CN100552125C - A kind of response type ultraviolet absorption agent and synthetic intermediate thereof and application - Google Patents

A kind of response type ultraviolet absorption agent and synthetic intermediate thereof and application Download PDF

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CN100552125C
CN100552125C CNB2006100479261A CN200610047926A CN100552125C CN 100552125 C CN100552125 C CN 100552125C CN B2006100479261 A CNB2006100479261 A CN B2006100479261A CN 200610047926 A CN200610047926 A CN 200610047926A CN 100552125 C CN100552125 C CN 100552125C
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response type
ultraviolet absorber
alkyl
absorption agent
ultraviolet absorption
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马疆
王东
刘深
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XINJI CHEMISTRY CO Ltd SHENYANG
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Abstract

The present invention relates to a kind of novel ultraviolet absorber that is used for the response type of COTTON FABRIC arrangement, its general structure is shown in structural formula (1): wherein: A is a quaternary ammonium salt group, and B is an aromatic amine compound.Its structure of response type ultraviolet absorption agent of the present invention is similar to REACTIVE DYES, therefore can carry out anti UV finishing to COTTON FABRIC according to the technique for applying of traditional REACTIVE DYES.In application process, under the condition of salt-free alkali-free, dye-uptake can reach more than 70%.Fabric after the arrangement has good washability.The aqueous solution of ultraviolet absorber is to staphylococcus aureus and Escherichia coli being the gram-positive bacteria of representative and Gram-negative bacteria is killed or inhibitory action.

Description

A kind of response type ultraviolet absorption agent and synthetic intermediate thereof and application
Technical field
The present invention relates to response type ultraviolet absorption agent, specifically is a kind of triazines ultraviolet absorber and synthetic intermediate and application that contains the response type of quaternary ammonium salt group.
Background technology
Entered since 20th century, a large amount of uses along with carbon fluorine series solvent and fluorine Lyons, a large amount of halide is trapped in the air sky, formed active halogen by ultraviolet light degradation, they so chain reaction takes place with ozone, cause the atmospheric ozone layer heavy damage, the ultraviolet ray that arrives ground is increased thereupon, the influence that the mankind are produced obviously increases.Because the minimizing of ozone layer concentration, the short wavelength ultraviolet that is radiated ground in the sunshine increases.Torrid areas particularly, solar radiation power is strong, if fabric is thin, then ultraviolet ray makes skin produce color spot, and may bring out canceration.Since the seventies, the report that white people residential areas such as Australia, the U.S., Canada, Europe have the cutaneum carcinoma incidence of disease to increase progressively in succession.
Wear very little clothes summer, and ultraviolet radiation sees through easily and makes the excessive ultraviolet ray irradiation of human body acceptance cause skin injury, even produce cutaneum carcinoma.As COTTON FABRIC, good permeability strong, the no static, comfortable and easy to wear of one of the most frequently used lining in summer, favored deeply with its hygroscopicity.But it is compared with other textile materials, and ultraviolet ray transmissivity is higher, the ultraviolet radiation preventing poor-performing, and on the market anti UV finishing agent at present is not because possess reactive functional groups, the fastness of arrangement back fabric is not very good.Therefore, exploitation is a kind of is applicable to that the anti UV finishing agent of COTTON FABRIC is very significant.
Summary of the invention
The object of the present invention is to provide a kind of triazines ultraviolet absorber and synthetic intermediate and application that contains the response type of quaternary ammonium salt group.The present invention is a parent with three polychlorostyrene piperazines, and quaternary ammonium salt is building up on the triazine parent, has obtained the ultraviolet absorber of response type; Because the existence of quaternary ammonium salt structure when the ultraviolet absorber of gained has uvioresistant performance, has also possessed antibacterial functions.
The present invention relates to a kind of response type ultraviolet absorption agent, its general structure as the formula (1):
Figure C20061004792600041
Wherein: A is a quaternary ammonium salt group, and structure is:
Wherein X is a halogen, and R is contraposition, meta-substituent.
Figure C20061004792600043
N1=1-4 wherein, n2=0-17;
Perhaps
Figure C20061004792600051
N1 wherein, n2 is the same.
Described group B structure is:
Figure C20061004792600052
Wherein: R 1Be H, R 2Be C 1-C 4Alkyl ,-CH 2CH 2SO 2CH 2CH 2OSO 3M, M are H, Li, Na, K; Perhaps R 1Be C 1-C 4Alkyl, R 2Be C 1-C 4Alkyl;
Perhaps be:
Figure C20061004792600053
R wherein 3Be H, Li, Na, K, C 1-C 8Alkyl;
Perhaps be:
R wherein 4Be C 1-C 4Alkyl;
Perhaps be:
Figure C20061004792600055
Wherein M is the same.
Described ultraviolet absorber can prepare according to the following procedure:
(1) the nitro thing is synthetic: 1-(end position halogen-alkoxyl)-4-nitrobenzene 5g is added in the reactor, add the tertiary amine 3g or the 3g above (tertiary amine double as reaction dissolvent) of group A part, 20～80 ℃ of reaction 2～18h; Adopt cyclohexane or n-hexane washing crude product, obtain the nitro thing;
(2) the amido thing is synthetic: nitro thing 7g, be dissolved in 30～150ml absolute ethyl alcohol, and it is in 36% concentrated hydrochloric acid that 8.5～30g stannous chloride is dissolved in 9～35g weight concentration, above-mentioned solution is under agitation dropped in the ethanolic solution of nitro thing, after 20～70 ℃ reaction 4～20h reaction finishes down, reduce to room temperature, add the 30%NaOH aqueous solution, transferring PH is 8～10, filters, and filtrate decompression obtains crude product, add anhydrous alcohol solution again, leach undissolved salt, ethanol is removed in decompression, obtains the amido thing.
(3) ultraviolet absorber is synthetic
Stir down and add three polychlorostyrene piperazine 0.4g in frozen water, group B 0.2～0.8g is added in the reactor, controlling reaction system PH with 10% sodium carbonate in the course of reaction is 6～7, react 2～4h down at 0～5 ℃, one contracts after reaction finishes, the aqueous solution of the amido thing of group A0.2～0.9g is added dropwise in the reaction system, and the PH of reaction system is 7～7.5, at 30～60 ℃ of reaction 4～10h down.After reaction finishes, filter, obtain crude product.Crude product adds the methyl alcohol dissolving, leaches insoluble matter, and decompression steams methyl alcohol, obtains ultraviolet absorber.
Described response type ultraviolet absorption agent is mainly used in the anti UV finishing of COTTON FABRIC.Its structure of response type ultraviolet absorption agent of the present invention is similar to REACTIVE DYES, therefore can carry out anti UV finishing to COTTON FABRIC according to the technique for applying of traditional REACTIVE DYES.In application process, under the condition of salt-free alkali-free, dye-uptake can reach more than 70%.Fabric after the arrangement has good washability.
The present invention has following advantage:
(1) ultraviolet absorber that the present invention relates to has the response type group in its structure, can combine with chemical bond with COTTON FABRIC, fabric fastness after the arrangement is good, have good water-wash resistance, after through the washing more than 30 times, anti-ultraviolet effect does not almost change.
(2) uvioresistant is effective after the textile finishing.When the response type ultraviolet absorption agent that the present invention relates to was used, use amount was 0.5% (o.w.f.), and TUV-B is 1.2%.
(3) technique for applying is simple.The technique for applying of the response type ultraviolet absorber that the present invention relates to can carry out anti UV finishing to cotton under the condition of salt-free alkali-free.
(4) the response type ultraviolet absorber that the present invention relates to has the anti-microbial property of wide spectrum.The aqueous solution of ultraviolet absorber is the gram-positive bacteria of representative and Gram-negative bacteria is killed or inhibitory action to staphylococcus aureus and Escherichia coli.
Description of drawings
Fig. 1 is the ultraviolet permeability schematic diagram of response type ultraviolet absorption agent arrangement back cotton.
The specific embodiment
Embodiment 1
Figure C20061004792600061
Preparation.
Synthetic route:
Figure C20061004792600071
Synthesizing of intermediate 1: p-nitrophenol 20g, NaOH 6g and water 200ml are added in the 500ml four-hole bottle, be heated to dissolving, add Bromofume 150g, TBAB 1g, 90 ℃ are reacted 12h down, after reaction finished, decompression removed and anhydrates and Bromofume, uses the hot ethanol dissolved residue, remove puzzled salt, cooling, product is separated out from ethanol, obtains the 28.3g product; Yield: 82%.The product fusing point is 64 ℃, and it is a target product;
Synthesizing of intermediate 2: with 8g intermediate 1 and 80mlNN-dimethyl lauryl amine, 60 ℃ are reacted 41h down, wash crude product with cyclohexane, obtain, and obtain product 14.17g intermediate 2, yield 95%;
Intermediate 2 structures are determined:
MP：105-106℃；
IR(KBr，cm -1)：2920，2840(CH 3(CH 2) 10CH 2-)；1510，1340(-NO 2)；1250，1050(Ar-O-CH 3)；860(C-NO 2)；
1H-NMR(300MHz，CDCl 3，δ)：0.857-0.902(t，3H)，1.255(br.s，16H)，1.384(br.s，2H)，1.842(br.s，2H)，3.524(s，6H)，3.624(br.s，2H)，4.328(br.s，2H)，4.742(br.s，2H)，7.078-7.105(d，2H)，8.192-8.219(d，2H)；
ESI-MS(m/z，M +-Br+H)：380.4。
Synthesizing of intermediate 3: 9g intermediate 2 is dissolved in the 60ml absolute ethyl alcohol, and stirring adds low-grade fever to dissolving, with 14.795g SnCl 22H 2O is dissolved in the 14.6ml concentrated hydrochloric acid, drops in the reactor, and 60 ℃ are reacted 46h down, after reaction finishes, reduce to room temperature, reactant liquor filters with in 40% the sodium hydrate aqueous solution and about pH=8, filtrate decompression obtains crude product, add anhydrous alcohol solution again, the undissolved salt of filtering, decompression removes in ethanol, obtain the 6.1g product, yield 73%;
Intermediate 3 structures are determined:
MP：79-82℃；
IR(KBr，cm -1)：3320，3200，1590(-NH 2)；2920，2830CH 3(CH 2) 10CH 2-)；1230，1060(Ar-O-CH 3)；
1H-NMR(300MHz，CDCl 3，δ)：0.856-0.900(t，3H)，1.248(br.s，16H)，1.332(br.s，2H)，1.793(br.s，2H)，3.434(s，6H)，3.544(br.s，2H)，4.202(br.s，2H)，4.324(br.s，2H)，6.635-6.679(m，4H)；
ESI-MS(m/z，M +-Br+H)：350.3。
Synthesizing of ultraviolet absorber 4: 15ml water places reactor, and three polychlorostyrene piperazine 0.371g (2.0mmol) are dissolved in the 10ml acetone, adds in the reactor, stirs.To be dissolved in the acetone amido benzoyl methylamine 0.300g (2.0mmol), this solution of dropping is transferred pH=6.5-7 with 10% aqueous sodium carbonate simultaneously in reactor, and 50min adds, and is reflected at 10 ℃ of reaction 3h down, and one contracts reacts end.0.858g intermediate 3 is soluble in water, in anti-device, drip this aqueous solution, transfer pH=7.5 with 10% aqueous sodium carbonate, be warming up to about 50 ℃ reaction 5h simultaneously.Reaction leaches solid after finishing, and solid is through washing, and cyclohexane is washed, and obtains the 1.135g product.Yield 82%;
The total recovery of ultraviolet absorber 4: 47%.
MP：158-160℃；
IR(KBr，cm -1)：3415(ArNH-)；3415，3270(ArCONH-)；2923，2852(CH 3(CH 2) 12CH 2-)；1612，1569，1307(ArCONH)；1060，1232(Ar-O-R)。
1H-NMR(300MHz，DMSO，δ)：0.806-0.849(t，3H)，1.181-1.263(d，18H)，1.720(s，2H)，2.820(s，3H)，3.210(s，6H)，3.426(s，2H)，3.835(s，2H)，4.366-4.533(d，2H)，7.071(s，2H)，7.611-7.793(d，2H)，7.864-7.883(d，2H)，7.911-7.974(d，2H)，10.193-10.397(d，1H)；
ESI-MS(m/z，[M-Br -] +)：610.5。
Embodiment 2
Figure C20061004792600081
Intermediate 1,2 and 3 syntheticly see embodiment 1;
Synthesizing of ultraviolet absorber 5: 15ml water places reactor, and three polychlorostyrene piperazine 0.371g (2.0mmol) are dissolved in the 10ml acetone, adds in the reactor, stirs.Adjacent amido benzoic acid 0.277g (2.0mmol) is soluble in water, add 10%NaCO 3Accent PH=7-8 drops to the sodium salt solution for preparing in the reactor, transfers pH=6.5-7 with 10% aqueous sodium carbonate simultaneously, and 1h adds, and is reflected at 10 ℃ of reaction 2.5h down, and one contracts reacts end.0.858g intermediate 3 is soluble in water, in anti-device, drip this aqueous solution, transfer pH=7.5 with 10% aqueous sodium carbonate, be warming up to about 50 ℃ reaction 4h simultaneously.Reaction is saltoutd with sodium chloride after finishing, and leaches precipitation, with saturated normal saline washing, obtains 1.205g after the drying, yield 86%.
The total recovery of ultraviolet absorber 5: 49%;
MP：164-166℃；
IR(KBr，cm -1)：3452(ArNH-)，2927，2852(CH 3(CH 2) 12CH 2-)；1608，1421(ArCOONa)；1232，1062(Ar-O-R)。
1H-NMR(300MHz，DMSO+(CF 3CO) 2O，δ)：0.853-0.864(d，3H)，1.196-1.329(t，18H)，1.759(s，2H)，3.179(s，6H)，3.415(s，2.H)，3.818-3.891(d，2H)，4.386-4.499(d，2H)，7.035-7.054(d，2H)，7.085-7.200(m，1H)，7.407-7.460(m，1H)，7.595-7.624(d，2H)，7.801-8.078(m，2H)；
ESI-MS(m/z，[M-Br --Na ++H +])：597.5。
Embodiment 3
Figure C20061004792600091
Intermediate 1,2 and 3 syntheticly see embodiment 1;
Synthesizing of ultraviolet absorber 6: 15ml water places reactor, and three polychlorostyrene piperazine 0.371g (2.0mmol) are dissolved in the 10ml acetone, adds in the reactor, stirs.Amido benzoyl dimethylamine 0.328g (2.0mmol) is dissolved in the acetone, drops in the reactor, transfer pH=6.5-7 with 10% aqueous sodium carbonate simultaneously, 1h adds, and is reflected at 10 ℃ of reaction 3h down, and one contracts reacts end.0.858g intermediate 3 is soluble in water, in anti-device, drip this aqueous solution, transfer pH=7.5 with 10% aqueous sodium carbonate, be warming up to about 50 ℃ reaction 5.5h simultaneously.Reaction leaches solid after finishing, and solid is through washing, and cyclohexane is washed, and obtains the 1.140g product, yield 81%.
The total recovery of ultraviolet absorber 6: 46%.
MP：＞250℃；
IR(KBr，cm -1)：3452(ArNH-)；2952，2852(CH 3(CH 2) 12CH 2-)，1620，1560，1303(ArCONR)；1236，1058(Ar-O-R)；
1H-NMR(300MHz，DMSO，δ)：0.817-0.854(t，3H)，1.158-1.281(t，18H)，1.711(s，2H)，2.962(s，6H)，3.130(s，6H)，3.334(s，2H)，3.752(s，2H)，4.426(s，2H)，6.951-6.979(d，2H)，7.330-7.405(m，1H)，7.443-7.473(d，2H)，7.662-7.691(d，2H)，7.672-7.884(m，1H)；
ESI-MS(m/z，[M-Br -])＝624.8。
Embodiment 4
Figure C20061004792600101
Intermediate 1,2 and 3 syntheticly see embodiment 1;
Synthesizing of ultraviolet absorber 7: 15ml water places reactor, and three polychlorostyrene piperazine 0.371g (2.0mmol) are dissolved in the 10ml acetone, adds in the reactor, stirs.Contraposition fat 0.748g (2.0mmol) adds to above-mentioned drips of solution in the reactor with 10% aqueous sodium carbonate accent pH=7-7.5, transfers pH=6.5-7 with 10% aqueous sodium carbonate simultaneously, adds about 1h, is reflected at 10 ℃ of reaction 3.5h down, and one contracts reacts end.0.858g intermediate 3 is soluble in water, in anti-device, drip this aqueous solution, transfer pH=7.5 with 10% aqueous sodium carbonate, be warming up to about 50 ℃ reaction 6h simultaneously.Reaction is saltoutd with sodium chloride after finishing, and leaches precipitation, with saturated normal saline washing, obtains the 1.573g product after the drying, yield 86%.
The total recovery 49% of ultraviolet absorber 7.
MP：154-157℃；
IR(KBr，cm -1)：3434(ArNH-)；2923，2852(CH 3(CH 2) 12CH 2-)，1612，1571，1294(ArCONH)；1294，1124(RSO 2R)，1230，1049(Ar-O-R)；
1H-NMR(300MHz，DMSO，δ)：0.821-0.845(t，3H)，1.230(s，18H)，1.700(s，2H)，3.138(s，6H)，3.394-3.414(2H)，3.451-3.527(t，2H)，3.598(s，2H)，3.658(s，2H)，3.796(s，2H)，4.062-4.082(t，2H)，4.439(s，2H)，6.987-7.012(d，2H)，7.471-7.603(d，2H)，7.727-7.753(d，2H)，7.800-7.857(d，2H)；
ESI-MS(m/z，[M-H-OSO 3Na-Br -])＝714.6
The dyeing of embodiment 5 response type ultraviolet absorption agents:
This response type ultraviolet absorption agent has reactive group, can carry out anti UV finishing to COTTON FABRIC.
Finishing technique: ultraviolet absorber 4 consumptions 0.5% (o.w.f.), bath raio: 1: 40, inhale color temperature: 40 ℃, color fixing temperature: 90 ℃.
Cotton boils 15min through boiling water before arrangement, ultraviolet absorber and cotton are joined in the dye bath, after inhaling look 15min under 40 ℃, is warming up to 90 ℃, and fixation 30min under this temperature after fixation finishes, takes out cotton, cleans with clear water, dries down for 60 ℃.
The water-wash resistance experiment: bath raio is 1: 100, room temperature, and standard soap powder 1g/L, the time 10min that soaps, clear water wash 3 times, and strand is done.
Cotton test after the arrangement: ultraviolet-uisible spectrophotometer: Lamda 900 (Labsphere integrating sphere)
Finishing effect as shown in Figure 1, as can be seen, cotton is after response type ultraviolet absorption agent arrangement, ultraviolet permeability obviously descends, and the capable good water-wash resistance of tool, after through the washing more than 30 times, anti-ultraviolet effect does not almost change.
The anti-microbial property test of the example 6 ultraviolet absorber aqueous solution:
The anti-microbial property test of the ultraviolet absorber aqueous solution: adopt minimal inhibitory concentration method (MIC).
Test bacterial classification: staphylococcus aureus (S.aureus) and Escherichia coli (E.coli).
Method: with 1ml 10 6～10 7The bacteria suspension of CFU/ml joins mixing in the ultraviolet absorber solution of 9ml variable concentrations successively.After 24 hours, take out the 100ul bacteria suspension successively, and rare with aseptic distilled water to 100ml.Therefrom take out 100ul and drop on the nutrient agar, cultivated 24 hours down for 37 ℃.Replace ultraviolet absorber solution to repeat top-operation with distilled water.
Evaluation criteria: with no bacterial growth is benchmark.
The minimal inhibitory concentration of three kinds of ultraviolet absorber aqueous solution of table 1
MIC(ppm) Ultraviolet absorber 4 Ultraviolet absorber 5 Ultraviolet absorber 6 Ultraviolet absorber 7
S.aureus 100 2000 250 250
E.coli 100 2000 250 250

Claims (4)

1. response type ultraviolet absorption agent is characterized in that: its general structure shown in (1),
Figure C2006100479260002C1
Wherein A is a quaternary ammonium salt group, and structure is:
Figure C2006100479260002C2
Wherein X is a halogen; R be between the position or para-orientating group;
Figure C2006100479260002C3
N1=1-4 wherein, n2=0-17;
Figure C2006100479260002C4
Perhaps
N1 wherein, n2 is the same;
Described group B structure is:
Wherein: R 1Be H, R 2Be C 1-C 4Alkyl or-CH 2CH 2SO 2CH 2CH 2OSO 3M, M are H, Li, Na or K; Perhaps R 1Be C 1-C 4Alkyl, R 2Be C 1-C 4Alkyl;
Perhaps be:
Figure C2006100479260002C6
R wherein 3Be H, Li, Na, K or C 1-C 8Alkyl;
Perhaps be:
R wherein 4Be C 1-C 4Alkyl;
Perhaps be:
Wherein M is the same.
2. according to the described response type ultraviolet absorption agent of claim 1, it is characterized in that: its general structure is as follows,
Figure C2006100479260003C1
Wherein: R 1Be H, R 2Be C 1-C 4Alkyl or-CH 2CH 2SO 2CH 2CH 2OSO 3M, M are H, Li, Na or K; Perhaps R 1Be C 1-C 4Alkyl, R 2Be C 1-C 4Alkyl.
3. according to the described response type ultraviolet absorption agent of claim 1, it is characterized in that: its general structure is as follows,
Wherein: R 1Be H, R 2Be C 1-C 4Alkyl or-CH 2CH 2SO 2CH 2CH 2OSO 3M, M are H, Li, Na or K; Perhaps R 1Be C 1-C 4Alkyl, R 2Be C 1-C 4Alkyl.
4. the application of the described response type ultraviolet absorption agent of claim 1 is characterized in that: described ultraviolet absorber is used as finishing agent, is mainly used to the anti UV finishing to COTTON FABRIC.
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