CN1712454A - Light-heat stabilizer methyl organic intercalation pigment and use thereof - Google Patents
Light-heat stabilizer methyl organic intercalation pigment and use thereof Download PDFInfo
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- CN1712454A CN1712454A CN 200410049671 CN200410049671A CN1712454A CN 1712454 A CN1712454 A CN 1712454A CN 200410049671 CN200410049671 CN 200410049671 CN 200410049671 A CN200410049671 A CN 200410049671A CN 1712454 A CN1712454 A CN 1712454A
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- ldhs
- pigment
- intercalation
- light
- hydrotalcite
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Abstract
A photo-thermal stabilized helianthine B inserting layer pigment and its use are disclosed. The process is carried out by inserting helianthine B anion into hydrotalcite intercalation from ion exchange method, substituting hydrotalcite intercalation anion with helianthine B anion, and obtaining inserting layer hydrotalcite LDHs-MO pigment. It achieves higher light stability and heat resistance, and can be used for paint and composite materials.
Description
Affiliated field:
The present invention relates to a kind of photo-thermal stable form tropeolin-D intercalation pigment and application thereof.
Background technology:
Tropeolin-D (Methyl Orange is abbreviated as MO) is a kind of orange azo organic dye, has obtained using widely in fields such as the painted and analytical chemistry of matrix material.But relatively poor because of its light, thermal characteristics, its range of application and result of use are greatly limited, the light, the thermostability that therefore improve tropeolin-D have crucial meaning.
Hydrotalcite (Layered Double Hydroxides, be abbreviated as LDHs) be a kind of anion type laminated clay,, thereby utilize this performance some function species can be inserted hydrotalcite layers, the supermolecular intercalation structure material that preparation has specific function because but it has the performance of intercalation assembling.
Document Mohd Zobir bin Hussein, Zulkarnain Zainal, Asmah Hi.Yahaya, Azirabinti Abd.Aziz, Materials Science and Engineering B88,2002,98-102, with the aqueous solution of matching stain naphthalene blue-black 10B with contain Mg
2+And Al
3+Aqueous solution, adjust the pH=10 of reaction system, obtaining interlayer is the anionic intercalated houghite of naphthalene blue-black 10B, this intercalation method is a coprecipitation method.Can the purpose of its research just obtains a kind of inorganic-organic nanocomposite, do not investigate product and use as a kind of novel pigment.
Document Umberto Costantino, Natascia Coletti, and Morena Nocchetti, Langmuir, 1999, among the 15:4454-4460, adopt the urea thermal synthesis method to obtain hydrotalcite [Zn earlier
0.67Al
0.33(OH)
2] [CO
3]
0.1650.4H
2O obtains hydrotalcite Zn with itself and NaCl and HCl reaction again
0.67Al
0.33(OH)
2Cl
0.330.4H
2O is again with Zn
0.67Al
0.33(OH)
2Cl
0.330.4H
2O is a precursor, and tropeolin-D (MO) is object, and assembling obtains intercalated houghite [Zn
0.67Al
0.33(OH)
2] [MO
0.31Cl
0.02] 0.85H
2O, but intercalation is incomplete, hydrotalcite layers still has chlorion to exist, and they have investigated the fluorescence of product.Its shortcoming is a precursor preparation method complexity.
Summary of the invention:
The purpose of this invention is to provide a kind of photo-thermal stable form tropeolin-D intercalation pigment; Another object of the present invention provides the purposes of this intercalation pigment.
The chemical general formula of the photo-thermal stable form intercalation pigment LDHs-MO of the present invention's preparation is:
[M
2+ 1-xM
3+ x(OH)
2](MO)
- x·mH
2O，
Wherein 0.2＜(X/1-X)＜0.5, m=1-3X/2; M
2+Be divalent-metal ion Mg
2+, Zn
2+, Ni
2+, Fe
2+Or Cu
2+In any one, M
3+Be trivalent metal ion Al
3+, Fe
3+Or Cr
3+In any one.LDHs-MO can be used as pigment and is used for PE, PP resin and coating, because the effect of hydrotalcite precursor, this pigment has better light, thermal stability.
The preparation process of LDHs-MO is as follows:
A. hydrotalcite is joined in the deionized water, the room temperature lower magnetic force stirs, and the hydrotalcite suspension that is mixed with concentration and is 0.02-0.1M is standby; Used hydrotalcite can adopt ion exchange method or coprecipitation method preparation, and its structural formula should satisfy: [M
2+ 1-xM
3+ x(OH)
2]
X+(A
N- X/n) mH
2O, wherein 0.2＜(X/1-X)＜0.5, m=1-3X/2; M
2+Be divalent-metal ion Mg
2+, Zn
2+, Ni
2+, Fe
2+Or Cu
2+In any one; M
3+Be trivalent metal ion Al
3+, Fe
3+Or Cr
3+In any one; A
N-Be CO
3 2-, NO
3 -Or Cl
-In any one;
B. MO is dissolved in the deionized water, makes its concentration be controlled at 0.1-0.3M;
C. the mol ratio according to MO and hydrotalcite precursor is the ratio of 2-4, mix in the hydrotalcite suspension adding container with the MO solution of step B preparation and steps A preparation, be to react 2-48h under 40-100 ℃ the condition in temperature, filter, wash neutrality, 60-100 ℃ of dry 24h obtains MO anion intercalation hydrotalcite LDHs-MO.
The intercalated houghite that obtains is carried out XRD, FT-IR, UV-VIS, ultimate analysis and TG-DTA etc. characterize demonstration, MO negatively charged ion intercalation has entered stratified material LDHs interlayer.
MO and LDHs-MO place simultaneously power be shine 4,8,12 and 16 minutes respectively under 1000 watts the ultraviolet lamp after, measure its aberration (AE) size with the full-automatic color measurement instrument of TC-P2A type, the results are shown in Table 1.As can be seen from Table 1, the light stability of intercalation pigment LDHs-MO is apparently higher than MO.
The light stability test-results of table 1.LDHs-MO and MO
Irradiation time (minute) 48 12 16
MO(ΔE) 4.77 8.14 10.44 12.84
LDHs-MO(ΔE) 0.10 0.12 0.58 0.59
It is that heating was taken out after 30 minutes in 100,150,200,250 and 300 ℃ the baking oven that intercalation pigment LDHs-MO and MO powder are placed on temperature respectively, with the UV-Vis spectrophotometer its thermostability is analyzed as can be known, MO is in the time of 250 ℃, the existing variation by a relatively large margin of its UV-Vis curve, and intercalation pigment LDHs-MO is in whole temperature range, its UV-Vis curve has no significant change, and almost coincides together.This just illustrates that intercalation pigment LDHs-MO has higher thermostability than MO.
This intercalation pigment LDHs-MO can be used in macromolecule polymeric material and the coating, and has tangible light, thermostability.
Description of drawings
Fig. 1 is the value of chromatism of MO and intercalation LDHs and the compound back of PP aging different time under UV-light thereof
Fig. 2 is the value of chromatism of MO and intercalation LDHs and the compound back of PP aging different time under 100 ℃ thereof
Embodiment
Embodiment 1:
A. with Mg (NO
3)
26H
2O (30.77g, 0.12mol) and Al (NO
3)
39H
2(22.51g 0.06mol) is dissolved in the 150mL deionization O; In addition with Na
2CO
3(12.72g, 0.12mol) and NaOH (11.52g, 0.29mol) be dissolved in the 150mL deionization, rapidly mixed ammonium/alkali solutions and mixing salt solution are rotated nucleation in the liquid film reactor in full back-mixing under the room temperature, with the slurries that obtain in 100 ℃ of crystallization 6h, centrifugation, with the sample that obtains wash to the pH value less than 8, dry 24h under 70 ℃ obtains Mg-Al-CO
3The LDHs precursor; With this hydrotalcite precursor (2.44g, 0.005mol) be dispersed in the 100ml deionized water stand-by.
B. be that 2.5 ratio takes by weighing MO (4.09g 0.0125mol), all is dissolved in the 100ml deionized water it according to the mol ratio of MO and LDHs precursor.
C. MO solution and LDHs precursor suspension are mixed in container, use rare HNO of 10% then
3Solution is adjusted the pH=3.5 of reaction system, and condensing reflux 2h filters, washs to pH value and is about 7,70 ℃ of dry 24h, assembles and obtains the anion intercalated LDHs material of MO.
The intercalation LDHs that adopts means analysis such as XRD, FT-IR, UV-Vis, ultimate analysis and TG-DTA and sign to obtain respectively, proving that this intercalation product interlayer anion is the MO negatively charged ion all, is the supermolecular intercalation structure material that a kind of crystal crystalline phase is single, structure is consistent.Intercalation pigment LDHs-MO is carried out after the test of light, thermostability as can be known, it is fast light, resistance toheat all is significantly improved than MO.
Embodiment 2:
A. get Zn (NO
3)
26H
2O (17.85g, 0.06mol), Al (NO
3)
39H
2O (11.26g, 0.03mol) and NaNO
3(4.53g 0.053mol) mixes, and is dissolved in 80ml and takes off CO
2Deionized water in.Other gets NaOH, and (5.60g 0.14mol) is dissolved in 50ml and takes off CO
2Deionized water in, place the 250ml there-necked flask.At N
2Protection slowly splashes into alkaline solution in the mixing salt solution down, and violent stirring stops to drip alkaline solution during to pH=6, then with pulpous state liquid ageing 24h under 70 ℃ temperature, last suction filtration, wash Zn-Al-NO
3The LDHs precursor; (3.58g 0.005mol) is dispersed in 200ml and takes off CO with this hydrotalcite precursor
2Deionized water in stand-by.
B. be that 2.5 ratio takes by weighing MO (4.09g 0.0125mol), makes it all be dissolved in 100ml and takes off CO according to the mol ratio of MO and LDHs precursor
2Deionized water in.
C. MO solution and LDHs precursor suspension are mixed in container, at N
2Protection is condensing reflux 6h down, filters, washs to pH value to be about 7,70 ℃ of dry 24h, assembles and obtains the anion intercalated LDHs material of MO.
The intercalation LDHs that adopts means analysis such as XRD, FT-IR, UV-Vis, ultimate analysis and TG-DTA and sign to obtain respectively, proving that this intercalation product interlayer anion is the MO negatively charged ion all, is the supermolecular intercalation structure material that a kind of crystal crystalline phase is single, structure is consistent.Intercalation pigment LDHs-MO is carried out after the test of light, thermostability as can be known, it is fast light, resistance toheat all is significantly improved than MO.
Embodiment 3:
Two kinds of LDHs-MO that respectively embodiment 1 and embodiment 2 obtained and MO are in the ratio that adds 0.2g pigment among per 100 gram PP, be pressed into print after being dispersed in LDHs-MO among the PP, once its aberration Δ E was surveyed in the every irradiation under the ultraviolet lamp of 1000W of these 3 kinds of prints in 15 minutes, test altogether 15 times, gained the results are shown in Figure 1.As can be seen from Figure 1, the photostabilization of intercalation pigment LDHs-MO is all more superior than MO, and the photostabilization of Mg-Al-MO better than Zn-Al-MO, and this mainly is because Mg-Al-NO
3The LDHs precursor compares Zn-Al-NO
3The cause of LDHs precursor good stability.
Respectively above-mentioned 3 kinds of prints are surveyed one time aberration Δ E behind the 1h that whenever is heated under 100 ℃ the temperature, test 15h altogether, gained the results are shown in 2.As can be seen from Figure 2, the thermotolerance of intercalation pigment LDHs-MO is all more superior than MO, and the thermotolerance of Mg-Al-MO better than Zn-Al-MO.
Embodiment 4:
Intercalation pigment LDHs-MO is used in the phenylpropyl alcohol coating, investigates its photostabilization and thermotolerance in coating.
Press the GB/T9577-2001 specified test, the asbestos cement plate that will be brushed with coating respectively is placed under the different temperature and heated 30 minutes, takes out then and surveys its aberration Δ E, just obtains the value of chromatism under the differing temps, each sample is surveyed three times, and averaging at last the results are shown in table 2.The asbestos cement plate that is brushed with coating is placed on following the irradiation 30 minutes of ultraviolet lamp that power is 1000W respectively, records total color difference, the luminosity equation of pigment in the coating and the fastness grade of fading with color measurement instrument then.Each sample is all surveyed three times, averages at last, and the gained data are as shown in table 3.
As can be seen from Table 2, intercalation pigment LDHs-MO is in whole temperature range, and its aberration Δ E all surpasses 5, and changes not quite, and MO is in the time of 278 ℃, and its aberration Δ E has reached 19.94 unexpectedly.According to GB/T9577-2001 regulation, in whole temperature range, even if 15 qualified as long as the aberration Δ E of paint film is no more than.Therefore LDHs-MO is used for the temp. variation resistant performance requirement that coating has arrived coating, and MO does not then reach.As can be seen from Table 3, intercalation pigment LDHs-MO also has good light fastness.
Table 2 temp. variation resistant performance data
110 ℃ 150 ℃ 200 ℃ 250 ℃ 278 ℃ of pigment titles
MO 3.98 6.98 10.44 12.68 19.94
Intercalation MO 2.77 3.10 3.52 4.37 4.85
Table 3 resistance to UV aging can data
The total color difference luminosity equation fastness grade of fading
The pigment title
ΔE＜15 ΔL TL
MO 8.71 0.21 2.5
Intercalation MO 0.79 0.04 4.5
Claims (3)
1. photo-thermal stable form intercalation pigment LDHs-MO, its chemical general formula is:
[M
2+ 1-xM
3+ x(OH)
2](MO)
- x·mH
2O，
Wherein 0.2＜(X/1-X)＜0.5, m=1-3X/2;
M
2+Be divalent-metal ion Mg
2+, Zn
2+, Ni
2+, Fe
2+Or Cu
2+In any one;
M
3+Be trivalent metal ion Al
3+, Fe
3+Or Cr
3+In any one.
2. the purposes of a photo-thermal stable form intercalation pigment LDHs-MO is characterized in that this intercalation pigment LDHs-MO can be used in macromolecule polymeric material, coating and the paint.
3. the purposes of a kind of photo-thermal stable form intercalation pigment LDHs-MO as claimed in claim 2 is characterized in that this intercalation pigment is mainly used in PE, PP resin and the coating.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100496713A CN1294213C (en) | 2004-06-24 | 2004-06-24 | Light-heat stabilizer methyl organic intercalation pigment and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100496713A CN1294213C (en) | 2004-06-24 | 2004-06-24 | Light-heat stabilizer methyl organic intercalation pigment and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1712454A true CN1712454A (en) | 2005-12-28 |
| CN1294213C CN1294213C (en) | 2007-01-10 |
Family
ID=35718261
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100496713A Expired - Fee Related CN1294213C (en) | 2004-06-24 | 2004-06-24 | Light-heat stabilizer methyl organic intercalation pigment and use thereof |
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| Country | Link |
|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982509A (en) * | 2010-10-08 | 2011-03-02 | 北京化工大学 | Acid yellow 17 intercalation pigment with light stability, thermal stability and supramolecular structure and preparation method thereof |
| CN101575504B (en) * | 2009-06-10 | 2012-07-11 | 北京化工大学 | Azo dye intercalation assembly material with photochromic function and preparation method thereof |
| CN102618074A (en) * | 2012-02-24 | 2012-08-01 | 山东大学 | Thermal stabilization type ponceau 2R intercalation hydrotalcite dye and preparation method thereof |
| CN104927086A (en) * | 2015-06-10 | 2015-09-23 | 安徽建筑大学 | Flame-retardant smoke-suppression agent and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001234088A (en) * | 2000-02-22 | 2001-08-28 | Yasushi Kubo | Method for producing coloring composition |
| CN1294211C (en) * | 2003-11-13 | 2007-01-10 | 北京化工大学 | Super molecular structure light thermal stable light fast brilliant red BBC dye and its intercalation method |
-
2004
- 2004-06-24 CN CNB2004100496713A patent/CN1294213C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575504B (en) * | 2009-06-10 | 2012-07-11 | 北京化工大学 | Azo dye intercalation assembly material with photochromic function and preparation method thereof |
| CN101982509A (en) * | 2010-10-08 | 2011-03-02 | 北京化工大学 | Acid yellow 17 intercalation pigment with light stability, thermal stability and supramolecular structure and preparation method thereof |
| CN102618074A (en) * | 2012-02-24 | 2012-08-01 | 山东大学 | Thermal stabilization type ponceau 2R intercalation hydrotalcite dye and preparation method thereof |
| CN102618074B (en) * | 2012-02-24 | 2014-12-03 | 山东大学 | Thermal stabilization type ponceau 2R intercalation hydrotalcite dye and preparation method thereof |
| CN104927086A (en) * | 2015-06-10 | 2015-09-23 | 安徽建筑大学 | Flame-retardant smoke-suppression agent and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1294213C (en) | 2007-01-10 |
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Granted publication date: 20070110 |