CN103361977A - Polyamide material with surface modified with quaternary ammonium salt and salicylaldehyde functional groups and preparation method of polyamide material - Google Patents
Polyamide material with surface modified with quaternary ammonium salt and salicylaldehyde functional groups and preparation method of polyamide material Download PDFInfo
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Abstract
The invention provides a polyamide material with the surface modified with quaternary ammonium salt and salicylaldehyde functional groups. The polyamide material has the characteristics that (1) a method for planting salicylaldehyde and quaternary ammonium salt functional groups on the surface of the polyamide material in a dot matrix manner is simple and feasible, and the planting density can be chemically adjusted according to a demand, (2) the uniformity of the surface modification of the polyamide material by salicylaldehyde and quaternary ammonium salt functional groups which are arranged in a dot matrix manner is high, and the microporous structure and the ventilating property of the polyamide material are not changed, (3) the quaternary ammonium salt and salicylaldehyde functional groups are used for modifying the surface of the polyamide material, so that the hydrophilcity of the surface of the polyamide material can be improved, and the killing antibiosis performance of the polyamide material is improved, and (4) the salicylaldehyde functional group on the surface of the polyamide material also has a function of selectively chelating and adsorbing heavy metal ions and can be also condensed with amino acid, semi carbazide or hydrazine to prepare Schiff base for chelated resin, a solid carrier catalyst, killing antibiosis, template synthetic peptide, a photoelectric material or a separation engineering material.
Description
Technical field
The present invention relates to a kind of polyamide functional material, particularly the polyamide material of quaternary ammonium salt and the finishing of salicylide functional group belongs to functional high polymer material field.
Technical background
Polyamide is the general designation of fatty polyamide and aromatic polyamides, has good combination property, no matter polyamide fiber, polyamide textiles, polyamide nonwoven fabric, PA membrane, or the composite of polyamide coating all is widely used in life and industrial a plurality of field.In actual applications polyamide material all require suitable ageing-resistant, the surface is antifog, surface conductance, case hardness, the performances such as surface hydrophilic and surface soiling.Obtain the polyamide material of surface property excellence, to the polyamide material surface modify be flexibly, simply, method efficiently, mainly contain: (1) surface chemistry deposition, (2) surface aggregate deposition, (3) surface coating is covered with paint, lacquer, colour wash, etc., and the monomer-grafted polymerization on (4) surface.The method of modifying that uses monomer to carry out glycerol polymerization on the polyamide material surface, the characteristics such as it is numerous in variety to have monomer available, and finishing is lasting.In recent years, use the tertiary amine function monomer in the graft polymerization reaction on polyamide fiber or PA membrane surface and further quaternary ammonium salinization reaction, can be at polyamide material surface access quaternary ammonium salt, the surface hydrophilicity of improved polyamide material not only, improved its antibacterial surface antifouling property, also improved opposing chemical degradation performance, be widely used in fields such as desalinization or sanitary wastewater processing.But the polyamide material finishing lack of homogeneity that adopts said method to make; Required function base after the modification can not fully expose, and represents characteristic and the effect of function base; Polyamide material surface graft copolymerization objects system is huge, causes the polyamide material micropore to stop up, and penetrating ability reduces; In addition the polyamide material surface is being carried out in the graft copolymerization modification, the monomer waste of raw materials that is caused by the monomer homopolymerization is serious.
For the defective of existing polyamide material surface modification technology and method, the inventor has proposed to use design and the technology of the construction unit modification polyamide material surface that contains quaternary ammonium salt and salicylide functional group.The low activity amide groups N-H key that the polyamide material surface appears and high active amino N-H key can carry out the number of chemical reaction, for example use the base reagent of sodium alkoxide, sodium hydride or butyl lithium, and the N-H key is taken off proton, produce N
-Can carry out ethoxyl etherification to the N-H key with the ring-opening reaction of oxirane; With the reaction of active acyl chloride compound, continue to produce acid amides or imide derivative, or carry out addition reaction with isocyanates, produce ureido derivatives; Thus, the N-H key chemical characteristic that the present invention appears according to the polyamide material surface and with the addition reaction capacity variance of polyisocyanates, effectively control forms the polyamide material that isocyanate group is contained on the surface; Contain the addition reaction of polyamide material and the tertiary amine groups alcohol of isocyanate group, formed again the surperficial polyamide material that contains tertiary amine groups; The quaternary ammonium salinization reaction of polyamide material and the 5-chloromethyl salicylaldehyde of tertiary amine groups is contained on the surface, the final salicylide of dot matrix arrangement and the decorative layer of quaternary ammonium salt functional group of having formed on the polyamide material surface.The effect that the present invention will realize is: (1) can carry out Chemical Regulation according to needs in the salicylide of polyamide material surface " plantation " dot matrix arrangement and the density of quaternary ammonium salt function base; (2) high, the microcellular structure that do not change polyamide material of the dot matrix arranged distribution uniformity of salicylide and quaternary ammonium salt functional group finishing polyamide material; (3) use quaternary ammonium salt functional group modification polyamide material surface, can improve the hydrophily on polyamide material surface, improve its anti-microbial property of killing livestock; (4) use salicylide functional group modification polyamide material surface, can improve the antibiotic property of killing livestock on polyamide material surface, the salicylide functional group also has selective chelating Adsorption of Heavy Metal Ions function, also can prepare schiff bases with amino acid, semicarbazides or hydrazine condensation, be used for chelating resin, solid-carried catalyst, antibiotic, the template synthetic peptide of killing livestock, photoelectric material or separation engineering material.
Summary of the invention
The invention provides the polyamide material of a kind of quaternary ammonium salt and the finishing of salicylide functional group, be by the addition reaction of polyamide material lip-deep low activity amide groups N-H and high active amino N-H and polyisocyanates, make the polyamide material that isocyanate group is contained on the surface; Polyamide material and tertiary amine groups alcohol that isocyanate group is contained on described surface carry out making the polyamide material that tertiary amine groups is contained on the surface in the addition reaction; The quaternary ammonium salinization reaction of polyamide material and the 5-chloromethyl salicylaldehyde of tertiary amine groups is contained on described surface, makes the polyamide material that salicylide and quaternary ammonium salt functional group are contained in the surface.
Described polyamide refers to fat polyamide or aromatic polyamides, and described polyamide material comprises a kind of in polyamide fiber, polyamide nonwoven fabric, polyamide lamina membranacea, polyamide fabric or the surperficial polyamide coating composite.
The present invention utilizes polyamide material surface N-H key chemism different, and the control reaction condition selectively with the addition reaction of polyisocyanates, is introduced the isocyanate function base of " density is suitable " on the polyamide material surface, see following signal reaction equation 1.:
Wherein said polyisocyanates is selected from structural formula shown in the general formula (I):
Alkyl in the described general formula (I) refers to a kind of in open chain aliphatic chain alkyl, cycloalkyl group or the aryl radical, hence one can see that, and that described polyisocyanates refers in open chain aliphatic chain alkyl polyisocyanates, cycloalkyl group polyisocyanates or the aryl radical polyisocyanates is a kind of, and n is selected from a kind of in 1,2,3,4 or 5.
The professional of this professional domain is well-known, and the polyamide material surface is floating greasy dirt and moisture, finish the addition reaction of polyamide material and polyisocyanates, must carry out scrubbing and dry the processing to polyamide material in advance.For the isocyanate function base that prevents the polyamide material surface further with the addition reaction of described urea groups or carbamate groups, disposable finishing wanted in the polyamide material after the activation and the addition reaction of polyisocyanates.
After isocyanate group was introduced on the polyamide material surface, the lip-deep isocyanate group of polyamide material can be carried out addition reaction with the compound that contains N-H, O-H, S-H or P-H key, makes respectively the construction unit that contains urea groups or carbamate groups.The present invention utilizes the addition reaction characteristic of isocyanate group and alcoholic extract hydroxyl group on the polyamide material surface, adopts tertiary amine groups alcohol for containing the compound of O-H key, further finishes addition reaction, introduces tertiary amine groups on the polyamide material surface, sees following signal reaction equation 2.:
Wherein said tertiary amine groups alcohol structural formula shown in general formula (II) or general formula (III):
R in general formula (II) or the general formula (III)
1And R
2Be selected from respectively C
1～C
20Alkyl, m are selected from 1～20 positive integer; The alkyl of described reaction equation in 2. refers to a kind of in open chain aliphatic group, aryl radical or the cycloalkyl group;
Through signal reaction equation process 2., the tertiary amine groups that introduce on the polyamide material surface has the nucleophilic substitution activity.Contain chemically active chloromethyl in the 5-chloromethyl salicylaldehyde molecular structure, can finish quaternary ammonium salinization reaction with tertiary amine groups, so just can introduce simultaneously quaternary ammonium salt and bigcatkin willow aldehyde functional group on the polyamide material surface of containing tertiary amine groups, see following signal reaction equation 3.:
Wherein reaction equation in 3. R
1And R
2Select respectively white C
1～C
20Alkyl, m are selected from 1～20 positive integer; Described alkyl refers to a kind of in open chain aliphatic group, cycloalkyl group or the aryl radical.
Through signal reaction equation process 3., on the polyamide material surface " plantation " quaternary ammonium salt and two kinds of function bases of salicylide, have dot matrix arrangement characteristics; " plantation " density of quaternary ammonium salt and two kinds of function bases of salicylide can be regulated by chemical reaction according to needs; Two kinds of function bases of the quaternary ammonium salt of " plantation " and salicylide on the polyamide material surface not only can significantly improve the polyamide material surface hydrophilicity and the anti-microbial property of killing livestock; Can also be selectively and heavy metal ion, hydroxylamine hydrochloride, amino acid, primary amine, hydrazides or hydrazine finish complex reaction or condensation reaction, be converted into complex or schiff bases, be applied in solid-phase catalyst, antibiotic, the chelating resin of killing livestock, photoelectric material or chemical probe field.
The concrete preparation method of quaternary ammonium salt provided by the invention and salicylide functional group finishing polyamide material is as described below:
Step 1: the polyamide material of isocyanate group is contained on the preparation surface
Get that the polyamide material of purge drying is immersed in the solvent, activate 2～24 hours under the room temperature; It is miscible in solvent to take by weighing polyisocyanates, adds an amount of promoter, is deployed into polyisocyanate solution; After taking out the polyamide material centrifuge dripping activated, contact with polyisocyanate solution, temperature control-15～150 ℃ reacts after 2～24 hours, leaches, washing, vacuumize, makes the polyamide material that isocyanate group is contained on the surface.
Wherein said polyamide refers to fat polyamide or aromatic polyamides, and described polyamide material comprises a kind of in polyamide fiber, polyamide nonwoven fabric, polyamide lamina membranacea, polyamide fabric or the surperficial polyamide coating composite;
Described polyisocyanates is selected from structural formula shown in the general formula (I):
Alkyl in the described general formula (I) refers to a kind of in open chain aliphatic group, cycloalkyl group or the aryl radical, hence one can see that, and that described polyisocyanates refers in open chain aliphatic group polyisocyanates, cycloalkyl group polyisocyanates or the aryl radical polyisocyanates is a kind of, and n is selected from a kind of in 1,2,3,4 or 5.
Described solvent refers to one or more in ethyl acetate, propyl acetate, butyl acetate, acetone, butanone, Isosorbide-5-Nitrae-dioxane, oxolane, glycol dimethyl ether, ethylene glycol diethyl ether or 1, the 2-dichloroethanes;
Described promoter is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, N, N-dimethyl benzylamine, pyridine, DMAP, N, N-dimethyl cyclohexyl amine, two (2-dimethylaminoethyl) ether, N, N, N ', N '-tetramethyl Alkylenediamine, N-ethylmorpholine, N-methylmorpholine, N, one or more in N '-diethyl piperazine, dibutyl tin laurate, two sad dibutyl tins or the dibenzoic acid dibutyl tin;
Described polyamide material: polyisocyanates: solvent: the mass ratio of promoter is 100: 10～100: 0～500: 0～30.
Step 2: the polyamide material of tertiary amine groups is contained on the preparation surface
Taking by weighing tertiary amine groups alcohol is dissolved in the solvent, add an amount of promoter, be deployed into the tertiary amine groups alcoholic solution, the temperature of control tertiary amine groups alcoholic solution is to-5～85 ℃, the polyamide material of isocyanate group and tertiary amine groups alcoholic solution haptoreaction were contained after 0.5～50 hour in the surface that step 1 is made, and filtered washing, oven dry namely makes the polyamide material that tertiary amine groups is contained on the surface.
Wherein said tertiary amine groups alcohol structural formula shown in general formula (II) or general formula (III):
R in general formula (II) or the general formula (III)
1And R
2Be selected from respectively C
1～C
20Alkyl, m are selected from 1～20 positive integer;
Described solvent refers to one or more in ethyl acetate, propyl acetate, butyl acetate, acetone, butanone, Isosorbide-5-Nitrae-dioxane, oxolane, glycol dimethyl ether, ethylene glycol diethyl ether or 1, the 2-dichloroethanes;
Described promoter is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, N, N-dimethyl benzylamine, pyridine, DMAP, N, N-dimethyl cyclohexyl amine, two (2-dimethylaminoethyl) ether, N, N, N ', N '-tetramethyl Alkylenediamine, N-ethylmorpholine, N-methylmorpholine, N, one or more in N '-diethyl piperazine, dibutyl tin laurate, two sad dibutyl tins or the dibenzoic acid dibutyl tin;
The polyamide material of isocyanate group is contained on described surface: tertiary amine groups alcohol: solvent: the mass ratio of promoter is 100: 10～100: 0～500: 0～30.
Step 3: the preparation of quaternary ammonium salt and salicylide functional group finishing polyamide material
Take by weighing the 5-chloromethyl salicylaldehyde and be dissolved in the solvent, make 5-chloromethyl salicylaldehyde solution; Control 5-chloromethyl salicylaldehyde solution temperature is to-5～95 ℃, the polyamide material of tertiary amine groups and 5-chloromethyl salicylaldehyde solution haptoreaction were contained after 2～12 hours in the surface that step 2 is made, filter, washing, dry, namely make the polyamide material of quaternary ammonium salt and the finishing of salicylide functional group.
Wherein said solvent refers to one or more in ethyl acetate, propyl acetate, butyl acetate, acetone, Isosorbide-5-Nitrae-dioxane, oxolane, glycol dimethyl ether, ethylene glycol diethyl ether or 1, the 2-dichloroethanes;
The polyamide material of tertiary amine groups is contained on described surface: the 5-chloromethyl salicylaldehyde: the mass ratio of solvent is 100: 10～150: 50～500.
Quaternary ammonium salt provided by the invention and salicylide functional group finishing polyamide material have following characteristics:
1. the method for preparing quaternary ammonium salt of the present invention and salicylide functional group finishing polyamide material is simple.
2. the quaternary ammonium salt of finishing polyamide material of the present invention and salicylide functional group are evenly distributed, and have dot matrix and arrange characteristics.
3. the quaternary ammonium salt of finishing polyamide material of the present invention belongs to two kinds of different materials of the antibacterial mechanisms of killing livestock with the salicylide functional group, mutually produces the antibiotic synergy of killing livestock, and can effectively reduce the resistance to the action of a drug of bacterial micro-organism.
Specific embodiment
By following embodiment quaternary ammonium salt provided by the invention and salicylide functional group finishing polyamide material and preparation method are further specified, its purpose is to understand better content of the present invention.
Embodiment 1TDI-Et
2The preparation of N-CMS-PA-66
The preparation of step 1, TDI-PA-66
The nylon-66 micro-filtration membrane of getting weight behind the purge drying and be model that 0.7751 gram Shanghai Chu setting analysis Instr Ltd. produces and be 50mm*0.45 μ m is immersed in Isosorbide-5-Nitrae-dioxane solvent, and activation is 24 hours under the room temperature.It is miscible in 2.5 milliliters of Isosorbide-5-Nitraes-dioxane solvent to take by weighing toluene di-isocyanate(TDI) 0.55 gram, adds an amount of DMAP, is deployed into toluene di-isocyanate(TDI) solution.After taking out the nylon-66 micro-filtration diaphragm centrifuge dripping that has activated, nylon-66 micro-filtration diaphragm is immersed in the toluene di-isocyanate(TDI) solution, temperature control to 60～65 ℃ confined reaction is after 2 hours, use the Isosorbide-5-Nitrae-reacted nylon-66 micro-filtration of dioxane solvent wash diaphragm, eliminate free toluene di-isocyanate(TDI), oven dry, namely be the nylon-66 micro-filtration membrane (referred to as TDI-PA-66) that isocyanate group is contained on the surface, weight is 0.9832 gram, and is for subsequent use.
Step 2, TDI-Et
2The preparation of N-PA-66
Take by weighing N, N-diethyl ethylene diamine 0.35 gram is dissolved in 5.5 milliliters of Isosorbide-5-Nitraes-dioxane solvent, adds an amount of DMAP, is deployed into N, N-diethyl ethylene diamine solution; The TDI-PAM-66 that step 1 is made is immersed in N, in the N-diethyl ethylene diamine solution, control temperature to 15～25 ℃, behind the confined reaction 2.5 hours, use Isosorbide-5-Nitrae-reacted diaphragm of dioxane solvent wash, eliminate free N, the N-diethyl ethylene diamine, oven dry namely is that the nylon-66 micro-filtration membrane of tertiary amine groups is contained (referred to as TDI-Et in the surface
2N-PA-66), weight is 1.1636 grams, and is for subsequent use.
Step 3, TIDI-Et
2The preparation of N-CMS-PA-66
Take by weighing 1.25 gram 5-chloromethyl salicylaldehydes and be dissolved in 5.5 milliliters of Isosorbide-5-Nitraes-dioxane solvent, be deployed into 5-chloromethyl salicylaldehyde solution; The TDI-Et that step 2 is made
2The N-PA-66 diaphragm is immersed in the 5-chloromethyl salicylaldehyde solution, control temperature to 5～15 ℃, behind the confined reaction 2.5 hours, use 1, the reacted diaphragm of 4-dioxane solvent wash, eliminate free 5-chloromethyl salicylaldehyde, oven dry namely is that the nylon-66 micro-filtration membrane of quaternary ammonium salt and salicylide functional group is contained (referred to as TDI-Et in the surface
2N-CMS-PA-66) weight is 1.4687 grams.
Embodiment 2DMI-Et
2The preparation of N-CMS-PA-66
According to method and the operating procedure of embodiment 1, the toluene di-isocyanate(TDI) in embodiment 1 step 1 is changed as methyl diphenylene diisocyanate (referred to as DMI), make DMI-Et
2N-CMS-PA-66.
Embodiment 3TDI-Et
2The preparation of NPEG-CMS-PA-66
According to method and the operating procedure of embodiment 1, with the N in embodiment 1 step 2, it is that single diethylin polyethylene glycol is (referred to as Et that the N-diethyl ethylene diamine changes
2NPEG), make TDI-Et
2NPEG-CMS-PA-66.
Embodiment 4TDI-Et
2The preparation of NPEG-CMS-PATT-PP
Method and operating procedure according to embodiment 1, the model that Shanghai Chu setting analysis Instr Ltd. in embodiment 1 step 1 is produced is that 50mm*0.45 μ m Nylon 66 Microfiltration Membrane changes as homemade 2,4, the PPTA aggregation deposition polypropylene non-woven fabric compound film sheet (referred to as PATT-PP) of 6-triamido toluene modification, N in the step 2, the N-diethyl ethylene diamine changes and is single diethylin polyethylene glycol, make 2 of surface bond quaternary ammonium salt and salicylide functional group, the PPTA aggregation deposition polypropylene non-woven fabric compound film sheet of 4,6-triamido toluene modification is (referred to as TDI-Et
2The NPEG-CMS-PATT-PP diaphragm).
Embodiment 5 quaternary ammonium salts and salicylide functional group finishing polyamide material film properties
Get respectively the TDI-Et of embodiment 1～4
2N-CMS-PA-66 diaphragm, DMI-Et
2N-CMS-PA-66 diaphragm, TDI-Et
2NPEG-CMS-PA-66 diaphragm, TDI-Et
2NPEG-CMS-PATT-PP diaphragm and former commercial nylon 66 micro-filtration diaphragms and homemade PATT-PP diaphragm record water contact angle θ and are respectively 25 °, 23 °, water infiltration, water infiltration, 43 ° and 75 °.The result shows the hydrophily that can efficiently improve described PA membrane material through technology provided by the invention and method.
Claims (2)
1. the polyamide material of a quaternary ammonium salt and the finishing of salicylide functional group, it is characterized in that making through following steps: step 1, by the addition reaction of the lip-deep amide groups N-H of polyamide material and amino N-H and polyisocyanates makes the polyamide material that isocyanate group is contained on the surface; Polyamide material and tertiary amine groups alcohol that isocyanate group is contained on step 2, described surface carry out addition reaction, make the polyamide material that tertiary amine groups is contained on the surface; The quaternary ammonium salinization reaction of polyamide material and the 5-chloromethyl salicylaldehyde of tertiary amine groups is contained on step 3, described surface, makes the polyamide material of salicylide and the finishing of quaternary ammonium salt functional group;
Wherein said polyamide refers to fat polyamide or aromatic polyamides, and described polyamide material comprises a kind of in polyamide fiber, polyamide nonwoven fabric, polyamide lamina membranacea, polyamide fabric or the surperficial polyamide coating composite;
Described polyisocyanates is selected from structural formula shown in the general formula (I):
Alkyl in the described general formula (I) refers to a kind of in open chain aliphatic group, cycloalkyl group or the aryl radical, hence one can see that, and that described polyisocyanates refers in open chain aliphatic group polyisocyanates, cycloalkyl group polyisocyanates or the aryl radical polyisocyanates is a kind of, and n is selected from a kind of in 1,2,3,4 or 5;
Described tertiary amine groups alcohol is selected from structural formula shown in general formula (II) or the general formula (III):
R in general formula (II) or the general formula (III)
1And R
2Be selected from respectively C
1～C
20Alkyl, m are selected from 1～20 positive integer.
2. according to the preparation method of quaternary ammonium salt claimed in claim 1 and salicylide finishing polyamide material, it is characterized in that comprising step as described below:
The polyamide material of isocyanate group is contained on step 1 preparation surface
Get that the polyamide material of purge drying is immersed in the solvent, activate 2～24 hours under the room temperature; It is miscible in solvent to take by weighing polyisocyanates, adds an amount of promoter, is deployed into polyisocyanate solution; After taking out the polyamide material centrifuge dripping activated, contact with polyisocyanate solution, extremely-15～150 ℃ of control reaction temperatures were reacted after 2～24 hours, leached, washing, vacuumize, made the polyamide material that isocyanate group is contained on the surface;
Wherein said polyamide is selected from as claimed in claim 1;
Described polyamide material is selected from as claimed in claim 1;
Described polyisocyanates is selected from as claimed in claim 1;
Described solvent refers to one or more in ethyl acetate, propyl acetate, butyl acetate, acetone, butanone, Isosorbide-5-Nitrae-dioxane, oxolane, glycol dimethyl ether, ethylene glycol diethyl ether or 1, the 2-dichloroethanes;
Described promoter is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, N, N-dimethyl benzylamine, pyridine, DMAP, N, N-dimethyl cyclohexyl amine, two (2-dimethylaminoethyl) ether, N, N, N ', N '-tetramethyl Alkylenediamine, N-ethylmorpholine, N-methylmorpholine, N, one or more in N '-diethyl piperazine, dibutyl tin laurate, two sad dibutyl tins or the dibenzoic acid dibutyl tin;
Described polyamide material: polyisocyanates: solvent: the consumption mass ratio of promoter is 100: 10～100: 0～500: 0～30;
The polyamide material of tertiary amine groups is contained on step 2 preparation surface
Taking by weighing tertiary amine groups alcohol is dissolved in the solvent, add an amount of promoter, be deployed into the tertiary amine groups alcoholic solution, the temperature of control tertiary amine groups alcoholic solution is to-5～85 ℃, the polyamide material of isocyanate group and tertiary amine groups alcoholic solution haptoreaction were contained after 0.5～50 hour in the surface that step 1 is made, and filtered washing, oven dry namely makes the polyamide material that tertiary amine groups is contained on the surface;
Wherein said tertiary amine groups alcohol is selected from as claimed in claim 1;
Described solvent refers to one or more in ethyl acetate, propyl acetate, butyl acetate, acetone, butanone, Isosorbide-5-Nitrae-dioxane, oxolane, glycol dimethyl ether, ethylene glycol diethyl ether or 1, the 2-dichloroethanes;
Described promoter is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, N, N-dimethyl benzylamine, pyridine, DMAP, N, N-dimethyl cyclohexyl amine, two (2-dimethylaminoethyl) ether, N, N, N ', N '-tetramethyl Alkylenediamine, N-ethylmorpholine, N-methylmorpholine, N, one or more in N '-diethyl piperazine, dibutyl tin laurate, two sad dibutyl tins or the dibenzoic acid dibutyl tin;
The polyamide material of isocyanate group is contained on described surface: tertiary amine groups alcohol: solvent: the consumption mass ratio of promoter is 100: 10～100: 0～500: 0～30;
Step 3: the preparation of quaternary ammonium salt and salicylide functional group finishing polyamide material
Take by weighing the 5-chloromethyl salicylaldehyde and be dissolved in the solvent, make 5-chloromethyl salicylaldehyde solution; Control 5-chloromethyl salicylaldehyde solution temperature is to-5～95 ℃, the polyamide material of tertiary amine groups and 5-chloromethyl salicylaldehyde solution haptoreaction were contained after 2～12 hours in the surface that step 2 is made, filter, washing, dry, namely make the polyamide material of quaternary ammonium salt and the finishing of salicylide functional group;
Wherein said solvent refers to one or more in ethyl acetate, propyl acetate, butyl acetate, acetone, Isosorbide-5-Nitrae-dioxane, oxolane, glycol dimethyl ether, ethylene glycol diethyl ether or 1, the 2-dichloroethanes;
The polyamide material of tertiary amine groups is contained on described surface: the 5-chloromethyl salicylaldehyde: the consumption mass ratio of solvent is 100: 10～150: 50～500.
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