CN1333005C - Supermolecular interlayer structured ultraviolet light absorbent, its preparation method and uses - Google Patents
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- CN1333005C CN1333005C CNB2005101347195A CN200510134719A CN1333005C CN 1333005 C CN1333005 C CN 1333005C CN B2005101347195 A CNB2005101347195 A CN B2005101347195A CN 200510134719 A CN200510134719 A CN 200510134719A CN 1333005 C CN1333005 C CN 1333005C
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Abstract
The present invention provides an ultraviolet light absorption agent with a supermolecule intercalation structure, and a preparation method and use thereof. The present invention utilizes the characteristic of hydrotalcite with intercalation assembly performance, and the anion (acid radical) of 5-benzotriazole-4-hydroxy-3-isobutyl-benzenesulfonic acid (5-benzotriazolyl-4-hydroxy-3-sec-butylbenze-nesulfonic acid, for short BZO) and supermolecule intercalation structural material of which the preparation interlaminar object is the of the BZO anion (C16H16N304S) <-> are inserted in the hydrotalcite interlayer. The chemical composition formula of the ultraviolet light absorption agent with a supermolecule intercalation structure is M (1-X) <2+>Mx<3+>(OH) 2 (C16H16N3O4S) X<->. mH2O; the absorption rate of the ultraviolet light absorption agent for 280 to 370 wavebands is greater than 90%. Compared with the intercalation object BZO, the heat stability of the ultraviolet light absorption agent with a supermolecule intercalation structure is obviously improved and the decomposition temperature of interlaminar species is about 450 DEG C. The ultraviolet light absorption agent with a supermolecule intercalation structure can be used as ultraviolet light absorbent to be used as light aging proof additive of resin which can easily generate light and oxygen degradation, such as polypropylene, polycarbonate, vinyl cyanide-butadiene-styrene copolymer (ABS), polyurethane, etc.
Description
Technical field
The present invention relates to the purposes of a kind of supermolecular interlayer structured ultraviolet light absorbent and preparation method thereof and this ultraviolet absorbers.
Background technology
Other high molecular polymer of Polyolefin and is easy to take place photochemical degradation under ultraviolet irradiation, thereby causes physical property to change, and reduces as elasticity, and material becomes fragile, and finally loses physical strength etc.5-benzotriazole-4-hydroxyl-3-isobutyl--Phenylsulfonic acid (5-benzotriazolyl-4-hydroxy-3-sec-butylbenzenesulfonic acid, be called for short BZO) UV-light is had strong sorption, UV-light to 200～400nm wave band has strong sorption, but, the report that domestic and foreign literature is studied this compound and use as uv-absorbing agent is few, and the bath that only is applied to wool or textiles is dyed fixation or added the report that suppresses the paper flavescence in the paper pulp.Investigate the thermostability of this compound and find that its color and luster transfers brown to by white when being heated to 120 ℃ of left and right sides, because structure changes, the uv-absorbing ability weakens greatly simultaneously.Use man-hour 5-benzotriazole-4-hydroxyl-3-isobutyl--Phenylsulfonic acid as ultraviolet absorbers if add at matrix material, because this compound Decomposition at high temperature, not only can't absorb the effect of ultraviolet ray performance anti-light aging, also will make the serious painted and pollution of composite product.In addition, 5-benzotriazole-4-hydroxyl-3-isobutyl--Phenylsulfonic acid at room temperature is slightly soluble in water, and soluble in water behind the salify, resistant to extraction and water-wash resistance are all relatively poor in matrix material, can't efficiently use for a long time.Therefore, as if the ultraviolet absorbers of wanting used as the polymer plastic goods, at first must improve its thermostability.
Hydrotalcite (Layered Double Hydroxides, be abbreviated as LDHs) be the important novel inorganic functional materials of a class, because of the Modulatory character of its structure and composition, obtained application more and more widely at composite rubber-plastic material aspect preparing as functional additive.LDHs has intercalation, and the control certain condition can thereby make structure and form corresponding the variation be taken place with the original negatively charged ion of displacement between new negatively charged ion interposed layer.Result of study shows that its thermostability increased substantially after the LDHs interlayer was inserted in organic anion.The present invention utilizes the interchangeability of LDHs interlayer ion, interlayer with 5-benzotriazole-4-hydroxyl-3-isobutyl--Phenylsulfonic acid negatively charged ion insertion LDHs precursor prepares the intercalation configuration ultraviolet absorbers that a kind of good heat stability also can improve the ageing resistance by ultraviolet light ability of matrix material.This intercalation configuration ultraviolet absorbers brought into play the LDHs laminate to the shielding effect of UV-light and 5-benzotriazole-4-hydroxyl-3-isobutyl--Phenylsulfonic acid negatively charged ion to the sorption of UV-light, will further strengthen the obstructing capacity of UV-light.
Document Qinglin He, Shu Yin, Tsugio Sato, " Synthesis and PhotochemicalProperties of Zinc-Aluminum Layered Double Hydroxide/Organic UV RayAbsorbing Molecule/Silica Nanocomposites ", Journal of Physics and Chemistry ofSolids, 65 (12), 395-402 (2004) has reported Whitfield's ointment, the preparation of 6 kinds of organic uv absorbers intercalated houghite materials such as benzophenone sodium sulfonate, wherein do not relate to 5-benzotriazole-4-hydroxyl-3-isobutyl--Phenylsulfonic acid, Wen Zhongwei studies any thermostability in 6 kinds of intercalation products, also not with the research contents of these 6 kinds of intercalation products as the plastics ultraviolet absorbers.
Document S.Guo, D.Li, W. Zhang, M.P, David G E., X.Duan, Preparation of ananionic azo pigment-pillared layered double hydroxide and the thermo-andphotostability of the resulting intercalated material, J.Solid State Chem.177,4597-4604 (2004) have prepared the LDHs of permanent bordeaux F5R intercalation, and the thermostability of product is significantly improved.
Summary of the invention
The purpose of this invention is to provide a kind of supermolecular interlayer structured ultraviolet light absorbent; Another object of the present invention provides a kind of method for preparing supermolecular interlayer structured ultraviolet light absorbent; A further object of the invention provides the purposes of such ultraviolet absorbers.
But the present invention utilizes hydrotalcite to have the performance of intercalation assembling, and at hydrotalcite layers intercalation assembling 5-benzotriazole-4-hydroxyl-3-isobutyl--Phenylsulfonic acid (BZO) negatively charged ion (acid group), object is BZO negatively charged ion (C between prepared layer
16H
16N
3O
4S)
-) the intercalation configuration material.
This supermolecular interlayer structured ultraviolet light absorbent chemical constitution formula is:
[M
2+ 1-xM
3+ x(OH)
2](C
16H
16N
3O
4S)
- xmH
2O，
0.2≤x≤0.33 wherein, m is an interlayer crystal water molecule number, 0≤m≤2;
M
2+, M
3+Represent laminate divalence, trivalent metal ion respectively, M
2+Be Mg
2+, Ni
2+, Zn
2+, Fe
2+Or Cu
2+In any, M
2+Preferred Zn
2+Or Mg
2+, M
3+Be Al
3+, Co
3+, Fe
3+, Ti
3+Or Ga
3+In any, M
3+Preferred Al
3+M+/M
3+Mol ratio is 2-4: 1.
The obvious decomposition temperature of this supermolecular interlayer structured ultraviolet light absorbent interlayer organic species about 450 ℃, to 280-370nm wave band uv absorption rate greater than 90%.
The concrete preparation process of supermolecular interlayer structured ultraviolet light absorbent is as follows:
A. in the reactor that band stirs, add respectively and take off CO
2Deionized water and hydrotalcite LDHs precursor also fully mix the hydrotalcite precursor suspension that configuration concentration is 0.05-0.15M;
Used hydrotalcite precursor is that interlayer anion is NO
3 -Or CO
3 2-Hydrotalcite, its structural formula is: [M
2+ 1-xM
3+ x(OH)
2] [NO
3 - xMH
2O] or [M
2+ 1-xM
3+ x(OH)
2] [CO
3 2- X/2MH
2O], 0.2≤x≤0.33 wherein, m is an interlayer crystal water molecule number, 0≤m≤2; M
2+/ M
3+Mol ratio is 2-4: 1; M
2+Be Mg
2+, Ni
2+, Zn
2+, Fe
2+Or Cu
2+In any, M
2+Preferred Zn
2+Or Mg
2+M
3+Be Al
3+, Co
3+, Fe
3+, Ti
3+Or Ga
3+Any in the trivalent metal ion, M
3+Preferred Al
3+The hydrotalcite preparation method sees patent CN99119385.7.
B. with BZO with take off CO
2The deionized water compound concentration is the aqueous solution of 0.05-0.2M, and adjusting the pH value of solution value with NaOH is 3.5-8, dissolves fully to BZO;
C. in the following stirring fast of nitrogen protection; the limit is with in the suspension in the described reactor of BZO solution adding steps A of step B preparation; the add-on of BZO solution should satisfy that to mix the ratio that can hold the anionic theoretical molar number of BZO in the system of back between BZO negatively charged ion mole number and hydrotalcite precursor layer be 1-3: 1; under 25-100 ℃ of temperature condition crystallization 2-10 hour; filter; washing, drying obtains the hydrotalcite of BZO intercalation.
Intercalated houghite is carried out XRD, IR characterize demonstration (seeing Fig. 1,2), negatively charged ion has been assembled into stratified material LDHs interlayer.Learn that by the TG-DTA analysis the obvious decomposition temperature of BZO is 240 ℃ of (see figure 3)s, and the obvious decomposition temperature of intercalation product is brought up to 450 ℃ of left and right sides (see figure 4)s, and do not had obvious variable color.The ultraviolet absorption curve of measuring by UV-vis shows, its to 280-370nm wave band uv absorption rate greater than 90% (see figure 5).
Supermolecular interlayer structured ultraviolet light absorbent of the present invention is well-dispersed in polypropylene, polycarbonate, urethane, the propylene cyanogen-butadiene-styrene copolymer (ABS) by mixing, is the ultraviolet light and aging contrast experiment with the pure material that does not add light oxidation stability analog assistant then.With the polypropylene is example, by measuring infrared spectrum, has compared the carbonyl peak (1730cm that represents polypropylene photooxidation droping degree
-1) and carboxyl (3346cm
-1) peak, find that BZO intercalation ultraviolet absorbers can obviously improve the ageing resistance by ultraviolet light performance (seeing Table 1) of polypropylene, ABS and urethane resin.
Advantage of the present invention is:
First intercalation to have prepared interlayer anion be the hydrotalcite material of univalent 5-benzotriazole-4-hydroxyl-3-isobutyl--Phenylsulfonic acid radical ion;
2. the thermostability of this kind intercalation configuration ultraviolet absorbers increases significantly than intercalation object BZO itself, obviously decomposition temperature has been brought up to about 450 ℃, can be used as the ageing resistance by ultraviolet light additive as polypropylene, propylene cyanogen-butadiene-styrene copolymer easy photooxidation droping macromolecular materials such as (ABS).
3. this kind intercalation configuration ultraviolet absorbers reaches more than 90% the uv absorption rate of 280-370nm wavelength band, has good uv-absorbing ability.
4. because hydrotalcite has the selectivity ion exchange property, the ultraviolet absorbers for preparing does not contain the beavy metal impurity of introducing in the general organic uv absorbers building-up process, can further improve the stability of matrix material.
Description of drawings:
Fig. 1 is the XRD spectra of embodiment 1 hydrotalcite precursor and the anion intercalated ultraviolet absorbers of BZO, and wherein: a is the XRD spectra of hydrotalcite precursor, and b is the XRD spectra of intercalation configuration ultraviolet absorbers.
Fig. 2 is the infrared spectrum of embodiment 1 hydrotalcite precursor, BZO and the anion intercalated ultraviolet absorbers of BZO, and wherein: a is the infrared spectrum of hydrotalcite precursor, and b is the infrared spectrum of BZO, and c is the infrared spectrum of the anion intercalated ultraviolet absorbers of BZO.
Fig. 3 is the TG-DTA curve of BZO.
Fig. 4 is the TG-DTA curve of the anion intercalated ultraviolet absorbers of embodiment 1 BZO.
Fig. 5 is the ultraviolet absorption curve of BZO and the anion intercalated ultraviolet absorbers of embodiment 1 BZO, and wherein: a is the absorption curve of BZO; B is the absorption curve of the anion intercalated ultraviolet absorbers of BZO.
Embodiment:
Embodiment 1:
Steps A: with 35.7g (0.12mol) solid Zn (NO
3)
26H
2O and 22.5g (0.06mol) solid Al (NO
3)
39H
2O is dissolved in except that CO
2Deionized water in, be mixed with the 150ml mixing salt solution; In addition 14.4g (0.36mol) solid NaOH is dissolved in except that CO
2Deionized water in, be mixed with the 150ml alkaline solution.Rapidly alkaline solution and salts solution are rotated nucleation in the liquid film reactor in full back-mixing under the room temperature, and make the slurries that obtain in 100 ℃ of crystallization 6h.After the centrifugation, to throw out wash and the pH value that makes washing water near 7, obtain ZnAl-NO in 70 ℃ of dry 24h at last
3-LDHs, its Zn
2+/ Al
3+=2: 1.
With ZnAl-NO
3-LDHs precursor is well-dispersed in and takes off CO
2In the deionized water, be mixed with the suspension of 0.10M.
Step B: under the room temperature BZO is dissolved in and takes off CO
2In the deionized water, be mixed with the 0.15M aqueous solution, add NaOH and adjust PH=7.
Step C: nitrogen protection and stir fast down that 1: the 1 by volume solution with step B preparation adds in the suspension of steps A preparation; 100 ℃ of down reactions 2 hours are filtered, and wash to pH to be about 7; 70 ℃ of dryings 24 hours obtain the anion intercalated ultraviolet absorbers of BZO.
By XRD and infrared analysis (seeing Fig. 1, Fig. 2) as can be known, hydrotalcite layers is apart from increasing to 2.32nm by 0.89, and the interlayer nitrate radical disappears, and has to be presented at than clear evidence new key formation is arranged between sulfonic acid group and hydrotalcite laminate.Can conclude that thus the BZO negatively charged ion has inserted hydrotalcite layers, have stronger interaction between Subjective and Objective, form supermolecular intercalation structure, be not that simple physics is mixed between Subjective and Objective.Analyze as can be known by TG-DTA, the obvious decomposition temperature of the anion intercalated ultraviolet absorbers interlayer of BZO species is about 450 ℃ of (see figure 4)s.UV-vis test (see figure 5) shows that maximum absorption band appears at the 365nm place, and specific absorption is 92%.
Embodiment 2
Steps A: press embodiment 1 preparation hydrotalcite suspension.
Step B: BZO is dissolved in takes off CO
2In the deionized water, be mixed with the 0.10M aqueous solution, its pH is 3.5.
Step C: nitrogen protection is stirred the BZO solution of simultaneously step B being prepared down fast and was added in 1: 1 by volume in the suspension of steps A preparation; at room temperature react 10h, filter, wash to pH and be about 7; 70 ℃ of dryings 24 hours obtain the anion intercalated ultraviolet absorbers of BZO.Test finds that maximum absorption band appears at the 357nm place, and specific absorption is 90%.
Embodiment 3:
Press embodiment 1 preparation hydrotalcite suspension, BZO is dissolved in takes off CO
2In the deionized water, be mixed with the 0.15M aqueous solution, add NaOH and adjust pH=8.Press the method for embodiment 1 precursor suspension and BZO solution were mixed in 1: 2 by volume, 100 ℃ of reactions 6 hours are filtered, and wash to pH to be about 7,70 ℃ of dryings 24 hours, obtain the anion intercalated ultraviolet absorbers of BZO.Test finds that maximum absorption band appears at the 335nm place, and specific absorption is 91%
Embodiment 4:
Choose MgAl-NO
3-LDHs and Mg
2+/ Al
3+=2: 1 hydrotalcite is a precursor, is mixed with 0.10M suspension.
With embodiment 1, the BZO solution of preparation 0.10M is to mix at 1: 3 by precursor suspension and BZO liquor capacity ratio, obtains the anion intercalated ultraviolet absorbers of BZO.Test finds that maximum absorption band appears at the 350nm place, and specific absorption is 93%.The obvious decomposition temperature of ultraviolet absorbers interlayer species is greater than 400 ℃.
Embodiment 5:
Choose MgAl-NO
3-LDHs hydrotalcite is a precursor, Mg
2+/ Al
3+=2: 1, be mixed with 0.15M suspension.With embodiment 1, the BZO solution of preparation 0.20M, and press precursor suspension and mix than 1: 1.5 with the BZO liquor capacity, finally obtain the anion intercalated ultraviolet absorbers of BZO.Test finds that maximum absorption band appears at the 345nm place, and specific absorption is 90%.The obvious decomposition temperature of undetermined interlayer species.
Application examples:
The anion intercalated ultraviolet absorbers of BZO of embodiment 1-5 preparation is added in polypropylene, the ABS resin by mass ratio 1%, and at wavelength region 250-380nm, the ultraviolet lamp of power 1000W shone 60 minutes down, and upset in 10 minutes is 1 time at interval.By GB GB/T1040-1992 test tensile strength, the results are shown in Table 1.
The anion intercalated ultraviolet absorbers of BZO of embodiment 1-5 preparation is added in the urethane resin by mass ratio 1%, and at wavelength region 250-380nm, the ultraviolet lamp of power 1000W shone 60 minutes down, and upset in 10 minutes is 1 time at interval.By GB GB/T528-98 test tensile strength, the results are shown in Table 1.
Table 1 batten tensile strength test result (MPa)
| Ultraviolet absorbers | Polypropylene | ABS | Urethane | The batten state |
| Do not have | 31.04 | 53.59 | 9.47 | Before the UV-irradiation |
| Do not have | 11.14 | 25.71 | 4.09 | After the UV-irradiation |
| Example 1 preparation | 27.36 | 48.33 | 8.56 | After the UV-irradiation |
| Example 2 preparations | 28.12 | 47.52 | 9.27 | After the UV-irradiation |
| Example 3 preparations | 27.83 | 49.05 | 8.83 | After the UV-irradiation |
| Example 4 preparations | 27.19 | 47.21 | 8.04 | After the UV-irradiation |
| Example 5 preparations | 27.04 | 46.47 | 8.21 | After the UV-irradiation |
Claims (8)
1. supermolecular interlayer structured ultraviolet light absorbent, its chemical constitution formula is:
[M
2+ 1-xM
3+ x(OH)
2](C
16H
16N
3O
4S)
- x·mH
2O
0.2≤x≤0.33 wherein, m is an interlayer crystal water molecule number, 0≤m≤2;
M
2+, M
3+Represent laminate divalence, trivalent metal ion respectively, M
2+Be Mg
2+, Ni
2+, Zn
2+, Fe
2+Or Cu
2+In any, M
3+Be Al
3+, Co
3+, Fe
3+, Ti
3+Or Ga
3+In any, M
2+/ M
3+Mol ratio is 2-4: 1; (C wherein
16H
16N
3O
4S)
-It is 5-benzotriazole-4-hydroxyl-3-isobutyl--Phenylsulfonic acid (being called for short BZO) acid group.
2. supermolecular interlayer structured ultraviolet light absorbent according to claim 1, the obvious decomposition temperature that it is characterized in that its interlayer BZO absorb greater than 90% the 280-370nm band ultraviolet about 450 ℃.
3. supermolecular interlayer structured ultraviolet light absorbent according to claim 1 is characterized in that M
2+Be Zn
2+Or Mg
2+, M
3+Be Al
3+
4. the preparation method of a supermolecular interlayer structured ultraviolet light absorbent, concrete steps are as follows:
A. add deionized water and hydrotalcite (being called for short LDHs) precursor respectively and also fully mix in the reactor that band stirs, configuration concentration is the hydrotalcite precursor suspension of 0.05-0.15M;
B. be the aqueous solution of 0.05-0.2M with BZO and deionized water compound concentration, adjusting the pH value of solution value with NaOH is 3.5-8, dissolves fully to BZO;
C. under nitrogen protection and quick agitation condition; the BZO solution of step B preparation is added in the suspension of steps A reactor; the add-on of BZO solution should satisfy that to mix the ratio that can hold the anionic theoretical molar number of BZO in the system of back between BZO negatively charged ion mole number and hydrotalcite precursor layer be 1-3: 1; under 25-100 ℃ of temperature condition crystallization 2-10 hour; filter; washing, drying obtains the anion intercalated hydrotalcite of BZO, and its chemical formula is: [M
2+ 1-xM
3+ x(OH)
2] (C
16H
16N
3O
4S)
- xMH
2O, 0.2≤x≤0.33 wherein, m is an interlayer crystal water molecule number, 0≤m≤2; M
2+, M
3+Represent laminate divalence, trivalent metal ion respectively, M
2+Be Mg
2+, Ni
2+, Zn
2+, Fe
2+Or Cu
2+In any, M
3+Be Al
3+, Co
3+, Fe
3+, Ti
3+Or Ga
3+In any, M
2+/ M
3+Mol ratio is 2-4: 1; (C wherein
16H
16N
3O
4S)
-Be BZO
-
5. the preparation method of supermolecular interlayer structured ultraviolet light absorbent according to claim 4, it is characterized in that: used hydrotalcite precursor is that interlayer anion is NO
3 -Or CO
3 2-Hydrotalcite, its structural formula is: [M
2+ 1-xM
3+ x(OH)
2] [NO
3 - xMH
2O] or [M
2+ 1-xM
3+ x(OH)
2] [CO
3 2- X/2MH
2O], 0.2≤x≤0.33 wherein, m is an interlayer crystal water molecule number, 0≤m≤2; M
2+/ M
3+Mol ratio is 2-4: 1; M
2+Be Mg
2+, Ni
2+, Zn
2+, Fe
2+Or Cu
2+In any; M
3+Be Al
3+, Co
3+, Fe
3+, Ti
3+Or Ga
3+Any in the trivalent metal ion.
6. the preparation method of supermolecular interlayer structured ultraviolet light absorbent according to claim 5 is characterized in that M
2+Be Zn
2+Or Mg
2+, M
3+Be Al
3+
7. the application of supermolecular interlayer structured ultraviolet light absorbent as claimed in claim 1 in easy photooxidation droping polymkeric substance.
8. the application of supermolecular interlayer structured ultraviolet light absorbent as claimed in claim 1 in polypropylene, polycarbonate, urethane, acrylonitrile-butadiene-styrene copolymer (abbreviation ABS plastic).
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| PCT/CN2006/001243 WO2007071132A1 (en) | 2005-12-19 | 2006-06-08 | Supermolecular intercalation-structured uv absorber as well as its preparation method and use |
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2005
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2006
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Also Published As
| Publication number | Publication date |
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| CN1803901A (en) | 2006-07-19 |
| WO2007071132A1 (en) | 2007-06-28 |
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