CN106631884B - A kind of quaternized Schiff Base Metal Complex, preparation method and application - Google Patents
A kind of quaternized Schiff Base Metal Complex, preparation method and application Download PDFInfo
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- CN106631884B CN106631884B CN201611268613.9A CN201611268613A CN106631884B CN 106631884 B CN106631884 B CN 106631884B CN 201611268613 A CN201611268613 A CN 201611268613A CN 106631884 B CN106631884 B CN 106631884B
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- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
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- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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Abstract
The invention discloses a kind of quaternized Schiff Base Metal Complexes, preparation method and application.Epoxychloropropane is reacted under conditions of sodium hydroxide is catalyst with pentaerythrite, obtains a kind of quaternizing agent TMPT；Quaternizing agent TMPT and 4- (lignocaine) salicylide is reacted after obtaining quaternized 4- (lignocaine) salicylide, quaternized 4- (lignocaine) salicylide and silk amino acid are reacted again, obtain quaternized amino Schiff base ligand, ligand compound is carried out using metal salt and ligand, obtains quaternized Schiff Base Metal Complex.Quaternized Schiff Base Metal Complex provided by the invention not only has preferable water solubility, but also can significantly improve the bleaching power of hydrogen peroxide, can be used for low temperature hydrogen peroxide bleaching fabric.
Description
Technical field
The present invention relates to textile auxiliary's synthesis technical fields, and in particular to a kind of quaternized amino Schiff base gold
Metal complex, preparation method and applications.
Background technique
Fabric bleaching is usually to carry out under high temperature basic conditions at present, and a large amount of water and the energy is caused to be wasted, more next
The requirement of construction economical and environment-friendly society is not met more.Therefore, hydrogen peroxide cold bleaching technology has received widespread attention.Biology
Enzymic catalytic reaction has the characteristics that high efficiency, specificity and mild condition, has more research in paper pulp bleaching industry.But
Biological enzyme limited source, thus using with biological enzyme function is similar or similar analogue enztme is come to carry out bleaching be to solve this
Problem effective ways.Metalloporphyrins, metal phthalocyanine complex, copper-amine complex, Macrocyclic polyamine metal complex etc. are imitative
Enzyme metal complex has preferable development prospect in this field.But various catalyst all exist accordingly in this field
Disadvantage, for example, metal phthalocyanine complex poorly water-soluble, the fabric after the bleaching of Macrocyclic polyamine metal complex again after dyeing, every
A period of time can have large-scale decoloration.
Amino Schiff base complex mostly has bioactivity, plays an important role in imitative enzyme catalysis field, but
It is this kind of complex there is toxicity height, water-soluble low problem is unfavorable for their popularization and use.Therefore one kind was found both
Complex toxicity can be made, which to reduce again, has complex that is preferably water-soluble, while also keeping higher catalytic activity, is this field
Research emphasis.It is main still to use sulfonation, carboxylation or introduce hydrophilic radical in parent compound at present in this field
The methods of, to improve water-soluble, reduction toxicity.And it is quaternised modified especially using the lower quaternizing agent progress of some toxicity
It is quaternised modified, water solubility not only can be improved but also toxicity can be effectively reduced.Therefore, a kind of quaternary ammonium of greater activity is found
Change Schiff Base Metal Complex to have great importance to Cotton Fabric Low Temperature Bleaching.
Summary of the invention
The present invention is directed to the deficiency in the presence of existing imitative enzymatic fabric bleaching technology, provides a kind of hypotoxicity, water-soluble
Property is good, can be catalyzed quaternized amino acid Schiff base metal complexes and its preparation of hydrogen peroxide bleaching fabric under cryogenic
Method.
To achieve the above object of the invention, the technical solution adopted by the present invention is that providing a kind of quaternized amino Schiff base
Metal complex and preparation method thereof includes the following steps:
(1) in the reaction vessel equipped with blender, condensing reflux pipe and thermometer, 1:0.4~0.5 in mass ratio will
Pentaerythrite and sodium hydroxide are added in reaction vessel, add 3~5 times of pentaerythrite quality of n,N-Dimethylformamide
Solvent is 1:2.8 by the mass ratio of pentaerythrite and epoxychloropropane under conditions of nitrogen protection, temperature are 60~75 DEG C
~3.1, epoxychloropropane is added dropwise in 1~2 h；After being added dropwise to complete reaction 20~for 24 hours, remove solvent, obtain quaternary ammoniated
Reagent TMPT；
(2) 1:1.5~1.9:3~4 in mass ratio, by quaternizing agent TMPT, 4- (lignocaine) salicylide and quality
The alcohol solvent that percent concentration is 50% is added in the reaction vessel equipped with blender, thermometer and condensation reflux unit, is opened
Stirring is opened, under conditions of nitrogen protection, temperature are 60~75 DEG C, reacts 9~12h；Again through cooling, solvent is removed, vacuum is dry
It is dry, obtain quaternized 4- (lignocaine) salicylide；
(3) 1:0.3~0.5:2~3 in mass ratio, by quaternized 4- (lignocaine) salicylide, serine and quality hundred
Dividing specific concentration is that 50% ethyl alcohol is added in the reaction vessel equipped with blender, thermometer and condensation reflux unit, is in temperature
Under conditions of 70~80 DEG C, 4~5h is reacted, quaternized amino Schiff base ligand is obtained；
(4) 1:0.7~0.8:5~6 in mass ratio, by quaternized amino Schiff base ligand, metal salt and quality hundred
The ethyl alcohol that point specific concentration is 50% be added to equipped with blender, thermometer, condensation reflux unit reaction vessel in, be in temperature
After keeping the temperature 8~12h under conditions of 25~30 DEG C, then 4~5h, the product that will be obtained are kept the temperature under conditions of temperature is 70~75 DEG C
Vacuum drying obtains a kind of quaternized Schiff Base Metal Complex.Wherein the metal salt is four acetate hydrates
One of manganese, copper acetate, Iron(III) chloride hexahydrate.
Technical solution of the present invention further includes the quaternized amino acid Schiff base metal complexes that above-mentioned preparation method obtains, with
And application of the quaternized amino acid Schiff base metal complexes in catalysis hydrogen peroxide bleaching cotton, fiber crops, silk fabrics.
In the technical solution of the present invention, the synthetic reaction formula of each step of quaternized amino acid Schiff base metal complexes is prepared
It is as follows:
The synthesis of quaternizing agent:
；
The synthesis of quaternized 4- (lignocaine) salicylide:
。
In technical solution of the present invention, quaternized 4- (lignocaine) salicylide is reacted with serine, obtained quaternized ammonia
The structural formula of base acid Schiff base ligand are as follows:
；
The general structure for the quaternized amino acid Schiff base metal complexes that technical solution of the present invention obtains are as follows:
；
Wherein, one of M Cu, Fe, Mn element.
The present invention uses pentaerythrite and epichlorohydrin reaction, obtains active higher, the lower quaternizing agent of toxicity,
Again by quaternizing agent and 4-(lignocaine) salicylide reacts, quaternized (lignocaine) salicylide is obtained, with silk ammonia
Acid is condensed to yield quaternized amino acid Schiff base ligand；Quaternized amino acid Schiff base ligand is coordinated with metal salt again,
Obtain quaternized amino acid Schiff base metal complexes.Quaternized amino acid Schiff base metal complexes provided by the invention,
It is applied to the principle for carrying out bleaching to cotton, fiber crops, silk fabrics: can be effectively catalyzed peroxidating using Schiff base metal complexes
The decomposition of object improves peroxide at a lower temperature to the bleaching power of fabric, and quaternized cationic group is easy to inhale again
It is attached to the fiber surface with negative electrical charge, keeps quaternized amino acid Schiff base metal complexes more in fabric surface catalysis
Decomposing hydrogen dioxide solution improves bleaching effect.
Due to the application of the above technical scheme, the present invention has the advantage that
1, the quaternizing agent that the present invention is reacted using pentaerythrite and epoxychloropropane for raw material, is a kind of toxicity
Low, activity is stronger, water-soluble preferable quaternizing agent, relative to traditional dimethyl suflfate, benzyl chloride, the examination such as halogenated alkane
Agent is in environmental protection advantageously.
2, the quaternized amino acid Schiff base metal complexes that the present invention synthesizes are water-soluble preferably, and can effectively improve peroxide
Compound cold bleaching ability, relative to traditional oxygen bleaching process, in terms of energy-saving and emission-reduction with good application prospect.
Detailed description of the invention
Fig. 1 is the infrared spectrum of quaternized amino acid Schiff base metal complexes in embodiment 1；
Fig. 2 is the infrared spectrum of quaternized amino acid Schiff base metal complexes in embodiment 2；
Fig. 3 is the infrared spectrum of quaternized amino acid Schiff base metal complexes in embodiment 3.
Specific embodiment
Technical solution of the present invention is further elaborated with reference to the accompanying drawings and examples.
Embodiment 1
A kind of quaternized amino acid Schiff base metal complexes provided in this embodiment, preparation method include following step
It is rapid:
1, in the reaction vessel equipped with blender, condensing reflux pipe and thermometer, 13.6g pentaerythrite and 5.5g is added
Sodium hydroxide adds 40.8g n,N-Dimethylformamide solvent, is heated to 60 DEG C, under the protection of nitrogen, in 1~2 h
Epoxychloropropane 38.1g is inside added dropwise dropwise, 20h is reacted after dripping, vacuum distillation removes solvent, and it is dry, obtain quaternized examination
Agent TMPT.
2, it is by quaternizing agent TMPT 5.1g, 4- (lignocaine) salicylide 7.7g and 15.3g mass percent concentration
50% ethyl alcohol is added in the container equipped with blender, thermometer and condensation reflux unit, under nitrogen protection, opens stirring
60 DEG C are heated to, 9h is reacted, it is cooling, solvent is removed, vacuum drying obtains quaternized 4- (lignocaine) salicylide.
3, it is by quaternized 4- (lignocaine) salicylide 12.8g, 4.2g serine and 25.6g mass percent concentration
50% ethyl alcohol is added in the reaction vessel equipped with blender, thermometer and condensation reflux unit, is heated to 70 DEG C, is reacted 4h, is obtained
To quaternized amino-acid schiff base ligand.
4, quaternized amino Schiff base ligand 1 3.8g and four water manganese acetate 9.8g are added to equipped with blender, temperature
Degree is counted, in the reaction vessel of condensation reflux unit, is added the ethyl alcohol that 69g mass concentration is 50%, is kept the temperature under conditions of 25 DEG C
8h, then in 70 DEG C of heating stirring 4h, obtained solution condensing crystallizing in high vacuum obtains quaternized amino Schiff base
Metal complex.
Referring to attached drawing 1, it is quaternized amino acid Schiff base metal complexes infrared spectrum provided in this embodiment.In figure
3433cm-1Place is the absorption peak of hydroxyl, 2923cm-1Place is CH3Stretching vibration peak, 1242cm-1Place is to shake outside the face-CH2-
Pendular oscillation, 1632cm-1Place is C=N stretching vibration peak, 1 407 cm-1 、975 cm-1There is the characteristic absorption of quaternary ammonium salt in place
Peak, the respectively strong absworption peak of C-N key stretching vibration and middle strong absworption peak show test result and quaternized amino acid Schiff
The structure of alkali metal complex matches.
Quaternized amino acid Schiff base metal complexes manufactured in the present embodiment are applied to catalysis hydrogen peroxide bleaching cotton to knit
Object, the compositing formula and process conditions of bleaching liquid are as follows:
30%H2O2 8g/L
Penetrating agent JFC 1g/L
Hydrogen peroxide bleaching stabilizer 0.5g/L
8 umol/L of complex provided in this embodiment
Bleaching liquid pH(is adjusted with sodium hydroxide) 10.5
Bath raio 1:20
Temperature (DEG C) 70
Time (min) 60
Bleaching and treating process process: cotton fabric → bleaching (70 DEG C, 60min) → hot water wash (70 DEG C, 5min) after kiering →
Cold water is washed → is dried.
By GB-8424.2-2001 " the objective ranking method that textile color stability tests opposite whiteness " measurement fabric
Whiteness；By " the textile fabric tensile property part 1: the measurement galley proof of ultimate strength and extension at break of GB/T 3923.1997
Method " measurement fabric ultimate strength；By the hair of FZ/T 01071-2008 " textile capillary effect test method " measurement fabric
Effect.
Quaternized amino acid Schiff base metal complexes manufactured in the present embodiment are on catalysis hydrogen peroxide bleaching cotton fabric
The results are shown in Table 1 for application performance test.
Table 1: the bleaching effect of cotton fabric
| Cotton fabric | Whiteness/% | Capillary effect/[cm (30 min)-1] | Strength retention (%) |
| Blank (no catalyst) | 71.0 | 3.0 | 96.1 |
| After bleaching | 77.3 | 11.7 | 91.2 |
Embodiment 2
1, in the reaction vessel equipped with blender, condensing reflux pipe and thermometer, 13.6 pentaerythrites and 5.8g is added
Sodium hydroxide adds 50.2g n,N-Dimethylformamide solvent, is heated to 65 DEG C, under the protection of nitrogen, in 1~2 h
Epoxychloropropane 39.2g is inside added dropwise dropwise, 22h is reacted after dripping, vacuum distillation removes solvent, and it is dry, obtain quaternized examination
Agent TMPT.
2, it is by quaternizing agent TMPT 5.1g, 4- (lignocaine) salicylide 8.2g and 18g mass percent concentration
50% ethyl alcohol is added in the container equipped with blender, thermometer and condensation reflux unit, under nitrogen protection, opens stirring
65 DEG C are heated to, 10h is reacted, it is cooling, solvent is removed, vacuum drying obtains quaternized 4- (lignocaine) salicylide.
3, it is by quaternized 4- (lignocaine) salicylide 12.8g, 5.4g serine and 30.6g mass percent concentration
50% ethyl alcohol is added in the reaction vessel equipped with blender, thermometer and condensation reflux unit, is heated to 70 DEG C, is reacted 5h, is obtained
To quaternized amino Schiff base ligand.
4, quaternized amino Schiff base ligand 1 3.8g and four water manganese acetate 10.2g are added to equipped with blender, temperature
Degree is counted, in the reaction vessel of condensation reflux unit, the ethyl alcohol that 70g mass percent concentration is 50% is added, in 25 DEG C of condition
Lower heat preservation 10h, then in 75 DEG C of heating stirring 4.5h, obtained solution is dried in a vacuum, and condensing crystallizing obtains quaternized
Schiff Base Metal Complex.
Referring to attached drawing 2, it is quaternized amino acid Schiff base metal complexes infrared spectrum provided in this embodiment.Figure
Middle 3426cm-1Place is the absorption peak of hydroxyl, 2925cm-1Place is CH3Stretching vibration peak, 1242cm-1Place is outside the face-CH2-
Rocking vibration, 1631cm-1Place is C=N stretching vibration peak, 1 434 cm-1 、911cm-1There is the characteristic absorption of quaternary ammonium salt in place
Peak, the respectively strong absworption peak of C-N key stretching vibration and middle strong absworption peak show test result and quaternized amino acid Schiff
The structure of alkali metal complex matches.
Quaternized amino acid Schiff base metal complexes manufactured in the present embodiment are applied to catalysis hydrogen peroxide bleaching silk
Fabric, the compositing formula and bleaching and treating process process of bleaching liquid are referring to embodiment 1.
Application performance test knot of the Schiff base metal complexes manufactured in the present embodiment on hydrogen peroxide bleaching real silk fabric
Fruit is as shown in table 2.
Table 2: the bleaching effect of real silk fabric
| Real silk fabric | Whiteness/% | Capillary effect/[cm (30 min)-1] | Strength retention (%) |
| Blank (no catalyst) | 70.1 | 4.1 | 96.2 |
| After bleaching | 76.5 | 12.7 | 86.3 |
Embodiment 3
1, in the reaction vessel equipped with blender, condensing reflux pipe and thermometer, 13.6 pentaerythrites and 6.1g is added
Sodium hydroxide adds 66.8g n,N-Dimethylformamide solvent, is heated to 70 DEG C, under the protection of nitrogen, in 1~2 h
Epoxychloropropane 41.6g is inside added dropwise dropwise, is reacted after dripping for 24 hours, vacuum distillation removes solvent, and it is dry, obtain reagent TMPT.
2, it is by quaternizing agent TMPT 5.1g, 4- (lignocaine) salicylide 9.6g and 20.4g mass percent concentration
50% ethyl alcohol is added in the container equipped with blender, thermometer and condensation reflux unit, under nitrogen protection, opens stirring
70 DEG C are heated to, 12h is reacted, it is cooling, solvent is removed, vacuum drying obtains quaternized 4- (lignocaine) salicylide.
3, it is by quaternized 4- (lignocaine) salicylide 12.8g, 6.4g serine and 38.4g mass percent concentration
50% ethyl alcohol is added in the reaction vessel equipped with blender, thermometer and condensation reflux unit, is heated to 75 DEG C, reacts 5h,
Obtain quaternized amino Schiff base ligand.
4, quaternized amino Schiff base ligand 1 3.8g and four water manganese acetate 10.2g are added to equipped with blender, temperature
Degree is counted, in the reaction vessel of condensation reflux unit, the ethyl alcohol that 75g mass percent concentration is 50% is added, in 25 DEG C of condition
Lower heat preservation 12h, then in 75 DEG C of heating stirring 5h, obtained solution is dried in a vacuum, and condensing crystallizing obtains quaternized ammonia
Base acid Schiff base metal complexes.
Referring to attached drawing 3, it is quaternized amino acid Schiff base metal complexes infrared spectrum provided in this embodiment.In figure
3426cm-1Place is the absorption peak of hydroxyl, 2965cm-1Place is CH3Stretching vibration peak, 1242cm-1Place is to shake outside the face-CH2-
Pendular oscillation, 1631cm-1Place is C=N stretching vibration peak, 1 400 cm-1 、910cm-1There is the characteristic absorption peak of quaternary ammonium salt in place,
The respectively strong absworption peak of C-N key stretching vibration and middle strong absworption peak, show test result and quaternized amino Schiff base
The structure of metal complex matches.
Quaternized amino acid Schiff base metal complexes manufactured in the present embodiment are applied to catalysis hydrogen peroxide bleaching hemp
Object, the compositing formula and bleaching and treating process process of bleaching liquid are referring to embodiment 1.
Quaternized Schiff Base Metal Complex answering on hydrogen peroxide bleaching linen manufactured in the present embodiment
It is as shown in table 3 with the performance test results.
Table 3: the bleaching effect of linen
| Linen | Whiteness/% | Capillary effect/[cm (30 min)-1] | Strength retention (%) |
| Blank (no catalyst) | 72.3 | 2.2 | 96.1 |
| After bleaching | 76.9 | 10.6 | 88.1 |
Claims (4)
1. a kind of preparation method of quaternized Schiff Base Metal Complex, it is characterised in that include the following steps:
(1) in the reaction vessel equipped with blender, condensing reflux pipe and thermometer, 1:0.4~0.5 in mass ratio, by season penta
Tetrol and sodium hydroxide are added in reaction vessel, and it is molten to add 3~5 times of pentaerythrite quality of n,N-Dimethylformamide
Agent, nitrogen protection, temperature be 60~75 DEG C under conditions of, by the mass ratio of pentaerythrite and epoxychloropropane be 1:2.8~
3.1, epoxychloropropane is added dropwise in 1~2 h；After being added dropwise to complete reaction 20~for 24 hours, remove solvent, obtain quaternary ammoniated examination
Agent TMPT, structural formula are；
(2) 1:1.5~1.9:3~4 in mass ratio, by quaternizing agent TMPT, 4- (lignocaine) salicylide and quality percentage
The alcohol solvent that specific concentration is 50% is added in the reaction vessel equipped with blender, thermometer and condensation reflux unit, and unlatching is stirred
It mixes, under conditions of nitrogen protection, temperature are 60~75 DEG C, reacts 9~12h；Again through cooling, solvent is removed, vacuum drying obtains
To quaternized 4- (lignocaine) salicylide；
(3) 1:0.3~0.5:2~3 in mass ratio, by quaternized 4- (lignocaine) salicylide, serine and mass percent
Concentration be 50% ethyl alcohol be added in the reaction vessel equipped with blender, thermometer and condensation reflux unit, temperature be 70~
Under conditions of 80 DEG C, 4~5h is reacted, quaternized amino Schiff base ligand is obtained；
(4) 1:0.7~0.8:5~6 in mass ratio, by quaternized amino Schiff base ligand, metal salt and mass percent
Concentration be 50% ethyl alcohol be added to equipped with blender, thermometer, condensation reflux unit reaction vessel in, temperature be 25~
After keeping the temperature 8~12h under conditions of 30 DEG C, then 4~5h, the product vacuum that will be obtained are kept the temperature under conditions of temperature is 70~75 DEG C
It is dry, obtain a kind of quaternized Schiff Base Metal Complex；
The general structure of the quaternized amino acid Schiff base metal complexes are as follows:
；
Wherein, one of M Cu, Fe, Mn element.
2. the preparation method of the quaternized Schiff Base Metal Complex of one kind according to claim 1, feature
Be: metal salt described in step (4) is one of four acetate hydrate manganese, copper acetate.
3. by the quaternized Schiff Base Metal Complex of one kind that claim 1 preparation method obtains；
The general structure of the quaternized amino acid Schiff base metal complexes are as follows:
；
Wherein, one of M Cu, Fe, Mn element.
4. a kind of application of quaternized Schiff Base Metal Complex as claimed in claim 3, it is characterised in that use
In to cotton, fiber crops, silk fabrics catalysis hydrogen peroxide bleaching.
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