CN1850787A - Supermolecular intercalation 2-phenylbenzimidazole-5-sulfonic acid, and its preparing method and use - Google Patents
Supermolecular intercalation 2-phenylbenzimidazole-5-sulfonic acid, and its preparing method and use Download PDFInfo
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- CN1850787A CN1850787A CN 200610080874 CN200610080874A CN1850787A CN 1850787 A CN1850787 A CN 1850787A CN 200610080874 CN200610080874 CN 200610080874 CN 200610080874 A CN200610080874 A CN 200610080874A CN 1850787 A CN1850787 A CN 1850787A
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- sulfonic acid
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- hydrotalcite
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Abstract
This invention discloses super molecule plant layer 2-benzene group benzimidazole-5 sulfonic acid and its preparation method and application. The character of brucite can be plant layer assembling packaged is used, anion of the 2-benzene group benzimidazole-5 sulfonic acid is inserted into the brucite layers, preparation layers guest is PSA anion super molecule plant layer structure. Its chemical formula is [M2+1-xM3+x(OH)2](C13H10N2O3S)-x.mH2O, absorptivity to 230-340nm wave band ultraviolet ray is more than 80 percent. The ultraviolet ray absorbing range and ability of the material is greatly improved compared to the PSA, and its interlayer substance obvious decomposition temperature is about 520 degree centigrade, its heat stability is improved compared to the PSA. The material can be used as ultraviolet light absorbent as polypropylene, polycarbonate, vinyl cyanide-butadiene styrol copolymer and polyurethane.
Description
Technical field
The present invention relates to a kind of supermolecular intercalation 2-Phenylbenzimidazole-5-sulfonic acid ultraviolet absorbers and preparation method thereof and application.
Background technology
The ozonosphere of the earth can absorb the most of ultraviolet ray in the solar ray, but still some can arrive earth surface, and this part ultraviolet energy is very high, can produce a series of detrimentally affect to Human's production life on the earth.For example, 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.2-Phenylbenzimidazole-5-sulfonic acid (2-Phenylbenzimidazole-5-Sulfonic Acid, write a Chinese character in simplified form PSA) can effectively absorb the 204-302nm UV-light, be used for makeup and water-borne coatings, domestic and foreign literature is used this compound in polymkeric substance report is few more.Investigate uv-absorbing (diffuse-reflectance) performance of this compound powder sample and find that maximum absorption appears at the 340nm place, peak shape is point, and absorption region is narrower.Be unsuitable for as the UV light stabilizing agent of polyolefine material and use.Simultaneously, this material at room temperature is slightly soluble in water, and is soluble in water behind the salify, and resistant to extraction and water-wash resistance are all relatively poor in polyolefine or other matrix material, can't efficiently use for a long time.In addition, this organism tool hypotoxicity is in the higher occasion of some service requirementss, such as using in the PP-R drinking-water pipe.Therefore,, at first must improve the uv-absorbing ability of its solid particulate, manage to improve its resistant to extraction and reduce toxicity as if the ultraviolet absorbers of wanting used as the polymer plastic goods.
Hydrotalcite (Layered Double Hydroxides is abbreviated as LDHs) is the important novel inorganic functional materials of a class, and its structure and composition have Modulatory character.This laboratory is obtaining great successes with hydrotalcite aspect the research of composite rubber-plastic material functional additive.LDHs has intercalation, and the original negatively charged ion of interlayer can be replaced by new negatively charged ion and replace under certain condition.Result of study shows, between the new negatively charged ion between hydrotalcite laminate and interposed layer interaction can take place, and makes some performance of the species between interposed layer take place to change significantly.The present invention utilizes the interchangeability of LDHs interlayer ion, 2-Phenylbenzimidazole-5-sulfonic acid anion is inserted the interlayer of LDHs precursor, prepare the good intercalation configuration ultraviolet absorbers that can be used for improving the ageing resistance by ultraviolet light ability of matrix material of a kind of uv absorption property.This intercalation configuration ultraviolet absorbers utilizes interaction between LDHs and 2-Phenylbenzimidazole-5-sulfonic acid anion to strengthen sorption to UV-light, and its thermostability and resistant to extraction also have further raising.
Document Y.Feng, D.Li, Y.Wang, David G.Evans, X.Duan, Synthesis andcharacterization of a UV absorbent-intercalated Zn-Al layered double hydroxide, Polym.Degrad.Stab.91,789-794 (2006) has prepared the LDHs of HMBA intercalation, and the ultraviolet light stability and the thermostability of product are significantly improved, but HMBA uv absorption property behind intercalation does not have considerable change.
Document Zhang Weifeng; Li Dianqing; Sun Meng, EvansD.G., Duan Xue; the assembling of supramolecular structure tropeolin-D intercalated houghite and photo and thermal stability research thereof; SCI, 10 (2004) have prepared the LDHs of tropeolin-D intercalation, and product has not only kept the color of tropeolin-D itself; and compare with tropeolin-D, its photostabilization and thermotolerance all are greatly improved.
Summary of the invention
The purpose of this invention is to provide a kind of supermolecular intercalation 2-Phenylbenzimidazole-5-sulfonic acid ultraviolet absorbers; Another object of the present invention provides a kind of preparation method who prepares supermolecular intercalation 2-Phenylbenzimidazole-5-sulfonic acid ultraviolet absorbers; 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 2-Phenylbenzimidazole-5-sulfonic acid (PSA) negatively charged ion (acid group), object is PSA negatively charged ion (C between prepared layer
13H
10N
2O
3S)
-) the intercalation configuration material.
This supermolecular interlayer structured ultraviolet light absorbent chemical constitution formula is:
[M
2+ 1-xM
3+ x(OH)
2](C
13H
10N
2O
3S)
- 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
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
2+/ M
3+Mol ratio is 2-4: 1.
Greater than 80%, maximum absorbance 87% appears at the 280nm place to this supermolecular interlayer structured ultraviolet light absorbent to 230-340nm wave band uv absorption rate, and the obvious decomposition temperature of interlayer organic species is about 520 ℃.
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 PSA 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 PSA;
C. in the following stirring fast of nitrogen protection; the limit is with in the suspension in the described reactor of PSA solution adding steps A of step B preparation; the add-on of PSA solution should satisfy that to mix the ratio that can hold the anionic theoretical molar number of PSA in the system of back between PSA 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 LDHs-PSA of PSA 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.Ultraviolet absorption curve by UV-vis diffuse reflection measuring powdered sample shows that greater than 80%, maximum absorbance 87% appears at 280nm place (see figure 3) to 230-340nm wave band uv absorption rate for it.Learn that by the TG-DTA analysis the obvious decomposition temperature of PSA is 450 ℃ of (see figure 4)s, and the obvious decomposition temperature of intercalation product 520 ℃ of left and right sides (see figure 5)s have been brought up to.
With supermolecular interlayer structured ultraviolet light absorbent of the present invention and not the common PSA of intercalation be well-dispersed in polypropylene, ABS, the urethane by mixing, be the ultraviolet light and aging contrast experiment with the virgin pp that does not add any stable analog assistant then.Find that PSA intercalation ultraviolet absorbers can obviously improve polyacrylic ageing resistance by ultraviolet light performance (seeing Table 1).
Advantage of the present invention is:
First intercalation to have prepared interlayer anion be the hydrotalcite material of univalent 2-Phenylbenzimidazole-5-sulfonate ion;
2. the uv absorption property of this kind intercalation configuration ultraviolet absorbers powdered sample increases significantly than PSA itself, thermostability has also obtained being improved to some extent, obviously decomposition temperature has been brought up to about 520 ℃, can be used as the ageing resistance by ultraviolet light additive as easy photooxidation droping macromolecular materials such as polypropylene.
3. this kind intercalation configuration ultraviolet absorbers reaches more than 80% the uv absorption rate of 230-340nm wavelength band, has good uv-absorbing ability.
4. because hydrotalcite has the selectivity ion exchange property, only have organic molecule to enter interlayer, the beavy metal impurity of leaving in the PSA building-up process is by filtering, and product purity gets a promotion.
5. this kind intercalation configuration ultraviolet absorbers is insoluble to non-strongly-acid solvent, and interlayer species and laminate bonding force are strong, and resistance to migration is good, and contact toxicity decreases.
Description of drawings:
Fig. 1 is the XRD spectra of embodiment 1 hydrotalcite precursor and LDHs-PSA, and wherein: a is the XRD spectra of hydrotalcite precursor, and b is the XRD spectra of LDHs-PSA.
Fig. 2 is the infrared spectrum of embodiment 1 hydrotalcite precursor, PSA and LDHs-PSA, and wherein: a is the infrared spectrum of hydrotalcite precursor, and b is the infrared spectrum of PSA, and c is the infrared spectrum of LDHs-PSA.
Fig. 3 is the ultraviolet absorption curve of the LDHs-PSA of PSA and embodiment 1 preparation, and wherein: a is the absorption curve of PSA; B is the absorption curve of LDHs-PSA.
Fig. 4 is the TG-DTA curve of PSA.
Fig. 5 is the TG-DTA curve of the LDHs-PSA of embodiment 1 preparation.
Embodiment:
Embodiment 1:
Steps A: with solid Zn (NO
3)
26H
2O 35.7g (0.12mol) and solid Al (NO
3)
39H
2O 22.5g (0.06mol) is dissolved in except that CO
2Deionized water in, be mixed with mixing salt solution (150ml); In addition solid NaOH 14.4g (0.36mol) is dissolved in except that CO
2Deionized water in, be mixed with alkaline solution (150ml).Rapidly alkaline solution and salts solution are rotated nucleation in the liquid film reactor in full back-mixing under the room temperature, the slurries that obtain are in 100 ℃ of following crystallization 6h.Centrifugation go out throw out and wash to filter cake pH value near 7, measure solid contents, the ZnAl-NO that obtains in 70 ℃ of dry 24h at last
3-LDHs, its Zn
2+/ Al
3+=2: 1.
With washed ZnAl-NO
3-LDHs filter cake is with taking off CO
2Deionized water preparation precursor suspension is also fully disperseed, and presses the suspension concentration 0.10M that dry solid content calculates.
Step B: with taking off CO
2Deionized water preparation PSA solution, concentration of aqueous solution 0.15M adds NaOH to PSA in right amount and dissolves fully, adjusts PH=7.
Step C: the solution of step B preparation was added in the suspension of steps A preparation in 1: 1 by volume and stir fast, nitrogen protection and 100 ℃ reaction 2 hours down, filtering precipitate washs to filtrate pH=7, and 70 ℃ of dryings 24 hours obtain LDHs-PSA.Its chemical formula is:
[Zn
0.67Al
0.33(OH)
2](C
13H
10N
2O
3S)
- 0.32·0.58H
2O。
By XRD and infrared analysis (seeing Fig. 1, Fig. 2) as can be known, hydrotalcite layers is apart from increasing to 2.64nm by 0.89, and the peak of nitrate radical disappears between infrared figure previous generation top layer, 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 hydrotalcite layers nitrate radical is replaced by the PSA negatively charged ion fully, be not that simple physics is mixed but had stronger chemical action between Subjective and Objective, formed supermolecular intercalation structure.UV-vis test (see figure 5) shows that maximum absorption band appears at the 280nm place, and specific absorption is 87%.Analyze as can be known by TG-DTA, the obvious decomposition temperature of LDHs-PSA interlayer species is about 450 ℃ of (see figure 4)s.
Embodiment 2
Steps A: press embodiment 1 preparation hydrotalcite suspension.
Step B: PSA is dissolved in takes off CO
2In the deionized water, be mixed with the 0.15M aqueous solution, add NaOH and adjust pH=8.
Step C: the PSA solution of step B preparation was added in the suspension of steps A preparation in 1: 1 by volume, pressing the method for embodiment 1 mixed precursor suspension and PSA solution in 1: 2 by volume, 100 ℃ were reacted 6 hours, filter, wash to pH and be about 7,70 ℃ of dryings 24 hours obtain LDHs-PSA, and its chemical formula is: [Zn
0.65Al
0.35(OH)
2] (C
13H
10N
2O
3S)
- 0.340.53H
2O.
Test finds that maximum absorption band appears at the 284nm place, and specific absorption is 86%.
Embodiment 3:
Press embodiment 1 preparation hydrotalcite suspension, PSA is dissolved in takes off CO
2In the deionized water, be mixed with the 0.10M aqueous solution, its pH is 3.0.Stir fast and logical nitrogen protection, at room temperature react 10h, filter, wash to filtrate pH and be about 7,70 ℃ of dryings 24 hours, obtain LDHs-PSA, its chemical formula is: [Zn
0.70Al
0.30(OH)
2] (C
13H
10N
2O
3S)
- 0.290.60H
2O.
Test finds that maximum absorption band appears at the 303nm place, and specific absorption is 80%
Embodiment 4:
Choose the MgAl-NO of preparation 0.10M
3-LDHs hydrotalcite is precursor suspension, wherein Mg
2+/ Al
3+=2: 1.
With embodiment 1, the PSA solution of preparation 0.10M is to mix precursor suspension and PSA solution at 1: 3 by volume, obtains LDHs-PSA, and its chemical formula is: [Mg
0.68Al
0.32(OH)
2] (C
13H
10N
2O
3S)
- 0.320.45H
2O.
Test finds that maximum absorption band appears at the 295nm place, and specific absorption is 84%.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 PSA solution of preparation 0.10M, and press precursor suspension and mix than 1: 2 with the PSA liquor capacity, finally obtaining LDHs-PSA, its chemical formula is: [Mg
0.64Al
0.36(OH)
2] (C
13H
10N
2O
3S)
- 0.360.42H
2O
Test finds that maximum absorption band appears at the 298nm place, and specific absorption is 81%.The obvious decomposition temperature of undetermined interlayer species.
Application examples:
The LDHs-PSA sample of embodiment 1-5 preparation is added in polypropylene, the ABS resin by mass ratio 2%, add in the urethane resin by mass ratio 1% again, 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 the tensile strength of GB GB/T1040-1992 test polypropylene, ABS resin, the tensile strength by GB GB/T528-98 test urethane resin the results are shown in Table 1 respectively.
As a comparison, PSA is added in polypropylene, the ABS resin by mass ratio 2%, add in the urethane resin by mass ratio 1%, 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 the respective standard 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 | 31.12 | 53.44 | 10.08 | Before the UV-irradiation |
| Do not have | 10.26 | 26.34 | 4.87 | After the UV-irradiation |
| PSA | 22.66 | 38.41 | 8.87 | After the UV-irradiation |
| Example 1 sample | 24.48 | 40.25 | 9.26 | After the UV-irradiation |
| Example 2 samples | 25.01 | 38.96 | 8.35 | After the UV-irradiation |
| Example 3 samples | 24.13 | 41.47 | 8.78 | After the UV-irradiation |
| Example 4 samples | 24.07 | 40.17 | 8.41 | After the UV-irradiation |
| Example 5 samples | 23.63 | 39.51 | 8.09 | After the UV-irradiation |
From the listed result of last table as seen, do not adding under the situation of uv-absorbing agent, the sample tensile strength descends significantly, and polypropylene, ABS, urethane have descended 67.03%, 50.71%, 51.69% respectively.The test data of adding the PSA sample is that polypropylene, ABS, urethane have descended 27.19%, 28.13%, 12.00% respectively.After adding the prepared ultraviolet absorbers LDHs-PSA of this patent, situation is clearly better, polypropylene, ABS, urethane (the pressing embodiment 1 data) 21.33%, 24.68%, 8.13% that descended respectively, compare with the sample that does not add uv-absorbing agent, the ageing resistance by ultraviolet light performance of material has obtained obvious improvement, also obviously is better than adding the sample of PSA.
Claims (6)
1. supermolecular intercalation 2-Phenylbenzimidazole-5-sulfonic acid, chemical constitution formula is:
[M
2+ 1-xM
3+ x(OH)
2](C
13H
10N
2O
3S)
- 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;
Greater than 80%, maximum absorbance 87% appears at the 280nm place to this supermolecular interlayer structured ultraviolet light absorbent to 230-340nm wave band uv absorption rate, and the obvious decomposition temperature of interlayer organic species is about 520 ℃.
2. supermolecular intercalation 2-Phenylbenzimidazole according to claim 1-5-sulfonic acid is characterized in that M in the described chemical formula
2+Be Zn
2+Or Mg
2+, M
3+Be Al
3+
3. the preparation method of supermolecular intercalation 2-Phenylbenzimidazole as claimed in claim 1-5-sulfonic acid, concrete steps are as follows:
A. in the reactor that band stirs, add respectively and take off CO
2Deionized water and hydrotalcite LDHs precursor also fully stir, and configuration concentration is the hydrotalcite precursor suspension of 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
3+Be Al
3+, Co
3+, Fe
3+, Ti
3+Or Ga
3+Any in the trivalent metal ion;
B. use 2-Phenylbenzimidazole-5-sulfonic acid (being abbreviated as PSA) and take off CO
2The deionized water compound concentration is the aqueous solution of 0.05-0.2M, is 3.5-8 with NaOH regulator solution pH value, dissolves fully to PSA;
C. under nitrogen protection; the limit is stirred fast with in the suspension in the described reactor of PSA solution adding steps A of step B preparation in the limit; the add-on of PSA solution should satisfy that to mix the ratio that can hold the anionic theoretical molar number of PSA in the system of back between PSA 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 LDHs-PSA of PSA intercalation.
4. the preparation method of supermolecular intercalation 2-Phenylbenzimidazole according to claim 3-5-sulfonic acid is characterized in that M
2+Be Zn
2+Or Mg
2+M
3+Be Al
3+
5. the application of the described supermolecular intercalation 2-Phenylbenzimidazole of claim 1-5-sulfonic acid is used as ultraviolet absorbers in easily by the poly-material of ultraviolet light and aging.
6. the application of the described supermolecular intercalation 2-Phenylbenzimidazole of claim 1-5-sulfonic acid is used as ultraviolet absorbers in polypropylene, ABS, polyurethane material.
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2006
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| WO2008086716A1 (en) * | 2007-01-16 | 2008-07-24 | Beijing University Of Chemical Technology | Layered double hydroxide complex inserted by dipeptiven and the preparation method thereof |
| CN102532189A (en) * | 2012-01-12 | 2012-07-04 | 西北师范大学 | Preparation method of super-molecule metal gel |
| CN102532189B (en) * | 2012-01-12 | 2014-07-23 | 西北师范大学 | Preparation method of super-molecule metal gel |
| CN104725670A (en) * | 2015-03-24 | 2015-06-24 | 北京化工大学 | Super-molecular structure phenolsulfonphthalein or derivative thereof intercalated ultraviolet blocking material and preparation method thereof |
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| CN107629310A (en) * | 2017-07-28 | 2018-01-26 | 北京化工大学 | A kind of supermolecular intercalation structure light stabilizer and preparation method thereof |
| CN107629310B (en) * | 2017-07-28 | 2020-07-24 | 北京化工大学 | Supermolecule intercalation structure light stabilizer and preparation method thereof |
| CN109016004A (en) * | 2018-08-31 | 2018-12-18 | 广德竹之韵工艺品厂 | A kind of mould proof uvioresistant processing method of bamboo wood |
| CN109266191A (en) * | 2018-08-31 | 2019-01-25 | 广德竹之韵工艺品厂 | A kind of open air bamboo product coating |
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