CN112457489B - Functional polyquaternium and preparation method thereof - Google Patents
Functional polyquaternium and preparation method thereof Download PDFInfo
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- CN112457489B CN112457489B CN202011432399.2A CN202011432399A CN112457489B CN 112457489 B CN112457489 B CN 112457489B CN 202011432399 A CN202011432399 A CN 202011432399A CN 112457489 B CN112457489 B CN 112457489B
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Abstract
A functional polyquaternium and its preparation method are provided. The functional polyquaternium of side chain methylol propionamide provided by the invention has the advantages that the preparation raw materials comprise 3- (N, N-dialkyl amino) propylamine, acrylamide, acrylate, a double alkylation reagent and formaldehyde, the reaction efficiency of each step is high, the side reaction is less, the raw materials are easy to obtain, the preparation method is simple, and the process is safe and efficient; the functional polyquaternium lateral connected with the hydroxymethyl propionamide has the hydrophilicity and the antibacterial function of common quaternary ammonium cation, not only can carry out quaternary ammonium cation crosslinking or modification on natural high polymer materials, but also can endow the modified materials with the antistatic function, the surfactant function and the softening agent function.
Description
Technical Field
The invention relates to a polyquaternium, in particular to a polyquaternium with a side chain containing (N-hydroxymethyl propionamide) used as a quaternary ammonium cation cross-linking agent or a modifier, belonging to the field of functional polymer materials.
Technical Field
Formaldehyde, glyoxal, glutaraldehyde, 1, 3-dimethylol urea, dimethylol dihydroxy ethylene urea, ethylene glycol diglycidyl ether, toluene diisocyanate, trichlorocyanogen compounds, terephthaloyl chloride compounds and the like are common small molecular crosslinking agents at present, and can perform condensation reaction, addition reaction, etherification reaction or esterification reaction for two times or more with O-H or N-H groups in the chain structure of the high molecular material. The product of 2, 2-dichloroethyl ether company optimized by the technology can also be used as a cross-linking agent or a double alkylating agent to generate cross-linking phenomena among synthetic materials such as polyvinyl alcohol, polyamide and the like, or natural polymer chains such as starch, cellulose, chitosan and the like, and the cross-linking phenomena can only be called as the cross-linking agent. The polyepoxy quaternary ammonium salt prepared by using a polyepoxy tertiary amine compound and epichlorohydrin as raw materials belongs to a class of polyepoxy cationic crosslinking agents, belongs to a class of functional crosslinking agents, and has an important role in cationization crosslinking and modification of paper, cellulose fibers or cellulose fabrics, or preparation of cationic starch with high cationic degree and high molecular weight, or preparation of polymer electrolyte gel and electronic imaging materials. For example, WO 2008022062, U.S. Pat. No. 5,989,6548,104086511,104086512,110204710,108385415,107574691,CN105688 discloses a batch of polyepoxy mono-quaternary ammonium salts, polyepoxy polyquaternary ammonium salts or polyepoxy polyquaternary ammonium salts. However, the side reaction of tertiary amine and epichlorohydrin is more, which affects the main reaction efficiency, the separation of main and side products is difficult, and the purity of the prepared main product is low.
Disclosure of Invention
The invention provides a functional polyquaternium, which is characterized in that the side chain contains (N-hydroxymethyl propionamide) polyquaternium, and the polyquaternium has a structure shown in a general formula (A):
wherein in the general formula (A)
Selection of C 2 ～C 18 Alkylene or
Wherein p is selected from natural numbers of 1 to 2000; r 1 And R 2 Are respectively selected from C 1 ～C 18 A hydrocarbon group, n is a natural number of 2 to 2000, and X is Cl, br, I or p-CH 3 -C 6 H 4 SO 3 Y has a structure represented by formula (B) or formula (C):
wherein R in the formula (C) 3 Is selected from C 1 ～C 18 A hydrocarbon radical or
Wherein R is 4 Is selected from C 1 ～C 18 And q is a natural number of 0 to 2000.
The invention provides a functional polyquaternary ammoniumThe salt is characterized in that the functional polyquaternium with a side chain containing an N-hydroxymethyl propionamide structural unit can perform condensation reaction with O-H or N-H group in synthetic materials such as polyvinyl alcohol, polyamide and the like or natural materials such as starch, cellulose, protein, animal leather, chitosan and the like to realize cationization crosslinking or modification of the functional polyquaternium, and has the functions and effects similar to those of the polyepoxy polyquaternium or the polyepoxy polyquaternium; and can be obtained by adjusting R in the general formula (A) 1 Or R 2 Or R in the general formula (C) 3 Or R 4 The size of the alkyl can also be adjusted by adjusting the p in the general formula (A) or the q value in the general formula (C), so that the functional polyquaternium and the modified high polymer material are endowed with the functions of hydrophilicity, water retention, skin affinity, hydrophobicity, antibiosis, antistatic property, softness and the like, thereby meeting the requirements of various fields of production and life. The functional polyquaternium with the structure shown in the general formula (A) contains a plurality of N-hydroxymethyl propionamide side chains, so that the grafting efficiency or the reaction efficiency of the functional polyquaternium on synthetic materials such as polyvinyl alcohol, polyamide and the like or natural high polymer materials such as starch, cellulose, protein, animal leather, chitosan and the like is ensured, the high efficiency of cationization modification of the materials, the completeness of cross-linking among high polymer chains and the diversification of functions of the modified materials are realized, the characteristics and the functions of the modified polymer materials are enriched, and the application range of the modified polymer materials is expanded.
The invention relates to a preparation method of functional polyquaternium, which comprises the following steps: weighing 3- (N, N-dialkyl amino) propylamine and a solvent in a reaction kettle, controlling the temperature of materials in the reaction kettle to be 0-60 ℃, and adding acrylamide and N into the reaction kettle while stirring 2 Under protection, after the reaction is carried out for 2 to 12 hours under heat preservation, adding acrylic ester, and continuing the reaction for 2 to 24 hours under heat preservation; then adding a double-alkylation reagent into the reaction kettle, raising the temperature of the materials in the reaction kettle to 50-115 ℃, reacting for 2-24 hours, and finishing quaternary ammonium salinization reaction. Reducing the temperature of the materials in the reaction kettle to room temperature, and filtering to obtain solid substances; dissolving the solid with solvent, putting the dissolved solid into a reaction kettle, adjusting the pH value of the material in the reaction kettle to be between 8.0 and 9.5, adding formaldehyde into the reaction kettle, controlling the temperature to be between 20 and 90 ℃, stirring and reacting for 2 to 2The functional polyquaternium with the structure shown in the general formula (A) is prepared after 4 hours of negative pressure distillation dehydration or atomization drying, and the preparation process of the functional polyquaternium with the general formula (A) can be known by referring to the following schematic reaction formula:
wherein R in the above reaction formula 1 And R 2 Are respectively selected from C 1 ～C 18 Hydrocarbyl radical, R 3 Is selected from C 1 ～C 18 A hydrocarbon radical or
Wherein q is selected from a natural number of 0 to 2000; of the formula (F) or of the formula (A)
Is selected from C 2 ～C 18 Alkylene or
Wherein p is selected from natural numbers of 1 to 2000; n is a natural number of 2-2000, X is Cl, br, I or p-CH 3 -C 6 H 4 SO 3 One of (a) and (b); y has a structure represented by formula (B) or formula (C):
wherein R in the formula (C) 3 Is selected from C 1 ～C 18 Hydrocarbyl or
Wherein said R is 4 Is selected from C 1 ～C 18 A hydrocarbon group, q is a natural number of 0 to 2000, R 5 Is selected from H or CH 3 。
The 3- (N, N-dihydrocarbylamino) propylamine has the structure shown in the general formula (D):
wherein R in the general formula (D) 1 And R 2 Refers to the hydrocarbyl group of 3- (N, N-dihydrocarbylamino) propylamine, and is independently selected from C 1 ～C 18 A hydrocarbyl group.
The solvent is selected from one or more of water, ethanol, propanol, isopropanol, N-butanol, isobutanol, tert-butanol, chloroform, trichloroethylene, 1, 2-dichloroethane, tetrahydrofuran, 1, 4-dioxane, ethyl acetate, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide or N, N-dimethylacetamide, and the mass amount of the solvent is 2-10 times of that of the 3- (N, N-dihydrocarbylamino) propylamine;
the molar amount of the acrylamide is 0.15 to 1.15 times of that of the 3- (N, N-dialkyl amino) propylamine;
the acrylate has a structure represented by the general formula (E):
wherein R in the general formula (E) 3 Is selected from C 1 ～C 18 Is a hydrocarbon radical or
Wherein R is 4 Is selected from C 1 ～C 18 Q is a natural number of 0 to 2000, R 5 Is selected from H or CH 3 (ii) a The molar amount of the acrylic ester is 1.05 to 1.5 times of that of the 3- (N, N-dialkyl amino) propylamine;
the double alkylating agent has a structure represented by general formula (F):
wherein in the general formula (F)
Is selected from C 2 ～C 18 Alkylene or
P is selected from natural number of 1-2000, X is selected from Cl, br, I or p-CH 3 -C 6 H 4 SO 3 One of (1); the dosage of the double alkylation reagent is 0.5 to 2.5 times of the molar weight of the 3- (N, N-dialkyl amino) propylamine;
the formaldehyde refers to one of aqueous solution with the mass percentage concentration of 30-80%, trioxymethylene, tetraformaldehyde or paraformaldehyde, and the dosage of the formaldehyde is 0.8-1.2 times of the molar dosage of acrylamide.
Compared with the prior art, the invention has the beneficial effects that:
(1) The functional polyquaternium provided by the invention has the advantages of easily available preparation raw materials, less side reactions in each preparation process, simple preparation method, safe and efficient reaction process and simple product separation in each step.
(2) The functional polyquaternium provided by the invention is easy to dissolve in water, and the aqueous solution of the functional polyquaternium is clear and transparent and has light appearance color.
(3) The functional polyquaternium provided by the invention has the reaction activity of a plurality of N-hydroxymethyl propionamide structural units, has the hydrophilicity and the antibacterial function of polyquaternium cations, can be used for performing quaternary ammonium cation crosslinking or modification on a natural high polymer material, and can endow the modified material with an antistatic function, a surfactant function and a softening agent function.
Detailed Description
The present invention provides a functional polyquaternium and a method for preparing the same, which are further illustrated by the following examples, which are intended to provide a better understanding of the present invention. Therefore, the functional polyquaternium 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 functional Polyquaternium (1)
Weighing 12 g of acrylamide and 120 g of ethanol, dissolving in a reaction kettle, controlling the temperature of a feed liquid in the reaction kettle to be 15-25 ℃, adding 20 g of 3- (N, N-dimethylamino) propylamine, stirring for reacting for 6 hours, then adding 25 g of methyl methacrylate, and continuing to stir for reacting for 6 hours to finish the Michelal addition reaction; adding 42 g of 1, 4-dibromobutane into a Michelal addition reaction product in a reaction kettle, raising the temperature of materials in the reaction kettle to 60-80 ℃, and carrying out temperature-controlled stirring reaction for 8 hours to complete the polyquaternium salinization reaction; reducing the temperature to precipitate solid, filtering and separating out liquid substances (including ethanol, unreacted acrylamide, methyl methacrylate and the like) in the reaction kettle. Dissolving the solid obtained by filtering with 120 g of water, adding 16 g of formaldehyde aqueous solution with the mass percentage concentration of 40%, adjusting the pH value of the materials in the reaction kettle to be more than or equal to 8.5, controlling the temperature to be 25-35 ℃, stirring and reacting for 24 hours, and then evaporating redundant formaldehyde aqueous solution under negative pressure to prepare 223 g of functional polyquaternium (1).
EXAMPLE 2 preparation of functional Polyquaternium (2)
According to the preparation method and the operation steps of example 1, the functional polyquaternium (2) can be prepared by changing 3- (N, N-dimethylamino) propylamine into 3- (N, N-dibenzylamino) propylamine and changing methyl methacrylate into methoxypolyethylene glycol-400 methacrylate.
EXAMPLE 3 preparation of functional Polyquaternium (3)
According to the preparation method and the operation steps of example 1, the functional polyquaternium (3) aqueous solution can be prepared by replacing methyl methacrylate with lauryloxypolyethyleneglycol-400 methacrylate.
Example 4 preparation of functional Polyquaternium (4)
The functional polyquaternium (4) was prepared by changing 1, 4-dibromobutane to 1, 4-p-dichlorobenzyl according to the preparation method and procedure of example 1.
EXAMPLE 5 preparation of functional Polyquaternium (5)
According to the preparation method and the operation steps of example 1, methyl methacrylate is changed into lauryloxypolyethyleneglycol-400 methacrylate, and 1, 4-dibromobutane is changed into 2, 2-dichloroethyl ether, so that the functional polyquaternium (4) can be prepared.
EXAMPLE 6 preparation of functional Polyquaternium (6)
According to the preparation method and the operation steps of example 1, methyl methacrylate is changed into lauryloxypolyethyleneglycol-400 methacrylate, and 1, 4-dibromobutane is changed into triethylene glycol di-p-toluenesulfonate to prepare the functional polyquaternium (6).
EXAMPLE 7 preparation of functional Polyquaternium (7)
According to the preparation method and the operation steps of the example 1, the functional polyquaternium (7) can be prepared by changing 3- (N, N-dimethylamino) propylamine into 3- (N, N-dibenzylamino) propylamine, methyl methacrylate into lauryloxypolyethylene glycol-400 methacrylate and 1, 4-dibromobutane into polyethylene glycol 600 bis-p-toluenesulfonate.
Example 8 fungicidal Activity of functional Polyquaternium salts (1-7)
According to the method of GB15979-2002, the functional polyquaternium of examples (1-7) is dissolved and diluted with water, and bactericide solutions with a mass percentage concentration of 0.1% are prepared respectively, and the foaming performance and the bactericidal performance are tested, and the results are shown in Table 1.
TABLE 1 Properties of the functional Polyquaterniums of examples 1-7
Claims (7)
1. A functional polyquaternium characterized by having a structure represented by the general formula (A):
wherein in the general formula (A)
Selecting C 2 ～C 18 Alkylene or
Wherein p is selected from natural numbers ranging from 1 to 2000; r 1 And R 2 Are respectively selected from C 1 ～C 18 A hydrocarbon group, n is a natural number of 2 to 2000, and X is Cl, br, I or p-CH 3 -C 6 H 4 SO 3 Y has a structure represented by formula (B) or formula (C):
wherein R in the formula (C) 3 Is selected from C 1 ～C 18 Hydrocarbyl or
Wherein R is 4 Is selected from C 1 ～C 18 And q is a natural number of 0 to 2000.
2. The method of claim 1, comprising the steps of:
weighing 3- (N, N-dialkyl amino) propylamine and a solvent in a reaction kettle, controlling the temperature of materials in the reaction kettle to be 0-60 ℃, and adding acrylamide and N into the reaction kettle while stirring 2 Under protection, after the reaction is carried out for 2 to 12 hours under heat preservation, adding acrylic ester, and continuing the reaction for 2 to 24 hours under heat preservation; then adding a double-alkylation reagent into the reaction kettle, increasing the temperature of materials in the reaction kettle to 50-115 ℃, reacting for 2-24 hours, and finishing quaternary ammonium salinization reaction; reducing the temperature of the materials in the reaction kettle to room temperature, and filtering to obtain solid substances; dissolving the solid by using a solvent, then placing the dissolved solid into a reaction kettle, adjusting the pH value of the material in the reaction kettle to be between 8.0 and 9.5, then adding formaldehyde into the reaction kettle, controlling the temperature to be between 20 and 90 ℃, stirring and reacting for 2 to 24 hours to prepare the functional polyquaternium with the structure shown in the general formula (A);
wherein in the general formula (A)
Selecting C 2 ～C 18 Alkylene or
Wherein p is selected from natural numbers of 1 to 2000; r 1 And R 2 Are respectively selected from C 1 ～C 18 A hydrocarbon group, n is a natural number of 2 to 2000, and X is Cl, br, I or p-CH 3 -C 6 H 4 SO 3 Y has a structure represented by formula (B) or formula (C):
wherein R in the formula (C) 3 Is selected from C 1 ～C 18 Hydrocarbyl or
Wherein R is 4 Is selected from C 1 ～C 18 A hydrocarbon group, wherein q is a natural number of 0 to 2000;
the molar amount of the acrylamide is 0.15 to 1.15 times of that of the 3- (N, N-dialkyl amino) propylamine;
the mass usage of the solvent is 2-10 times of that of the 3- (N, N-dialkyl amino) propylamine;
the molar amount of the acrylic ester is 1.05 to 1.5 times of that of the 3- (N, N-dialkyl amino) propylamine;
the molar amount of the double alkylation reagent is 0.5 to 2.5 times of that of the 3- (N, N-dihydrocarbylamino) propylamine;
the molar dosage of the formaldehyde is 0.8 to 1.2 times of that of the acrylamide.
3. The method of claim 2, wherein the 3- (N, N-dihydrocarbylamino) propylamine has a structure represented by the following general formula (D):
wherein R in the general formula (D) 1 And R 2 Refers to the hydrocarbyl group of 3- (N, N-dihydrocarbylamino) propylamine, and is independently selected from C 1 ～C 18 A hydrocarbyl group.
4. The method of claim 2, wherein the acrylate has a structure represented by formula (E):
wherein R in the general formula (E) 3 Is selected from C 1 ～C 18 Is a hydrocarbon radical or
Wherein R is 4 Is selected from C 1 ～C 18 Q is a natural number of 0 to 2000, R 5 Is selected from H.
5. The method of claim 2, wherein the double alkylating agent has a structure of formula (F):
wherein in the general formula (F)
Is selected from C 2 ～C 18 Alkylene or
Wherein p is selected from natural numbers of 1-2000, and X is selected from Cl, br, I or p-CH 3 -C 6 H 4 SO 3 One kind of (1).
6. The method of claim 2, wherein the concentration of formaldehyde is 30-80% by mass of one of formalin and paraformaldehyde.
7. The method of claim 2, wherein the solvent is one or more selected from the group consisting of water, ethanol, isopropanol, N-butanol, isobutanol, t-butanol, chloroform, trichloroethylene, 1, 2-dichloroethane, tetrahydrofuran, 1, 4-dioxane, ethyl acetate, N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.
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| CN103193807A (en) * | 2013-04-08 | 2013-07-10 | 淮海工学院 | Water-soluble functional monomer containing quaternary ammonium salt and Schiff base compound and preparation method |
| WO2016062481A1 (en) * | 2014-10-22 | 2016-04-28 | Henkel Ag & Co. Kgaa | Hair treatment products containing a comb copolymer ii |
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| CN103193807A (en) * | 2013-04-08 | 2013-07-10 | 淮海工学院 | Water-soluble functional monomer containing quaternary ammonium salt and Schiff base compound and preparation method |
| WO2016062481A1 (en) * | 2014-10-22 | 2016-04-28 | Henkel Ag & Co. Kgaa | Hair treatment products containing a comb copolymer ii |
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