CN104928919A - Soft coordinative antibiosis brush type multi-season ammonium salt textile finishing agent and preparation method thereof - Google Patents

Soft coordinative antibiosis brush type multi-season ammonium salt textile finishing agent and preparation method thereof Download PDF

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CN104928919A
CN104928919A CN201510404713.9A CN201510404713A CN104928919A CN 104928919 A CN104928919 A CN 104928919A CN 201510404713 A CN201510404713 A CN 201510404713A CN 104928919 A CN104928919 A CN 104928919A
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soft
ammonium salt
finishing agent
type multi
quaternary ammonium
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CN104928919B (en
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林璟
杜嘉睿
陈依婷
陈富群
陈婉玲
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Guangzhou University
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Guangzhou University
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Abstract

The invention provides a soft coordinative antibiosis brush type multi-season ammonium salt textile finishing agent. In the structure formula (please see the formula in the specification) of the soft coordinative antibiosis brush type multi-season ammonium salt textile finishing agent, R1, R2, R3, R4, R5 and R6 each represents for N or a molecular formula (please see the molecular formula in the specification), and at least one of R1, R2, R3, R4, R5 and R6 represents for the molecular formula (please see the molecular formula in the specification). The soft coordinative antibiosis brush type multi-season ammonium salt textile finishing agent has multiple long chain alkyl chain sections with soft characteristics and a controllable number, is controllable in structure, and has a good antibacterial property and certain flexibility. The positive ion charge density is controlled in an experiment by regulating and controlling the reaction raw material ratio, the molecular structure can present the high-density positive charge property, and therefore more bacteria with negative charges can be powerfully adsorbed, and structures of the bacteria are broken so that the aims of killing the bacteria or inhibiting the growth of the bacteria can be achieved. Meanwhile, the multiple long chain alkyl chain sections with soft characteristics are adsorbed on textile surfaces, and therefore good soft performance is achieved.

Description

A kind of soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent and preparation method thereof
Technical field
The present invention relates to a kind of multi-quaternary ammonium salt fabric finishing agent, refer to a kind of soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent especially, the invention still further relates to a kind of preparation method of soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent.
Background technology
Fabric through using and washing repeatedly, easily occur hardening, become fragile and the problem such as feel is coarse, affect comfort level when people wear and vision.After soft finish, people are when contacting textiles, are easy to slide between fiber, make fabric become soft.Also need antibacterial effect except submissive, meet people and multi-functional the stating of textile finishing is asked.
All there is shortcoming in the antiseptic of mineral-type, complex class and some organics, exists and the physics of textile fabric or the problem such as chemical interactions difference and soft poor durability although flatness is good though softener contains comparatively Long carbon chain (C12-C16).There is its storage stability shortcoming in emulsion-type softener product and soft finish is uneven or the not defect such as color inhibition.And quaternary ammonium salt organic antiseptic has the excellent specific properties such as high sterilizing ability, low toxicity, spectrum be wide, inexpensive and has submissive effect simultaneously.
Use more antiseptic to be inorganic antiseptic and the quaternary ammonium salts etc. such as silver both at home and abroad at present, softener has quaternary ammonium salt and this two large class of modified silicon oil.Fabric finishing agent major part function singleness in the market, has its research report of finishing agent that is soft and antibacterial action concurrently less, and its gaps in market.
Summary of the invention
The present invention proposes a kind of soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent, and overcomes the difficult water solubility problems of bi-quaternary ammonium salt and quaternaries softener on market.
The present invention proposes a kind of preparation method of soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent, overcome Antibacterial agent preparation method of the prior art complicated, the problem that softener stability is short of, effect is poor and antibacterial and submissive two kinds of functions cannot be worked in coordination with in identical product.
Technical scheme of the present invention is achieved in that a kind of soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent, and its structural formula is as follows:
R in formula 1for N or r 2for N or r 3for N or r 4for N or r 5for N or r 6for N or and R 1, R 2, R 3, R 4, R 5, R 6having one at least is
A preparation method for soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent, comprises the steps:
Step one: add 4 in the reactor, 4'-diaminodiphenylmethane four glycidyl amine (AG80) and diethanol amine, at 50-100 DEG C of temperature, the reaction time is 3-8h, final synthesis modification AG80, obtains pure modification AG80 after the operation such as decompression distillation, drying;
Step 2: modification AG80 step one obtained and chloro-hexadecane join in reactor after being fully dissolved in solvent, at 50-100 DEG C of temperature, obtain crude product after reactant is reacted 10-20h among reactor, then after purification processes, obtain end product soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent.
Preferably, AG80 described in described step one and described diethanol amine amount of substance are than being 1:(4 ~ 6.5); The amount of substance ratio of modification AG80 and described chloro-hexadecane described in described step 2 is: 1:n (n=1 ~ 13).
Preferably, the solvent in step 2 is N-N dimethyl formamide, butanone, butyl acetate, methylisobutylketone, dioxane, dimethyl formamide.
Beneficial effect of the present invention is:
1, soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent of the present invention, can be obtained the finishing agent of different quaternized degree, make it have good antibiotic property and certain compliance by regulation and control modification AG80 and the mol ratio of chloro-hexadecane.
2, relative to market product, soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent of the present invention has better bactericidal properties and compliance.Relative to Small molecular cation quaternary ammonium salt, with multiple quaternary ammonium salt cationic in soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent molecular structure of the present invention, its cationic charge density is controlled by regulation and control reaction raw materials proportioning, the high density positive charge that can show, strongly can adsorb the bacterium of more multi-band negative electrical charge, destroy bacterium cell structure, prevent bacterial growth, reach high bactericidal properties effect; The long alkyl chain section being adsorbed on fabric face increases, and can strengthen its softness.
3, soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent of the present invention has good water-soluble, can broader applications in fields such as fabric finishing agent, daily use chemicals disinfectant, metallic weapon disinfectant, medical article sterilizing agent, water paint bactericide, water color ink bactericide, Aqueous Adhesives bactericide.The preparation method that the present invention proposes a kind of soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent is simple, and cost is lower.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is that the molecular structure of the brush-type multi-quaternary ammonium salt fabric finishing agent S-1 of final gained in the embodiment of the present invention 1 is characterized by examination of infrared spectrum;
Fig. 2 is that the brush-type multi-quaternary ammonium salt fabric finishing agent S-1 that obtains of the embodiment of the present invention 1 is to colibacillary MIC resolution chart;
Fig. 3 is that the brush-type multi-quaternary ammonium salt fabric finishing agent S-1 that obtains of the embodiment of the present invention 1 is to the MIC resolution chart of staphylococcus aureus;
Fig. 4 is the change curve of fabric softness after arrangement corresponding to the mass concentration of the different aqueous solution of the brush-type multi-quaternary ammonium salt fabric finishing agent S-3 that brush-type multi-quaternary ammonium salt fabric finishing agent S-2, embodiment 3 that brush-type multi-quaternary ammonium salt fabric finishing agent S-1, embodiment 2 that the embodiment of the present invention 1 obtains obtain obtain.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
50.0g (0.1188 mole) AG80 and 75g (0.7125 mole) diethanol amine is added in 250ml round-bottomed flask, under reaction temperature is 90 DEG C of conditions, reaction time is 5h, obtain first step product-modification AG80, obtain pure modification AG80 through decompression distillation, vacuum tank drying;
Get 2.69g (0.0032 mole) modification AG80 to add 10g (0.038 mole) chloro-hexadecane and pour reactor into after being fully dissolved in N-N dimethyl formamide, at 80 DEG C of temperature, reaction time is 12h, synthesis end product brush-type multi-quaternary ammonium salt fabric finishing agent, after the operation such as decompression distillation, drying, obtain pure soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent S-1, its quaternized degree is 98.3%.
Embodiment 2
50.0g (0.1188 mole) AG80 and 75g (0.7125 mole) diethanol amine is added in 250ml round-bottomed flask, under reaction temperature is 80 DEG C of conditions, reaction time is 4h, obtain first step product-modification AG80, obtain pure modification AG80 through decompression distillation, vacuum tank drying;
Get 5.33g (0.0063 mole) modification AG80 to add 10g (0.038 mole) chloro-hexadecane and pour reactor into after being fully dissolved in butanone, at 90 DEG C of temperature, reaction time is 14h, synthesis end product brush-type multi-quaternary ammonium salt fabric finishing agent, after the operation such as decompression distillation, drying, obtain pure soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent S-2, its quaternized degree is 80.5%.
Embodiment 3
50.0g (0.1188 mole) AG80 and 75g (0.7125 mole) diethanol amine is added in 250ml round-bottomed flask, under reaction temperature is 100 DEG C of conditions, reaction time is 7h, obtain first step product-modification AG80, obtain pure modification AG80 through decompression distillation, vacuum tank drying;
Get 6.81g (0.0081 mole) modification AG80 to add 10g (0.038 mole) chloro-hexadecane and pour reactor into after being fully dissolved in N-N dimethyl formamide and butanone, at 95 DEG C of temperature, reaction time is 13h, synthesis end product brush-type multi-quaternary ammonium salt fabric finishing agent, after the operation such as decompression distillation, drying, obtain pure soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent S-3, its quaternized degree is 60.5%.
The soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent prepared by above method all has good water-soluble.
The molecular structure of the soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent S-1 of final gained is characterized as shown in annex map 1 by examination of infrared spectrum, 3363cm -1left and right be the absworption peak of-OH key.2936cm -1left and right belong to-(CH 2-) stretching vibration peak of n, 1649cm -1and 1521cm -1left and right be the C=C absworption peak of phenyl ring skeletal vibration, 1363cm -1for-the CH that is connected with quaternary nitrogen cation 2flexural vibrations peak, 1106cm -1left and right belong to C-C lstretching vibration absworption peak, 800cm -1the contraposition of phenyl ring replaces absworption peak, 905cm -1absworption peak be stretching vibration between quaternary nitrogen atoms and adjacent carbons, this peak can as the important references differentiating quaternary ammonium compound.Above characteristic peak analysis result shows that quaternary ammonium compound is successfully synthesized.
The soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent S-1 of example 1 gained is to the antibiotic property of Escherichia coli and staphylococcus aureus by carrying out minimal inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) measurements determination is described, and test result is as follows:
Be illustrated in figure 2 soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent S-1 to colibacillary MIC resolution chart, its MIC value is 7.81 μ g/mL;
Figure 3 shows that soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent S-1 is to the antibacterial situation of staphylococcus aureus, its MIC value is 15.63 μ g/mL.
Soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent S-1 all shows stronger antibiotic property to Escherichia coli and staphylococcus aureus.
In Fig. 2, numbering 1=500 μ g/ml, numbering 2=250 μ g/ml, numbering 3=125 μ g/ml, numbering 4=62.5 μ g/ml, numbering 5=31.25 μ g/ml, numbering 6=15.63 μ g/ml, numbering 7=7.81 μ g/ml, numbering 8=3.91 μ g/ml.Cultivate 16h.
In Fig. 3, numbering 1=500 μ g/ml, numbering 2=250 μ g/ml, numbering 3=125 μ g/ml, numbering 4=62.5 μ g/ml, numbering 5=31.25 μ g/ml, numbering 6=15.63 μ g/ml, numbering 7=7.81 μ g/ml, numbering 8=3.91 μ g/ml.Cultivate 16h.
In above example, the measurement result of the aqueous solution pliability of the soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent of gained as shown in Figure 4, along with the increase of finishing agent mass concentration, the hard and soft degree of fabric reduces thereupon, shows that the softness of finish fabric improves.Quaternized degree is higher, and fabric becomes more and more submissiveer.This is because increasing along with finishing agent, the quaternary ammonium salt be gathered on fabric gets more and more, and the film continuity that fiber is formed also is become better and better, and shows as flexibility good.After the amount of finishing agent arrives certain concentration, the continuity of film is stable, and the impact of concentration on flexibility diminishes.Therefore the finishing agent mass concentration of optimum is 0.5%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (4)

1. a soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent, is characterized in that its structural formula is as follows:
r in formula 1for N or r 2for N or r 3for N or r 4for N or r 5for N or r 6for N or and R 1, R 2, R 3, R 4, R 5, R 6having one at least is
2. a preparation method for soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent as claimed in claim 1, is characterized in that comprising the steps:
Step one: add 4 in the reactor, 4'-diaminodiphenylmethane four glycidyl amine (AG80) and diethanol amine, at 50-100 DEG C of temperature, the reaction time is 3-8h, final synthesis modification AG80, obtains pure modification AG80 after the operation such as decompression distillation, drying;
Step 2: modification AG80 step one obtained and chloro-hexadecane join in reactor after being fully dissolved in solvent, at 50-100 DEG C of temperature, obtain crude product after reactant is reacted 10-20h among reactor, then after purification processes, obtain end product soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent.
3. the preparation method of soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent as claimed in claim 2, is characterized in that: AG80 described in described step one and described diethanol amine amount of substance are than being 1:(4 ~ 6.5); The amount of substance ratio of modification AG80 and described chloro-hexadecane described in described step 2 is: 1:n (n=1 ~ 13).
4. the preparation method of soft Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent as claimed in claim 2, is characterized in that: the solvent in step 2 is N-N dimethyl formamide, butanone, butyl acetate, methylisobutylketone, dioxane, dimethyl formamide.
CN201510404713.9A 2015-07-10 2015-07-10 A kind of softness Synergistic antimicrobial brush-type multi-quaternary ammonium salt fabric finishing agent and preparation method thereof Active CN104928919B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107057897A (en) * 2017-03-13 2017-08-18 广州泰成生化科技有限公司 A kind of new situ cleaning agent and preparation method thereof

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WO2006115547A2 (en) * 2005-04-20 2006-11-02 Dendritic Nanotechnologies, Inc. Dendritic polymers with enhanced amplification and interior functionality
CN1946772A (en) * 2004-04-20 2007-04-11 德瑞迪克纳米科技公司 Dendritic polymers with enhanced amplification and interior functionality
CN101029113A (en) * 2007-02-28 2007-09-05 中山大学 Reactive polymer antibacterial agent, its production and use
CN103382157A (en) * 2013-08-13 2013-11-06 佛山市日丰企业有限公司 Process for preparing hexadecyl methyl 2-hydroxyethyl ammonium bromide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1946772A (en) * 2004-04-20 2007-04-11 德瑞迪克纳米科技公司 Dendritic polymers with enhanced amplification and interior functionality
WO2006115547A2 (en) * 2005-04-20 2006-11-02 Dendritic Nanotechnologies, Inc. Dendritic polymers with enhanced amplification and interior functionality
CN101029113A (en) * 2007-02-28 2007-09-05 中山大学 Reactive polymer antibacterial agent, its production and use
CN103382157A (en) * 2013-08-13 2013-11-06 佛山市日丰企业有限公司 Process for preparing hexadecyl methyl 2-hydroxyethyl ammonium bromide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107057897A (en) * 2017-03-13 2017-08-18 广州泰成生化科技有限公司 A kind of new situ cleaning agent and preparation method thereof

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