CN1212325C - Production of quaternary containing fluoro chains structure and uses thereof - Google Patents
Production of quaternary containing fluoro chains structure and uses thereof Download PDFInfo
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- CN1212325C CN1212325C CN 03129038 CN03129038A CN1212325C CN 1212325 C CN1212325 C CN 1212325C CN 03129038 CN03129038 CN 03129038 CN 03129038 A CN03129038 A CN 03129038A CN 1212325 C CN1212325 C CN 1212325C
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Abstract
The present invention discloses a method for preparing quaternary ammonium salt containing a fluoro chain structure and an application thereof. The cotton fabric treated by the quaternary ammonium salt of the present invention simultaneously has hydrophobicity and antibacterial performance. The cotton fabric can be endowed with multiple performance by a dressing agent, the problems of compounding and compatibility brought by using multiple dressing agents can be avoided, and the processing process is simple. The hydrophobicity and antibacterial performance provided by the dressing agent make the dressing agent have great development potential in the certain fields such as cotton fabric for hospital. The quaternary ammonium salt containing a fluoro chain structure of the present invention is a compound containing the general formula of the structure.
Description
Technical field
The present invention relates to quaternary ammonium salt, manufacture method of fluorine chain structure and uses thereof.Specifically, relate to a class and have multi-functional fluorine-containing quaternary ammonium salt, manufacture method and uses thereof such as broad spectrum antibacterial, water and oil repellant and easy soil release characteristics.
Background technology
Find that from nineteen thirty-five Domark chlorination benzal hemlock has intensive microorganism killing activity, opened up cats product thus as since the research field of antiseptic-germicide, the quaternaries cation antiseptic-germicide is efficient because of having, fast, wide spectrum, low toxicity, lowly stimulate, readily biodegradable, and with advantages such as other tensio-active agent compatibleness are good, various fields (Chen Yongjun etc. such as health care, oilfield exploitation, water treatment, foodstuffs industry, agricultural and daily life have been widely used in, refining of petroleum and chemical industry, 1997,28 (1), 56).On the other hand, because not only hydrophobic but also oleophobic of fluorocarbon chain, and very weak interaction makes fluorocarbon surfactant present very high surfactivity in water between the fluorocarbon chain, promptly low-down surface tension.The surface tension of fluorocarbon surfactant in the aqueous solution of very low concentration of a lot of different structures can reach 15～16mN/m.This is the inaccessiable surfactivitys of other any non-fluorine surfactants.Because of its these above-mentioned advantages, fluorocarbon surfactant is widely used in fields such as medical treatment, oil, weaving, glass material, give material low surface energy, reduce surface tension, play effect (Ceng Yuhua, fluorocarbon surfactant, Chemical Industry Press such as water and oil repellant anti-soil, 2001,158).But at some specific areas, only give the material anti-microbial property or the water and oil repellant performance is not enough, sometimes employed material is strict with all having aspect water and oil repellant anti-soil and the anti-microbial property.Such as the medical worker wears protection clothes in Operation theatre, prevents that bacterium from infecting on one's body the medical worker from patient on one's body, and the medical worker may contact blood or be implied with the body fluid of the pathogenic agent that blood carries in surgical procedures simultaneously.Therefore, medical clothes and patient's strqw cover should possess liquid repellent performance and anti-microbial property.At present, generally be respectively material to be carried out the modification arrangement, to obtain to possess the material of liquid repellent and antibiotic two kinds of performances by antibiotic and two kinds of finishing compositions of water and oil repellant anti-soil.Improve the cost of product so greatly, and can bring the compatibility issue between the finishing composition.
Summary of the invention
The technical issues that need to address of the present invention are at the existing shortcoming of above-mentioned technology, and a quaternary ammonium salt that has the good fluorine-containing chain structure of broad spectrum antibacterial and water and oil repellant antifouling property roughly the same the time is provided.
Another technical problem that the present invention need solve provides the manufacture method of all good multi-functional quaternary ammonium salt of above-mentioned various characteristics.
Another technical problem that the present invention need solve provide all good multi-functional quaternary ammonium salt of fluorine-containing chain structure of above-mentioned various characteristics as surface modification reagent, especially for the application of the multifunctional finishing auxiliary of fabric in the textile industry.
The quaternary ammonium salt of the fluorine-containing chain structure of the present invention is the compound with one of following general structure:
General formula 1: fluorine-containing chain and diallyl structure quaternary ammonium salt:
Wherein, n=2～10;
Y comprises the alkane chain, contains ether, the segment of thioether group, carbonyl, ester group, amide group, alkenyl or alkynyl etc.; Preferred Y is the alkane chain, contain the segment of ether, ester group;
X comprises Cl, Br or I;
R comprises C
1～C
18Alkyl, contain substituting group or do not contain substituent aromatic group or the trimethoxy alkyl silane in a kind of, trimethoxy alkyl silane general structure is:
(MO)
3Si (CH
2) r, r=1～8, preferred L is methyl or ethyl; Preferred R is methyl, trimethoxy propyl silane base.
Bibliographical information is arranged, and on the N atom, the introducing of undersaturated alkane chain can improve the anti-microbial activity of its quaternary ammonium salt greatly.
General formula 2: fluorine-containing chain and heterocycle structure quaternary ammonium salt:
Wherein, n=2～10;
R-Ar
N+-Y-(CF
2)nF X
-
Ar
N+Represent nitrogen heterocyclic rings such as imidazoles, pyridine;
R represents C
1～C
18The alkane chain or contain substituting group or do not contain substituent aromatic group or the trimethoxy alkyl silane, trimethoxy alkyl silane general structure is: (MO)
3Si (CH
2) r, r=3-8; M is the same; Preferred R is trimethoxy propyl silane base or trimethoxy ethylsilane base;
Segments such as Y represents the alkane chain, contains ether, thioether group, carbonyl, ester group, amide group, alkenyl or alkynyl; Preferred Y is the alkane chain, contain the segment of ether, ester group;
X represents Cl, Br, I.
The quaternary ammonium salt of preferred fluorine-containing chain structure comprises:
The preparation method of the quaternary ammonium salt of fluorine-containing chain of the present invention and diallyl structure comprises the steps:
(1) p-methyl benzenesulfonic acid ester cpds 1 is being contained K
2CO
3Solvent in carry out the N alkylated reaction with diallyl amine, back flow reaction 15～30h, preferred 24h obtains the important tertiary amine intermediate that contains the diallyl structure 2;
Said solvent should be selected the bigger solvent of specific inductivity, preferred acetonitrile or Nitromethane 99Min., and its reaction yield is higher.
Said p-methyl benzenesulfonic acid ester cpds 1 can adopt document: (J.Org.Chem.64 (1999) 4969) disclosed method is prepared.
(2) intermediate 2 carries out quaterisation with haloalkane, promptly obtains the fluorine-containing chain and the diallyl structure quaternary ammonium salt of general formula 1.Reaction times is 2～96 hours, and temperature of reaction is 25～90 ℃; Solvent selects specific inductivity bigger, and preferred solvent is Nitromethane 99Min., acetonitrile etc.
Its reaction expression is:
R, X, Y, n are same as above.
The preparation method of fluorine-containing chain of the present invention and heterocycle structure quaternary ammonium salt comprises the steps:
(1) adopts the synthetic nitrogenous heterocyclic compound 3 and 4 of document (J.Mater.Chem.12 (2002) 1355-1362) disclosed method earlier.
(2) with the product nitrogen-containing heterocycle compound of step (1), in solvent, carry out quaterisation with fluorine-containing halohydrocarbon again, temperature of reaction is 25～95 ℃, reaction times is 2～96 hours, promptly obtain fluorine-containing chain of the present invention and heterocycle structure quaternary ammonium salt, solvent selects specific inductivity bigger, and preferred solvent is Nitromethane 99Min., acetonitrile etc.
Its reaction expression is:
R, X, Y, n, Ar
N+Same as above.
The quaternary ammonium salt of fluorine-containing chain structure of the present invention can be used for fabric-treating agent, and to prepare the fabric that has liquid repellent performance and anti-microbial property simultaneously, treatment process is similar with (organosilicon material and application 5 (1999) 19-22) document disclosed method, and the present invention repeats no more.
The performance test of the cotton fabric after the textile finishing after adopting following method to quaternary ammonium salt processing of the present invention, the result shows, possess excellent liquid repellent performance and anti-microbial property simultaneously, only need a kind of finishing composition can give fabric multiple performance, saved cost, avoided the compatibility problem that adopts multiple finishing composition and additive to bring, excellent liquid repellent that finishing composition provided and anti-microbial property make it at some specific areas (as hospital's textiles) bigger potentiality to be exploited be arranged.
AATCC 22-1985 method is adopted in the water repellency test.
Refuse oily testing method and adopt AATCC 118-1983 method
Water-wash resistance: method for washing adopts AATCC 124-1984 method
The anti-microbial property test:
Test strain uses streptococcus aureus (ATCC 6538) and intestinal bacteria (8099); The antibacterial tests method adopts bacterium to count assay method (AATCC 100-1988).
Embodiment
Embodiment 1
Press earlier the synthetic fluorine-containing p-toluenesulfonic esters (F (CF2) 8CH2CH2CH2OTs) of the open method of document (J.Org.Chem.64 (1999) 4969).Get its 6.996g (11.1mmol) and diallyl amine 1.451g (14.9mmol) and K
2CO
32.538g (18.4mmol) be added in the 35ml acetonitrile, reflux and stir 24h.TLC follows the tracks of, the most of reaction of raw material, stopped reaction.With solid filtering, be spin-dried for solvent in the filtrate, the resistates silica gel column chromatography, with sherwood oil: it is as follows that ethyl acetate (20: 1) obtains its related data of a colourless transparent liquid 4.14g (productive rate 67%):
1HNMR (300MHz, CDCl
3) δ 1.75 (m, 2H), 2.08 (m, 2H), 2.50 (t, J=6.9Hz, 2H), 3.09 (d, J=6.9Hz, 4H), 5.16 (m, 4H), 5.84 (m, 2H);
19F NMR (282MHz, CDCl
3) δ-80.75 (t, J=9.9Hz 3F) ,-114.16 (m, 2F) ,-121.99--121.94 (m, 6F) ,-122.76 (s, 2F) ,-123.46 (s, 2F) ,-126.12 (s, 2F); IR (thinfilm) 3084,2984,2812,1645,1243,1209,1152,1114,997,923,705,656cm
-1MS m/z 557 (3), and 530 (6), 110 (100), 69 (11), 41 (51). ultimate analysis (W%): molecular formula is C
17H
16F
17The compound 4 theoretical elements (W%) of N are: C, 36.64; H, 2.89; N, 2.51. carries out ultimate analysis, and actual result is as follows: C, 36.57; H, 3.10; N, 2.67%.
Resulting fluorine-containing alkadiene propyl group tertiary amine 1.382g of last step (2.48mmol) and methyl iodide 1.075g (7.60mmol) are positioned in the single port bottle, add the 3ml anhydrous acetonitrile, react 24h down at 60 ℃.TLC follows the tracks of raw material and disappears.Drain solvent and get the thick object of a reddish-brown, after anhydrous diethyl ether washing (5ml * 6), drain ether, blend a pale yellow powder 1.547g (productive rate 89%).Its related data is as follows:
1H NMR (300MHz, CDCl
3) δ 2.18-2.40 (m, 4H), 3.34 (s, 3H), 3.71 (t, J=7.2Hz 2H), 4.30 (d, J=6.9Hz 4H), 5.83 (m, 4H), 6.03 (m, 2H);
19F NMR (282MHz, CDCl
3) δ-79.90 (t, J=9.9Hz 3F) ,-112.64 (m, 2F) ,-120.78--121.08 (m, 6F) ,-121.90 (s, 2F) ,-122.31 (s, 2F) ,-125.32 (s, 2F); IR (KBr) 3005,2974,1478,1253,1204,1153,1116,954,887,703,657cm
-1MS m/z 531 (3M+-I-C
3H
5), 504 (7), 168 (5), 127 (3), 110 (5), 84 (100), 41 (31), 69 (9); Ultimate analysis (W%): molecular formula is C
18H
19F
17The theoretical element of NI compound (W%) is:: C, 30.92; H, 2.74; N, 2.00. carries out ultimate analysis, and actual result is as follows:: C, 31.17; H, 2.74; N, 1.84%.
Containing the fluorine-containing alkadiene propyl group of Trimethoxy silane class quaternary ammonium salt is by fluorine-containing alkadiene propyl group tertiary amine 0.487g (0.874mmol) and trimethoxy (1-iodine propyl group) silane ((CH
3O)
3SiCH
2CH
2CH
2I) 0.485g (1.67mmol) is positioned in the single port bottle, adds the 2ml acetonitrile, reacts 24h down at 60 ℃.TLC follows the tracks of and finds that most of raw material reaction is complete.Drain solvent and get the thick object of a reddish-brown, after anhydrous diethyl ether washing (5ml * 6), drain ether, blend a pale yellow powder 0.488g (productive rate 65%).Its related data is as follows:
1H NMR (300MHz, CDCl
3) δ 0.611 (m, 2H), 1.88 (m, 2H), 2.18-2.40 (m, 4H), 3.57 (s, 9H), 3.68 (t, J=7.2Hz 2H), 4.18 (d, J=6.9Hz 4H), 5.83 (m, 4H), 6.03 (m, 2H);
19F NMR (282MHz, CDCl
3) δ-80.11 (t, J=9.9Hz 3F) ,-113.55 (m, 2F) ,-121.6--122.07 (m, 6F) ,-123.90 (s, 2F) ,-124.51 (s, 2F) ,-125.32 (s, 2F); IR (KBr) 3018,2984,1614,1323,1209,1155,1101,966,894,718,668cm
-1MS m/z 720 (66 M+-I), 516 (11), 168 (2), 127 (4), 110 (10), 84 (100), 41 (70), 69 (9); Ultimate analysis (W%): molecular formula is C
23H
31F
17NO
3The theoretical element of the compound of SiI (W%) is::: C, 32.60; H, 3.69; N, 1.65. carries out ultimate analysis, and actual result is as follows: C, 32.18; H, 3.21; N, 1.39%.
The above-mentioned quaternary ammonium salt that contains iodide ion is soluble in water, add the strong base chlorion resin anion(R.A) of doubling dose, stirring at room is filtered, and lyophilization is removed water, promptly obtains the identical quaternary ammonium salt of chloride ion-containing structure.
Embodiment 2
It is synthetic nitrogenous to press document (J.Mater.Chem.12 (2002) 1355-1362) disclosed method
Heterogeneous ring compound 3 and 4.
The synthetic of fluorine-containing chain and imidazole ring quaternary ammonium salt is with compound 3 2.310g (10.0mmol) and 1-iodo-1H, 1H, 2H, 2H-perfluoro decane (F (CF
2)
8CH
2CH
2I) 5.865g (10.2mmol) is put in the 50ml single port bottle, adds the 10ml anhydrous acetonitrile, reacts 24h down at 80 ℃.TLC follows the tracks of and finds that most of raw material reaction is complete.Drain solvent and get a yellow thick object, after anhydrous diethyl ether washing (10ml * 4), drain ether, it is as follows to obtain its related data of a faint yellow solid 7.412g (productive rate 92%):
1H NMR (300MHz, CDCl
3) δ 0.40-0.48 (m, 2H), 1.67-1.82 (m, 2H), 2.81 (m, 2H), 3.40 (s, 9H), 3.80 (t, J=7.0Hz, 2H), 4.50 (t, 2H), 7.36 (s, 1H), 7.45 (s, 1H), 8.48 (s, 1H);
19F NMR (282MHz, CDCl
3) δ-81.41 (t, J=9.9Hz 3F) ,-113.85 (m, 2F) ,-121.91--122.37 (m, 6F) ,-123.75 (s, 2F) ,-124.59 (s, 2F) ,-125.42 (s, 2F); MS m/z 677 (M
+-I, 100%); Molecular formula is C
19H
23F
17N
2O
3The theoretical element of the compound of SiI (W%) is::: C, 28.34; H, 2.88; N, 3.48. carries out ultimate analysis, and actual result is as follows: C, 28.55; H, 3.18; N, 3.82%.
The synthetic of the quaternary ammonium salt of fluorine-containing chain and pyridine ring is with compound 4 2.440g (10.75mmol) and 1-iodo-1H, 1H, 2H, 2H-perfluoro decane (F (CF
2)
8CH
2CH
2I) 6.011g (10.47mmol) is put in the 50ml single port bottle, adds the 15ml anhydrous acetonitrile, reacts 24h down at 80 ℃.TLC follows the tracks of and finds that most of raw material reaction is complete.Drain solvent and get a yellow thick object, after anhydrous diethyl ether washing (15ml * 6), drain ether, it is as follows to obtain its related data of a faint yellow solid 7.633g (productive rate 91%):
1H NMR (300MHz, CDCl
3) δ 0.86-0.95 (m, 2H), 2.60-2.68 (m, 2H), 2.82 (m, 2H), 3.40 (s, 9H), 4.50 (t, 2H), 7.04-7.07 (m, 2H), 8.39-8.42 (m, 2H);
19F NMR (282MHz, CDCl
3) δ-81.01 (t, J=9.9Hz 3F) ,-113.65 (m, 2F) ,-121.83--122.29 (m, 6F) ,-123.68 (s, 2F) ,-124.47 (s, 2F) ,-125.38 (s, 2F); MS m/z 675 (M
+-I, 100%); Molecular formula is C
20H
22F
17NO
3The theoretical element of the compound of SiI (W%) is::: C, 29.94; H, 2.76; N, 1.75. carries out ultimate analysis, and actual result is as follows: C, 30.22; H, 2.88; N, 1.69%.
Embodiment 3
The synthetic quaternary ammonium salt that embodiment 1 is prepared is used for the finishing functions of fabric, step is as follows: quaternary ammonium salt is made into 1% the aqueous solution, add 0.1% penetrating agent JFC again, fabric two is soaked two roll (liquid carrying rate 80%), preliminary drying (105 ℃, 2 minutes), bake (130 ℃, 4 minutes), washing, oven dry.The The performance test results of the cotton fabric after the arrangement sees Table 1.
Test result is as shown in table 1 below:
Table 1
| Finishing of cotton textiles not | Arrangement back cotton fabric | After putting cotton fabric washing 100 times in order | ||
| Water repellency | 0 | 90 | 85 | |
| The oil repellent energy | 0 | 6 | 5 | |
| Anti-microbial property (%) | Streptococcus aureus | 0 | 99.9 | 98.6 |
| Intestinal bacteria | 0 | 99.9 | 98.3 | |
As can be known from Table 1, the cotton fabric of putting in order not only has good water and oil repellant performance, and has outstanding anti-microbial property.Degradation is considerably less after washing 100 times, illustrates to have extraordinary weather resistance.Because the strong reactivity of siloxane bond makes this finishing composition to carry out modification to multiple material.
Embodiment 4
The quaternary ammonium salt anti-microbial activity is measured
Quaternary ammonium salt antibacterial effect to embodiment 2 is measured.The size of selected MIC (minimal inhibitory concentration μ g/ml) value reflection antibacterial effect, and select for use industrial sterilizing agent domiphen bromide commonly used (chemistry dodecyl dimethyl ethylbenzene oxygen ethyl brometo de amonio by name) to be reference.
Experimental technique is with reference to minimal inhibitory concentration determination test (nutrient broth dilution method) in " disinfection technology standard 2002 editions " of Ministry of Health of the People's Republic of China's promulgation.With the fungistat mixed dissolution of different concns in nutrient broth medium, by bacterial growth whether inoculated bacteria then, determines that antiseptic-germicide suppresses to be tried the minimum concentration of bacteria growing, be minimal inhibitory concentration (MinimalInhibitory Concentration, MIC).
The bacterium of being tried that experiment is selected for use is: intestinal bacteria (8099) (Gram-negative bacteria) and streptococcus aureus (ATCC 6538) (gram-positive microorganism)
Selected antiseptic-germicide structure to be measured is as follows:
Anti-bacteria test result is as shown in table 2:
Table 2
| Antiseptic-germicide to be measured | Minimal inhibitory concentration (MIC, μ g/ml) | |
| Intestinal bacteria | Streptococcus aureus | |
| Domiphen bromide | 25 | 1.0 |
| a | 7.8 | 7.8 |
| b | 8.0 | 4.0 |
| c | 1.6 | 1.8 |
| d | 1.2 | 1.2 |
Claims (6)
1. the quaternary ammonium salt of a fluorine-containing chain structure is characterized in that, for having the compound of following general structure:
Wherein, n=2～10;
Y is the alkane chain;
X comprises Cl, Br or I;
R is the trimethoxy alkyl silane, and trimethoxy alkyl silane general structure is: (MO)
3Si (CH
2) r, r=1～8, M is methyl or ethyl.
2. the quaternary ammonium salt of fluorine-containing chain structure according to claim 1 is characterized in that, R is trimethoxy propyl silane base or trimethoxy ethylsilane base.
3. the quaternary ammonium salt of fluorine-containing chain structure according to claim 1 is characterized in that, the quaternary ammonium salt of fluorine-containing chain structure is:
4. according to the preparation method of the quaternary ammonium salt of each described fluorine-containing chain structure of claim 1～3, it is characterized in that, comprise the steps:
(1) the p-methyl benzenesulfonic acid ester cpds is being contained K
2CO
3Solvent in carry out the N alkylated reaction with diallyl amine, back flow reaction 15～30h obtains containing the tertiary amine intermediate of diallyl structure;
(2) intermediate and haloalkane carry out quaterisation, promptly obtain the quaternary ammonium salt of fluorine-containing chain structure, and the reaction times is 2～96 hours, and temperature of reaction is 25～90 ℃.
5. the preparation method of the quaternary ammonium salt of fluorine-containing chain structure according to claim 4 is characterized in that, said solvent is selected from acetonitrile or Nitromethane 99Min..
6. according to the application of the quaternary ammonium salt of each described fluorine-containing chain structure of claim 1～3, it is characterized in that, be used to prepare the treatment agent of the fabric that has liquid repellent performance and anti-microbial property simultaneously.
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|---|---|---|---|
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| CN100376550C (en) * | 2006-09-28 | 2008-03-26 | 四川大学 | Quaternary bis-ammonium salt diamine fluoride and preparation method thereof |
| CN103572594A (en) * | 2013-11-20 | 2014-02-12 | 苏州大学 | Antibacterial agent containing fluorinated alkyl quaternary ammonium salt, and preparation method and application of antibacterial agent |
| WO2017144180A1 (en) * | 2016-02-25 | 2017-08-31 | Universität Innsbruck | Crosslinkable composition and method for producing a coated article |
| CN113683536B (en) * | 2021-08-19 | 2023-01-13 | 浙江三元纺织有限公司 | Preparation of betaine type quaternary ammonium salt antibacterial agent and method for applying same to fabric finishing |
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