CN106750526A - One class DOPO derivatives and fire retardant and fire proofing comprising it - Google Patents

Abstract

The application is related to a kind of compound that can be used as novel halogen-free flame-retardant agent, is obtained under acidic catalyst effect by aryl ketones and DOPO classes compound.Not only flame retardant effect is good for the compound, and with good heat endurance and chemical stability.

Description

A class of DOPO derivatives and flame retardants and flame retardant materials comprising them

The present invention is a divisional case of a patent application with an application date of July 14, 2014, an application number of 201410333261.5, and a patent application titled "A Class of DOPO Derivatives, Its Preparation Method and Application".

technical field

The application relates to a halogen-free flame retardant and a preparation process thereof.

Background technique

Polymer materials are widely used in electronic appliances, automobiles, construction, textiles and other industries. However, due to the flammability of polymer materials, it is necessary to add flame retardants in actual use to meet the requirements of fire safety. Traditionally, brominated flame retardants are usually added to polymer materials to achieve flame retardant effects. However, when brominated flame retardants burn, they will produce strong irritating hydrogen bromide gas, thick smoke, and even some strong carcinogenic substances, which limits the use of brominated flame retardants. The European Union has formulated laws and regulations such as REACH and RoHS to restrict the use of certain brominated flame retardants, so the industry has begun to turn to halogen-free flame retardants.

In terms of halogen-free flame retardants, phosphorus-based flame retardants have attracted the most attention because of their high efficiency, friendliness to humans and the environment. However, the existing phosphorus-based flame retardants have disadvantages such as high volatility, low heat resistance, strong plasticity and/or poor chemical stability, which are limited by the processing and application fields of polymer materials. At present, the research on it is mainly focused on the development of phosphorus-based flame retardants with high thermal and chemical stability and low volatility.

Due to the good thermal and chemical stability of compounds containing phosphorus-carbon bonds, phosphonate halogen-free flame retardants have been applied. For example, dialkylphosphinates, especially aluminum diethylphosphinate, are used as flame retardants for nylon and polyester, see US Pat. No. 4,036,811. However, dialkylphosphinates are corrosive, especially at high temperatures. In addition, aluminum dialkylphosphinate is a solid, which will reduce the fluidity of the product and affect the manufacture of complex devices.

Phosphonates, especially cyclic phosphonates, have also been reported as flame retardants. WO2010135398 reported a derivative of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), which contains two phosphorus centers (DiDOPO) in one molecule, and has good Thermally stable and flame retardant, but structurally limited to vinyl bridges (-CH ₂ CH ₂ -) between 2 phosphorus centers. US8536256 describes DiDOPO with different bridges as a flame retardant for epoxy resins, this patent application does not include aryl substituted vinyl bridges.

The above-mentioned DiDOPO flame retardants are prepared by the Michaelis-Becker reaction of DOPO and dihaloalkanes under the action of a strong base, which not only requires expensive strong bases, but also has a low yield.

Japanese published patent JPH11-106619 reports DiDOPO, a derivative of DOPO. This patent application does not mention aromatic-substituted vinyl bridges, and is only applicable to polyester fibers. These DiDOPOs are prepared by the Michaelis-Becker reaction of DOPO and dihaloalkanes under the action of a strong base.

Japanese Laid-Open Patent JP2001270993 describes the derivative of DOPO, DiDOPO, and the DiDOPO bridge chain in this patent application does not describe the vinyl bridge chain substituted by aromatic groups. The examples shown in this patent application contain DiDOPO with longer than vinyl bridge chains, too long chains lead to increased plasticizing properties of DiDOPO, resulting in a decrease in heat deflection temperature of engineering plastic products. The examples shown in this patent application also include hydroxy or alkoxy substituted bridges. The introduction of hydroxyl groups reduces the thermal stability of flame retardants, which is unfavorable to the processing of engineering plastics. The introduction of the alkoxy group increases the oxidation performance, which will lead to the early degradation of the polymer material.

One object of the present invention is to provide a kind of halogen-free flame retardant based on DOPO compound, this halogen-free flame retardant not only has good flame retardant effect, but also has very high thermal stability and chemical stability, can overcome existing DiDOPO Disadvantages of insufficient chemical resistance and strong plasticity.

Contents of the invention

In order to solve the above problems, the application provides a compound, characterized in that it has a chemical structural formula as shown in formula (1):

in

Ar is optionally selected from C3-C18 heteroaryl or C6-C18 aryl;

R ₁ and R ₂ are independently selected from hydrogen, C1-C18 alkyl, C3-C18 heteroaryl, C6-C18 aryl;

R ₃ , R ₄ , R ₅ and R ₆ are independently selected from hydrogen, C1-C18 alkyl, C3-C18 heteroaryl, C6-C18 aryl;

m, n, k and p are independently selected from 0, 1, 2, 3, 4;

Any hydrogen atom on the aryl or heteroaryl aromatic ring can be independently substituted by any C1-C18 alkyl group.

Preferably, R ₁ and R ₂ are both hydrogen, m=n=k=p=0.

Preferably, R ₁ is hydrogen, R ₂ is aryl, m=n=k=p=0.

Preferably, R ₁ is hydrogen, R ₂ is alkyl, m=n=k=p=0.

In the present application, the aryl group and heteroaryl group are the groups formed after losing any hydrogen atom on the aromatic ring in the molecule of the aromatic compound. When the aromatic ring does not contain N, O, S and other heteroatoms, the formed group is an aryl group; when the aromatic ring contains N, O, S and other heteroatoms, the formed group is a heteroaryl group. Aromatic compounds that form aryl or heteroaryl groups. There may be no substituents or substituents on the aromatic rings. Typical substituents are alkyl, carboxyl, hydroxyl, halo, etc.

In the present application, the C3-C18 heteroaryl group is a group formed after losing any hydrogen atom on the aromatic ring in an aromatic compound molecule containing a heterocyclic aromatic ring with 3-18 carbon atoms. C3-C18 means that the number of carbon atoms on the heterocyclic aromatic ring in the heteroaryl group is 3-18. A heterocyclic aromatic ring is an aromatic ring containing heteroatoms such as N, O, and S. Aromatic compounds containing heterocyclic aromatic rings, including condensed ring aromatic ring compounds formed by heterocyclic rings and benzene rings, such as benzofuran, the group formed by losing any hydrogen atom on the benzene ring or furan ring is heteroaromatic base.

In the present application, the C6-C18 aryl group is a group formed after losing any hydrogen atom on the aromatic ring in an aromatic compound molecule with 6-18 carbon atoms in the aromatic ring and no heteroatoms on the aromatic ring . C6-C18 means that the number of carbon atoms on the aromatic ring containing no heteroatoms in the aryl group is 6-18. An aromatic compound that does not contain a heteroatom aromatic ring refers to a conjugated aromatic ring system that does not contain heteroatoms such as N, O, and S.

The C1-C18 alkyl group is a straight-chain alkyl group with 1-18 carbon atoms, a branched alkyl group with 1-18 carbon atoms, or an alkyl group containing an aromatic ring. The alkyl group containing an aromatic ring is an aromatic compound with an alkyl substituent on the aromatic ring, which is formed after losing any hydrogen atom on the alkyl group in the molecule.

Preferably, the alkyl group is a saturated hydrocarbon group, that is, a hydrocarbon group obtained by losing one hydrogen atom in an alkane molecule, including straight-chain alkyl groups and branched-chain alkyl groups. Further preferably, the alkyl group is optionally selected from methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, isobutyl, pentyl or hexyl.

In the present application, the aromatic ring may be a monocyclic aromatic ring, a polycyclic aromatic ring or a condensed aromatic ring. Wherein, the monocyclic aromatic ring may be a benzene ring, or a five-membered or six-membered heterocyclic ring containing heteroatoms such as N, O, and S. The polycyclic aromatic ring contains a plurality of benzene rings and/or heterocycles, and no carbon atoms are shared between benzene rings, between benzene rings and heterocycles, or between heterocycles, such as bi benzene ring. The fused-ring aromatic ring contains multiple benzene rings and/or heterocycles, and there are shared carbon atoms between benzene rings, between benzene rings and heterocycles, and between heterocycles, such as Naphthalene ring, benzofuran ring, etc.

According to common knowledge in this field, common heteroaryl groups include furyl, benzofuryl, isobenzofuryl, pyrrolyl, indolyl, isoindolyl, thienyl, benzo[b]thienyl, benzene A[c]thienyl, imidazolyl, benzimidazolyl, purinyl, pyrazolyl, indazolyl, oxazolyl, benzoxazolyl, isoxazolyl, benzisoxazolyl, thiazolyl , benzothiazolyl, pyridyl, quinolinyl, isoquinolyl, pyrazinyl, quinoxalinyl, acridinyl, pyrimidinyl, quinazolinyl, pyridazinyl, phthalazinyl and cinnolinyl . Common aryl groups include phenyl, naphthyl, anthracenyl, and phenanthrenyl.

Preferably, the heteroaryl is optionally selected from furyl, benzofuryl; the aryl is optionally selected from phenyl, naphthyl, indenyl, fluorenyl, methylphenyl, ethylphenyl, propyl Phenyl, butylphenyl, dimethylphenyl, isopropylphenyl, isobutylphenyl, or tert-butylphenyl.

Typically, the structural formula of the compound is selected from one of formula (2), formula (3), formula (4), formula (5), formula (6), and formula (7),

The present application also provides a preparation method of the above-mentioned compound, which is characterized in that the aryl ketone and the DOPO compound are reacted under the action of an acidic catalyst;

Wherein, the aryl ketone is optionally selected from one or more compounds of the formula (8);

The DOPO compounds are optionally selected from one or more of the compounds having the structural formula (9);

In formula (8), Ar is optionally selected from C3～C18 heteroaryl or C6～C18 aryl; R and R2 are independently selected from _hydrogen , _C1 ～C18 alkyl, C3～C18 heteroaryl group, C6～C18 aryl group;

In formula (9), R ₇ and R ₈ are independently selected from hydrogen, C1-C18 alkyl, C3-C18 heteroaryl, C6-C18 aryl;

q and j are independently selected from 0, 1, 2, 3, 4;

Any hydrogen atom on the aryl or heteroaryl aromatic ring can be independently substituted by any C1-C18 alkyl group.

Preferably, the aryl ketone is selected from acetophenone, 2-naphthophenone, furanetophenone, 1-naphthophenone, propiophenone, indenophenone, fluorene ethyl ketone, and phenyl benzyl ketone one or more.

Preferably, the acidic catalyst contains hydrogen chloride and/or hydrogen bromide, or contains a substance capable of producing hydrogen chloride and/or hydrogen bromide in the presence of hydroxyl groups, or contains a substance that can produce hydrogen chloride and/or bromide in the presence of water. hydrogen substance.

Preferably, the acidic catalyst contains any one or a mixture of any of hydrogen chloride, hydrogen bromide, phosphorus trichloride, and phosphorus oxychloride.

Preferably, the reaction temperature is 0-250°C, and more preferably, the reaction temperature is 80-200°C. If the temperature is lower than 0°C, the reaction rate will be slow; if the temperature is higher than 250°C, the by-products will increase in large quantities.

The reaction can be carried out under normal pressure, positive pressure or negative pressure.

Preferably, the molar ratio of DOPO compound, aryl ketone and acidic catalyst is DOPO compound: aryl ketone: acidic catalyst=5～1:1:0.02～10; further preferred range is DOPO compound: aromatic Base ketone: molar ratio of acidic catalyst=3～1:1:0.1～10; a further preferred range is DOPO compound: aryl ketone: molar ratio of acidic catalyst=2.5～1:1:0.1～0.9; wherein , the number of moles of the catalyst is calculated by the number of moles of chlorine and/or bromine contained in the catalyst.

Wherein, DOPO compound, aryl ketone and acidic catalyst can be mixed in any order, and all or part of any two can be mixed first, and then the remaining part and the third component can be added. Preferably, DOPO and aryl ketone are mixed first, and then the acidic catalyst is slowly added dropwise.

Optionally, the reaction system contains an inert solvent.

Preferably, the inert solvent is optionally selected from one or more of cyclohexane, methylcyclohexane, toluene, benzene, xylene, hexane, heptane, octane, cumene, tert-butylbenzene kind.

The reaction mechanism of DOPO compounds and aryl ketones is as follows:

DOPO compounds attack the carbonyl group of aryl ketones to produce α-OH phosphonate, and the hydroxyl group is then replaced by nucleophilic hydrogen chloride or hydrogen bromide to produce water and α-chloro or bromophosphonate, which are regenerated by elimination reaction. Hydrogen chloride or hydrogen bromide and a substituted vinyl phosphonate containing C=C are generated, and then a second molecule of DOPO compound is added to C=C to generate a compound having the structural formula (1).

According to common knowledge in the art, the chemical name of DOPO is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. The DOPO compounds described in this application include DOPO and DOPO derivatives. DOPO derivatives refer to the hydrogen atoms on the benzene ring in the chemical structural formula of DOPO replaced by other substituents. Common substituents include methyl, ethyl, isopropyl, tert-butyl, chloro, etc.

The present application also provides a flame retardant, which is characterized by containing any of the above-mentioned compounds and/or compounds prepared according to any of the above-mentioned methods. Those skilled in the art can add other flame retardants or additives to the compounds described in this application according to actual needs, so as to achieve better flame retardant effect.

Preferably, the flame retardant also contains one or more mixtures selected from melamine polyphosphate, melamine cyanurate, aluminum diethylphosphinate or ammonium polyphosphate.

Preferably, the flame retardant also contains additives; the additives include stabilizers, processing aids, anti-dripping agents, pigments, dyes, carbon-forming catalysts, dispersants, nucleating agents and the like.

The present application also provides a flame retardant material, which is characterized in that it contains any of the above-mentioned compounds and/or compounds prepared according to any of the above-mentioned methods. Those skilled in the art can select a compound with a specific structure among the compounds conforming to the formula (1) according to the actual needs, according to the field of application of the material and the requirements for the performance of the material.

The present application also provides a flame-retardant polymer material, which is characterized in that it contains any of the above-mentioned compounds and/or compounds prepared according to any of the above-mentioned methods.

Preferably, in the flame-retardant polymer material, the weight of the compound conforming to the formula (1) accounts for 1-40% of the total weight of the flame-retardant polymer material, the preferred range is 3-30%, and the more preferred range is 5%. ~25%.

Preferably, the polymer material is thermoplastic resin or thermosetting resin.

According to common knowledge in the field, there is no chemical bond connection between thermoplastic polymer resin molecules, and it has the properties of softening by heat and hardening by cooling. Thermoplastic polymers are usually formed by extrusion and injection molding, but are not limited to these two processes.

Preferably, the thermoplastic resin is selected from polyethylene, polypropylene, polystyrene, high impact polystyrene, polyamide, polyester, polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS ) and one or more mixtures of polyethers.

According to common knowledge in the art, polyamide is a polymer containing -NH-C(O)-amide group in its structural unit, and its typical preparation method includes condensation or development of dicarboxylic acid and diamine or amino acid or lactam Synthesis of ring polymerization.

Preferably, the thermoplastic resin is selected from one or a mixture of copolymers of polyamide 6 and polyamide 66, polyamide 6, and polyamide 66.

According to common knowledge in the art, polyester is a polymer containing -O-C(O)-ester bond in its structural unit, and its typical preparation includes the condensation reaction of dicarboxylic acid and dihydric alcohol.

Preferably, the thermoplastic resin is selected from one or a mixture of polybutylene terephthalate, polyethylene terephthalate, and polytrimethylene terephthalate.

According to common knowledge in the field, thermosetting resins are macromolecules with chemical bonds between molecules. Thermosetting resins are formed after heating or free radical initiation or photoinitiation or chemical reaction, and will no longer soften, flow or dissolve after being heated.

Preferably, the thermosetting polymer resin is selected from one or a mixture of epoxy resins, polyurethanes and unsaturated resins.

Preferably, the thermosetting polymer resin is bisphenol A epoxy resin and/or novolak epoxy resin.

The beneficial effects of the technical solution described in the application are:

In the compound described in the present application, the bridge chain structure connecting two DOPO compounds is a vinyl group containing an aryl group. Due to the short bridge chain, the compound molecule has rigidity, which greatly avoids plasticity. The aryl group on the vinyl group increases the steric hindrance, which not only greatly increases its chemical stability, but also reduces the volatility of the compound, thereby overcoming the shortcomings of the known DiDOPO flame retardants.

It should be understood that within the scope of the technical solutions disclosed in this application, the above-mentioned technical features of this application and the technical features specifically described in the following (such as embodiments) can be combined with each other to form a new or preferred technology plan. Due to space limitations, we will not repeat them here.

Unless otherwise defined, all professional and scientific terms used herein have the same meanings as commonly understood by those skilled in the art. In addition, any methods and materials similar or equivalent to those described can be applied to the methods of the present application. The preferred implementation methods and materials described herein are for demonstration purposes only.

Description of drawings

Fig. 1 is the nuclear magnetic resonance phosphorus spectrum of the product of embodiment 1.

Fig. 2 is the proton nuclear magnetic resonance spectrum of embodiment 1 product.

Fig. 3 is the nuclear magnetic resonance phosphorus spectrum of the product of embodiment 2.

Fig. 4 is the proton nuclear magnetic resonance spectrum of embodiment 2 product.

detailed description

The above-mentioned features mentioned in this application, or the features mentioned in the embodiments can be combined arbitrarily. All the features disclosed in the specification of this case can be used in combination with any combination, and each feature disclosed in the specification can be replaced by any alternative feature that provides the same, equivalent or similar purpose. Therefore, unless otherwise specified, the disclosed features are only general examples of equivalent or similar features.

Below in conjunction with embodiment, further set forth the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. For the experimental methods without specific conditions indicated in the following examples, usually follow the conventional conditions or the conditions suggested by the manufacturer. Percentages and parts are by weight unless otherwise indicated.

Unless otherwise specified, the raw materials used in this application were purchased through commercial channels and used directly without special treatment.

Unless otherwise specified, this application uses a Bruker 400MHz AVANCE III magnetic resonance instrument to perform ¹ H-NMR and ³¹ P-NMR characterizations on the products obtained in the examples. Phosphorus spectrum characterization conditions are hydrogen decoupling, pre-delay D1 = 10 seconds, scan times greater than 16, solvent CDCl ₃ , and 85% phosphoric acid as positioning standard sample.

In the examples, the calculation method of the yield is: (product weight/theoretical weight of product)×100%. Wherein the theoretical weight of the product is calculated based on the amount of aryl ketone in the raw material.

Embodiment 1 has the preparation of formula (2) structure compound

DOPO (86.40 g, 0.40 mol), acetophenone (24.05 g, 0.20 mol) and 10 ml of xylene were added to a three-necked flask equipped with a thermometer, a water separator, a magnetic stir bar and a constant pressure funnel. Under nitrogen protection, the mixture was heated to 154°C, and phosphorus oxychloride was added dropwise. POCl ₃ (30.25g) was slowly added dropwise to the reaction solution within 25 hours, and the fraction was collected in a water separator, keeping the reaction temperature at 154-160°C. After dropping phosphorus oxychloride, keep warm for half an hour. After cooling, add 120g of isopropanol, stir under reflux, most of the crude product dissolves after softening, and the system becomes turbid. Stirring was stopped, cooled, and a large amount of product precipitated after standing for a period of time. Suction filtration, the solid product was first washed with a small amount of isopropanol, the filtrate was collected, and then washed three times with an appropriate amount of deionized water. The product was a white solid powder. After collection, it was dried at 110° C. for 13 hours to obtain 89 g of product with a yield of 83.2%.

The obtained product is characterized by H spectrum and P spectrum on a magnetic resonance instrument, and its phosphorus spectrum is shown in Figure 1 for details, and the data is ³¹ PNMR (85% H ₃ PO ₄ =0 ppm): 34.2-37.0 ppm (multiple peaks); See Figure 2 for details of the hydrogen spectrum. The data are ¹ HNMR (CDCl ₃ , TMS): 6.2-8.0 (multiple peaks, 21H), 3.3-3.8 (multiple peaks, 1H), 2.5-3.0 (multiple peaks, 2H).

Embodiment 2 has the preparation of formula (3) structure compound

DOPO (86.40 g, 0.40 mol) and naphthalene ethyl ketone (34.04 g, 0.20 mol) were added into a three-necked flask equipped with a thermometer, a magnetic stir bar and a constant pressure funnel. Under nitrogen protection, the mixture was heated to 170°C, and phosphorus oxychloride was added dropwise. POCl ₃ (15.96g) was slowly added dropwise to the reaction solution within 20 hours, keeping the reaction temperature at 170-180 degrees. After dropping phosphorus oxychloride, keep warm for half an hour. The ³¹ P NMR spectrum showed no starting material. Cool, add 50ml of 90% ethanol to dissolve, then dropwise add about 60ml of 2.5% Na ₂ CO ₃ solution to adjust the pH of the reaction solution to 6-7, reflux for half an hour and suction filter to obtain a white solid product. Yield 70.6%.

The resulting product was characterized by H spectrum and P spectrum on a magnetic resonance instrument, and its phosphorus spectrum is shown in Figure 3. The data is ³¹ PNMR (85% H ₃ PO ₄ =0ppm): 34.0-37.0ppm (multiple peaks); See Figure 4 for details of the hydrogen spectrum. The data are ¹ HNMR (CDCl ₃ ): 6.0-8.0 (multiple peaks, 23H), 3.6-3.8 (multiple peaks, 1H), 2.8-3.1 (multiple peaks, 2H).

Example 3

According to the preparation method in Example 1, phosphorus oxychloride was changed into 13.7 grams of phosphorus trichloride to obtain a compound having the structure of formula (2). Yield 75.8%.

Example 4

According to the preparation method in Example 1, phosphorus oxychloride was changed to SO ₂ Cl ₂ (the amount used was 5% of the molar amount of DOPO), to obtain the compound with the structure of formula (2). Yield 60.2%.

Example 5

According to the preparation method in Example 1, phosphorus oxychloride was changed into concentrated hydrochloric acid (the amount of hydrogen chloride was 10 times the molar amount of DOPO), and the compound with the structure of formula (2) was obtained. Yield 55.3%.

Example 6

According to the preparation method in Example 1, but changing phosphorus oxychloride to phosphorus tribromide (the amount used is 30% of the DOPO molar weight), the compound with the structure of formula (2) was obtained. The yield was 91.0%.

Embodiment 7 has the preparation of formula (7) structure compound

DOPO (21.60 g, 0.10 mol) and phenylbenzyl ketone (9.81 g, 0.05 mol) were added to a three-necked flask equipped with a thermometer, a water separator, a magnetic stir bar and a constant pressure funnel. Under nitrogen protection, the mixed solution was heated to 110° C., and a mixed solution of 4.74 g of phosphorus oxychloride and 20 ml of toluene was started to be added dropwise. Slowly raise the temperature to 200 degrees within 7 hours, and at the same time collect the distillate in the water trap and drop it back into the reaction flask. The ³¹ P nuclear magnetic spectrum shows that there is no DOPO raw material. Cool, add 50ml of 90% ethanol to dissolve, then dropwise add about 2.5% Na ₂ CO ₃ solution to adjust the pH of the reaction solution to 6-7, and reflux for half an hour to obtain a white solid product by suction filtration. Yield 60.0%.

³¹ PNMR (85% H ₃ PO ₄ =0 ppm): 35.1, 36.2 ppm (2 peaks); ¹ H NMR (CDCl ₃ ): 6.1-7.9 (multiple peaks, 26H), 4.18 (1H), 4.13 (1H).

Example 8

The American GE 141R PC polycarbonate plastic raw material (referred to as PC), Ciba antioxidant 1010 (the main chemical composition is tetrakis [β (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester ), the product obtained in Example 1 was mixed according to the weight ratio of 58.2:0.12:1.8, mixed in an internal mixer with a rotating speed of 50 rpm, and the temperature was set at 270 ° C, and it was taken out after 5 minutes to cool and dry. Then fill it into a mold, preheat it in a flat vulcanizing machine at 270°C for 10 minutes, hold the pressure at 10MPa for 4 minutes, and then cold press it. According to the national combustion test standard GB/T 2408-2008 test, the flame retardant level is 3.2mm UL94V-0.

Example 9

The American GE 141R PC polycarbonate plastic raw material (referred to as PC), Ciba antioxidant 1010 (the main chemical composition is tetrakis [β (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester ), the product obtained in Example 2 was mixed according to the weight ratio of 58.0:0.12:2.0, mixed in an internal mixer with a rotating speed of 50 rpm, and the temperature was set at 270 ° C, and it was taken out after 5 minutes to cool and dry. Then fill it into a mold, preheat it in a flat vulcanizing machine at 270°C for 10 minutes, hold the pressure at 10MPa for 4 minutes, and then cold press it. According to the national combustion test standard GB/T 2408-2008, the flammability level is 3.2mm UL94V-0.

Implementation column 10

2.16g DICY (dicyandiamide) is dissolved in DMF (dimethylformamide), is mixed with the solution that mass fraction is 10%, then 8.61g embodiment 1 gained product and 39.23g bisphenol A epoxy resin are dissolved in In the above DMF at 60° C., an epoxy resin composition was obtained after stirring and mixing. The obtained warm varnish was impregnated with glass fiber cloth (7628, 0.18mm), and dried in an oven at 150°C for 5 minutes to obtain a prepreg. Finally, 8 pieces of semi-pregs were stacked, heated at 175°C under a pressure of 25Kg/cm ³ , and pressed for 90 minutes to obtain a copper-clad laminate substrate. After the flame retardant test, the flame resistance of the substrate reaches UL 94V-0 level.

Although the present invention is disclosed as above with preferred embodiments, it is not used to limit the claims. Any person skilled in the art can make some possible changes and modifications without departing from the concept of the present invention. Therefore, the present invention The scope of protection should be based on the scope defined by the claims of the present invention.

Claims (10)

1. A compound, characterized in that, has a chemical structural formula as shown in formula (1): in Ar is optionally selected from C3-C18 heteroaryl or C6-C18 aryl; R ₁ and R ₂ are independently selected from hydrogen, C1-C18 alkyl, C3-C18 heteroaryl, C6-C18 aryl; R ₃ , R ₄ , R ₅ and R ₆ are independently selected from hydrogen, C1-C18 alkyl, C3-C18 heteroaryl, C6-C18 aryl; m, n, k and p are independently selected from 0, 1, 2, 3, 4; Any hydrogen atom on the aryl or heteroaryl aromatic ring can be independently substituted by any C1-C18 alkyl group. 2. The compound according to claim 1, wherein the heteroaryl is optionally selected from furyl, benzofuryl; The aryl is optionally selected from phenyl, naphthyl, indenyl, fluorenyl; Any hydrogen atom on the aryl aromatic ring can be independently substituted by any C1-C18 alkyl group selected from methylphenyl, ethylphenyl, propylphenyl, butylphenyl, dimethyl phenyl, isopropylphenyl, isobutylphenyl or tert-butylphenyl. 3. The compound according to claim 1, wherein R ₁ or R ₂ is hydrogen, m=n=k=p=0. 4. compound according to claim 1, is characterized in that, the structural formula of described compound is selected from formula (2), formula (3), formula (4), formula (5), formula (6) and formula ( One of 7): 5. A flame retardant, characterized in that it contains the compound according to any one of claims 1-4. 6. A flame retardant material, characterized in that it contains the compound according to any one of claims 1-4. 7. A flame-retardant polymer material, characterized in that it contains the compound and polymer material according to any one of claims 1-4. 8. The flame-retardant polymer material according to claim 7, wherein the weight of the compound according to any one of claims 1-4 accounts for 1-40% of the total weight of the flame-retardant polymer material; Preferably, the weight of the compound according to any one of claims 1-4 accounts for 3-30% of the total weight of the flame-retardant polymer material; Further preferably, the weight of the compound according to any one of claims 1-4 accounts for 5-25% of the total weight of the flame-retardant polymer material. 9. The flame-retardant polymer material according to claim 7 or 8, characterized in that the polymer material is selected from at least one of thermoplastic resins and thermosetting resins. 10. The flame-retardant polymer material according to claim 7 or 8, characterized in that, the polymer material is selected from the group consisting of polyethylene, polypropylene, polystyrene, high-impact polystyrene, polyamide, One or a mixture of polyester, polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyether, epoxy resin, polyurethane, unsaturated resin.