CN103865102A - phosphaphenanthrene-containing ring compound intercalated modified hydrotalcite and preparation method thereof - Google Patents
phosphaphenanthrene-containing ring compound intercalated modified hydrotalcite and preparation method thereof Download PDFInfo
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- CN103865102A CN103865102A CN201410066694.9A CN201410066694A CN103865102A CN 103865102 A CN103865102 A CN 103865102A CN 201410066694 A CN201410066694 A CN 201410066694A CN 103865102 A CN103865102 A CN 103865102A
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Abstract
The invention relates to phosphaphenanthrene-containing ring compound intercalated modified hydrotalcite and a preparation method thereof, belonging to the field of organic modification of nano-clay. The preparation method comprises the steps of firstly enabling a DOPO (phosphaphenanthrene) compound and MA (maleic acid) to perform an addition reaction to obtain DOPO-MA; adding hydrotalcite and deionized water into a three-necked flask, heating to 100 DEG C, and stirring to form an emulsion; then slowly adding DOPO-MA powder into the emulsion for a plurality of times, and enabling double-carboxyl in the DOPO-MA to react with interlayer carbonate of the hydrotalcite so as to ensure that the DOPO-MA replaces the carbonate to enter the interlayer. The phosphaphenanthrene-containing ring compound intercalated modified hydrotalcite and the preparation method thereof, disclosed by the invention, aim to enable a fire retardant containing flame-retardant elements such as phosphorus and the like to enter the interlayer of the hydrotalcite under the effects of positive and negative charges so as to obtain novel phosphaphenanthrene compound intercalated modified hydrotalcite which can be blended with a variety of resin matrixes; the flame retardant property of the hydrotalcite is comprehensively improved, the interlay spacing of the hydrotalcite is also enlarged, and the dispersibility and compatibility of the phosphaphenanthrene-containing ring compound intercalated modified hydrotalcite in the resin matrixes are improved.
Description
Technical field
The present invention relates to the anion-modified field of a kind of hydrotalcite layers, be specifically related to a kind of containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof.
Background technology
Before and after 1842, find one of naturally occurring layered clay mineral hydrotalcite-based compound Mg in Sweden
6al
2(OH)
16cO
34H
2o(LDHs) since, because of its have interlayer object the moon from protect kind and quantity Modulatory character, interlayer ion interchangeability, grain size and distribution Modulatory character, high thermal stability, acid-basicity and by MgO
6the octahedra rib that is mutually total to, the laminate structure that interlayer forms by hydrogen bond, makes it be applied widely and demonstrate good prospect in fields such as Industrial Catalysis, biological medicine, environment protection, electronic material, nano composite material, fire retardant materials.
Nineteen forty-two, Feitknecht etc. have gone out LDHs by coprecipitation method synthetic, and propose the imagination of double-layer structure model.1969, Allmann, by single crystal structure determination, determined the laminate structure of LDHs.70～eighties of 20th century, the application aspect catalyzer of LDHs and product of roasting thereof has obtained broad research.In recent years, the preparation chemistry of intercalation LDHs functional materials has made great progress, and the employing coprecipitation methods such as Chen are prepared SDS modified hydrotalcite, then prepares the nano combined material of PMA/OZnAl-LDH by in-situ polymerization; The employing coprecipitation methods such as Francis have been prepared SDBS modified hydrotalcite, further the compound modified hydrotalcite/PE-g-MAH/LDPE nano composite material that prepared of melting.Utilize the diversity of LDHs structure, by between functional object interposed layer, regulate its performance by changing intercalation assembling condition with multiple intercalation assemble method, can develop many function supermolecular intercalation LDHs materials.
Phospho hetero phenanthrene cyclic cpds DOPO-MA, in containing ignition-proof element P, and owing to containing two carboxyls in molecule, acid more by force can with the interlayer CO of LDHs
3 2-thereby reaction enters between LDHs laminate.DOPO-MA enters (DM-LDH) after LDHs interlayer, because the size of its molecule itself is larger, contribute to increase LDHs interlamellar spacing, while being polymer blending, easily peel off, DOPO-MA is originally as phosphorus-containing matter simultaneously, its consistency in macromole be can improve, thereby its flame retardant resistance and thermostability performance improved.
Summary of the invention
The object of the invention is to be that preparation is a kind of containing phospha phenanthrene ring compound intercalation modifying hydrotalcite, the fire retardant of phosphor-containing flame-proof element is inserted into hydrotalcite layers by chemical reaction, when improving hydrotalcite flame retardant properties, improve its dispersiveness and consistency in resin matrix comprehensively.
For achieving the above object, the present invention adopts following technical scheme:
A kind of containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, its feature comprises the following steps: first hydrotalcite and deionized water are added to there-necked flask, heating and with magnetic agitation make its form emulsion, then the gradation of DOPO-MA powder is slowly joined in above-mentioned emulsion, enter interlayer and obtain product D M-LDH thereby utilize two carboxyls in DOPO-MA to react with the interlayer carbonate of hydrotalcite to make DOPO-MA to replace carbonate.After question response finishes, filter and use whose cleaning of deionized water, dry.
Described in step of the present invention containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, it is characterized in that hydrotalcite chemical formula used is Mg
6al
2(OH)
16cO
34H
2o is magnesium aluminum-hydrotalcite.
Described in step of the present invention containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, it is characterized in that after 5-30 mass parts hydrotalcite and the mixing of 200-300 parts by volume deionized water, be heated to 90-100 ℃, magnetic agitation rotating speed is 30-50r/s, continues 20min and forms emulsion.
Described in step of the present invention containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, it is characterized in that DOPO-MA is self-control, be dissolved in respectively in dimethylbenzene and tetrahydrofuran (THF) and form clear solution than 1.3:1 by amount of substance by DOPO and toxilic acid, again toxilic acid tetrahydrofuran solution is slowly splashed in DOPO xylene solution, and react under 100 ℃ of conditions, underpressure distillation, the solid of separating out is DOPO-MA product, filtration washing, vacuum-drying 10h.
Described in step of the present invention containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, it is characterized in that DOPO-MA to divide and join for 5-10 time in hydrotalcite emulsion, its add-on is hydrotalcite 2 times.
Described in step of the present invention containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, it is characterized in that system reaction times in there-necked flask is 8-10h, temperature of reaction is 80-100 ℃, magnetic agitation rotating speed is 30-50r/s.
Described in step of the present invention containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, while it is characterized in that filtering, millipore filtration used aperture is 0.3-0.6 μ m, filter paper is conventional filter paper.
Described in step of the present invention containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, it is characterized in that product vacuum drying oven dry 10-20h at 40-50 ℃.
The present invention has prepared the organically-modified hydrotalcite of a kind of brand-new interlayer, will be intercalation into hydrotalcite layers containing phospha phenanthrene ring Compound D OPO[MA, and technique is simple, and raw material is easy to get, and preparation amount is large, and transformation efficiency is high, can be used as a kind of novel high molecular fire retardant additive.
In practical application, modified hydrotalcite prepared by the present invention can with the blend of various kinds of resin matrix, thereby the nano composite material of obtaining.After organically-modified, can well improve flame retardant properties and the mechanical property of matrix resin material, improve its dispersed, poor problem of consistency in resin matrix simultaneously.
Accompanying drawing explanation
Fig. 1 is the chemical equation of a kind of synthetic DOPO-MA of providing of the embodiment of the present invention;
Fig. 2 is a kind of modified hydrotalcite of providing of the embodiment of the present invention and the XRD comparison diagram of original hydrotalcite
Fig. 3 is a kind of modified hydrotalcite of providing of the embodiment of the present invention and the infrared analysis comparison diagram of original hydrotalcite.
Fig. 4 is a kind of modified hydrotalcite of providing of the embodiment of the present invention and the thermogravimetic analysis (TGA) comparison diagram of original hydrotalcite.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is carried out to comparatively detailed explanation.
Embodiment 1:
(1) getting 70.2gDOPO and 29g toxilic acid is dissolved in respectively in dimethylbenzene and tetrahydrofuran (THF) and forms clear solution, again toxilic acid tetrahydrofuran solution is slowly splashed in there-necked flask in DOPO xylene solution with constant pressure funnel, stir and react 10-12h under 100 ℃ of conditions, underpressure distillation, the solid of separating out is DOPO-MA product, filtration washing, vacuum-drying 10h
10g hydrotalcite is joined 250ml there-necked flask is housed, add 100ml deionized water, stir 20min at 80 ℃, treat that it forms milkiness shape, keeps temperature-resistant.20gDOPO-MA powder is added to 4g at every turn, in the time that it no longer produces bubble, continue to add and be divided into 5 times, after not producing gas in solution, control pH at 3.5-4.5, stirring with magnetic stirring apparatus at 30r/s, after reaction 8h, filter and obtain with vacuum drying oven baking 12h the modified hydrotalcite (DM-LDH) of DOPO-MA intercalation at 60 ℃.
Modified hydrotalcite and hydrotalcite are carried out to infrared analysis, Comparatively speaking, modified hydrotalcite the 2925 and 2854 appearance-CH2 of place-peak, there is the stretching vibration peak of P-Ph at 1586 and 1472 places, there is the stretching vibration absorption peak of P=O at 1198 places, occur the dibasic C-H of phenyl ring out-of-plane deformation vibration absorption peak at 756 places.The characteristic peak of the CO32-at 1371 places has disappeared.Simultaneously flexible, the flexural vibration peak of the Mg-O-Al of laminate 780,680cm
-1all all occur, illustrate that veneer structure still exists.More than can illustrate, DOPO-MA has successfully replaced carbonate.
In order further to verify modified hydrotalcite and modified hydrotalcite to be carried out to XRD analysis, by (003), (006) the crystal face diffraction peak that can see DM-LDH in figure compared with LDH, all move to low angle, wherein the 2 θ angles of (003) diffraction peak move to 4.16 by 11.57 °, the d(003 calculating through Bragg equation accordingly) value becomes 2.12nm from 0.76nm; 110 peaks do not become substantially, illustrate that its veneer structure is not damaged.This also can illustrate that DOPO-MA has successfully replaced carbonate, and has expanded interlamellar spacing.
Further checking, carries out thermogravimetric analysis to hydrotalcite and modified hydrotalcite again, can see that the thermolysis of modified hydrotalcite is divided into 2 sections, and the first stage is the charing of deviating from of middle water and hydroxyl and DOPO-MA, and subordinate phase is the further decomposition of charcoal layer.
Embodiment 2:
Getting 70.2gDOPO and 29g toxilic acid is dissolved in respectively in dimethylbenzene and tetrahydrofuran (THF) and forms clear solution, again toxilic acid tetrahydrofuran solution is slowly splashed in there-necked flask in DOPO xylene solution with constant pressure funnel, stir and react 10-12h under 100 ℃ of conditions, underpressure distillation, the solid of separating out is DOPO-MA product, filtration washing, vacuum-drying 10h
10g hydrotalcite is joined 250ml there-necked flask is housed, add 100ml deionized water, stir 20min at 80 ℃, treat that it forms milkiness shape, keeps temperature-resistant.20gDOPO-MA powder is added to 4g at every turn, in the time that it no longer produces bubble, continue to add and be divided into 5 times, after not producing gas in solution, control pH at 3.5-4.5, stirring with magnetic stirring apparatus at 30r/s, after reaction 10h, filter and obtain with vacuum drying oven baking 12h the modified hydrotalcite (DM-LDH) of DOPO-MA intercalation at 60 ℃.
Embodiment 3:
Getting 70.2gDOPO and 29g toxilic acid is dissolved in respectively in dimethylbenzene and tetrahydrofuran (THF) and forms clear solution, again toxilic acid tetrahydrofuran solution is slowly splashed in there-necked flask in DOPO xylene solution with constant pressure funnel, stir and react 10-12h under 100 ℃ of conditions, underpressure distillation, the solid of separating out is DOPO-MA product, filtration washing, vacuum-drying 10h
10g hydrotalcite is joined 250ml there-necked flask is housed, add 100ml deionized water, stir 20min at 100 ℃, treat that it forms milkiness shape, keeps temperature-resistant.20gDOPO-MA powder is added to 4g at every turn, in the time that it no longer produces bubble, continue to add and be divided into 5 times, after not producing gas in solution, control pH at 3.5-4.5, stirring with magnetic stirring apparatus at 30r/s, after reaction 8h, filter and obtain with vacuum drying oven baking 12h the modified hydrotalcite (DM-LDH) of DOPO-MA intercalation at 60 ℃.
Embodiment 4:
Getting 70.2gDOPO and 29g toxilic acid is dissolved in respectively in dimethylbenzene and tetrahydrofuran (THF) and forms clear solution, again toxilic acid tetrahydrofuran solution is slowly splashed in there-necked flask in DOPO xylene solution with constant pressure funnel, stir and react 10-12h under 100 ℃ of conditions, underpressure distillation, the solid of separating out is DOPO-MA product, filtration washing, vacuum-drying 10h
10g hydrotalcite is joined 250ml there-necked flask is housed, add 100ml deionized water, stir 20min at 90 ℃, treat that it forms milkiness shape, keeps temperature-resistant.20gDOPO-MA powder is added to 5g at every turn, in the time that it no longer produces bubble, continue to add and be divided into 4 times, after not producing gas in solution, control pH at 3.5-4.5, stirring with magnetic stirring apparatus at 30r/s, after reaction 8h, filter and obtain with vacuum drying oven baking 12h the modified hydrotalcite (DM-LDH) of DOPO-MA intercalation at 60 ℃.
Embodiment 5:
Getting 70.2gDOPO and 29g toxilic acid is dissolved in respectively in dimethylbenzene and tetrahydrofuran (THF) and forms clear solution, again toxilic acid tetrahydrofuran solution is slowly splashed in there-necked flask in DOPO xylene solution with constant pressure funnel, stir and react 10-12h under 100 ℃ of conditions, underpressure distillation, the solid of separating out is DOPO-MA product, filtration washing, vacuum-drying 10h
20g hydrotalcite is joined 250ml there-necked flask is housed, add 200ml deionized water, stir 20min at 90 ℃, treat that it forms milkiness shape, keeps temperature-resistant.40gDOPO-MA powder is added to 5g at every turn, in the time that it no longer produces bubble, continue to add and be divided into 8 times, after not producing gas in solution, control pH at 3.5-4.5, stirring with magnetic stirring apparatus at 30r/s, after reaction 8h, filter and obtain with vacuum drying oven baking 12h the modified hydrotalcite (DM-LDH) of DOPO-MA intercalation at 60 ℃.
Claims (9)
1. one kind contains phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, it is characterized in that: DOPO-MA is intercalation into carbon hydrotalcite layers by chemical reaction and charge force.
2. one kind contains phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, its feature comprises the following steps: first hydrotalcite and deionized water are added to there-necked flask, heating and with magnetic agitation make its form emulsion, then the gradation of DOPO-MA powder is slowly joined in above-mentioned emulsion, thereby utilizing two carboxyls in DOPO-MA to react with the interlayer carbonate of hydrotalcite to make DOPO-MA replace carbonate enters interlayer.After question response finishes, filter and use whose cleaning of deionized water, dry.
3. according to claim 2 containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, it is characterized in that hydrotalcite chemical formula used is Mg
6al
2(OH)
16cO
34H
2o is magnesium aluminum-hydrotalcite.
4. according to claim 2 containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, it is characterized in that after 5-30 mass parts hydrotalcite and the mixing of 200-300 parts by volume deionized water, be heated to 90-100 ℃, magnetic agitation rotating speed is 30-50r/s, continues 20min and forms emulsion.
5. according to claim 2 containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, it is characterized in that DOPO-MA is self-control, be dissolved in respectively in dimethylbenzene and tetrahydrofuran (THF) and form clear solution than 1.3:1 by amount of substance by DOPO and toxilic acid, again toxilic acid tetrahydrofuran solution is slowly splashed in DOPO xylene solution, and react under 100 ℃ of conditions, underpressure distillation, the solid of separating out is DOPO-MA product, filtration washing, vacuum-drying 10h.
6. according to claim 2 containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, it is characterized in that DOPO-MA to divide and join for 5-10 time in hydrotalcite emulsion, its add-on is hydrotalcite 2 times.
7. the phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof that contains according to claim 2, is characterized in that system reaction times in there-necked flask is 8-10h, and temperature of reaction is 80-100 ℃, and magnetic agitation rotating speed is 30-50r/s.
8. according to claim 2 containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, while it is characterized in that filtering, millipore filtration used aperture is 0.3-0.6 μ m, and filter paper is conventional filter paper.
9. according to claim 2 containing phospha phenanthrene ring compound intercalation modifying hydrotalcite and preparation method thereof, it is characterized in that product vacuum drying oven dry 10-20h at 40-50 ℃.
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| CN105062227A (en) * | 2015-09-01 | 2015-11-18 | 绿园宝业（北京）贸易有限公司 | Organic anion intercalated hydrotalcite/regenerated polyethylene material special for pipeline corrosion prevention and preparation method thereof |
| CN106398003A (en) * | 2016-11-09 | 2017-02-15 | 安徽中翰高分子科技有限公司 | Flame-retardant electro-conductive thermoplastic vulcanized rubber material |
| CN106753148A (en) * | 2016-12-07 | 2017-05-31 | 安徽艾蒂贝生物有限公司 | A kind of special unsaturated polyester resin adhesive of quartzite slate |
| CN109251358A (en) * | 2018-08-06 | 2019-01-22 | 厦门大学 | A kind of layered double-hydroxide fire retardant and preparation method thereof that polyacid intercalation surface is covalent modified |
| CN110423393A (en) * | 2019-07-31 | 2019-11-08 | 深圳市通产丽星股份有限公司 | A kind of composite material and preparation method and LPG tank |
| CN114907666A (en) * | 2022-06-02 | 2022-08-16 | 安徽粟米塑业有限公司 | Flame-retardant high-strength ABS plastic |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105062227A (en) * | 2015-09-01 | 2015-11-18 | 绿园宝业（北京）贸易有限公司 | Organic anion intercalated hydrotalcite/regenerated polyethylene material special for pipeline corrosion prevention and preparation method thereof |
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| CN106753148A (en) * | 2016-12-07 | 2017-05-31 | 安徽艾蒂贝生物有限公司 | A kind of special unsaturated polyester resin adhesive of quartzite slate |
| CN109251358A (en) * | 2018-08-06 | 2019-01-22 | 厦门大学 | A kind of layered double-hydroxide fire retardant and preparation method thereof that polyacid intercalation surface is covalent modified |
| CN110423393A (en) * | 2019-07-31 | 2019-11-08 | 深圳市通产丽星股份有限公司 | A kind of composite material and preparation method and LPG tank |
| CN114907666A (en) * | 2022-06-02 | 2022-08-16 | 安徽粟米塑业有限公司 | Flame-retardant high-strength ABS plastic |
| CN114907666B (en) * | 2022-06-02 | 2023-05-30 | 安徽粟米塑业有限公司 | Flame-retardant high-strength ABS plastic |
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