CN114874265B - Rare earth flame retardant complex and preparation method and application thereof - Google Patents

Rare earth flame retardant complex and preparation method and application thereof Download PDF

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CN114874265B
CN114874265B CN202210502882.6A CN202210502882A CN114874265B CN 114874265 B CN114874265 B CN 114874265B CN 202210502882 A CN202210502882 A CN 202210502882A CN 114874265 B CN114874265 B CN 114874265B
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flame retardant
rare earth
ddp
phosphate
solution
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CN114874265A (en
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林凤龙
宋立军
张炎
吴银财
王胜龙
王辛坤
陈丽彬
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Xiamen Institute of Rare Earth Materials
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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  • Organic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention discloses a rare earth flame-retardant complex, a preparation method and application thereof, wherein the structural formula of the rare earth flame-retardant complex is Ln which is selected from Y, la, ce, pr, nd, sm, eu, gd, tb and Dy. The invention has excellent flame retardant synergistic performance, and can effectively improve the flame retardant efficiency of the phosphorus-nitrogen flame retardant and reduce the addition amount of the phosphorus-nitrogen flame retardant when being matched with the phosphorus-nitrogen flame retardant. The rare earth flame-retardant complex can be applied to a plurality of fields of engineering plastics, polymer films, polymer fibers, coatings, rubber and the like, and the flame retardant property of the product is improved.

Description

Rare earth flame retardant complex and preparation method and application thereof
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a rare earth flame-retardant complex, a preparation method and application thereof.
Background
In recent years, high molecular materials are widely used in various fields such as electronics, high-speed rail ships, aerospace and the like due to the advantages of light weight, high strength, easiness in processing and the like. However, the polymer material mostly consists of C, H, O and other elements, belongs to an intrinsic flammable and combustible material, and is easy to cause property loss due to fire. In addition, the high polymer material generates a large amount of smoke and toxic gas when being burnt, which causes great threat to the life health of people. Therefore, the flame-retardant modification of the high polymer material has important significance for widening the application field and protecting the life health of people.
In the prior art, flame retardants mainly comprise intumescent flame retardants, halogen flame retardants, nitrogen flame retardants, phosphorus flame retardants, metal hydroxide flame retardants and the like. The halogen flame retardant mainly comprises chlorine flame retardant and bromine flame retardant, but the halogen flame retardant has a certain negative effect on health, environment and performance of final products, so the application of the halogen flame retardant is gradually limited and has been a trend of development. However, flame retardants such as intumescent flame retardants, nitrogen flame retardants and phosphorus flame retardants do not contain halogen, but have low flame retardant efficiency, and a large proportion is required to be added to exert flame retardant effect, so that the performance and processability of the product are greatly affected. Similar problems exist with metal hydroxide flame retardants.
With the improvement of environmental protection consciousness of people, similar to the European Union RoHS requirement and REACH list, china also puts forward higher and higher requirements on the high polymer flame retardant. Therefore, development of a novel halogen-free, low-smoke and efficient flame retardant and a flame retardant technology are technical problems which are urgent to be solved currently.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a rare earth flame retardant complex.
The invention also aims to provide a preparation method of the rare earth flame-retardant complex.
Still another object of the present invention is to provide a flame retardant polymer material.
The technical scheme of the invention is as follows:
A rare earth flame retardant complex has a structural formula Ln selected from Y, la, ce, pr, nd, sm, eu, gd, tb and Dy.
In a preferred embodiment of the present invention, ln is Ce or La.
The preparation method of the rare earth flame retardant complex comprises the following steps:
(1) Dissolving Ln (NO 3)3·6H2 O in deionized water to obtain solution A, dispersing DDP ([ (6-oxo-6H-dibenzo [ C, e ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid) in deionized water to obtain suspension B, (2) adding 10-25% ammonia solution into the suspension B until DDP is completely dissolved to obtain solution C with pH of 6-8;
(3) Dropwise adding the solution A into the solution C, continuously stirring at 30-50 ℃, continuously reacting at room temperature for 0.5-3h after the dropwise adding, centrifuging, and fully washing with deionized water to obtain a solid product;
(4) And (3) carrying out vacuum drying on the solid product at 90-120 ℃ until the weight is constant, thus obtaining the rare earth flame retardant complex.
In a preferred embodiment of the invention, ln (NO 3)3·6H2 O to deionized water ratio is 1-5 mmol:10-50 mL) in solution A and DDP to deionized water ratio is 1-5 mmol:10-50 mL in suspension B.
Further preferably, the molar ratio of Ln (NO 3)3·6H2 O to DDP) is 1:1-3.
The flame-retardant polymer material comprises the rare earth flame-retardant complex, a polymer material, a halogen-free flame retardant, an anti-dripping agent and a processing aid.
In a preferred embodiment of the present invention, the above-mentioned rare earth flame retardant complex, polymer material, halogen-free flame retardant, anti-dripping agent and processing aid are 0.2 to 3%, 79.0 to 92.6%, 7 to 17%, 0.1 to 0.5% and 0.1 to 0.5% by mass in this order.
In a preferred embodiment of the present invention, the polymer material is selected from at least one of polyethylene, polypropylene, polyoxymethylene, polycarbonate, polyamide, polyester, acrylonitrile-butadiene-styrene copolymer, polyurethane, polymethyl methacrylate, polyphenylene sulfide, polyphenylene oxide, polystyrene, ethylene-vinyl acetate copolymer, ethylene propylene diene monomer, natural rubber, and epoxy resin.
In a preferred embodiment of the present invention, the halogen-free flame retardant is selected from the group consisting of ammonium polyphosphate, melamine phosphate, melamine polyphosphate, melamine cyanurate, bis (diphenyl) phosphate, m-phenylene bis (diphenyl) phosphate, dimethyl methylphosphonate, triphenyl phosphate, aluminum phosphite, diethyl aluminum hypophosphite, 2-carboxyethyl phenyl hypophosphorous acid, piperazine phosphate, piperazine pyrophosphate, dimethyl methylphosphonate, tris (neopentyl glycol phosphate) methylamine, 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2) octane, [ 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2) octane ] phosphate melamine salt, [ 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2) octane ] phenylsilane, 9-10-dihydro-oxo-10-phosphaphenanthrene and 10- (2, 2) hydroxy-10-phenanthrene oxide.
In a preferred embodiment of the present invention, the anti-dripping agent is selected from at least one of polytetrafluoroethylene, fullerene, graphene, halloysite nanotube, silicon carbide whisker, hexaphenoxy cyclotriphosphazene and 1,3, 5-tetrafluoro-1, 3-diphenoxy cyclotriphosphazene .
In a preferred embodiment of the invention, the processing aid is selected from at least one of EBS, antioxidant 1010, pentaerythritol, tris (2-hydroxyethyl) isocyanate.
The rare earth flame-retardant complex can be applied to a plurality of fields of engineering plastics, polymer films, polymer fibers, coatings, rubber and the like, and the flame retardant property of the product is improved.
The beneficial effects of the invention are as follows:
1. the invention has excellent flame retardant synergistic performance, and can effectively improve the flame retardant efficiency of the phosphorus-nitrogen flame retardant and reduce the addition amount of the phosphorus-nitrogen flame retardant when being matched with the phosphorus-nitrogen flame retardant.
2. The invention has few synthesis steps, is simple and easy to operate; the energy consumption is low, and high temperature and high pressure are not required; the reaction time is short, and the reaction yield is high; organic solvent is not used in the reaction process, and the method belongs to a green and environment-friendly preparation method.
3. The flame-retardant polymer material disclosed by the invention has high flame-retardant grade and excellent mechanical properties.
Drawings
FIG. 1 is a scanning electron micrograph of La@DDP prepared in examples 1 to 2 of the present invention.
FIG. 2 is an infrared test spectrum of La@DDP prepared in examples 1 to 2 of the present invention.
FIG. 3 is a thermogravimetric plot of La@DDP prepared in examples 1 to 2 of the present invention.
FIG. 4 is a digital photograph of burning residual carbon analysis, scanning electron microscope photograph and EDS spectrum of comparative example 7 and example 7 of the present invention (comparative example 7 (a, b, c, d); example 7 (e, f, g, h)).
Detailed Description
The technical scheme of the invention is further illustrated and described below by the specific embodiments in combination with the accompanying drawings.
Example 1
(1) La (NO 3)3·6H2 O (1 mmo 1) was dissolved in 10mL of deionized water to obtain solution A, and DDP (1 mmole) was dispersed in 10mL of deionized water to obtain suspension B;
(2) To suspension B was added an aqueous ammonia solution of 10% until DDP was completely dissolved, giving solution C, pH about 6.
(3) Transferring the solution C to a three-neck flask, dropwise adding the solution A into the solution C through a dropping funnel, continuously stirring at 30 ℃, continuously reacting for 0.5h at room temperature after the dropwise adding, centrifuging, and washing with deionized water for at least 3 times to obtain a solid product;
(4) And (3) carrying out vacuum drying on the solid product at 90 ℃ to constant weight to obtain the rare earth flame retardant complex La@DDP shown in figures 1 to 3.
The yield of the obtained rare earth flame retardant complex La@DDP is 99.0%.
Example 2
(1) La (NO 3)3·6H2 O (1 mmol) was dissolved in 10mL deionized water to give solution A and DDP (1.5 mmol) was dispersed in 20mL deionized water to give suspension B;
(2) To suspension B was added an aqueous ammonia solution of 10% until DDP was completely dissolved, giving solution C, pH about 7.
(3) Transferring the solution C to a three-neck flask, dropwise adding the solution A into the solution C through a dropping funnel, continuously stirring at 30 ℃, continuously reacting for 1h at room temperature after the dropwise adding, centrifuging, and washing with deionized water for at least 3 times to obtain a solid product;
(4) And (3) carrying out vacuum drying on the solid product at 90 ℃ to constant weight to obtain the rare earth flame retardant complex La@DDP shown in figures 1 to 3.
The yield of the obtained rare earth flame retardant complex La@DDP is 98.2%.
Example 3
(1) Ce (NO 3)3·6H2 O (1 mmol) was dissolved in 10mL deionized water to give solution A and DDP (3 mmol) was dispersed in 30mL deionized water to give suspension B;
(2) To suspension B was added an aqueous ammonia solution of 10% until DDP was completely dissolved, giving solution C, pH about 7.
(3) Transferring the solution C to a three-neck flask, dropwise adding the solution A into the solution C through a dropping funnel, continuously stirring at 40 ℃, continuously reacting for 2 hours at room temperature after the dropwise adding, centrifuging, and washing with deionized water for at least 3 times to obtain a solid product;
(4) And (3) carrying out vacuum drying on the solid product at 90 ℃ until the weight is constant, and obtaining the rare earth flame-retardant complex Ce@DDP.
The yield of the obtained rare earth flame retardant complex Ce@DDP is 97.5.
Example 4
(1) Y (NO 3)3·6H2 O (1 mmol) was dissolved in 10mL deionized water to give solution A and DDP (3 mmol) was dispersed in 30mL deionized water to give suspension B;
(2) To suspension B, an aqueous ammonia solution of 15% concentration was added until DDP was completely dissolved, giving solution C, pH about 8.
(3) Transferring the solution C to a three-neck flask, dropwise adding the solution A into the solution C through a dropping funnel, continuously stirring at 40 ℃, continuously reacting for 2 hours at room temperature after the dropwise adding, centrifuging, and washing with deionized water for at least 3 times to obtain a solid product;
(4) And (3) carrying out vacuum drying on the solid product at 90 ℃ until the weight is constant, and obtaining the rare earth flame-retardant complex Ce@DDP.
The yield of the obtained rare earth flame retardant complex Y@DDP is 97.0%.
Example 5
The La@DDP prepared in the example 1 is applied to a flame retardant polymer, and comprises the following specific components: polypropylene: 92.6%, la@DDP:0.2% ammonium polyphosphate: 7.0%, hexaphenoxy cyclotriphosphazene: 0.1%, EBS:0.1%.
Weighing the raw materials according to the proportion, and putting the raw materials into a high-speed mixer for uniform mixing to form a premix; and adding the premix into a double-screw extruder for melt extrusion, granulating in a bracing mode, and finally drying to obtain the flame-retardant polymer material based on the rare earth flame-retardant complex, and performing relevant performance tests.
Examples 6 to 14 and comparative examples 1 to 7
Examples 6-14 and comparative examples 1-7 were prepared as in example 5, the specific formulation compositions were as in Table 1, and the La@DDP and Ce@DDP were prepared as in examples 1 and 3, respectively. A comparison of comparative example 7 and example 7 is shown in fig. 4.
Table 1 formulation compositions of examples 5-14 and comparative examples 1-7
Table 2 summary of the properties of examples 5-14 and comparative examples 1-6
As can be seen from examples 1-4, the rare earth flame retardant complex prepared by the invention has the advantages of simple preparation method and high yield. As can be seen from the data of example 7 and comparative example 1/2/3 in Table 2, the rare earth flame retardant complex and the halogen-free flame retardant have good synergistic effect, and can greatly improve the flame retardant efficiency, so that the V-0 flame retardant grade can be achieved with fewer addition ratios. The anti-dripping agent provided by the invention can effectively prevent the dripping phenomenon generated when the polymer burns. The compound flame-retardant system can play a flame-retardant role in gas phase and condensed phase simultaneously. In the condensed phase, on the one hand, degradation products such as phosphoric acid and polyphosphoric acid, which are generated by decomposition of the halogen-free flame retardant at high temperature, catalyze the formation of the carbon layer, and remain in the carbon layer in the form of p=o and P-O-C. On the other hand, rare earth ions and oxides thereof generated by the decomposition of La@DDP at high temperature have the capability of catalyzing esterification and transesterification reactions. Phosphate obtained by decomposing the halogen-free flame retardant can further react with carbonate through transesterification under the catalysis of La, so that a more compact three-dimensional network carbon layer structure is formed, heat and oxygen transfer to an underlying substrate are reduced, and meanwhile combustible volatile matters entering a gas phase are also reduced. In the gas phase, oxygen and combustible gas are diluted by gas generated by decomposing the halogen-free flame retardant, phosphorus-containing free radicals are released in the thermal decomposition process of La@DDP and diffuse into the gas phase, and combustion is interrupted and inhibited by quenching high-activity free radicals such as OH, H and the like generated by breaking high molecular chains, so that the degradation process of the polymer is slowed down. Thus, under the dual action of condensed phase and gas phase flame retardance, continuous dense highly graphitized carbon residue is produced, which is beneficial to reducing heat and oxygen transfer, and eventually slowing down or even preventing the combustion process.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, i.e., the invention is not to be limited to the details of the invention.

Claims (9)

1. A rare earth synergistic flame retardant complex is characterized in that: the structure is as follows
Ln is Ce or La.
2. The method for preparing the rare earth synergistic flame retardant complex according to claim 1, which is characterized in that: the method comprises the following steps:
(1) Adding 10-25% ammonia water solution to the suspension B until the DDP is completely dissolved to obtain solution C with pH value of 6-8, wherein the DDP is [ (6-oxy- (6H) -dibenzo- (C, e) (1, 2) -oxaphosphorin-6-one) methyl ] -succinic acid;
(3) Dropwise adding the solution A into the solution C, continuously stirring at 30-50 ℃, continuously reacting at room temperature for 0.5-3h after the dropwise adding, centrifuging, and fully washing with deionized water to obtain a solid product;
(4) And (3) carrying out vacuum drying on the solid product at 90-120 ℃ until the weight is constant, thus obtaining the rare earth synergistic flame retardant complex.
3. The method of manufacturing as claimed in claim 2, wherein: in the solution A, ln (the ratio of NO 3)3·6H2 O to deionized water is 1-5mmol:10-50mL, and in the suspension B, the ratio of DDP to deionized water is 1-5mmol:10-50mL.
4. A method of preparation as claimed in claim 3, wherein: the molar ratio of Ln (NO 3)3·6H2 O to DDP is 1:1-3.
5. A flame-retardant polymer material is characterized in that: the raw materials comprise the rare earth synergistic flame retardant complex, a high polymer material, a halogen-free flame retardant, an anti-dripping agent and a processing aid.
6. A flame retardant polymeric material according to claim 5, wherein: the high polymer material is at least one selected from polyethylene, polypropylene, polyformaldehyde, polycarbonate, polyamide, polyester, acrylonitrile-butadiene-styrene copolymer, polyurethane, polymethyl methacrylate, polyphenylene sulfide, polyphenylene oxide, polystyrene, ethylene-vinyl acetate copolymer, ethylene propylene diene monomer, natural rubber and epoxy resin.
7. A flame retardant polymeric material according to claim 5, wherein: the halogen-free flame retardant is selected from at least one of ammonium polyphosphate, melamine phosphate, melamine polyphosphate, melamine cyanurate, bis (diphenyl) phosphate, isophthaloyl bis (diphenyl) phosphate, dimethyl methylphosphonate, triphenyl phosphate, aluminum phosphite, diethyl aluminum hypophosphite, 2-carboxyethyl phenyl hypophosphite, piperazine phosphate, piperazine pyrophosphate, dimethyl methylphosphonate, tris (neopentyl glycol phosphate) methylamine, 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2) octane, [ 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2) octane ] phosphate melamine salt, [ 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2) octane ] phenylsilane, 9-10-dihydro-oxo-10-phosphaphenanthrene-10-oxide, and 10- (2, 5-dihydroxy-phenyl) -10-dihydro-9-phosphaphenanthrene-10-oxide.
8. A flame retardant polymeric material according to claim 5, wherein: the anti-dripping agent is at least one selected from polytetrafluoroethylene, fullerene, graphene, halloysite nanotube, silicon carbide whisker, hexaphenoxy cyclotriphosphazene and 1,3, 5-tetrafluoro-1, 3-diphenoxy cyclotriphosphazene.
9. A flame retardant polymeric material according to claim 5, wherein: the processing aid is at least one selected from EBS, antioxidant 1010, pentaerythritol and tri (2-hydroxyethyl) isocyanate.
CN202210502882.6A 2022-05-10 2022-05-10 Rare earth flame retardant complex and preparation method and application thereof Active CN114874265B (en)

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CN115260819B (en) * 2022-08-31 2023-04-25 青岛海洋新材料科技有限公司 Preparation method and product of flame-retardant spray polyurea
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