CN107513179B - One kind ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent and preparation method thereof - Google Patents
One kind ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of ultraviolet absorbers of supermolecular intercalation structure containing auxiliary agent and preparation method thereof.Ultraviolet absorber and organic weak reductant are innovatively assembled to LDHs interlayer by the present invention jointly, light degradation using the uv absorption property barrier ultraviolet light of ultraviolet absorber to plastics absorbs highly reactive form of oxygen using the reduction of the organic weak reductant of auxiliary agent to reduce the photooxidation of plastics.Because there is collaboration anti-light aging effect in the ultraviolet absorber of LDHs interlayer and organic weak reductant, the anti-light aging performance that ultraviolet absorber and organic weak reductant are total to intercalation LDHs is substantially better than ultraviolet absorber list intercalation configuration LDHs, overcomes the ineffective disadvantage of current ultraviolet absorber list intercalation LDHs anti-light aging；Also have many advantages, such as that heat resistance is high, resistance to migration is good, light-protection energy is excellent simultaneously, can be widely applied to the fields such as plastics, coating.Preparation method of the present invention is easy to operate, raw material sources enrich, is convenient for industrialized production.
Description
Fields
The present invention relates to a kind of ultraviolet absorbers of supermolecular intercalation structure containing auxiliary agent and preparation method thereof.
Background technique
Ultraviolet absorber is that one kind can inhibit the UV light-induced functional material for causing plastic degradation, and action principle is main
It is to realize the target of light protection by absorbing and shifting UV energy or shield ultraviolet light.Ultraviolet absorber is generally with physics
Mixed mode is compound with plastics, and ultraviolet absorber is highly dispersed in plastic substrate, to give full play to the guarantor of ultraviolet absorber
Effect is protected, the photooxidative degradation of plastics is reduced, achievees the purpose that extend plastics service life.But most of ultraviolet absorber exists
It the disadvantages of volatile, easy to migrate, thermal stability is poor, limits its scope of application.
Hydrotalcite (Layered Double Hydroxides, be abbreviated as LDHs) is by positively charged metal hydroxide
Nitride layer plate and negatively charged interlayer anion are connected the compound formed with weak chemical bond, main layer board metallic element
Composition, main layer board charge density and distribution, interlayer object anion species and quantity, host-guest interaction etc. all have can
The characteristic of modulation, therefore can use the characteristic in hydrotalcite layers insertions function anion, to be prepared with special
The functional material of property.
Document Chai H, Xu X, Lin Y, et al.Synthesis and UV absorption properties of
2,3-dihydroxynaphthalene-6-sulfonate anion-intercalated Zn–Al layered double
Hydroxides [J] .Polymer Degradation and stability, 2009,94 (4): 744-749 is with ZnAl-NO3-
LDH is presoma, is assembled into ultraviolet absorber 2- alpha naphthylamine -1,5- disulfonic acid (NADA) success intercalation using ion-exchange
ZnAl-LDH interlayer constructs supermolecular intercalation structure ZnAl-NADA-LDH UV absorbing material；By ZnAl-NADA-LDH and gather
The UV absorption of the compound preparation LDH/PP composite material of propylene (PP), ultra-violet analysis discovery LDH/PP laminated film is apparently higher than PP
Film, light ageing test result show that the introducing of LDH improves the photostability of PP.
Document Chai H, Lin Y, Evans D G, et al.Synthesis and UV absorption
properties of 2-naphthylamine-1,5-disulfonic acid intercalated Zn-Al layered
double hydroxides[J].Industrial&Engineering Chemistry Research,2008,47(9):
2855-2860 is using ZnAl-LDH as presoma, using ion-exchange by ultraviolet absorber 2,3- dihydroxy naphthlene -6- sulfonic acid
(DNSA) success intercalation is assembled into ZnAl-LDH interlayer, constructs supermolecular intercalation structure ZnAl-DNSA-LDH UV absorbing material；
By ZnAl-DNSA-LDH and the compound preparation LDH/PP composite material of PP, ultra-violet analysis finds the ultraviolet suction of LDH/PP laminated film
Receipts are apparently higher than PP film, and light ageing test result shows that being introduced into for LDH slows down carbonyl absorption peak in PP photo aging process
It advances the speed.
Document Cui G-J, Xu X-Y, Lin Y-J, et al.Synthesis and UV Absorption
Properties of 5,5′-Methylenedisalicylic Acid-Intercalated Zn-Al Layered
Double Hydroxides[J].Industrial&Engineering Chemistry Research,2009,49(2):
448-453 is assembled 5,5 '-methylenesalicylics (MDSA) success intercalation using ZnAl-LDH as presoma, using ion-exchange
To ZnAl-LDH interlayer, supermolecular intercalation structure ZnAl-MDSA-LDH UV absorbing material, light ageing test result table are constructed
Bright, being introduced into of LDH slows down advancing the speed for carbonyl absorption peak in PP photo aging process.
Although above-mentioned document is prepared for a variety of supermolecular intercalation structure ultraviolet absorbers, it has the light protective capability of PP
Limit, PP still will be slow degradation in use.For the light stability for further promoting PP, it is more excellent to be badly in need of a kind of performance
Different ultraviolet absorber.
Summary of the invention
The purpose of the present invention is to provide a kind of UV absorbing materials of supermolecular intercalation structure containing auxiliary agent and preparation method thereof.
Ultraviolet absorber and organic weak reductant are innovatively assembled to LDHs interlayer by the present invention jointly, utilize ultraviolet suction
Light degradation of the uv absorption property barrier ultraviolet light of agent to plastics is received, is that auxiliary agent absorbs highly reactive form of oxygen using organic weak reductant
To reduce the photooxidation of plastics, its anti-light aging effect is improved.
The ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent prepared by the present invention, is abbreviated as AB-LDH, chemical general formula are as follows:
[M2+ 1-xM3+ x(OH)2](A-)y(B-)z·cH2O
Wherein M2+And M3+It is divalent and trivalent metal cation in main layer board, M respectively2+For Mg2+、Zn2+、Ni2 +、Ca2+、Fe2+、Cu2+In any one or two kinds, preferably Mg2+、Zn2+One of, M3+For Al3+、Co3+、Ti3+、Fe3 +、Cr3+One or both of, preferably Al3+；A-For the anion of organic weak reductant A, B-For ultraviolet absorber yin from
Son；X is M3+/(M2++M3+) molar ratio, x=y+z, and 0.2≤x≤0.4,0.05 < y < 0.35,0.05 < z < 0.35；C is
Intermediary water Molecules, 0.4 < c < 1.
Organic weak reductant A is comprising in potassium sorbate, stannous citrate sodium, L-threonine sodium, sodium ascorbate
It is one or more.
The ultraviolet absorber B is para aminobenzoic acid sodium salt, p- methoxy cinnamic acid sodium, sodium salicylate, 2- hydroxyl-
4- methoxy benzophenone -5- sodium sulfonate, coumarin-3-carboxy acid's sodium, sodium cinnamate, benzotriazole -4- hydroxyl-benzene sulfonic acid sodium salt,
One or more of 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID sodium.
The ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent of the present invention, specific preparation process is as follows:
A. M is weighed2+、M3+Nitrate or chlorate be dissolved in the deionized water of removing carbon dioxide that be configured to salt-mixture molten
Liquid, wherein M2+With M3+Molar ratio be 2-4, M3+Molar concentration be 0.05-0.8mol/L.
It weighs ultraviolet absorber and organic weak reductant is dissolved in and is made into total mol concentration in solvent as 0.05-0.5mol/L's
Solution adds it in above-mentioned mixing salt solution and forms mixed solution A；Wherein ultraviolet absorber and organic weak reductant rub
Your ratio is 0.15-7, and the sum of mole of ultraviolet absorber and organic weak reductant anion and M3+The ratio of moles total number
For 1-3, i.e. nA+nB=1-3nM 3+；
The solvent is the deionized water of removing carbon dioxide or the mixed solvent of itself and polar solvent, the polarity
Solvent is ethyl alcohol, ethylene glycol or glycerine, is selected corresponding according to that can dissolve ultraviolet absorber used and organic weak reductant
Solvent.
Organic weak reductant A is stannous citrate sodium, in L-threonine sodium, sodium ascorbate, potassium sorbate
It is one or more.
The ultraviolet absorber B is para aminobenzoic acid sodium salt, p- methoxy cinnamic acid sodium, sodium salicylate, 2- hydroxyl-
4- methoxy benzophenone -5- sodium sulfonate, coumarin-3-carboxy acid's sodium, sodium cinnamate, benzotriazole -4- hydroxyl-benzene sulfonic acid sodium salt,
One or more of 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID sodium.
B. the aqueous slkali B that molar concentration is 0.05-1mol/L is prepared, the alkali is NaOH, KOH or ammonium hydroxide.
C. under nitrogen protection and stirring, mixed solution A and aqueous slkali B are mixed, wherein the mole of alkali is that step A is molten
M in liquid2+With M3+1.8-2 times of the sum of mole, i.e. nOH -=1.8-2 (nM 2++nM 3+).Reaction generates precipitating, by the heavy of generation
Shallow lake centrifuge washing 3 times, the slurries of 1-100g/L are then configured to, add ultraviolet absorber and organic weak reductant, wherein purple
The additional amount of outer absorbent and organic weak reductant is contained M in slurries3+0.1-0.3 times of mole, then at 50-150 DEG C
Under be stirred to react 4-24 hours, cooling, filtration product is simultaneously washed 4-9 times, by filter cake 60-100 DEG C dry 12-24 hours to obtain the final product
To the ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent.
Because there is collaboration anti-light aging effect, the UV absorption in the ultraviolet absorber of LDHs interlayer and organic weak reductant
The anti-light aging performance of material is substantially better than the ultraviolet absorber intercalation LDHs without auxiliary agent.
Fig. 1 is the XRD spectra of the ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent prepared by embodiment 1, shows its tool
There is single crystal phase structure and ultraviolet absorber and organic weak reductant have successfully been assembled into LDHs interlayer.
Fig. 2 is the FT-IR spectrogram of the ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent prepared by embodiment 1, is as a result shown
Show that ultraviolet absorber and organic weak reductant have successfully been assembled into LDHs interlayer.
Fig. 3 is light protecting effect figure of the ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent prepared by embodiment 1 to PP,
Ultraviolet absorber and organic weak reductant are total to intercalation LDH and are substantially better than ultraviolet absorber to the light protecting effect of PP as shown in Figure 3
Single intercalation LDH.
Advantages of the present invention: the ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent prepared by the present invention has heat resistance
The advantages that height, resistance to migration are good, light-protection can be excellent, can be widely applied to the fields such as plastics, coating.Used preparation side
Method is simple, raw material sources enrich, is convenient for industrialized production.
Detailed description of the invention:
Fig. 1 is the XRD spectra that ultraviolet absorber prepared by embodiment 1 and organic weak reductant are total to intercalation LDH.
Fig. 2 is the FT-IR spectrogram that ultraviolet absorber prepared by embodiment 1 and organic weak reductant are total to intercalation LDH.
Fig. 3 is that ultraviolet absorber prepared by embodiment 1 and organic weak reductant are total to intercalation LDH to the light protecting effect of PP
Figure.A is polypropylene in figure, and b is 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid intercalation LDH/ polypropylene composite, and c is mountain
Pears acid and 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid are total to intercalation LDH/ polypropylene composite.
Specific embodiment:
Embodiment 1:
Step A: 1.5g (5.0mmol) Mg (NO is weighed3)2·6H2O and 0.938g (2.5mmol) Al (NO3)3·9H2O is molten
CO is removed in 30ml2Deionized water in be made into mixing salt solution.
Weigh 1.083g (2.5mmol) potassium sorbate and 0.825g (2.5mmol) ESCALOL 567-
5- sodium sulfonate is dissolved in the deionized water of 40ml removing carbon dioxide and the in the mixed solvent of ethylene glycol composition, in nitrogen protection and stirring
Under the conditions of be uniformly mixed wiring solution-forming, be added in above-mentioned salting liquid.
Step B: it weighs 0.6g NaOH and is dissolved in the deionized water of 30ml removing carbon dioxide and be made into aqueous slkali.
Step C: under nitrogen protection and stirring, the solution hybrid reaction that step A, B is prepared generates precipitating, by generation
Precipitating centrifuge washing 3 times, then plus the deionized water of 120ml removing carbon dioxide is configured to slurries, weighs 0.1083g respectively
(0.25mmol) potassium sorbate and 0.0825g (0.25mmol) 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid sodium are added to slurry
In liquid, then precipitating is placed in 100 DEG C of water-baths and reacts 6h, after reaction by reaction product centrifugation, washing 6 times, will be centrifuged
The product of acquisition is placed in drying in 100 DEG C of baking ovens and for 24 hours, obtains the ultraviolet absorber of supramolecular structure containing auxiliary agent [Mg0.66Al0.34
(OH)2](C6H7O2)0.17(C14H11O6S)0.17·0.63H2O。
Contrast sample preparation: 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid intercalation LDH is prepared using same method
[Mg0.66Al0.34(OH)2](C14H11O6S)0.34·0.56H2O.Difference is that 2- hydroxyl -4- methoxyl group is only added in step A
Benzophenone -5- sodium sulfonate, dosage are 1.65g (5mmol).
Fig. 1 and Fig. 2 shows that sorbic acid and 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid have been intercalation into MgAl- jointly
LDHs interlayer.
Fig. 3 shows [Mg prepared by embodiment 10.66Al0.34(OH)2](C6H7O2)0.17(C14H11O6S)0.17·0.63H2O pairs
The light protecting effect of PP is better than contrast sample [Mg0.66Al0.34(OH)2](C14H11O6S)0.34·0.56H2O。
Embodiment 2:
Step A: 2.25g (7.5mmol) Mg (NO is weighed3)2·6H2O and 0.938g (2.5mmol) Al (NO3)3·9H2O is molten
CO is removed in 40ml2Deionized water in be made into mixing salt solution.
It weighs 0.497g (2.5mmol) sodium ascorbate and 0.4g (2.5mmol) sodium salicylate is dissolved in removing carbon dioxide
In deionized water, it is uniformly mixed wiring solution-forming under nitrogen protection and stirring condition, is added in salting liquid.
Step B: it weighs 0.8g NaOH and is dissolved in the deionized water of 45ml removing carbon dioxide and be made into aqueous slkali.
Step C: under nitrogen protection and stirring, the solution hybrid reaction that step A, B is prepared generates precipitating, by generation
Precipitating centrifuge washing 3 times, then plus the deionized water of 120ml removing carbon dioxide is configured to slurries, weighs 0.0497g respectively
(0.25mmol) sodium ascorbate and 0.04g (0.25mmol) sodium salicylate are added in slurries, and precipitating is then placed in 95 DEG C
15h is reacted in water-bath, and after reaction by reaction product centrifugation, washing 6 times, the product that centrifugation obtains is placed in 80 DEG C of baking ovens
Dry 22h, obtains the ultraviolet absorber of supramolecular structure containing auxiliary agent [Mg0.66Al0.34(OH)2](C6H7O6)0.17(C7H5O3)0.17·
0.6H2O。
Embodiment 3:
Step A: 3g (10.0mmol) Mg (NO is weighed3)2·6H2O and 0.938g (2.5mmol) Al (NO3)3·9H2O is dissolved in
45ml removes CO2Deionized water in be made into mixing salt solution.
It weighs 1.083g (2.5mmol) potassium sorbate and 0.3978g (2.5mmol) para aminobenzoic acid sodium salt is dissolved in except dioxy
Change the deionized water of carbon and the in the mixed solvent of ethylene glycol, wiring solution-forming is uniformly mixed under nitrogen protection and stirring condition, is added
Enter into salting liquid.
Step B: it weighs 1g NaOH and is dissolved in the deionized water of 25ml removing carbon dioxide and be made into aqueous slkali.
Step C: under nitrogen protection and stirring, the solution hybrid reaction that step A, B is prepared generates precipitating, by generation
Precipitating centrifuge washing 3 times, then plus the deionized water of 120ml removing carbon dioxide is configured to slurries, weighs 0.1083g respectively
(0.25mmol) potassium sorbate and 0.0398g (0.25mmol) para aminobenzoic acid sodium salt are added in slurries, then set precipitating
12h is reacted in 100 DEG C of water-baths, after reaction by reaction product centrifugation, washing 6 times, the product that centrifugation obtains is placed in 90
Dry 18h, obtains the ultraviolet absorber of supramolecular structure containing auxiliary agent [Mg in DEG C baking oven0.66Al0.34(OH)2](C6H7O2)0.17
(C7H6NO2)0.17·0.6H2O。
Embodiment 4:
Step A: 1.5g (5.0mmol) Mg (NO is weighed3)2·6H2O and 0.938g (2.5mmol) Al (NO3)3·9H2O is molten
Mixing salt solution is made into the deionized water of 30ml removing carbon dioxide.
Weigh 0.4635g (1.25mmol) distannous citrate and 0.5005g (2.5mmol) p- methoxy cinnamic acid
Sodium is dissolved in the deionized water of removing carbon dioxide and the in the mixed solvent of ethylene glycol, is uniformly mixed under nitrogen protection and stirring condition
Wiring solution-forming is added in salting liquid.
Step B: it weighs 0.6g NaOH and is dissolved in the deionized water of 35ml removing carbon dioxide and be made into aqueous slkali.
Step C: under nitrogen protection and stirring, the solution hybrid reaction that step A, B is prepared generates precipitating, by generation
Precipitating centrifuge washing 3 times, then plus the deionized water of 120ml removing carbon dioxide is configured to slurries, weighs 0.0465g respectively
(0.125mmol) distannous citrate and the p- methoxy cinnamic acid sodium of 0.0501g (0.25mmol) are added in slurries, so
Precipitating is placed in 90 DEG C of water-baths afterwards and reacts 10h, after reaction by reaction product centrifugation, washing 6 times, the production that centrifugation is obtained
Object is placed in 100 DEG C of baking ovens dry 20h, obtains the ultraviolet absorber of supramolecular structure containing auxiliary agent [Mg0.66Al0.34(OH)2]
(C6H6O8Sn)0.11(C10H9O3)0.23·0.6H2O。
Embodiment 5:
Step A: 2.25g (7.5mmol) Mg (NO is weighed3)2·6H2O and 0.938g (2.5mmol) Al (NO3)3·9H2O is molten
Mixing salt solution is made into the deionized water of 30ml removing carbon dioxide.
Weigh 0.298g (2.5mmol) L-threonine sodium and 0.8258g (2.5mmol) 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID
Sodium is dissolved in the deionized water of removing carbon dioxide, and wiring solution-forming is uniformly mixed under nitrogen protection and stirring condition, is added to salt
In solution.
Step B: it weighs 0.8g (20mmol) NaOH and is dissolved in the deionized water of 40ml removing carbon dioxide and be made into aqueous slkali.
Step C: under nitrogen protection and stirring, the solution hybrid reaction that step A, B is prepared generates precipitating, by generation
Precipitating centrifuge washing 3 times, then plus the deionized water of 120ml removing carbon dioxide is configured to slurries, weighs 0.0298g respectively
(0.25mmol) L-threonine sodium and 0.0826g (0.25mmol) 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID sodium are added in slurries, so
Precipitating is placed in 95 DEG C of water-baths afterwards and reacts 9h, after reaction by reaction product centrifugation, washing 6 times, the production that centrifugation is obtained
Object is placed in drying in 90 DEG C of baking ovens and for 24 hours, obtains the ultraviolet absorber of supramolecular structure containing auxiliary agent [Mg0.66Al0.34(OH)2]
(C6H7O2)0.17(C13H9N2O3S)0.17·0.6H2O。
Embodiment 6:
Step A: 3g (10mmol) Mg (NO is weighed3)2·6H2O and 0.938g (2.5mmol) Al (NO3)3·9H2O is dissolved in
Mixing salt solution is made into the deionized water of 45ml removing carbon dioxide.
It weighs 0.497g (2.5mmol) sodium ascorbate and 0.5304g (2.5mmol) coumarin-3-carboxy acid's sodium is dissolved in and removing
In the deionized water of carbon dioxide, wiring solution-forming is uniformly mixed under nitrogen protection and stirring condition.
Step B: it weighs 1g (25mmol) NaOH and is dissolved in the deionized water of 35ml removing carbon dioxide and be made into aqueous slkali.
Step C: under nitrogen protection and stirring, the solution hybrid reaction that step A, B is prepared generates precipitating, by generation
Precipitating centrifuge washing 3 times, then plus the deionized water of 120ml removing carbon dioxide is configured to slurries, weighs 0.0497g respectively
(0.25mmol) sodium ascorbate and 0.053g (0.25mmol) coumarin-3-carboxy acid's sodium are added in slurries, then will precipitating
It is placed in 95 DEG C of water-baths and reacts 6h, after reaction by reaction product centrifugation, washing 6 times, the product that centrifugation obtains is placed in 95
Dry 16h, obtains the ultraviolet absorber of supramolecular structure containing auxiliary agent [Mg in DEG C baking oven0.66Al0.34(OH)2](C6H7O6)0.17
(C10H5O4)0.17·0.6H2O。
Embodiment 7:
Step A: 1.5g (5mmol) Mg (NO is weighed3)2·6H2O and 0.938g (2.5mmol) Al (NO3)3·9H2O is dissolved in
Mixing salt solution is made into the deionized water of 30ml removing carbon dioxide.
Weigh 0.4635g (1.25mmol) distannous citrate and 0.7332g (2.5mmol) benzotriazole -4- hydroxyl -
Benzene sulfonic acid sodium salt and 0.1g (2.5mmol) NaOH are dissolved in the deionized water of removing carbon dioxide, in nitrogen protection and stirring condition
Uniformly mixed wiring solution-forming down, is added in salting liquid.
Step B: with embodiment 1.
Step C: under nitrogen protection and stirring, the solution hybrid reaction that step A, B is prepared generates precipitating, by generation
Precipitating centrifuge washing 3 times, then plus the deionized water of 120ml removing carbon dioxide is configured to slurries, weighs 0.0464g respectively
(0.125mmol) distannous citrate and 0.0733g (0.25mmol) benzotriazole -4- hydroxyl-benzene sulfonic acid sodium salt and 0.01g
(0.25mmol) NaOH is added in slurries, and then precipitating is placed in 100 DEG C of water-baths and reacts 8h, after reaction produces reaction
The product that centrifugation obtains is placed in 100 DEG C of baking ovens dry 18h, obtains the purple of supramolecular structure containing auxiliary agent by object centrifugation, washing 6 times
Outer absorbent [Mg0.66Al0.34(OH)2](C6H6O8Sn)0.11(C6H4N3O4S)0.23·0.6H2O。
Claims (4)
1. a kind of ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent, chemical general formula are as follows:
[M2+ 1-xM3+ x(OH)2](A-)y(B-)z·cH2O
Wherein x=y+z, 0.2≤x≤0.4,0.05 < y < 0.35,0.05 < z < 0.35, c are intermediary water molecular number, 0.4 < c < 1；
M2+For Mg2+、Zn2+、Ni2+、Ca2+、Fe2+、Cu2+In any one or two kinds, M3+For Al3+、Co3+、Ti3+、Fe3+、Cr3+
One or both of；
A-For the anion of organic weak reductant A, the machine weak reductant A is potassium sorbate, stannous citrate sodium, L- Soviet Union ammonia
One of sour sodium, sodium ascorbate are a variety of；
B-For the anion of ultraviolet absorber B, the ultraviolet absorber B is para aminobenzoic acid sodium salt, p- methoxy cinnamic acid
Sodium, sodium salicylate, 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid sodium, coumarin-3-carboxy acid's sodium, sodium cinnamate, benzo three
One of azoles -4- hydroxyl-benzene sulfonic acid sodium salt, 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID sodium are a variety of.
2. the ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent according to claim 1, it is characterized in that M2+For Mg2+、Zn2+
One of, M3+For Al3+。
3. a kind of method for preparing the ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent described in claim 1, specific steps are such as
Under:
A. M is weighed2+、M3+Nitrate or chlorate be dissolved in the deionized water of removing carbon dioxide and be configured to mixing salt solution,
Middle M2+With M3+Molar ratio be 2-4, M3+Molar concentration be 0.05-0.8mol/L；
The M2+For Mg2+、Zn2+、Ni2+、Ca2+、Fe2+、Cu2+In any one or two kinds；M3+For Al3+、Co3+、Ti3+、
Fe3+、Cr3+One or both of；
It weighs ultraviolet absorber and organic weak reductant is dissolved in and is made into total mol concentration in solvent as the molten of 0.05-0.5mol/L
Liquid is added in above-mentioned mixing salt solution and forms mixed solution A, wherein the molar ratio of ultraviolet absorber and organic weak reductant
For 0.15-7, and the sum of mole of ultraviolet absorber and organic weak reductant anion and M3+The ratio of the sum of mole is 1-
3；The solvent is the deionized water of removing carbon dioxide or the mixed solvent of itself and polar solvent, the polar solvent are
Ethyl alcohol, ethylene glycol or glycerine select corresponding solvent according to that can dissolve ultraviolet absorber used and organic weak reductant；
Organic weak reductant A is one of stannous citrate sodium, L-threonine sodium, sodium ascorbate, potassium sorbate
Or it is a variety of；
The ultraviolet absorber B is para aminobenzoic acid sodium salt, p- methoxy cinnamic acid sodium, sodium salicylate, 2- hydroxyl -4- first
Oxygroup benzophenone -5- sodium sulfonate, coumarin-3-carboxy acid's sodium, sodium cinnamate, benzotriazole -4- hydroxyl-benzene sulfonic acid sodium salt, 2- benzene
One or more of base benzimidazole -5- sodium sulfonate；
B. the aqueous slkali B that molar concentration is 0.05-1mol/L is prepared, the alkali is NaOH, KOH or ammonium hydroxide；
C. under nitrogen protection and stirring, mixed solution A and aqueous slkali B are mixed, wherein the mole of alkali is in step solution A
M2+With M3+1.8-2 times of the sum of mole；Reaction generates precipitating, will precipitate centrifuge washing 3 times, is then added to the water and is configured to
The slurries of 1-100g/L；Ultraviolet absorber and organic weak reductant are added, wherein ultraviolet absorber and organic weak reductant
Additional amount is contained M in slurries3+It 0.1-0.3 times of mole, is then stirred to react at 50-150 DEG C 4-24 hours, cooling,
Filtration product is simultaneously washed 4-9 times, and i.e. to obtain supermolecular intercalation structure containing auxiliary agent ultraviolet within dry 12-24 hours at 60-100 DEG C for filter cake
Absorbent.
4. the preparation method of the ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent according to claim 3, it is characterized in that M2+
For Mg2+、Zn2+One of, M3+For Al3+。
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