CN101289220A - Selective infrared absorption material of aminodiacetic acid intercalation structure and method for preparing same - Google Patents
Selective infrared absorption material of aminodiacetic acid intercalation structure and method for preparing same Download PDFInfo
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Abstract
The invention relates to a selective infrared absorption material of amino adipate with an intercalation structure which is shorten as IDAs-LDHs and the molecular formula thereof is (M<2+>)1-x(M<3+>)x(OH)2(A<2->a(B<n->b.mH2O. The invention also relates to a preparation method of the selective infrared absorption material of the amino adipate with the intercalation structure, which is characterized in that hydrotalcite LDHs is taken as a precursor, and organic matter of aminoacetic acid is intercalated between the hydrotalcite LDHs layers by an ion-exchange method and then assembled to obtain the IDAs-LDHs with a good crystal phase structure and excellent performance. The absorptivity of the IDAs-LDHs material for absorbing infrared ray with various wave bands is increased by more than 45 percent to 79 percent compared with that of the hydrotalcite LDHs precursor, by 20 percent compared with the hydrotalcite in 7 to 25mum and by more than 105 percent compared with the hydrotalcite in 10 to 14mum, so the IDAs-LDHs material has excellent infrared absorption ability and is a good infrared absorption material.
Description
Technical field
The present invention relates to outer absorbing material of a kind of amino oxalic acid intercalation configuration selectivity and preparation method thereof.
Background technology
In recent years, the infrared ray absorption material is being brought into play important effect as the important function auxiliary agent aspect the raising agricultural film heat-insulating property.At present, the heat preserving agent that domestic plastic sheeting for farm use enterprise uses mainly is the mineral substance class, and kind has kaolin, talcum powder, diatomite, silica, sericite, lime carbonate etc.But reason owing to chemical constitution, structure and particle form, the infrared ray absorption ability of these materials is lower, and association have stray crystal mutually and particle bigger, directly cause its dispersing property in plastic sheeting for farm use bad, influence the visible light transmissive performance, quicken plastic sheeting for farm use aging and reduction plastic sheeting for farm use work-ing life and result of use.Iminodiethanoic acid (IDA), N-(2-hydroxyethyl) iminodiethanoic acid (HIDA) and methyliminodiacetic acid (MIDA) are white crystalline powder shape thing, are the infrared ray absorption materials (IDAs) of a class excellent performance, at 1600-700cm
-1The infrared rays wave band at place has good absorptive character.Main as amberlite fat raw material, metal finishing material, agricultural chemicals raw material, as complexing agent, be used for organic synthesis etc.But the IDAs thermostability is relatively poor, easily decomposes during high temperature, and IDAs itself is acid strong and have corrodibility, directly contact the performance of the material that can accelerate the failure with plastics, so its range of application is restricted.
Hydrotalcite (Layered Double Hydroxides is abbreviated as LDHs) is the important novel inorganic functional materials of a class, and especially in recent years, hydrotalcite has had new application aspect plastics additive.Performance and favorable photo-thermal stability that the intercalation that utilizes hydrotalcite to have is assembled have very high using value with it as plastics additive body or carrier.Therefore, utilize the ion exchange property of hydrotalcite, IDAs is inserted into the thermostability that hydrotalcite layers can improve IDAs,, can prepare the compound infrared absorbing agents of organic/inorganic of good heat stability in conjunction with the infrared ray absorption performance of IDAs itself.The effect of " the molecule container " of LDHs laminate, make IDAs negatively charged ion and laminate interact and the carboxylic acid group can not be directly and plastics have an effect, the infrared absorption performance that the infrared shielding of combination water talcum laminate itself and IDAs self structure are determined, this kind novel material can be used as infrared absorbing agents and is applied in the polyolefine.
Document [1] Xu Guozhi, Guo Canxiong, Duan Xue, Jiang Chuangeng, the infrared absorption performance of the two hydroxyl complex hydroxides of PE film laminate, applied chemistry, investigated the magnesium aluminum-hydrotalcite powder as being incubated the variation that filler is added to material property behind the polyethylene agricultural film by means such as X-ray powder diffraction, infrared spectra, scanning electronic microscope, heat analysiss, image analysiss among 1999 (16) 3:45-48, and with dose heat preserving agent commonly used---the film of talcum powder compares.The result shows that the infrared absorption performance of PE/ hydrotalcite film obviously is better than PE/ talcum powder film; And the dispersing property of solid powder in film, through performance, thermostability and the mechanical property etc. of film visible light all are not subjected to obvious influence.Infrared spectroscopic study to the hydrotalcite powder shows. its significant infrared absorption effect is mainly because of due to the special laminate structure and chemical constitution of hydrotalcite.
Document [2] is rectified celebrating pool, Zhao Yun, Xie Hui, D.G.Evans, Duan Xue, the intercalation of hydrotalcite and selectivity infrared absorption performance thereof, applied chemistry, 2002, Vol 19, No.10 is a precursor with magnalium carbonate hydrotalcite among the 1011-1013, is medium with the deionized water, has assembled MgAl-CO with ion exchange method
3SO
4-LDHs hydrotalcite is found SO
4 2-Part enters MgAl-CO
3-LDHs interlayer, the MgAl-CO of formation
3SO
4-LDHs hydrotalcite still keeps former LDHs laminate structure, and the selectivity infrared absorption performance of novel LDHs in the heat radiation wavelength region obviously strengthens.
Summary of the invention
The purpose of this invention is to provide a kind of selective infrared absorption material of aminodiacetic acid intercalation structure; Another object of the present invention provides the preparation method of this infrared absorbing material.
Selective infrared absorption material of aminodiacetic acid intercalation structure provided by the invention is abbreviated as: IDAs-LDHs, and it is a supramolecular structure, and crystalline structure is the crystalline structure of houghite material, and its molecular formula is:
(M
2+)
1-x(M
3+)
x(OH)
2(A
2-)
a(B
n-)
b·mH
2O
M wherein
2+Be Zn
2+, Mg
2+, Ni
2+, Cu
2+, Fe
2+, Co
2+, Ca
2+, Mn
2+In any or two kinds, M
2+Preferred Zn
2+, Mg
2+, Cu
2+, Fe
2+, Ca
2+, Mn
2+In any or two kinds, more preferably Zn
2+And/or Mg
2+
M
3+Be Al
3+, Fe
3+, Cr
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any, M
3+Preferred Al
3+, Co
3+, Fe
3+, more preferably Al
3+
A represents amino oxalic acid compounds, is abbreviated as IDAs, and A is any in iminodiethanoic acid (IDA), N-(2-hydroxyethyl) iminodiethanoic acid (HIDA), the methyliminodiacetic acid (MIDA);
B
N-For carrying capacity is the inorganic anion of n, B in the IDAs-LDHs chemical formula
N-Can not exist or for CO
3 2-, NO
3 -, Cl
-, Br
-, I
-, OH
-, H
2PO
4 -In any, two kinds or three kinds;
0.1<X<0.8; A, b are respectively A
2-And B
N-Quantity, 2a+n * b=X;
M is a crystal water quantity, 0.01<m<4.
The concrete preparation process of selective infrared absorption material of aminodiacetic acid intercalation structure is as follows:
A. hydrotalcite LDHs precursor is scattered in except that CO
2Deionized water in and fully mix the hydrotalcite precursor suspension that configuration concentration is about 0.2-0.3M;
Used LDHs structural formula is: (M
2+)
1-x(M
3+)
x(OH)
2(B
N-)
bMH
2O, wherein M
2+Be Zn
2+, Mg
2+, Ni
2+, Cu
2+, Fe
2+, Co
2+, Ca
2+, Mn
2+In any or two kinds, preferred Zn
2+, Mg
2+, Cu
2+, Fe
2+, Ca
2+, Mn
2+In any or two kinds, more preferably Zn
2+And/or Mg
2+M
3+Be Al
3+, Fe
3+, Cr
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any, M
3+Preferred Al
3+, Co
3+, Fe
3+, more preferably Al
3+B
N-For carrying capacity is the inorganic anion of n, be CO
3 2-, NO
3 -, Cl
-, Br
-, I
-, OH
-, H
2PO
4 -In any, two kinds or three kinds; 0.1<X<0.8; B is B
N-Quantity, n * b=X; M is a crystal water quantity, 0.01<m<4.
B. IDAs is dissolved in except that CO
2Deionized water in compound concentration be the aqueous solution of 0.2-0.3M, add in the reactor that band stirs, be 4-5 with rare NaOH regulator solution pH value;
Described IDAs is any in iminodiethanoic acid (IDA), N-(2-ethyl) iminodiethanoic acid (HIDA), the methyliminodiacetic acid (MIDA);
C. under nitrogen protection, Yi Bian stir fast, the hydrotalcite precursor suspension with the steps A preparation adds in the reactor of step B on one side, and under 90-100 ℃ of temperature crystallization 5-8 hour, filter, to wash, drying obtains the IDAs-LDHs intercalated houghite.
The intercalated houghite that obtains is carried out XRD, FT-IR, ICP, elemental analysis, show that the IDAs negatively charged ion has been assembled into hydrotalcite layers, the infrared absorption curve of measuring by FT-IR shows, IDAs-LDHs is to 7-14 μ m, 7-25 μ m, 9-11 μ m, each wave band infrared ray absorption of 10-14 μ m reaches more than the 45-79% than the increase of LDHs precursor, reach 20% than talcum powder in 7-25 μ m increase, reach more than 105% in 10-14 μ m increase.
Advantage of the present invention is:
First intercalation to have prepared interlayer anion be the hydrotalcite material of IDAs; The preparation method's intercalation precursor that is adopted is easy to preparation, and technology is simple, and cost is low.
2. this kind intercalation infrared absorbing material is to 7-14 μ m, 7-25 μ m, and 9-11 μ m, each wave band infrared ray absorption of 10-14 μ m reaches more than the 45-79% than the increase of LDHs precursor, increases at 7-25 μ m than talcum powder to reach 20%, increases at 10-14 μ m to reach more than 105%.Have good infrared absorbance, expanded the scope of infrared absorbent.
Description of drawings
Fig. 1 is the XRD figure of IDAs-LDHs among the embodiment 1.
Fig. 2 is a FT-IR spectrogram among the embodiment 1, and wherein: a is the infrared permeation rate curve of LDHs precursor, and b is the infrared permeation rate curve of IDAs-LDHs, and c is the infrared permeation rate curve of IDAs.
Fig. 3 is a FT-IR spectrogram among the embodiment 1, and wherein: a is the infrared permeation rate curve of IDAs-LDHs, and b is talcous infrared permeation rate curve.
Embodiment
Embodiment 1
Steps A: with the solid Al (NO of 45.0g (0.12mol)
3)
39H
2Solid Mg (the NO of O and 61.5g (0.24mol)
3)
26H
2O is dissolved in except that CO
2Deionized water in be made into 300ml mixing salt solution A; In addition 28.8g (0.72mol) solid NaOH is dissolved in except that CO
2Deionized water in be made into 300ml alkaline solution B.Under the room temperature rapidly with alkaline solution and salts solution nucleation in full back-mixing rotation liquid film reactor, with the 100 ℃ of crystallization 6h of slurries that obtain, centrifugation, with the sample that obtains wash to pH value near 7, must hydrotalcite precursor filter cake.Take a morsel in 70 ℃ of dry 24h, obtain MgAl-NO
3-LDHs, its Mg
2+/ Al
3+=2: 1.
Get the above-mentioned filter cake of 18.9g (0.015mol) with removing CO
2The deionized water ultra-sonic dispersion, be mixed with 150ml suspension.
Step B: take by weighing 6.0g (0.045mol) iminodiethanoic acid (IDA) and be dissolved in except that CO
2Deionized water in be configured to 100ml solution, and adding rare NaOH, to regulate its pH value be 4.
Step C: under nitrogen protection, the precursor slurry that steps A is made adds in the solution of step B preparation rapidly, and crystallization 6h under 100 ℃ of temperature filters, with removing CO
2Deionized water wash be about 7,70 ℃ of dryings 24 hours to pH, obtain IDA intercalation configuration infrared absorbing material MgAl-IDA-LDHs.
Adopt TG/DTA, ICP and elemental analysis method that product is analyzed, characterized, determine its chemical formula/consist of: Mg
0.616Al
0.384(OH)
2(C
4H
5NO
4 2-)
0.186(NO
3 -)
0.0120.66H
2O.Wherein, the quality percentage composition of iminodiethanoic acid (IDA) is 25.3%, and the quality percentage composition of water is 12.3%.
Under same once start condition, to MgAl-NO
3-LDHs and MgAl-IDA-LDHs sample carry out the infrared quantitative test, at 7-14 μ m, and 7-25 μ m, 9-11 μ m, 7-14 μ m has carried out integration to the infrared rays transmitance respectively, has calculated the infrared rays average transmittances in each wavelength region, and calculation result is listed in table 1.
Average transmittances T (%) in each wavelength region of table 1.
Calculate and MgAl-NO by table 1
3-LDHs compares, and MgAl-IDA-LDHs reduces percentage in the infrared rays transmitance of each wave band, the results are shown in table 2.
Table 2
With under the once start condition, talcum powder and MgAl-IDA-LDHs sample are carried out the infrared quantitative test, at 7-14 μ m, 7-25 μ m, 9-11 μ m, 7-14 μ m has carried out integration to the infrared rays transmitance respectively, calculated the infrared rays average transmittances in each wavelength region, calculation result is listed in table 3.
Average transmittances T (%) in each wavelength region of table 3.
Calculate MgAl-IDA-LDHs with respect to the reduction percentage of talcum powder by table 3, the results are shown in table 4 at each wavelength region average transmittances.
Table 4
From the table data as can be seen, MgAl-IDA-LDHs is to the specific absorption MgAl-NO of each wavelength band of infrared rays
3-LDHs increase reaches more than the 45-79%, increases at 7-25 μ m than talcum powder to reach 20%, increases at 10-14 μ m to reach more than 105%, has good infrared absorbance.
Embodiment 2
Steps A: MgAl-NO
3The preparation of-LDHs is with embodiment 1.
Get the above-mentioned filter cake of 22.7g (0.015ml) with removing CO
2The deionized water ultra-sonic dispersion, be mixed with 150ml suspension.
Step B: take by weighing 8.0g (0.045ml) N-(2-hydroxyethyl) iminodiethanoic acid (HIDA) and be dissolved in except that CO
2Deionized water in be configured to 150ml solution, and adding NaOH, to regulate its pH value be 4.
Step C: under nitrogen protection, the precursor slurry that steps A is made adds in the solution of step B preparation rapidly, and crystallization 6h under 100 ℃ of temperature filters, with removing CO
2Deionized water wash be about 7,70 ℃ of dryings 24 hours to pH, obtain HIDA intercalation configuration infrared absorbing material MgAl-HIDA-LDHs.
Adopt TG/DTA, ICP and elemental analysis method that product is analyzed, characterized, determine its chemical formula/consist of: Mg
0.604Al
0.396(OH)
2(C
6H
9NO
5 2-)
0.189(NO
3 -)
0.0180.54H
2O.Wherein, the quality percentage composition of N-(2-hydroxyethyl) iminodiethanoic acid (HIDA) is 32.1%, and the quality percentage composition of water is 9.4%.
Embodiment 3
Steps A: MgAl-NO
3The preparation of-LDHs is with embodiment 1.
Get the above-mentioned filter cake of 25.0g (0.015ml) with removing CO
2The deionized water ultra-sonic dispersion, be mixed with 150ml suspension.
Step B: take by weighing 6.6g (0.045ml) methyliminodiacetic acid (MIDA) and be dissolved in except that CO
2Deionized water in be configured to 150ml solution, and adding NaOH, to regulate its pH value be 4.
Step C: under nitrogen protection, the precursor slurry that steps A is made adds in the solution of step B preparation rapidly, and crystallization 6h under 100 ℃ of temperature filters, with removing CO
2Deionized water wash be about 7,70 ℃ of dryings 24 hours to pH, obtain MIDA intercalation configuration infrared absorbing material MgAl-MIDA-LDHs.
Adopt TG/DTA, ICP and elemental analysis method that product is analyzed, characterized, determine its chemical formula/consist of: Mg
0.618Al
0.382(OH)
2(C
5H
7NO
4 2-)
0.186(NO
3 -)
0.010.67H
2O.Wherein, the quality percentage composition of methyliminodiacetic acid (MIDA) is 27.6%, and the quality percentage composition of water is 12.2%.
Embodiment 4
Steps A: with 35.68g (0.12ml) Zn (NO
3)
26H
2O, 30.76g (0.12ml) Mg (NO
3)
26H
2O and 45g (0.12ml) Al (NO
3)
39H
2O is dissolved in except that CO
2Deionized water in be made into 300ml mixing salt solution A; In addition 28.8g (0.72ml) NaOH is dissolved in except that CO
2Deionized water in be made into 300ml alkaline solution B.Under the room temperature rapidly with alkaline solution and salts solution nucleation in full back-mixing rotation liquid film reactor, with the 100 ℃ of crystallization 6h of slurries that obtain, centrifugation, with the sample that obtains wash to pH value near 7, must hydrotalcite precursor filter cake.Take a morsel in 70 ℃ of dry 24h, obtain ZnMgAl-NO
3-LDHs, its Zn
2+/ Mg
2+/ Al
3+=1: 1: 1.
Get the above-mentioned filter cake of 22.3g (0.015ml) with removing CO
2The deionized water ultra-sonic dispersion, be mixed with 150ml suspension.
Step B: take by weighing 6.0g (0.045ml) iminodiethanoic acid (IDA) and be dissolved in except that CO
2Deionized water in be configured to 150ml solution, and adding NaOH, to regulate its pH value be 4.
Step C: under nitrogen protection, the precursor slurry that steps A is made adds in the solution of step B preparation rapidly, and crystallization 6h under 100 ℃ of temperature filters, with removing CO
2Deionized water wash be about 7,70 ℃ of dryings 24 hours to pH, obtain IDA intercalation configuration infrared absorbing material ZnMgAl-IDA-LDHs.
Adopt TG/DTA, ICP and elemental analysis method that product is analyzed, characterized, determine its chemical formula/consist of: Zn
0.344Mg
0.334Al
0.322(OH)
2(C
4H
5NO
4 2-)
0.156(NO
3 -)
0.010.43H
2O.Wherein, the quality percentage composition of iminodiethanoic acid (IDA) is 20.2%, and the quality percentage composition of water is 7.7%.
Embodiment 5
Steps A: ZnMgAl-NO
3The preparation of-LDHs is with embodiment 4.
Get the above-mentioned filter cake of 24.6g (0.015ml) with removing CO
2The deionized water ultra-sonic dispersion, be mixed with 150ml suspension.
Step B: take by weighing 8.0g (0.045ml) N-(2-hydroxyethyl) iminodiethanoic acid (HIDA) and be dissolved in except that CO
2Deionized water in be configured to 150ml solution, and adding NaOH, to regulate its pH value be 4.
Step C: under nitrogen protection, the precursor slurry that steps A is made adds in the solution of step B preparation rapidly, and crystallization 6h under 100 ℃ of temperature filters, with removing CO
2Deionized water wash be about 7,70 ℃ of dryings 24 hours to pH, obtain HIDA intercalation configuration infrared absorbing material ZnMgAl-HIDA-LDHs.
Adopt TG/DTA, ICP and elemental analysis method that product is analyzed, characterized, determine its chemical formula/consist of: Zn
0.344Mg
0.332Al
0.324(OH)
2(C
6H
9NO
5 2-)
0.154(NO
3 -)
0.0160.78H
2O.Wherein, the quality percentage composition of N-(2-hydroxyethyl) iminodiethanoic acid (HIDA) is 23.6%, and the quality percentage composition of water is 12.2%.
Embodiment 6
Steps A: ZnMgAl-NO
3The preparation of-LDHs is with embodiment 4.
Get the above-mentioned filter cake of 20.0g (0.015ml) with removing CO
2The deionized water ultra-sonic dispersion, be mixed with 150ml suspension.
Step B: take by weighing 6.6g (0.045ml) methyliminodiacetic acid (MIDA) and be dissolved in except that CO
2Deionized water in be configured to 150ml solution, and adding NaOH, to regulate its pH value be 4.
Step C: under nitrogen protection, the precursor slurry that steps A is made adds in the solution of step B preparation rapidly, and crystallization 8h under 90 ℃ of temperature filters, with removing CO
2Deionized water wash be about 7,70 ℃ of dryings 24 hours to pH, obtain MIDA intercalation configuration infrared absorbing material ZnMgAl-MIDA-LDHs.
Adopt TG/DTA, ICP and elemental analysis method that product is analyzed, characterized, determine its chemical formula/consist of: Zn
0.340Mg
0.328Al
0.332(OH)
2(C
5H
7NO
4 2-)
0.159(NO
3 -)
0.0140.83H
2O.Wherein, the quality percentage composition of methyliminodiacetic acid (MIDA) is 20.9%, and the quality percentage composition of water is 13.3%.
Claims (6)
1. selective infrared absorption material of aminodiacetic acid intercalation structure is abbreviated as: IDAs-LDHs, and it is a supramolecular structure, and crystalline structure is the crystalline structure of houghite material, and its chemical formula is:
(M
2+)
1-x(M
3+)
x(OH)
2(A
2-)
a(B
n-)
b·mH
2O
M wherein
2+Be Zn
2+, Mg
2+, Ni
2+, Cu
2+, Fe
2+, Co
2+, Ca
2+, Mn
2+In any or two kinds.M
3+Be Al
3+, Fe
3+, Cr
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any;
A represents amino oxalic acid compounds, is abbreviated as IDAs, and A is any in iminodiethanoic acid (IDA), N-(2-ethyl) iminodiethanoic acid (HIDA), the methyliminodiacetic acid (MIDA);
B
N-For carrying capacity is the inorganic anion of n, B in the IDAs-LDHs chemical formula
N-Can not exist or for CO
3 2-, NO
3 -, Cl
-, Br
-, I
-, OH
-, H
2PO
4 -In any, two kinds or three kinds;
0.1<X<0.8; A, b are respectively A
2-And B
N-Quantity, 2a+n * b=X;
M is a crystal water quantity, 0.01<m<4.
2. selective infrared absorption material of aminodiacetic acid intercalation structure according to claim 1 is characterized in that described M
2+Be Zn
2+, Mg
2+, Cu
2+, Fe
2+, Ca
2+, Mn
2+In any or two kinds, M
3+Be Al
3+, Co
3+, Fe
3+
3. selective infrared absorption material of aminodiacetic acid intercalation structure according to claim 1 is characterized in that described M
2+Be Zn
2+And/or Mg
2+, M
3+Be Al
3+
4. the preparation method of a selective infrared absorption material of aminodiacetic acid intercalation structure as claimed in claim 1, concrete preparation process is as follows:
A. hydrotalcite LDHs precursor is scattered in except that CO
2Deionized water in and fully mix the hydrotalcite precursor suspension that configuration concentration is about 0.2-0.3M;
Used LDHs structural formula is: (M
2+)
1-x(M
3+)
x(OH)
2(B
N-)
bMH
2O, wherein M
2+Be Zn
2+, Mg
2+, Ni
2+, Cu
2+, Fe
2+, Co
2+, Ca
2+, Mn
2+In any or two kinds; M
3+Be Al
3+, Fe
3+, Cr
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any; B
N-For carrying capacity is the inorganic anion of n, be CO
3 2-, NO
3 -, Cl
-, Br
-, I
-, OH
-, H
2PO
4 -In any, two kinds or three kinds; 0.1<X<0.8; B is B
N-Quantity, n * b=X; M is a crystal water quantity, 0.01<m<4;
B. IDAs is dissolved in except that CO
2Deionized water in compound concentration be the aqueous solution of 0.2-0.3M, add in the reactor that band stirs, be 4-5 with rare NaOH regulator solution pH value;
Described IDAs is any in iminodiethanoic acid (IDA), N-(2-ethyl) iminodiethanoic acid (HIDA), the methyliminodiacetic acid (MIDA);
C. under nitrogen protection, Yi Bian stir fast, the hydrotalcite precursor suspension with the steps A preparation adds in the reactor of step B on one side, and under 90-100 ℃ of temperature crystallization 5-8 hour, filter, to wash, drying obtains the IDAs-LDHs intercalated houghite.
5. the preparation method of selective infrared absorption material of aminodiacetic acid intercalation structure according to claim 4 is characterized in that described M
2+Be Zn
2+, Mg
2+, Cu
2+, Fe
2+, Ca
2+, Mn
2+In any or two kinds, M
3+Be Al
3+, Co
3+, Fe
3+
6. the preparation method of selective infrared absorption material of aminodiacetic acid intercalation structure according to claim 4 is characterized in that described M
2+Be Zn
2+And/or Mg
2+, M
3+Be Al
3+
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CN104353406A (en) * | 2014-11-17 | 2015-02-18 | 海南大学 | Double hydroxide and preparation method thereof, as well as magnetic phosphorus removal adsorbent and preparation method thereof |
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2008
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Publication number | Priority date | Publication date | Assignee | Title |
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CN101597474B (en) * | 2009-07-03 | 2012-10-17 | 北京化工大学 | Glyphosine intercalated structural selective infrared absorbing material as well as preparation method and application thereof |
CN104353406A (en) * | 2014-11-17 | 2015-02-18 | 海南大学 | Double hydroxide and preparation method thereof, as well as magnetic phosphorus removal adsorbent and preparation method thereof |
CN115232361A (en) * | 2022-07-13 | 2022-10-25 | 塔里木大学 | Vermiculite infrared barrier material and preparation method and application thereof |
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