran, 1, 4-dioxane, methanol, ethanol, propanol, isopropanol, N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.
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| CN116283667A (en) * | 2023-03-06 | 2023-06-23 | 江苏海洋大学 | Functional isocyanate crosslinking agent and preparation method thereof |
| CN116283674A (en) * | 2023-03-06 | 2023-06-23 | 江苏海洋大学 | Isocyanate crosslinking agent containing disulfo betaine and preparation method thereof |
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| CN116217448A (en) * | 2023-03-06 | 2023-06-06 | 江苏海洋大学 | Preparation method of isocyanate crosslinking agent containing double quaternary ammonium cations and double sulfobetaines |
| CN116283667A (en) * | 2023-03-06 | 2023-06-23 | 江苏海洋大学 | Functional isocyanate crosslinking agent and preparation method thereof |
| CN116283674A (en) * | 2023-03-06 | 2023-06-23 | 江苏海洋大学 | Isocyanate crosslinking agent containing disulfo betaine and preparation method thereof |
| CN116217448B (en) * | 2023-03-06 | 2023-11-17 | 江苏海洋大学 | Preparation method of isocyanate crosslinking agent containing double quaternary ammonium cations and double sulfobetaines |
| CN116283674B (en) * | 2023-03-06 | 2023-11-24 | 江苏海洋大学 | Isocyanate crosslinking agent containing disulfo betaine and preparation method thereof |
| CN116283667B (en) * | 2023-03-06 | 2023-12-29 | 江苏海洋大学 | Functional isocyanate crosslinking agent and preparation method thereof |
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