CN101544782A - Supermolecular structural 5,5'-methylene disalicylic acid intercalation ultraviolet absorption material and preparation method thereof - Google Patents

Supermolecular structural 5,5'-methylene disalicylic acid intercalation ultraviolet absorption material and preparation method thereof Download PDF

Info

Publication number
CN101544782A
CN101544782A CN200910084222A CN200910084222A CN101544782A CN 101544782 A CN101544782 A CN 101544782A CN 200910084222 A CN200910084222 A CN 200910084222A CN 200910084222 A CN200910084222 A CN 200910084222A CN 101544782 A CN101544782 A CN 101544782A
Authority
CN
China
Prior art keywords
mdsa
ultraviolet absorption
ldhs
znal
methylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN200910084222A
Other languages
Chinese (zh)
Inventor
李殿卿
徐向宇
林彦军
崔国静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN200910084222A priority Critical patent/CN101544782A/en
Publication of CN101544782A publication Critical patent/CN101544782A/en
Pending legal-status Critical Current

Links

Images

Landscapes

  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention provides a supermolecular structural 5,5'-methylene disalicylic acid intercalation ultraviolet absorption material and a preparation method thereof. The supermolecular structural 5,5'-methylene disalicylic acid intercalation ultraviolet absorption material is abbreviated as ZnAl-MDSA-LDHs; the molecular formula of the material is (Zn<2+>1-xAl<3+>xOH2)<x+>(C15H10O6)<2->x/2.mH2O; and hydrotalcite ZnAl-NO3-LDHs is used as a precursor, and 5,5'-methylene disalicylic acid is intercalated between ZnAl-NO3-LDHs layers by adopting an ion-exchange method and assembled to form the ZnAl-MDSA-LDHs with good crystal phase structure and excellent performance. The ultraviolet absorption rate of the ZnAl-MDSA-LDHs material in a wave band range of between 250 and 370 nanometers is over 80 percent, and the material has good ultraviolet absorption capability and is a good ultraviolet absorption material. The material begins combustion decomposition of interlayer negative ions at 370 DEG C, reaches a peak value temperature of a heat release peak at 435 DEG C, has strong thermal stability, and is an excellent photo-thermal stabilizing agent. The capability of resisting ultraviolet light degradation can be greatly improved by adding the ZnAl-MDSA-LDHs into a polymeric material such as polypropylene and the like.

Description

Supramolecular structure 5,5 '-methylene-bis Whitfield's ointment intercalation ultraviolet absorption material and preparation method thereof
Technical field
The present invention relates to a kind of supramolecular structure 5,5 '-methylene-bis Whitfield's ointment intercalation ultraviolet absorption material and preparation method thereof.
Background technology
Environmental pollution brings ultraviolet increasing considerably, because of photochemical effect and biological effect that ultraviolet ray produced very remarkable, cause that other high molecular polymers of Polyolefin and are aging, cause its performance to reduce, material becomes fragile, finally lose physical strength, therefore be necessary to study uvioresistant additive efficiently.5,5 '-the salicylic English name of methylene-bis is 5,5 '-Methylenedisalicylic acid, be abbreviated as MDSA, have the good absorption performance at 250～370nm wave band, outward appearance is a white powder, be slightly soluble in water under the room temperature, soluble in water behind the one-tenth sodium salt, Chang Zuowei medicine synthetic intermediate is used for pharmaceutical industry more.MDSA high temperature easily decomposes down, and resistant to extraction and water-wash resistance are all relatively poor in matrix material, make its range of application 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 is having new application aspect plastics additive, the auxiliary agent.Intercalation assembling performance and the favorable photo-thermal stability of utilizing hydrotalcite to have have very high using value with it as plastics additive or carrier.Therefore, utilize the ion exchange property of hydrotalcite, MDSA is inserted into the thermostability that hydrotalcite layers can increase substantially MDSA,, can prepare the compound uv-absorbing agent of organic/inorganic of good heat stability in conjunction with the uv absorption property of MDSA itself.After the MDSA negatively charged ion enters the LDHs interlayer, LDHs plays the effect of " molecule container ", MDSA ion and laminate interact make the carboxylic acid group can not be directly and metal or plastics have an effect, the uv absorption property that the ultraviolet shielded and MDSA self structure of combination water talcum laminate itself is determined, show that by experiment this kind novel material can be used as photostabilizer and is applied in the polyolefine.
Document [1] 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): in 267～272 with ZnAl-CO 3-LDHs is precursor (main body), is dispersion medium with ethylene glycol, has assembled salicylate (object) intercalated houghite ZnAl-[o-HO (C with ion exchange method 6H 4) COO]-LDHs, 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.
Document [2] Dianqing Li, Zhenjun Tuo, David G.Evans, Xue Duan *.Preparation of5-benzotriazolyl-4-hydroxy-3-sec-butylbenzenesulfon ateanion-pillaredlayered doublehydroxide and its photostabilizing effect on polypropylene.Journal of Solid State Chemistry, 2006,179, in 3114～3120 5-benzotriazole base-4-hydroxyl-3-isobutyl-benzene sulfonic acid is successfully inserted hydrotalcite layers, pass through electrostatic force, covalent linkage and hydrogen bond etc. interact between main body laminate and object organic ion, under the prerequisite that original UV absorbing properties does not influence, inorganic laminate performance intercepts action of ultraviolet radiation, has improved its thermostability greatly.
Document [3] Tang, P.G.; Xu, X.Y.; Lin.Y.J.; Li, D.Q.Enhancement of the Thermo-andPhotostability of an Anionic Dye by Intercalation in a Zinc-Aluminum Layered DoubleHydroxide Host.Ind.Eng.Chem.Res.2008,47, prepared the hydrotalcite of Acid Chrome Deep Yellow GG intercalation among the 2478-2483, the thermostability of product is significantly improved.
Document [4] Chai, H.; Lin, Y.J.; Evans, D.G.; Li, D.Q.Synthesis and UV AbsorptionProperties of 2-Naphthylamine-1.5-disulfonic Acid Intercalated Zn-Al Layered DoubleHydroxide.Ind.Eng.Chem.Res.2008,47, among the 2855-1860 with 2-naphthylamines-1,5-disulfonic acid intercalation ZnAl-LDHs, obtain have the intercalation product of excellent uv absorption property and thermal stability, and be successfully applied in the polypropylene, obtain good anti-photooxidation resistance effect.
Summary of the invention
Purpose of the present invention provide a kind of supramolecular structure 5,5 '-methylene-bis Whitfield's ointment intercalation ultraviolet absorption material; Another object of the present invention provide this kind supramolecular structure 5,5 '-preparation method of methylene-bis Whitfield's ointment intercalation ultraviolet absorption material.
Supramolecular structure 5,5 provided by the invention '-methylene-bis Whitfield's ointment intercalation ultraviolet absorption material, write a Chinese character in simplified form ZnAl-MDSA-LDHs, its molecular formula is [Zn 2+ 1-xAl 3+ x(OH) 2] X+(C 15H 10O 6) 2- X/2MH 2O, wherein Zn 2+/ Al 3+Mol ratio is 2～4:1, and the value of x changes with mole number, and m is an interlayer crystal water molecule number, 0.65≤m≤0.85.
The interlayer anion of ZnAl-MDSA-LDHs begins to decompose when temperature is 370-375 ℃, reaches the peak temperature of exothermic peak in the time of 435 ℃; All above 80%, the maximal ultraviolet absorption peak appears at 350～370nm place, specific absorption 85～90% to the uv-absorbing rate of 250～370nm wave band for it.
Supramolecular structure 5,5 '-the concrete preparation process of methylene-bis Whitfield's ointment intercalation ultraviolet absorption material is as follows:
A. with hydrotalcite LDHs precursor with except that CO 2Deionized water add in the reactor that band stirs and fully mix the suspension that compound concentration is 0.05～0.15mol/L;
The structural formula of used LDHs precursor is [Zn 2+ 1-xAl 3+ x(OH) 2] X+(NO 3 -) xMH 2O, wherein Zn 2+/ Al 3+Mol ratio is 2～4:1;
B. with 5,5 '-the methylene-bis Whitfield's ointment, be abbreviated as MDSA, be dissolved in except that CO 2Deionized water in be mixed with the aqueous solution that concentration is 0.05～0.2mol/L, adjusting the pH value of solution value with NaOH is 4～10, dissolves fully to MDSA; The pH value is 5-9 preferably;
C. the ratio by negatively charged ion mole number in the described hydrotalcite precursor of MDSA negatively charged ion mole number and steps A is 1～5:1; be preferably 2～4:1; MDSA solution is joined short mix in the reactor of steps A; under nitrogen protection, stir fast, crystallization is 5～24 hours under 50～100 ℃ of temperature; crystallization condition is a crystallization 6～18 hours under 70-100 ℃ of temperature preferably; filter, washing, drying obtains the hydrotalcite of ZnAl-MDSA-LDHs intercalation.
The intercalated houghite that obtains has been carried out following sign:, show that the MDSA negatively charged ion has been assembled into hydrotalcite layers by X-ray powder diffraction (XRD), infrared (IR), ultimate analysis illness that has not attacked the vital organs of the human body.(be called for short: TG-DTA) the results are shown in Figure 1, Fig. 2, the result shows that the temperature of initial decomposition of its intercalation product is 375 ℃, has improved 95 ℃ for 280 ℃ than the temperature of initial decomposition of MDSA to its thermogravimetric differential thermal analysis of carrying out.See Fig. 3 with the ultraviolet absorption curve that the UV, visible light analytical procedure is measured, by Fig. 3 find out its to the uv-absorbing rate of 250～370nm wave band all above 80%.
Reaching this uv-absorbing material not, the MDSA of intercalation is well-dispersed in the polypropylene (PP) by mixing, and make MDSA/PP, ZnAl-MDSA-LDHs/PP and pure PP sample film, be the ultraviolet ageing contrast experiment, by measuring three's infrared spectrum, compared hydroxyl peak (see figure 4) and the carbonyl peak (see figure 5) of representing polypropylene photooxidation droping degree, found that MDSA intercalated houghite uv-absorbing material can obviously improve polyacrylic ageing resistance by ultraviolet light performance.
The invention has the beneficial effects as follows:
First intercalation prepared interlayer anion be 5,5 of divalence '-methylene-bis salicylate ionic hydrotalcite material;
2. this kind intercalation ultraviolet absorption material all above 80%, has good uv absorption property to the uv-absorbing rate of 250～370nm wave band, has expanded the scope of UV light absorber.
3. the Heat stability is good of this kind intercalation material, temperature of initial decomposition has been brought up to 370-375 ℃, and very strong thermal stability is arranged.
4. as polyacrylic additive the photodegradative ability of its uvioresistant is increased substantially with ZnAl-MDSA-LDHs.
Description of drawings
Fig. 1 is the TG-DTA curve of MDSA.
Fig. 2 is the TG-DTA curve of ZnAl-MDSA-LDHs.
Fig. 3 is the ultraviolet absorption curve of sample, and wherein: a is ZnAl-NO 3The ultraviolet absorption curve of-LDHs, b are the ultraviolet absorption curves of MDSA, and c is the ultraviolet absorption curve of ZnAl-MDSA-LDHs.
Fig. 4 is that the hydroxyl peak intensity of the PP film of the PP film that added MDSA, ZnAl-MDSA-LDHs and pure PP film is with the ultra violet lamp time variation diagram.
Fig. 5 is that the carbonyl peak intensity of the PP film of the PP film that added MDSA, ZnAl-MDSA-LDHs and pure PP film is with the ultra violet lamp time variation diagram.
Specimen and interpolation sample used among Fig. 1-5 are all taken from embodiment 1.
Embodiment
Embodiment 1
Steps A: with the solid Al (NO of 45.0g (0.12mol) 3) 39H 2Solid Zn (the NO of O and 71.4g (0.24mol) 3) 26H 2O is dissolved in except that CO 2Deionized water in, be mixed with the 300mL mixing salt solution; Take by weighing the NaOH of 28.8g (0.72mol), be dissolved in except that CO 2Deionized water in, be mixed with the 300mL alkaline solution; Under the room temperature two kinds of solution are added quick nucleation in the rotation liquid film reactor with identical flow velocity, the slurries that obtain are moved to 100 ℃ of crystallization 6h of 1000mL flask, centrifugation is with removing CO 2Deionized water wash be about 7,70 ℃ of dry 24h to the pH of washing water, obtain ZnAl-MDSA-LDHs, its Zn 2+/ Al 3+=2:1.
Getting above-mentioned filter cake 5.98g (0.005mol) uses except that CO in four-hole boiling flask 2The deionized water ultra-sonic dispersion, be mixed with 75mL suspension.
Step B: take by weighing 1.44g (0.005mol) MDSA and 0.36g NaOH (0.009mol) and be dissolved in 75mL except that CO 2Deionized water in, fast agitation condition adds appropriate amount of NaOH down to adjust pH value is 6.98, prepares the aqueous solution of MDSA.
Step C: under nitrogen protection, the solution with step B preparation joins in the precursor slurry of steps A preparation rapidly, and at 100 ℃ of following crystallization 6h, centrifugation is with removing CO 2Deionized water wash be about 7,70 ℃ of dry 24h to pH, obtain MDSA intercalation configuration uv-absorbing material ZnAl-MDSA-LDHs.
The intercalated houghite that obtains is carried out signs such as XRD, IR, ultimate analysis, and to draw its chemical formula be Zn 0.66Al 0.34(OH) 2(MDSA) 0.170.83H 2O.
The initial decomposition temperature of ZnAl-MDSA-LDHs is 375 ℃, and its strongest ultraviolet absorption peak appears at 350～370nm place, specific absorption 85～90%.
Embodiment 2
Steps A: preparation ZnAl-NO 3-LDHs precursor slurry, method is identical with steps A among the embodiment 1.
Step B: take by weighing 1.44g (0.005mol) MDSA and 0.36g NaOH (0.009mol) and be dissolved in 75mL except that CO 2Deionized water in, fast agitation condition adds appropriate amount of NaOH down to adjust pH value is 10.03, prepares the aqueous solution of MDSA.
Step C: under nitrogen protection, the solution with step B preparation joins in the precursor slurry of steps A preparation rapidly, and at 80 ℃ of following crystallization 12h, centrifugation is with removing CO 2Deionized water wash be about 7,70 ℃ of dry 24h to pH, obtain MDSA intercalation configuration uv-absorbing material ZnAl-MDSA-LDHs.
The intercalated houghite that obtains is carried out signs such as XRD, IR, ultimate analysis, and to draw its chemical formula be Zn 0.66Al 0.34(OH) 2(MDSA) 0.140.75H 2O.
The initial decomposition temperature of ZnAl-MDSA-LDHs is 370 ℃, and its strongest ultraviolet absorption peak appears at 350～370nm place, specific absorption 85～90%.
Embodiment 3
Steps A: preparation ZnAl-NO 3-LDHs precursor slurry, method is identical with steps A among the embodiment 1.
Step B: take by weighing 1.44g (0.005mol) MDSA and 0.36g NaOH (0.009mol) and be dissolved in 75mL except that CO 2Deionized water in, fast agitation condition adds appropriate amount of NaOH down to adjust pH value is 4.12, prepares the aqueous solution of MDSA.
Step C: under nitrogen protection, the solution with step B preparation joins in the precursor slurry of steps A preparation rapidly, and at 90 ℃ of following crystallization 10h, centrifugation is with removing CO 2Deionized water wash be about 7,70 ℃ of dry 24h to pH, obtain MDSA intercalation configuration uv-absorbing material ZnAl-MDSA-LDHs.
The intercalated houghite that obtains is carried out signs such as XRD, IR, ultimate analysis, and to draw its chemical formula be Zn 0.66Al 0.34(OH) 2(MDSA) 0.150.68H 2O.
The initial decomposition temperature of ZnAl-MDSA-LDHs is 372 ℃, and its strongest ultraviolet absorption peak appears at 350～365nm place, specific absorption 85～90%.
Embodiment 4
Steps A: preparation ZnAl-NO 3-LDHs precursor slurry, method is identical with steps A among the embodiment 1.
Step B: take by weighing 2.88g (0.01mol) MDSA and 0.72g NaOH (0.018mol), make NO 3 -Be 1:4 with object MDSA ionic charge ratio, be dissolved in 75mL and remove CO 2Deionized water in, fast agitation condition adds appropriate amount of NaOH down to adjust pH value is 7.10, prepares the aqueous solution of MDSA.
Step C: under nitrogen protection, the solution with step B preparation joins in the precursor slurry of steps A preparation rapidly, and at 60 ℃ of following crystallization 18h, centrifugation is with removing CO 2Deionized water wash be about 7,70 ℃ of dry 24h to pH, obtain MDSA intercalation configuration uv-absorbing material ZnAl-MDSA-LDHs.
The intercalated houghite that obtains is carried out signs such as XRD, IR, ultimate analysis, and to draw its chemical formula be Zn 0.66Al 0.34(OH) 2(MDSA) 0.170.83H 2O.
The initial decomposition temperature of ZnAl-MDSA-LDHs is 370 ℃, and its strongest ultraviolet absorption peak appears at 350～370nm place, specific absorption 85～90%.
Embodiment 5
Steps A: preparation ZnAl-NO 3-LDHs precursor slurry, method is identical with steps A among the embodiment 1.
Step B: take by weighing 2.88g (0.01mol) MDSA and 0.72g NaOH (0.018mol), make NO 3 -Be 1:4 with object MDSA ionic charge ratio, be dissolved in 75mL and remove CO 2Deionized water in, fast agitation condition adds appropriate amount of NaOH down to adjust pH value is 9.88, prepares the aqueous solution of MDSA.
Step C: under nitrogen protection, the solution with step B preparation joins in the precursor slurry of steps A preparation rapidly, and at 80 ℃ of following crystallization 12h, centrifugation is with removing CO 2Deionized water wash be about 7,70 ℃ of dry 24h to pH, obtain MDSA intercalation configuration uv-absorbing material ZnAl-MDSA-LDHs.
The intercalated houghite that obtains is carried out signs such as XRD, IR, ultimate analysis, and to draw its chemical formula be Zn 0.66Al 0.34(OH) 2(MDSA) 0.170.83H 2O.
The initial decomposition temperature of ZnAl-MDSA-LDHs is 370 ℃, and its strongest ultraviolet absorption peak appears at 350～370nm place, specific absorption 85～90%.
Embodiment 6
Steps A: preparation ZnAl-NO 3-LDHs precursor slurry, method is identical with steps A among the embodiment 1.
Step B: take by weighing 2.88g (0.01mol) MDSA and 0.72g NaOH (0.018mol), make NO 3 -Be 1:4 with object MDSA ionic charge ratio, be dissolved in 75mL and remove CO 2Deionized water in, fast agitation condition adds appropriate amount of NaOH down to adjust pH value is 4.45, prepares the aqueous solution of MDSA.
Step C: under nitrogen protection, the solution with step B preparation joins in the precursor slurry of steps A preparation rapidly, and at 90 ℃ of following crystallization 10h, centrifugation is with removing CO 2Deionized water wash be about 7,70 ℃ of dry 24h to pH, obtain MDSA intercalation configuration uv-absorbing material ZnAl-MDSA-LDHs.
The intercalated houghite that obtains is carried out signs such as XRD, IR, ultimate analysis, and to draw its chemical formula be Zn 0.66Al 0.34(OH) 2(MDSA) 0.170.83H 2O.
The initial decomposition temperature of ZnAl-MDSA-LDHs is 370 ℃, and its strongest ultraviolet absorption peak appears at 350～370nm place, specific absorption 85～90%.

Claims (5)

  1. A supramolecular structure 5,5 '-methylene-bis Whitfield's ointment intercalation ultraviolet absorption material, be called for short ZnAl-MDSA-LDHs, its molecular formula is [Zn 2+ 1-xAl 3+ x(OH) 2] X+(C 15H 10O 6) 2- X/2MH 2O, wherein Zn 2+/ Al 3+Mol ratio is 2～4:1, and the value of x changes with mole number, and m is an interlayer crystal water molecule number, 0.65≤m≤0.85.
  2. 2. supramolecular structure 5,5 according to claim 1 '-methylene-bis Whitfield's ointment intercalation ultraviolet absorption material, it is characterized in that its interlayer anion begins to decompose when temperature is 370-375 ℃, reach the peak temperature of exothermic peak in the time of 435 ℃; All above 80%, the maximal ultraviolet absorption peak appears at 350～370nm place, specific absorption 85～90% to the uv-absorbing rate of 250～370nm wave band for it.
  3. 3. preparation supramolecular structure 5 as claimed in claim 1, the method for 5 '-methylene-bis Whitfield's ointment intercalation ultraviolet absorption material, concrete preparation process is as follows:
    A. with the hydrotalcite precursor with except that CO 2Deionized water add in the reactor that band stirs and fully mix the suspension that compound concentration is 0.05～0.15mol/L;
    The structural formula of used hydrotalcite precursor is [Zn 2+ 1-xAl 3+ x(OH) 2] X+(NO 3 -) xMH 2O, wherein Zn 2+/ Al 3+Mol ratio is 2～4:1;
    B. with 5,5 '-the methylene-bis Whitfield's ointment, be called for short MDSA, be dissolved in except that CO 2Deionized water in be mixed with the aqueous solution that concentration is 0.05～0.2mol/L, adjusting the pH value of solution value with NaOH is 4～10, dissolves fully to MDSA;
    C. the ratio by negatively charged ion mole number in the described hydrotalcite precursor of MDSA negatively charged ion mole number and steps A is 1～5:1; MDSA solution is joined short mix in the reactor of steps A; under nitrogen protection; stir fast; crystallization is 5～24 hours under 50～100 ℃ of temperature; filter, washing, drying obtains the hydrotalcite of ZnAl-MDSA-LDHs intercalation.
  4. 4. preparation supramolecular structure 5 according to claim 3, the method for 5 '-methylene-bis Whitfield's ointment intercalation ultraviolet absorption material is characterized in that the pH value of the MDSA solution of step B preparation is 5-9.
  5. 5. preparation supramolecular structure 5 according to claim 3, the method for 5 '-methylene-bis Whitfield's ointment intercalation ultraviolet absorption material is characterized in that the ratio of negatively charged ion mole number in the described MDSA negatively charged ion of step C mole number and the hydrotalcite precursor is 2～4:1; Described crystallization condition is a crystallization 6～18 hours under 70-100 ℃ of temperature.
CN200910084222A 2009-05-15 2009-05-15 Supermolecular structural 5,5'-methylene disalicylic acid intercalation ultraviolet absorption material and preparation method thereof Pending CN101544782A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200910084222A CN101544782A (en) 2009-05-15 2009-05-15 Supermolecular structural 5,5'-methylene disalicylic acid intercalation ultraviolet absorption material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200910084222A CN101544782A (en) 2009-05-15 2009-05-15 Supermolecular structural 5,5'-methylene disalicylic acid intercalation ultraviolet absorption material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN101544782A true CN101544782A (en) 2009-09-30

Family

ID=41192173

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200910084222A Pending CN101544782A (en) 2009-05-15 2009-05-15 Supermolecular structural 5,5'-methylene disalicylic acid intercalation ultraviolet absorption material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN101544782A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101817947A (en) * 2010-04-06 2010-09-01 四川大学 Wideband ultraviolet absorber for polyolefin and preparation method thereof
CN101817937A (en) * 2010-03-26 2010-09-01 北京化工大学 Supermolecular structural 5,5'-sulfenyl disalicylic acid intercalation ultraviolet absorbing material and preparation method thereof
CN103694552A (en) * 2012-09-28 2014-04-02 中国石油天然气股份有限公司 Thermo-oxidative aging resistant polypropylene composition and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101817937A (en) * 2010-03-26 2010-09-01 北京化工大学 Supermolecular structural 5,5'-sulfenyl disalicylic acid intercalation ultraviolet absorbing material and preparation method thereof
CN101817947A (en) * 2010-04-06 2010-09-01 四川大学 Wideband ultraviolet absorber for polyolefin and preparation method thereof
CN101817947B (en) * 2010-04-06 2012-07-25 四川大学 Wideband ultraviolet absorber for polyolefin and preparation method thereof
CN103694552A (en) * 2012-09-28 2014-04-02 中国石油天然气股份有限公司 Thermo-oxidative aging resistant polypropylene composition and preparation method thereof
CN103694552B (en) * 2012-09-28 2016-02-10 中国石油天然气股份有限公司 A kind of heat oxygen aging resistance polypropene composition and preparation method thereof

Similar Documents

Publication Publication Date Title
CN1333005C (en) Supermolecular interlayer structured ultraviolet light absorbent, its preparation method and uses
Shang et al. Effect of acetic acid on morphology of Bi2WO6 with enhanced photocatalytic activity
Wang et al. Solar photocatalytic degradation of methylene blue by mixed metal oxide catalysts derived from ZnAlTi layered double hydroxides
CN103394327B (en) Silanized functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof
CN103274437B (en) Three-dimensional flower-like layered double hydroxide and preparation method thereof
US20120161090A1 (en) Rutile-type titanium oxide crystal and mid-infrared filter using the same
Li et al. Fabrication of intercalated p-aminobenzoic acid into Zn-Ti layered double hydroxide and its application as UV absorbent
Qu et al. Precursor preparation of Zn–Al layered double hydroxide by ball milling for enhancing adsorption and photocatalytic decoloration of methyl orange
CN109071259A (en) The method for producing new nano material
CN104874365A (en) Carboxymethyl cellulose ion intercalated hydrotalcite-like composite material, and preparation method and application thereof
Shang et al. Preparation and characterization of rose-like NiO nanostructures
Li et al. Preparation of 5-benzotriazolyl-4-hydroxy-3-sec-butylbenzenesulfonate anion-intercalated layered double hydroxide and its photostabilizing effect on polypropylene
CN103394326A (en) Amino functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof
Bouteraa et al. Zn-M-CO3 layered double hydroxides (M= Fe, Cr, or Al): Synthesis, characterization, and removal of aqueous indigo carmine
CN101173118B (en) Supramolecular structured 2-naphthylamine-1,5-disulfonic acid intercalation ultraviolet absorption material and method for producing the same
Zhou et al. Enhanced photocatalytic performance of spherical BiOI/MnO 2 composite and mechanism investigation
CN103394329B (en) Carboxyl functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof
Gayathri et al. Effect of method of preparation on the photocatalytic activity of NiAl2O4
Cao et al. Inorganic–organic hybrid pigment fabricated in the preparation process of organic pigment: Preparation and characterization
CN101544782A (en) Supermolecular structural 5,5&#39;-methylene disalicylic acid intercalation ultraviolet absorption material and preparation method thereof
CN102618074B (en) Thermal stabilization type ponceau 2R intercalation hydrotalcite dye and preparation method thereof
CN108298591A (en) A kind of synthetic method of hexagon iron titanate nanometer sheet material and application
CN105289576B (en) A kind of ZnAl-LDO@Nb2O5The preparation method of catalysis material
CN103191783B (en) Zinc sulfide-benzoic acid nano composite photocatalytic material and preparation method thereof
CN101274770B (en) Anionic surfactant intercalation titanium-based hydrotalcite and preparation thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20090930