CN100383197C - Sulfosalicylic with super molecular inserting layer structure, its preparation process and use - Google Patents
Sulfosalicylic with super molecular inserting layer structure, its preparation process and use Download PDFInfo
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- CN100383197C CN100383197C CNB2006100121745A CN200610012174A CN100383197C CN 100383197 C CN100383197 C CN 100383197C CN B2006100121745 A CNB2006100121745 A CN B2006100121745A CN 200610012174 A CN200610012174 A CN 200610012174A CN 100383197 C CN100383197 C CN 100383197C
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- ldhs
- sulfosalicylic
- hydrotalcite
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Abstract
The present invention provides a sulfosalicylic acid with a supermolecule intercalation structure, a preparation method thereof and application thereof, which is characterized in that sulfosalicylic acid (for short SSA) radical ions can be assembled in the hydrotalcite interlayer in an intercalation mode by utilizing the intercalation assembly performance of the hydrotalcite; a preparation interlaminar object is a material LDHs-SSA of SSA anions, wherein the absorption ratio of the LDHs-SSA is greater than 80% within a wave band of 250 to 350 nm and can achieve about 88% at 335 nm, and the heat decomposition temperature is about 560 DEG C. Experimental data indicates that the LDHs-SSA performs powerful ultraviolet degradation effect when the LDHs-SSA is added in polymeric materials, such as polypropylene, vinyl cyanide-butadiene-styrene copolymer, etc., so the LDHs-SSA can be used as a light stabilizing agent applied to polyolefin materials.
Description
Technical field
The present invention relates to the purposes of a kind of Sulfosalicylic with super molecular inserting layer structure and preparation method thereof and this photostabilizer.
Background technology
Sulphosalicylic acid (5-Sulfosalicylic acid dihydrate is abbreviated as SSA) Chinese another name is the sulphur salicylic acid, because of its can with complexing colour generation such as iron copper, be widely used in identifying in other material elements such as iron copper, also can be used for quantitative analysis.Sulphosalicylic acid can be dissolved in ether, soluble in water and ethanol, 120 ℃ of fusing points.SSA at 250-350nm to the specific absorption of UV-light greater than 60%, the specific absorption at the 340nm place has reached 80%, its thermostability is strong inadequately, is easy to during high temperature decompose, greatly about 530 ℃ of oxygenolysis that take fire.Because the sulfonic group oxidisability of SSA is very strong, and SSA itself has very strong acidity, directly contact with metal, plastics etc. and can make metallic corrosion, thereby the plastics oxidation quickens that it is aging, therefore makes the range of application of SSA and result of use be subjected to great restriction.
Hydrotalcite (Layered Double Hydroxides is abbreviated as LDHs) is the important novel inorganic functional materials of a class, and particularly in recent years, hydrotalcite has had new application aspect plastics additive.Performance that the intercalation that utilizes hydrotalcite to have is assembled and good photo-thermal are stable, and it is had very high using value as plastics additive body or carrier.Therefore, utilize the ion exchange property of hydrotalcite, the interlayer that SSA is inserted into LDHs can increase substantially the thermostability of SSA, in conjunction with SSA this in the ultraviolet region absorption characteristic, can prepare the organic/inorganic composite light stabilizer of good heat stability.Herein, the LDHs laminate has been given full play to the effect of " molecule container ", SSA ion and laminate interact make sulfonic group can not be directly and metal or plastics have an effect, the uv absorption property that the ultraviolet shielded and SSA self structure of combination water talcum laminate itself is determined, and show that by test this kind novel material can be used as photostabilizer and is applied in the polyolefine.
Document V.Prevot, C.Forano, and J.P.Besse, Syntheses and Thermal and ChemicalBehaviors of Tartrate and Succinate Intercalated Zn
3Al and Zn
2Cr Layered DoubleHydroxides Inorg.Chem.1998,37, among the 4293-4301 Tartaric acid and succsinic acid are successfully inserted hydrotalcite layers, improved its thermostability greatly.
Document Xing Ying, Li Dianqing, Evans D.G., Duan Xue, the assembling of supramolecular structure salicylate intercalated houghite and structure and performance study, chemical journal 2003 (2): among the 267-272 with zinc-aluminium hydrotalcite Zn
2Al-CO
3-LDHs is precursor (main body), is dispersion medium with ethylene glycol, has assembled salicylate (object) intercalated houghite Zn with ion exchange method
2Al[o-HO (C
6H
4) COO] LDH, find, main body hydrotalcite laminate and object are with electrostatic force and interaction of hydrogen bond, and the supramolecular structure material ultraviolet-resistant effect that obtains strengthens and has stability preferably, have prepared a kind of novel inorganic-organic compound ultraviolet blocking material that collects shielding and absorb dual-use function.
Summary of the invention
The purpose of this invention is to provide a kind of Sulfosalicylic with super molecular inserting layer structure; Another object of the present invention provides a kind of preparation method who prepares Sulfosalicylic with super molecular inserting layer structure; A further object of the invention provides the purposes of this Sulfosalicylic with super molecular inserting layer structure.
Sulfosalicylic with super molecular inserting layer structure provided by the invention: but be to utilize hydrotalcite to have the performance of intercalation assembling, at hydrotalcite layers intercalation assembling sulphosalicylic acid (writing a Chinese character in simplified form SSA) radical ion, object is the anionic material of SSA between prepared layer, can be expressed as LDHs-SSA.
LDHs-SSA molecular formula provided by the invention is:
[M
2+ 1-xM
3+ x(OH)
2](C
7H
4O
6S)
- x/2mH
2O
0.2≤x≤0.33 wherein, m is an interlayer crystal water molecule number, its laminate divalence, Tricationic mol ratio M
2+/ M
3+=2-4: 1; Divalent-metal ion can be Mg
2+, Ni
2+, Zn
2+, Fe
2+, or Cu
2+In any, preferred Zn
2+Or Mg
2+Trivalent metal ion can be Al
3+, Co
3+, Fe
3+, Ti
3+Or Ga
3+In any, preferred Al
3+
The heat decomposition temperature of LDHs-SSA is 560～564 ℃, has improved about 30 ℃ than the heat decomposition temperature of SSA; Greater than 80%, the specific absorption maximum reaches 88% to LDHs-SSA in the specific absorption of 250～350nm ultraviolet region.
The preparation route of LDHs-SSA is:
With interlayer anion is NO
3 -Or CO
3 2-Hydrotalcite (be abbreviated as: LDHs-NO
3Or LDHs-CO
3) precursor, adopt ion exchange method, under acidity or neutrallty condition, the SSA acid ion is replaced original negatively charged ion between the hydrotalcite precursor layer, obtain the LDHs-SSA that interlayer is the SSA acid radical anion.
Concrete preparation process is as follows:
A. be NO with interlayer anion
3 -Or CO
3 2-The hydrotalcite precursor be made into the suspension that concentration is 0.05-0.15M, place reactor fully to stir;
Interlayer anion is NO
3 -Or CO
3 2-Hydrotalcite front body structure formula be: [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] (wherein 0.2≤x≤0.33, m is an interlayer crystal water molecule number), its laminate divalence, Tricationic mol ratio M
2+/ M
3+=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.M
2+Preferred Zn
2+Or Mg
2+, M
3+Preferred Al
3+
B. be the aqueous solution of 0.05-0.2M with the SSA compound concentration, adjust the solution pH value with NaOH and be about neutrality; Ratio by negatively charged ion mole number in the described hydrotalcite precursor of SSA negatively charged ion mole number and steps A is 0.8-2: 1, SSA solution is joined short mix in the above-mentioned reactor, under 25-100 ℃ of temperature condition crystallization 2-24 hour, filter, washing, drying obtains the hydrotalcite of SSA intercalation.
The intercalated houghite that obtains is carried out XRD, IR, elemental analysis demonstration, and the SSA negatively charged ion has been assembled into hydrotalcite LDHs interlayer, proves that the product that obtains is LDHs-SSA.Analyze by TG-DTA and to learn, the temperature of initial decomposition of this LDHs-SSA is than 30 ℃ of the raisings of pure SSA; The ultraviolet absorption curve of measuring by UV-vis shows that it absorbs greater than 80% the 250-350nm band ultraviolet.
Join in polyolefine such as polypropylene, propylene cyanogen-butadiene-styrene copolymer (ABS), polycarbonate fully mixed with 1% weight ratio LDHs-SSA, compare experiment with the polyolefine that does not have any auxiliary agent of admixture then, the result shows that admixture has the polyolefine mechanical property of LDHs-SSA to improve a lot, shown the very strong photodegradative ability of uvioresistant (seeing Table 1,2).
Advantage of the present invention is:
First intercalation to have prepared interlayer anion be the hydrotalcite material of the sulphosalicylic acid radical ion of divalence; The preparation method's intercalation precursor that is adopted is easy to preparation, and technology is simple, and the low intercalation reaction of cost is easy to carry out;
2. this kind intercal type photostabilizer reaches more than 80% the ultraviolet absorption of 250-350nm wavelength band, has good uv-absorbing ability.
3. the Heat stability is good of this kind intercal type photostabilizer, anionic combustion decomposition between genetic horizon just in the time of about 560 ℃ has very high heat resistanceheat resistant performance.
4. as polyolefinic additive polyolefinic mechanical property is improved a lot with LDHs-SSA, and have the photodegradative ability of strong uvioresistant.
Description of drawings:
Fig. 1 is the XRD spectra of embodiment 1 hydrotalcite precursor and LDHs-SSA, and wherein: a is the XRD spectra of LDHs, and b is the XRD spectra of LDHs-SSA.
Fig. 2 is LDHs, SSA among the embodiment 1 and the infrared spectrum of LDHs-SSA, and wherein: a is the infrared spectrum of LDHs, and b is the infrared spectrum of SSA, and c is the infrared spectrum of LDHs-SSA.
Fig. 3 is the TG-DTA curve of SSA.
Fig. 4 is the TG-DTA curve of the intercalation zinc-aluminium hydrotalcite of SSA.
Fig. 5 is LDHs, SSA and the LDHs-SSA ultraviolet absorption curve among the embodiment 1, and wherein: a is the absorption curve of LDHs; B is the absorption curve of SSA; C is the absorption curve of LDHs-SSA.
Embodiment:
Embodiment 1:
Steps A: preparation ZnAl-NO
3-LDHs precursor filter cake, wherein Zn
2+/ Al
3+=2: 1, the hydrotalcite preparation method sees patent CN99119385.7.
Step B: get above-mentioned filter cake 3.45g (0.01mol) with removing CO
2Deionized water fully disperse, be mixed with 150ml suspension, violent stirring.Take by weighing 3.81g (0.015mol) SSA and 1.2g (0.03mol) NaOH again, be dissolved in 150ml and remove CO
2Deionized water in, be configured to solution.Under nitrogen protection, in 2 hours, this SSA drips of solution is added in the above-mentioned LDHs suspension, 100 ℃ of following reaction 2h filter, and wash to PH to be about 7,70 dry 24 hours, obtain SSA intercalation configuration photostabilizer LDHs-SSA.
The intercalated houghite that obtains is carried out signs such as XRD, IR, ultimate analysis draw, its chemical formula is;
Zn
0.64Al
0.36(OH)
2[o-HO(C
6H
3)COOSO
3]
0.18·0.50H
2O
The heat decomposition temperature of LDHs-SSA is 560 ℃, and the maximal ultraviolet absorption peak of LDHs-SSA appears at the 335nm place, and specific absorption is 88%.
Embodiment 2:
Step is with embodiment 1, and difference is Zn
2+/ Al
3+Prepare SSA intercalation configuration photostabilizer at=3: 1.
The intercalated houghite that obtains is carried out signs such as XRD, IR, ultimate analysis draw, its chemical formula is;
Zn
0.77Al
0.23(OH)
2[o-HO(C
6H
3)COOSO
3]
0.115·0.51H
2O
The heat decomposition temperature of LDHs-SSA is 562 ℃, and the maximal ultraviolet absorption peak of LDHs-SSA appears at the 337nm place, and specific absorption is 86%.
Embodiment 3:
Preparation ZnAl-CO
3-LDHs precursor, wherein Zn
2+/ Al
3+=2: 1.Prepare SSA intercalation configuration photostabilizer according to embodiment 1 step B again.
The intercalated houghite that obtains is carried out signs such as XRD, IR, ultimate analysis draw, its chemical formula is;
Zn
0.67Al
0.33(OH)
2[o-HO(C
6H
3)COOSO
3]
0.165·0.63H
2O
The heat decomposition temperature of LDHs-SSA is 560 ℃, and the maximal ultraviolet absorption peak of LDHs-SSA appears at the 335nm place, and specific absorption is 86%.
Embodiment 4:
Preparation MgAl-CO
3-LDHs precursor, wherein Mg
2+/ Al
3+=2: 1.Prepare SSA intercalation configuration photostabilizer according to embodiment 1 step B again.
The intercalated houghite that obtains is carried out signs such as XRD, IR, ultimate analysis draw, its chemical formula is;
Mg
0.67Al
0.33(OH)
2[o-HO(C
6H
3)COOSO
3]
0.165·0.52H
2O
The heat decomposition temperature of LDHs-SSA is 564 ℃, and the maximal ultraviolet absorption peak of LDHs-SSA appears at the 336nm place, and specific absorption is 87%.
Embodiment 5:
Press embodiment 1 steps A, B operation is treated after the precursor slurry temperature reaches 100 ℃ B to be splashed into, and in 70 ℃ of reactions 12 hours, filters, and washs to PH to be about 7,70 ℃ of dryings 24 hours, obtains SSA intercalation configuration photostabilizer.
The intercalated houghite that obtains is carried out signs such as XRD, IR, ultimate analysis draw, its chemical formula is;
Zn0.66Al0.34(OH)2[o-HO(C6H3)COOSO3]0.17·0.74H2O
The heat decomposition temperature of LDHs-SSA is 560 ℃, and the maximal ultraviolet absorption peak of LDHs-SSA appears at the 335nm place, and specific absorption is 87%
Application examples 1:
The LDHs-SSA of embodiment 1 preparation is added in the polypropylene by mass ratio 1%, and at wavelength region 250-380nm, the ultraviolet lamp of power 1000W shone 120 minutes down, sampling in per 20 minutes, the tensile property test is done in every interval upset in 10 minutes 1 time then on omnipotent puller system, the results are shown in Table 1.
Table 1 measuring mechanical property result
Data as can be seen from table, adding the polyacrylic every mechanical property of 1%LDHs-SSA all increases than virgin pp, and each degradation is slower after UV-irradiation, and after promptly LDHs-SSA was added in explanation, polypropylene had had very strong ultraviolet light degradation capability.
Application examples 2
The anion intercalated ultraviolet absorbers of SSA of embodiment 1 preparation is added in propylene cyanogen-butadiene-styrene copolymer (ABS) by mass ratio 1%, at wavelength region 250-380nm, the ultraviolet lamp of power 1000W shone 120 minutes down, sampling in per 20 minutes, every interval upset in 10 minutes 1 time, on omnipotent puller system, do the tensile property test then, the results are shown in Table 2.
Table 2 measuring mechanical property result
As can be seen from Table 2, the purer ABS of every mechanical property that adds the ABS of 1%LDHs-SSA increases, and each degradation is slower after UV-irradiation, and after promptly LDHs-SSA was added in explanation, ABS had had very strong ultraviolet light degradation capability.
Claims (5)
1. a Sulfosalicylic with super molecular inserting layer structure is abbreviated as LDHs-SSA, and its molecular formula is:
[M
2+ 1-xM
3+ x(OH)
2](C
7H
4O
6S)
- x/2·mH
2O
0.2≤x≤0.33 wherein, m is an interlayer crystal water molecule number, its laminate divalence, Tricationic mol ratio M
2+/ M
3+=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+In any;
The heat decomposition temperature of LDHs-SSA is 560～564 ℃, and greater than 80%, maximum reaches 88% to LDHs-SSA in the specific absorption of 250～350nm ultraviolet region.
2. Sulfosalicylic with super molecular inserting layer structure according to claim 1 is characterized in that the M of molecular formula
2+Be Zn
2+Or Mg
2+M
3+Be Al
3+
3. the preparation method of a Sulfosalicylic with super molecular inserting layer structure as claimed in claim 1, concrete preparation process is as follows:
A. be NO with interlayer anion
3 -Or CO
3 2-The hydrotalcite precursor be made into the suspension that concentration is 0.05-0.15M, place reactor fully to stir;
Interlayer anion is NO
3 -Or CO
3 2-Hydrotalcite front body structure formula be: [M
2+ 1-xM
3+ x(OH)
2] [NO
3 - x MH
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, its laminate divalence, Tricationic mol ratio M
2+/ M
3+=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;
B. be the aqueous solution of 0.05-0.2M with the SSA compound concentration, adjust the solution pH value with NaOH and be about neutrality; Ratio by negatively charged ion mole number in the described hydrotalcite precursor of SSA negatively charged ion mole number and steps A is 0.8-2: 1, SSA solution is joined short mix in the above-mentioned reactor, under 25-100 ℃ of temperature condition crystallization 2-24 hour, filter, washing, drying obtains the hydrotalcite of SSA intercalation.
4. a Sulfosalicylic with super molecular inserting layer structure as claimed in claim 1 is used as ultraviolet absorbers in easily by the polymeric material of ultraviolet light and aging.
5. a Sulfosalicylic with super molecular inserting layer structure as claimed in claim 1 is used as ultraviolet absorbers in polypropylene, ABS, polyurethane material.
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|---|---|---|---|---|
| CN100463892C (en) * | 2007-01-16 | 2009-02-25 | 北京化工大学 | Decomposing process for salicylic acid and its isomer using hydrotalcite |
| CN107418577A (en) * | 2017-03-27 | 2017-12-01 | 北京化工大学 | Pillared Mg Al Tb hydrotalcites of a kind of 5 sulfosalicylic acid intercalation and preparation method thereof |
| CN107513179B (en) * | 2017-07-28 | 2019-06-11 | 北京化工大学 | One kind ultraviolet absorber of supermolecular intercalation structure containing auxiliary agent and preparation method thereof |
| CN108193552A (en) * | 2017-12-07 | 2018-06-22 | 常州市沃兰特电子有限公司 | A kind of preparation method of water solubility paper fibre light stabilizer |
| CN109206749A (en) * | 2018-09-03 | 2019-01-15 | 安庆市航海印务有限公司 | A kind of preparation method of plastic products |
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|---|---|---|---|---|
| CN1288078A (en) * | 1999-09-14 | 2001-03-21 | 北京化工大学 | Method for synthesis of well-dispersed and super fine anion laminated material |
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| CN1507778A (en) * | 2002-12-13 | 2004-06-30 | 北京化工大学 | Supermolecular structure glyphosate slow release agent and preparing method thereof |
-
2006
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288078A (en) * | 1999-09-14 | 2001-03-21 | 北京化工大学 | Method for synthesis of well-dispersed and super fine anion laminated material |
| WO2001090235A1 (en) * | 2000-05-26 | 2001-11-29 | Rhodia Chimie | Use of hydrotalcite as filler in polymer compositions |
| CN1467177A (en) * | 2002-06-24 | 2004-01-14 | 北京化工大学 | Method for assembling anion type supramolecular intercalation structure material |
| CN1507778A (en) * | 2002-12-13 | 2004-06-30 | 北京化工大学 | Supermolecular structure glyphosate slow release agent and preparing method thereof |
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