CN101831085B - Phosphorus-based organic matter intercalation structure selective infrared absorption material, preparation method and application thereof - Google Patents
Phosphorus-based organic matter intercalation structure selective infrared absorption material, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a phosphorus-based organic matter intercalation structure selective infrared absorption material, a preparation method and the application thereof. The infrared absorption material can be simplified into POH-LDHs, and has the molecular formula of (M2+) 1-x (Al3+) x(OH) 2(An-) a(NO3-) b. mH2O. The preparation method of the material comprises the steps of: taking hydrotalcite as precursor; adopting an ion exchange method to insert phosphorus-based organic matter negative ion into the hydrotalcite layer; and assembling, and obtaining the phosphorus-based organic matter intercalation structure selective infrared absorption material with good crystalline phase structure. The infrared absorption material has excellent infrared absorption capability, and is better in the infrared absorption effect than MgAl-CO3-LDHs, thus being a good infrared absorption material. The material is suitable for being applied to a thin polymer film of polyethylene or ethylene-vinlacetate copolymer, etc.
Description
Technical field
The present invention relates to a kind of selective infrared absorbing material and preparation method thereof and application, be specifically related to phosphorus-based organic matter intercalation structure selective infrared absorption material and preparation method thereof and application.
Background technology
New LDPE (film grade) polyolefins materials such as (LDPE) is because of its good snappiness, light transmission and workability, has remarkable advantages at the insulation plastic sheeting for farm use aspect preparing.Although polyvinyl resin has been widely used in preparing agricultural film; But its infrared rays transmitance is higher; Heat-insulating property is relatively poor, and daytime can scatter and disappear with the form of infrared emanation at night from the heat that sunshine absorbs very soon in the face of land, therefore studies infrared absorbing material and makes an addition in the polyvinyl resin; When keeping its good light permeability, improve the ir absorption performance and be always one of focus that people pay close attention to.
It is 7-25 μ m (1428-400cm that the quantity of radiant energy overwhelming majority of dispelling the heat to atmosphere from earth surface night concentrates on wavelength
-1) middle infrared, peak value is 9-11 μ m (1111-909cm
-1).The infra-red absorption material is being brought into play important effect as the important function auxiliary agent aspect the raising agricultural film heat-insulating property.In order to improve the heat-insulating property of polyvinylidene film, inorganic additivess such as talcum powder, china clay are used to absorption, obstruct and reflects infrared light, have played certain insulation effect.But these natural inorganic materials are relatively poor because of the ir absorption performance, and there are defective in composition, structure and crystal morphology, especially contain the impurity that some make the plastic sheeting for farm use accelerated deterioration, reduced it as the result of use of infrared absorbing material in plastic sheeting for farm use.In addition; The ununiformity of these material grains sizes; Directly influenced mechanical property, stability and the visible light transmissive performance of plastic sheeting for farm use, be necessary that therefore the mineral filler that synthetic a kind of purity is high, the ir absorption performance is good and grain size is controlled is used for the plastic sheeting for farm use preparation as infrared absorbing material.
Hydrotalcite (Layered Double Hydroxides is called for short LDHs) is an anionoid type lamellar compound, and its chemical constitution general formula is [M
2+ 1-xM
3+ x(OH)
2]
X+(A
N-)
X/nMH
2O, wherein, M
2+, M
3+Represent divalence and trivalent metal cation respectively, A
N-Be interlayer anion.Because laminate structure that LDHs is unique and laminate are formed and the adjustable sex change of interlayer anion, make it obtain at aspects such as catalysis, electrochemistry, stripping technique and medicine to use widely.In early-stage Study, nucleation/crystallization isolation technology of adopting this laboratory to found has prepared outward appearance and has been laminated structure, crystalline structure is complete, particle diameter is little, particle size distribution range is narrow MgAl-CO
3-LDHs makes an addition to it and prepares polyvinylidene film in polyvinyl resin, because of MgAl-CO
3-LDHs interlayer CO
3 2-V
3Vibration has produced the ir absorption stronger than traditional material at 7-8 μ m, has obtained practical application as the plastic sheeting for farm use heat preserving agent.Yet, MgAl-CO
3The IR wavelength that-LDHs absorbs exists significantly to absorb defective not in the ultrared peak value scope of surface radiation at night, has limited its application in the insulation plastic sheeting for farm use to a certain extent.
Document [1] Xu Guozhi, Guo Canxiong, Duan Xue, Jiang Chuangeng; The ir absorption performance of the two hydroxyl complex hydroxides of PE film laminate; Applied chemistry; 1999 (16) 3:45-48 have investigated the magnesium aluminum-hydrotalcite powder as being incubated the variation that filler is added to material property behind the polyethylene agricultural film through means such as X-ray powder diffraction, ir spectra, sem, heat analysiss, image analysiss, and with dose heat preserving agent commonly used---the film of talcum powder compares.The result shows that the ir absorption performance of PE/ hydrotalcite film obviously is superior to 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 do not receive obvious influence.Infrared spectroscopic study to the hydrotalcite powder shows, its significant ir absorption effect is mainly because of due to the special laminate structure and chemical constitution of hydrotalcite.
Document [2] Wang Liangyu, Cui Hailong, Jiao Hongwen; Hydrotalcite is to the infrared spectroscopic study of plastic sheeting for farm use performance impact; Journal of Inorganic Materials; 2009 (24) 4:853-858 use IR to study the influence to plastic sheeting for farm use optical property, transmittance, infrared gas barrier rate and heat-insulating property of import hydrotalcite, homemade hydrotalcite and talcum powder respectively.The result shows homemade hydrotalcite particle diameter greater than the import hydrotalcite, and the goods haze value rises about 1.5%.Compare the infrared barrier better effects if of the made plastic sheeting for farm use of hydrotalcite with talcum powder commonly used.Find out that from infrared spectrogram homemade or import hydrotalcite is at 1100～1200cm
-1Do not have ir absorption in the wave-number range, absorption peak is at 1360cm
-1The wave number place, there is certain deviation at 9～11 the strongest mum wavelength places with the absorption energy, therefore add in the plastic sheeting for farm use awaiting further to study as heat preserving agent.
Document [3] is rectified celebrating pool, Zhao Yun, Xie Hui, D.G.Evans, Duan Xue; The intercalation of hydrotalcite and selectivity ir 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 gets into MgAl-CO
3-LDHs interlayer, the MgAl-CO of formation
3SO
4-LDHs hydrotalcite still keeps former LDHs laminate structure, and the selectivity ir absorption performance of novel LDHs in the heat radiation wavelength region obviously strengthens.
In order to make hydrotalcite as a kind of good infra-red absorption additive; Can utilize its ion exchangeable; To in ir radiation peak value scope, there be the strong negatively charged ion that absorbs to be inserted between the hydrotalcite laminate, obtain having the intercalation configuration hydrotalcite of good ir absorption performance.Phosphino-group in the organic structures such as ATMP, methylenediphosphonate(MDP), hydroxyl acetylene phosphoric acid, pmida98, phosphoryl acetate, phosphenylic acid, aminomethyl phosphonic acids, vinyl phosphonate and methane phosphoric acid makes it have strong ir absorption at the 9-11 mu m range.Therefore confirm that being inserted in 9-11 μ m at the LDHs interlayer has strong ATMP, methylenediphosphonate(MDP), hydroxyl acetylene phosphoric acid, pmida98, phosphoryl acetate, phosphenylic acid, aminomethyl phosphonic acids, vinyl phosphonate and the methane phosphoric acid that absorbs.Utilize the ion exchange property of hydrotalcite; These are contained the phosphino-organism be inserted into hydrotalcite layers; The infrared absorbing material that can prepare a kind of good heat stability, size of particles is little, particle size distribution range is narrow, the ir absorption performance is excellent, this kind novel material can be used as infrared absorbing agents and is applied in the polyolefine.
Summary of the invention
The purpose of this invention is to provide one type of phosphorus-based organic matter intercalation structure selective infrared absorption material and preparation method thereof and application.
Phosphorus-based organic matter intercalation structure selective infrared absorption material provided by the invention is abbreviated as POH-LDHs, and its molecular formula is:
(M
2+)
1-x(Al
3+)
x(OH)
2(A
n-)
a(NO
3 -)
b·mH
2O
M wherein
2+Be Zn
2+Or Mg
2+
A
N-Represent the interlayer carrying capacity be n contain phosphino-organism negatively charged ion, be C
3H
12NO
9P
3 2-, CH
6O
6P
2 3-, C
2H
8O
7P
2 3-, C
5H
10NO
7P
2-, C
2H
5O
5P
2-, C
6H
7O
3P
2-, CH
6NO
3P
2-, C
2H
5O
3P
2-Or CH
5O
3P
2-In any one;
NO in the POH-LDHs chemical formula
3 -Can not exist; 0.1＜X＜0.8; A, b is respectively A
N-And NO
3 -Quantity, n * a+b=X; M is a crystal water quantity, 0.01＜m＜4.
It is a supramolecular structure, and crystalline structure is the crystalline structure of houghite material.
The concrete preparation process of phosphorus-based organic matter intercalation structure selective infrared absorption material is following:
A. be that the hydrotalcite precursor of nitrate ion is scattered in the deionized water with interlayer anion, fully mixing compound concentration is the hydrotalcite precursor suspension of 0.2-0.8mol/L;
Used hydrotalcite front body structure formula is: (M
2+)
1-x(Al
3+)
x(OH)
2(NO
3 -)
xMH
2O, wherein 0.1＜X＜0.8; M
2+Be Zn
2+Or Mg
2+M is a crystal water quantity, 0.01＜m＜4;
B. will contain the phosphino-organism and be dissolved in that compound concentration is the aqueous solution of 0.2-0.8mol/L in the deionized water, and it will be added in the reactor drum that band stirs, and use NaOH to adjust the pH value of solution value and be 4-10;
C. under nitrogen protection, Yi Bian stir fast, the hydrotalcite precursor suspension with the steps A preparation joins in the reactor drum of step B on one side, makes that containing the organic molar weight of phosphino-is 1-3 times of nitrate radical molar weight in the hydrotalcite; The pH value of regulation system is to 5-11,60-100 ℃ of temperature refluxed crystallization 4-8 hour, filters, and washing, drying obtains the POH-LDHs intercalated houghite.
The intercalated houghite that obtains is carried out signs such as XRD (see figure 1), FT-IR (see figure 2), ICP, ultimate analysis, TG-DTA (see figure 3), show that containing phosphino-organism negatively charged ion has been assembled into hydrotalcite layers.
Respectively with MgAl-CO
3-LDHs and POH-LDHs add in the Vilaterm polymeric materialss such as (PE) by 4% mass content and process 120 μ m films.Infrared absorption curve through FT-IR measures is seen Fig. 4,6, compares MgAl-CO by Fig. 4,6 visible POH-LDHs/PE films in the infra-red absorption of 9-11 μ m
3-LDHs/PE film increases more than the 14-46%.Visible light transmissive rate curve through UV-vis measures is seen Fig. 5,7, is not compared with the PE film in the transmitance of 380-780nm visible-range and is obviously descended by Fig. 5,7 visible POH-LDHs/PE films.Through to the tensile strength of POH-LDHs/PE material and the test of elongation at break, the interpolation of POH-LDHs is to the not obviously influence of mechanical property of PE.
Conclusion: the PE film that adds POH-LDHs at the ir-absorbance of 9-11 mu m range apparently higher than adding MgAl-CO
3The film of-LDH shows significant selectivity ir absorption performance.Simultaneously, the interpolation of POH-LDHs is to the visible light permeability and the not obviously influence of mechanical property of Vilaterm (PE).
Advantage of the present invention is:
1. use ion exchange method to prepare interlayer anion for containing the organic hydrotalcite material of phosphino-; The preparing method's intercalation precursor that is adopted is easy to preparation, and technology is simple, and cost is low.
2. add in Vilaterm polymeric materialss such as (PEs) by 4% content POH-LDHs and process 120 μ m films, the POH-LDHs/PE film is to the specific absorption MgAl-CO of infrared radiation peak value 9-11 mu m range
3The increase of-LDHs/PE film reaches more than the 14-46%, reaches more than the 398-584% than the increase of PE film.POH-LDHs has good infrared absorbance, has expanded the scope of infrared absorbent.
3. owing to adopt nucleation/crystallization isolation method to prepare precursor; The grain-size of the POH-LDHs that intercalation obtains is less; Help seeing through of visible light, so the visible light transmissivity that the POH-LDHs/PE film is compared with the PE film in the 380-780nm scope does not descend significantly.
4.POH-LDHs interpolation to the not obviously influence of the mechanical property of Vilaterm (PE).
Description of drawings
Fig. 1-be XRD figure among the embodiment 1, wherein: a is MgAl-NO
3The XRD figure of-LDHs, b are the XRD figures of MgAl-ATMP-LDHs.
Fig. 2 is a FT-IR spectrogram among the embodiment 1, and wherein: a is MgAl-NO
3The infrared permeation rate curve of-LDHs, b are the infrared permeation rate curves of MgAl-ATMP-LDHs, and c is MgAl-CO
3The infrared permeation rate curve of-LDHs.
Fig. 3 is a TG-DTA curve among the embodiment 1, and wherein: a is MgAl-NO
3The TG-DTA curve of-LDHs, b are the TG-DTA curves of MgAl-ATMP-LDHs.
Fig. 4 is a FT-IR spectrogram in the application examples 1, and wherein: a is the infrared permeation rate curve of PE film, and b is the infrared permeation rate curve of MgAl-ATMP-LDHs/PE film, and c is MgAl-CO
3The infrared permeation rate curve of-LDHs/PE film.
Fig. 5 is a UV-vis spectrogram in the application examples 1, and wherein: a is the visible light transmissive rate curve of PE film, and b is the visible light transmissive rate curve of MgAl-ATMP-LDHs/PE film, and c is MgAl-CO
3The visible light transmissive rate curve of-LDHs/PE film.
Fig. 6 is a FT-IR spectrogram in the application examples 2, and wherein: a is the infrared permeation rate curve of PE film, and b is the infrared permeation rate curve of MgAl-PMIDA-LDHs/PE film, and c is MgAl-CO
3The infrared permeation rate curve of-LDHs/PE film.
Fig. 7 is a UV-vis spectrogram in the application examples 2, and wherein: a is the visible light transmissive rate curve of PE film, and b is the visible light transmissive rate curve of MgAl-PMIDA-LDHs/PE film, and c is MgAl-CO
3The visible light transmissive rate curve of-LDHs/PE film.
Embodiment
Embodiment 1
Steps A: with 45.0g (0.12mol) solid Al (NO
3)
39H
2O and 61.5g (0.24mol) solid Mg (NO
3)
26H
2O is dissolved in except that CO
2Be made into 300ml mixing salt solution A in the deionized water; In addition 28.8g (0.72mol) solid NaOH is dissolved in and is made into 300ml alkaline solution B in the deionized water.Under the room temperature rapidly with alkaline solution and salts solution nucleation in full back-mixing rotation liquid film reactor, with 100 ℃ of crystallization 6h of the slurries that obtain, spinning, with the sample that obtains wash to pH value near 7, must hydrotalcite precursor filter cake.It is MgAl-NO that its molecular formula is measured in the dry back of sampling
3-LDHs, its Mg
2+/ Al
3+=2: 1.
Get 30g and (contain 0.02mol NO
3 -) above-mentioned filter cake is with removing CO
2The deionized water ultra-sonic dispersion is mixed with 150ml suspension-s.
Step B: take by weighing 12g (0.04mol) ATMP (English is abbreviated as ATMP) and be dissolved in except that CO
2Be configured to 100ml solution in the deionized water, and its pH value of adding NaOH solution adjusting is 7.
Step C: under nitrogen protection; The suspension-s of steps A preparation is splashed in the solution that step B makes; At 65 ℃ of temperature refluxed crystallization 6h, filter, be about 7 with absolute ethanol washing to pH; 70 ℃ of dryings 24 hours obtain ATMP (ATMP) intercalation configuration infrared absorbing material MgAl-ATMP-LDHs.
Adopt TG/DTA, ICP and elemental analysis method that product is analyzed, characterized, the result sees Fig. 1-3; Confirm its chemical formula/consist of: Mg
0.668Al
0.332(OH)
2(C
3H
12NO
9P
3 2-)
0.1560.36H
2O.
Embodiment 2
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 100 ℃ of crystallization 6h of the slurries that obtain, spinning, 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 30g and (contain 0.02mol NO
3 -) above-mentioned filter cake is with removing CO
2The deionized water ultra-sonic dispersion, be mixed with 150ml suspension-s.
Step B: take by weighing 9.1g (0.04mol) pmida98 (English is abbreviated as PMIDA) and be dissolved in except that CO
2Deionized water in be configured to 100ml solution, and adding NaOH, to regulate its pH value be 7.5.
Step C: under nitrogen protection, the precursor slurry that rapidly steps A is made adds in the solution of step B preparation, and crystallization 6h under 60 ℃ of temperature filters, with removing CO
2Deionized water wash be about 7,70 ℃ of dryings 24 hours to pH, obtain pmida98 (PMIDA) intercalation configuration infrared absorbing material MgAl-PMIDA-LDHs.
Adopt TG/DTA, ICP and elemental analysis method that product is analyzed, characterized, confirm its chemical formula/consist of: Mg
0.686Al
0.314(OH)
2(C
5H
8NO
7P
2-)
0.1570.42H
2O.
Embodiment 3
Steps A: with 45.0g (0.12mol) solid Al (NO
3)
39H
2O and 71.4g (0.24mol) solid Zn (NO
3)
36H
2O is dissolved in except that CO
2Be made into 300ml mixing salt solution A in the deionized water; In addition 28.8g (0.72mol) solid NaOH is dissolved in except that CO
2Be made into 300ml alkaline solution B in the deionized water.Under the room temperature rapidly with alkaline solution and salts solution nucleation in full back-mixing rotation liquid film reactor, with 100 ℃ of crystallization 6h of the slurries that obtain, spinning, with the sample that obtains wash to pH value near 7, must hydrotalcite precursor filter cake.It is ZnAl-NO that its molecular formula is measured in the dry back of sampling
3-LDHs, its Zn
2+/ Al
3+=2: 1.
Get 30g and (contain 0.017mol NO
3 -) above-mentioned filter cake is with removing CO
2The deionized water ultra-sonic dispersion is mixed with 150ml suspension-s.
Step B: take by weighing 10.2g (0.034mol) ATMP (ATMP) and be dissolved in except that CO
2Be configured to 100ml solution in the deionized water, and its pH value of adding NaOH solution adjusting is 7.
Step C: under nitrogen protection; The suspension-s of steps A preparation is splashed in the solution that step B makes; At 65 ℃ of temperature refluxed crystallization 6h, filter, be about 7 with absolute ethanol washing to pH; 70 ℃ of dryings 24 hours obtain ATMP (ATMP) intercalation configuration infrared absorbing material ZnAl-ATMP-LDHs.
Adopt TG/DTA, ICP and elemental analysis method that product is analyzed, characterized, confirm its chemical formula/consist of: Zn
0.67Al
0.33(OH)
2(C
3H
12NO
9P
3 2-)
0.1650.52H
2O.
Embodiment 4
Steps A: with 45.0g (0.12mol) solid Al (NO
3)
39H
2O and 71.4g (0.24mol) solid Zn (NO
3)
36H
2O is dissolved in except that CO
2Be made into 300ml mixing salt solution A in the deionized water; In addition 28.8g (0.72mol) solid NaOH is dissolved in except that CO
2Be made into 300ml alkaline solution B in the deionized water.Under the room temperature rapidly with alkaline solution and salts solution nucleation in full back-mixing rotation liquid film reactor, with 100 ℃ of crystallization 6h of the slurries that obtain, spinning, with the sample that obtains wash to pH value near 7, must hydrotalcite precursor filter cake.It is ZnAl-NO that its molecular formula is measured in the dry back of sampling
3-LDHs, its Zn
2+/ Al
3+=2: 1.
Get 30g and (contain 0.017mol NO
3 -) above-mentioned filter cake is with removing CO
2The deionized water ultra-sonic dispersion is mixed with 150ml suspension-s.
Step B: take by weighing 7.7g (0.034mol) pmida98 (PMIDA) and be dissolved in except that CO
2Be configured to 100ml solution in the deionized water, and its pH value of adding NaOH solution adjusting is 7.5.
Step C: under nitrogen protection, the suspension-s of steps A preparation is splashed in the solution that step B makes, at 60 ℃ of temperature refluxed crystallization 6h, filter, with removing CO
2Deionized water and alcoholic acid mixing solutions wash to pH and are about 7,70 ℃ of dryings 24 hours, obtain pmida98 (PMIDA) intercalation configuration infrared absorbing material ZnAl-PMIDA-LDHs.
Adopt TG/DTA, ICP and elemental analysis method that product is analyzed, characterized, confirm its chemical formula/consist of: Zn
0.646Al
0.354(OH)
2(C
5H
8NO
7P
2-)
01770.67H
2O.
Application examples 1
Step 1: with MgAl-CO
3The MgAl-ATMP-LDHs that obtains among-LDHs and the embodiment 1 grinds 1min respectively in the high speed mill.
Step 2: get MgAl-CO in the step 1
3-LDHs and each 4g of MgAl-ATMP-LDHs sample, mixing on mixing roll with 5g PE respectively, get corresponding M gAl-CO
3-LDHs/PE and MgAl-ATMP-LDHs/PE masterbatch.
Step 3: get MgAl-CO in the step 2
3-LDHs/PE and each 2.25g of MgAl-ATMP-LDHs/PE masterbatch with the mixing compressing tablet system film of 22.75g PE, obtain hydrotalcite content and are the MgAl-CO that 4% smooth thickness is about 120 μ m
3-LDHs/PE and MgAl-ATMP-LDHs/PE composite material film.
Under identical conditions, above-mentioned film is carried out the infrared quantitative test, obtain MgAl-CO
3The infrared spectrum of-LDHs/PE and MgAl-ATMP-LDHs/PE composite material film, the result sees Fig. 4; Through the infrared integration software that carries, at the 9-11 mu m waveband its infrared rays transmitance is carried out integration, and calculate the infrared rays average transmittances T (%) of each wavelength region, the result lists in table 1.The MgAl-ATMP-LDHs/PE film is at the transmitance and the MgAl-CO of 9-11 mu m waveband
3-LDHs/PE film is compared the percentage ratio of decline and is also listed in table one.
Table 1.LDHs/PE film is at the infrared average transmittances of 9-11 mu m range
According to the relation of absorbancy (A) with transmitance (T): A=log (1/T), can find out that by table 1 the MgAl-ATMP-LDHs/PE film is to the specific absorption MgAl-CO of infrared radiation peak value 9-11 mu m range
3The increase of-LDHs/PE film reaches more than 44%, reaches more than 584% than the increase of PE film.MgAl-ATMP-LDHs has good infrared absorbance, shown MgAl-ATMP-LDHs advantage as selective infrared absorbing material in plastic sheeting for farm use.
Fig. 5 is PE film, MgAl-ATMP-LDHs/PE film and MgAl-CO
3-LDHs/PE film is at the visible light transmissive rate curve of 380-780nm scope.The average visible light transmissivity of each sample that obtains through integration is listed in table 2.
Table 2.LDHs/PE film is at the visible light average transmittances of 380-780nm scope
Can find out, owing to adopt the MgAl-CO of nucleation/crystallization isolation method preparation
3The particle diameter of-LDHs and MgAl-ATMP-LDHs is less, helps seeing through of visible light, so MgAl-ATMP-LDHs/PE film and MgAl-CO
3The visible light transmissivity that-LDHs/PE film is compared with the PE film in the 380-780nm scope does not significantly descend.
MgAl-ATMP-LDHs/PE, MgAl-CO
3The tensile strength of-LDHs/PE and PE and elongation at break test are at microcomputer control electronics universal testing machine (CMT3140, Shenzhen SANS Test Machine Co., Ltd.; Shenzhen; China) carry out on, sample is one group by each experiment direction, and every group of sample is no less than 5.Test result is averaged, and sees table 3.
The mechanical property of table 3.LDHs/PE
By table 3 data, behind the interpolation hydrotalcite, the elongation at break of PE increases to some extent, explains that the interpolation of nano level hydrotalcite particles has certain toughening effect to PE.Tensile strength decreases, but the reduction value is very little.It is thus clear that the addition of 4% hydrotalcite is very little to the mechanical property influence of PE.
Application examples 2
Step 1: with MgAl-CO
3The MgAl-PMIDA-LDHs that obtains among-LDHs and the embodiment 2 grinds 1min respectively in the high speed mill.
Step 2: get MgAl-CO in the step 1
3-LDHs and each 4g of MgAl-PMIDA-LDHs sample, mixing on mixing roll with 5g PE respectively, get corresponding M gAl-CO
3-LDHs/PE and MgAl-PMIDA-LDHs/PE masterbatch.
Step 3: get MgAl-CO in the step 2
3-LDHs/PE and each 2.25g of MgAl-PMIDA-LDHs/PE masterbatch with the mixing compressing tablet system film of 22.75g PE, obtain hydrotalcite content and are the MgAl-CO that 4% smooth thickness is about 120 μ m
3-LDHs/PE and MgAl-PMIDA-LDHs/PE composite material film.
Under identical conditions, above-mentioned film is carried out the infrared quantitative test, obtain MgAl-CO
3The infrared spectrum of-LDHs/PE and MgAl-PMIDA-LDHs/PE composite material film, the result sees Fig. 9; Through the infrared integration software that carries, at the 9-11 mu m waveband its infrared rays transmitance is carried out integration, and calculate the infrared rays average transmittances T (%) of each wavelength region, the result lists in table 4.The MgAl-PMIDA-LDHs/PE film is at the transmitance and the MgAl-CO of 9-11 mu m waveband
3-LDHs/PE film is compared the percentage ratio of decline and is also listed in table one.
Table 4.LDHs/PE film is at the infrared average transmittances of 9-11 mu m range
According to the relation of absorbancy (A) with transmitance (T): A=log (1/T), can find out that by table 4 the MgAl-PMIDA-LDHs/PE film is to the specific absorption MgAl-CO of infrared radiation peak value 9-11 mu m range
3The increase of-LDHs/PE film reaches more than 14%, reaches more than 398% than the increase of PE film.MgAl-PMIDA-LDHs has good infrared absorbance, shown MgAl-PMIDA-LDHs advantage as selective infrared absorbing material in plastic sheeting for farm use.
Figure 10 is PE film, MgAl-PMIDA-LDHs/PE film and MgAl-CO
3-LDHs/PE film is at the visible light transmissive rate curve of 380-780nm scope.The average visible light transmissivity of each sample that obtains through integration is listed in table 5.
Table 5.LDHs/PE film is at the visible light average transmittances of 380-780nm scope
Can find out, owing to adopt the MgAl-CO of nucleation/crystallization isolation method preparation
3The particle diameter of-LDHs and MgAl-PMIDA-LDHs is less, helps seeing through of visible light, so MgAl-PMIDA-LDHs/PE film and MgAl-CO
3The visible light transmissivity that-LDHs/PE film is compared with the PE film in the 380-780nm scope does not significantly descend.
MgAl-PMIDA-LDHs/PE, MgAl-CO
3The tensile strength of-LDHs/PE and PE and elongation at break test are at microcomputer control electronics universal testing machine (CMT3140, Shenzhen SANS Test Machine Co., Ltd.; Shenzhen; China) carry out on, sample is one group by each experiment direction, and every group of sample is no less than 5.Test result is averaged, and sees table 6.
The mechanical property of table 6.LDHs/PE
By table 6 data, behind the interpolation hydrotalcite, the elongation at break of PE increases to some extent, explains that the interpolation of nano level hydrotalcite particles has certain toughening effect to PE.Tensile strength decreases, but the reduction value is very little.It is thus clear that the addition of 4% hydrotalcite is very little to the mechanical property influence of PE.
Application examples 3
Step 1: with step 1 in the application examples 1.
Step 2: get 4g MgAl-CO in the step 1
3-LDHs and 4g MgAl-ATMP-LDHs sample with uniform mixture on mixing roll the mixing 15min of 5g Injecatable EVA Copolymer (EVA) with PE (mass ratio is 1: 1), get MgAl-CO respectively
3-LDHs/PE-EVA, MgAl-ATMP-LDHs/PE-EVA masterbatch.
Step 3: get MgAl-CO in the step 2
3-LDHs/PE-EVA, each 2.25g of MgAl-ATMP-LDHs/PE-EVA masterbatch masterbatch with the mixing compressing tablet system film of uniform mixture of 22.75g PE and EVA (mass ratio is 1: 1), obtain hydrotalcite content and are the MgAl-CO that 4% smooth thickness is about 120 μ m
3-LDHs/PE-EVA and MgAl-ATMP-LDHs/PE-EVA composite material film.
Application examples 4
Step 1: with step 1 in the application examples 2.
Step 2: get 4g MgAl-CO in the step 1
3-LDHs and 4g MgAl-PMIDA-LDHs sample with uniform mixture on mixing roll the mixing 15min of 5g Injecatable EVA Copolymer (EVA) with PE (mass ratio is 1: 1), get MgAl-CO respectively
3-LDHs/PE-EVA, MgAl-PMIDA-LDHs/PE-EVA masterbatch.
Step 3: get MgAl-CO in the step 2
3-LDHs/PE-EVA, each 2.25g of MgAl-PMIDA-LDHs/PE-EVA masterbatch masterbatch with the mixing compressing tablet system film of uniform mixture of 22.75g PE and EVA (mass ratio is 1: 1), obtain hydrotalcite content and are the MgAl-CO that 4% smooth thickness is about 120 μ m
3-LDHs/PE-EVA and MgAl-PMIDA-LDHs/PE-EVA composite material film.
Claims (5)
1. phosphorus-based organic matter intercalation structure selective infrared absorption material, its molecular formula is:
(M
2+)
1-x(Al
3+)
x(OH)
2(A
n-)
a(NO
3 -)
b·mH
2O
M wherein
2+Be Zn
2+Or Mg
2+
A
N-Represent the interlayer carrying capacity be n contain phosphino-organism negatively charged ion, be C
3H
12NO
9P
3 2-, CH
6O
6P
2 3-, C
2H
8O
7P
2 3-, C
5H
10NO
7P
2-, C
2H
5O
5P
2-, C
6H
7O
3P
2-, CH
6NO
3P
2-, C
2H
5O
3P
2-Or CH
5O
3P
2-
NO in the chemical formula
3 -Or do not exist; 0.1＜X＜0.8; A, b is respectively A
N-And NO
3 -Quantity, n * a+b=X; M is a crystal water quantity, 0.01＜m＜4.
2. method for preparing the described phosphorus-based organic matter intercalation structure selective infrared absorption material of claim 1, concrete preparation process is following:
A. be that the hydrotalcite precursor of nitrate ion is scattered in the deionized water with interlayer anion, fully mixing compound concentration is the hydrotalcite precursor suspension of 0.2-0.8mol/L;
B. will contain the phosphino-organism and be dissolved in that compound concentration is the aqueous solution of 0.2-0.8mol/L in the deionized water, and it will be added in the reactor drum that band stirs, and use NaOH to adjust the pH value of solution value and be 4-10;
C. under nitrogen protection, Yi Bian stir fast, the hydrotalcite precursor suspension with the steps A preparation joins in the reactor drum of step B on one side, makes that containing the organic molar weight of phosphino-is 1-3 times of nitrate radical molar weight in the hydrotalcite; The pH value of regulation system is to 5-11,60-100 ℃ of temperature refluxed crystallization 4-8 hour, filters, and washing, drying obtains target product.
3. the method for preparing phosphorus-based organic matter intercalation structure selective infrared absorption material according to claim 2 is characterized in that the said interlayer anion of steps A is that the structural formula of the hydrotalcite precursor of nitrate ion is: (M
2+)
1-x(Al
3+)
x(OH)
2(NO
3 -)
xMH
2O, wherein 0.1＜X＜0.8; M
2+Be Zn
2+Or Mg
2+M is a crystal water quantity, 0.01＜m＜4.
4. the method for preparing phosphorus-based organic matter intercalation structure selective infrared absorption material according to claim 2 is characterized in that the described phosphino-organism negatively charged ion that contains of step B, is C
3H
12NO
9P
3 2-, CH
6O
6P
2 3-, C
2H
8O
7P
2 3-, C
5H
10NO
7P
2-, C
2H
5O
5P
2-, C
6H
7O
3P
2-, CH
6NO
3P
2-, C
2H
5O
3P
2-Or CH
5O
3P
2-In a kind of.
5. the application of phosphorus-based organic matter intercalation structure selective infrared absorption material as claimed in claim 1 in polymeric materials.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070415A (en) * | 2007-06-15 | 2007-11-14 | 浙江大学 | Polyvinyl chloride/nano hydrotalcite composite resin preparing method |
| CN101376722A (en) * | 2008-10-10 | 2009-03-04 | 北京化工大学 | Selective infrared absorption material with phosphor-containing intercalation structure, and preparation and use thereof |
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|---|---|---|---|---|
| CN101070415A (en) * | 2007-06-15 | 2007-11-14 | 浙江大学 | Polyvinyl chloride/nano hydrotalcite composite resin preparing method |
| CN101376722A (en) * | 2008-10-10 | 2009-03-04 | 北京化工大学 | Selective infrared absorption material with phosphor-containing intercalation structure, and preparation and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| 孟锦宏.山梨酸、乳酸和草甘膦插层水滑石的组装及其超分子结构与性能研究.《中国博士学位论文全文数据库 工程科技I辑》.2005,(第7期),第78-82页. * |
| 矫庆泽等.水滑石的插层及其选择性红外吸收性能.《应用化学》.2002,第19卷(第10期), * |
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