CN109206663B

CN109206663B - Novel nitrogen-containing organic antimony flame retardant and preparation method thereof

Info

Publication number: CN109206663B
Application number: CN201710535528.2A
Authority: CN
Inventors: 邱仁华; 张德奖
Original assignee: Hunan University
Current assignee: Hunan University
Priority date: 2017-07-03
Filing date: 2017-07-03
Publication date: 2020-09-04
Anticipated expiration: 2037-07-03
Also published as: CN109206663A

Abstract

The invention relates to a novel nitrogen-containing organic antimony flame retardant and a preparation method thereof. The method is characterized in that a common organic solvent is used as a reaction solvent, diphenyl antimony chloride containing a bridged nitrogen atom ligand and cheap and easily-obtained aryl boric acid are used as raw materials, and a nickel (II) catalytic reaction is adopted to obtain the novel nitrogen-containing organic antimony flame retardant (I) with high yield and high selectivity. The test result shows that the novel nitrogen-containing organic antimony flame retardant reaches the national standard in the aspects of two important flame retardant performance indexes of limited oxygen index and vertical combustion, and obtains excellent flame retardant effect. The flame retardant has the advantages of no halogen, low toxicity, small addition amount, good compatibility with polymer materials and the like.

Description

Novel nitrogen-containing organic antimony flame retardant and preparation method thereof

[ technical field ] A method for producing a semiconductor device

The invention relates to the field of flame retardants, in particular to a novel nitrogen-containing organic antimony flame retardant and a preparation method thereof.

[ background of the invention ]

The development of high molecular polymer materials is driven by the rapid development of modern information technology. At present, polymer-based materials have been widely used in various fields of national defense construction and national economy. However, most of polymeric materials, such as general-purpose polyethylene, polypropylene, polystyrene, etc., are flammable or combustible, and the tragedy of fire caused by toxic and harmful smoke released by the burning of polymeric materials is rising year by year. Statistics show that the main reason of casualties in fire is not fire, but the smoke and toxic gas released in combustion seriously endanger the safety of people's life and property. Therefore, how to improve the flame retardancy and suppress the generation of smoke of synthetic polymer and natural polymer materials has become an urgent problem to be solved.

The flame retardant, also called fire retardant or fire retardant, is one of the important additives for synthesizing high molecular material, and has the functions of making the synthetic material possess fire-retarding property, self-extinguishing property and smoke-eliminating property. The fire retardant mainly comprises phosphorus, nitrogen, silicon, halogen, expansion type and inorganic filler. Inorganic flame retardants were the first type of flame retardants to be developed and used, but they have many drawbacks, such as toxic gases, fumes and corrosive substances released during combustion, which severely affect the environment, and secondly, when added in large amounts, which affect the mechanical properties of the materials. Halogen flame retardants are one of the largest organic flame retardants in the world today. The halogen flame retardant has high flame retarding efficiency, and is widely used in electronics and building industry, and the main varieties are styrene and its copolymer, thermoplastic engineering plastic and epoxy resin. However, with the increasing environmental protection, the use of halogen-based flame retardants is greatly restricted, mainly because of the release of toxic and harmful gases. Therefore, the development of halogen-free organic flame retardants is a focus of research.

The antimony-containing flame retardant is also a flame retardant with wider application, and mainly comprises an inorganic antimony flame retardant and an organic antimony flame retardant, wherein the antimony trioxide is an inorganic antimony flame retardant with mature application. The organic antimony fire retardant mainly comprises triphenyl antimony and triphenyl antimony dibromide. Antimony flame retardants are generally used in combination with other flame retardants to enhance their flame retardant properties. The nitrogen-containing flame retardant is widely used in the field of fireproof materials because of the advantages of colorless, halogen-free, low toxicity, low smoke, no generation of corrosive gas, ultraviolet resistance and the like. The development of the nitrogen-containing organic antimony flame retardant can effectively utilize the advantages of the nitrogen flame retardant and the antimony flame retardant and greatly improve the flame retardant property of the nitrogen-containing organic antimony flame retardant and the antimony flame retardant.

[ summary of the invention ]

The invention aims to provide a novel nitrogen-containing organic antimony flame retardant and a preparation method thereof.

In order to achieve the above purpose, the invention provides the following technical scheme:

a preparation method of a novel nitrogen-containing organic antimony (III) flame retardant (I) is characterized in that diphenyl antimony chloride and aryl boric acid containing a bridged nitrogen atom ligand are used as raw materials, a common organic solvent is used as a preparation solvent, a common inorganic salt is used as a reaction promoter, a Ni (II) complex is used as a catalyst, the reaction is carried out for 8-12h at the temperature of 100-120 ℃, and the yield is 75-97%.

The flame retardant is a novel nitrogen-containing organic antimony flame retardant, and the structural formula (I) is as follows:

wherein R is₁、R₂、R₃、R₄、R₅The group is one or more of hydrogen, methyl, methoxy, ethyl, tert-butyl, ethoxy, isopropyl, cyano, n-butyl and phenyl; r₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The group is one or more of hydrogen, methyl, ethyl, isopropyl and tert-butyl; r₁₄、R₁₅、R₁₆、R₁₇、R₁₈The group is one or more of hydrogen, methyl, methoxy, ethoxy, ethyl, tert-butyl, isopropyl, cyano, formyl, acetyl, n-butyl, phenyl, vinyl and ethynyl.

The novel nitrogen-containing organic antimony flame retardant is characterized in that R₁、R₂、R₃、R₄、R₅The group is one or more of hydrogen, methyl, methoxyl, ethyl, tert-butyl, ethoxyl, isopropyl, cyano, n-butyl and phenyl.

The novel nitrogen-containing organic antimony flame retardant is characterized in that R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The group is one or more of hydrogen, methyl, ethyl, isopropyl and tert-butyl.

The novel nitrogen-containing organic antimony flame retardant is characterized in that R₁₄、R₁₅、R₁₆、R₁₇、R₁₈The group is one or more of hydrogen, methyl, methoxy, ethyl, tert-butyl, ethoxy, isopropyl, cyano, formyl, acetyl, n-butyl, phenyl, vinyl and ethynyl.

The preparation method of the novel nitrogen-containing organic antimony flame retardant is characterized in that diphenyl antimony chloride and aryl boric acid containing a bridged nitrogen atom ligand are used as raw materials, a common organic solvent is used as a preparation solvent, a common inorganic salt is used as a reaction promoter, a Ni (II) complex is used as a catalyst, and the novel nitrogen-containing organic antimony flame retardant (I) is obtained with high yield and high selectivity.

The preparation method of the novel nitrogen-containing organic antimony flame retardant is characterized in that the accelerator used for preparing the novel nitrogen-containing organic antimony flame retardant is one of potassium nitrate, potassium acetate, potassium carbonate, sodium carbonate, cesium carbonate, sodium bicarbonate, potassium hydrogen phosphate, potassium dihydrogen phosphate, potassium tert-butoxide, sodium tert-butoxide and sodium acetate.

The preparation method of the novel nitrogen-containing organic antimony flame retardant is characterized in that a catalyst used for preparing the novel nitrogen-containing organic antimony flame retardant is one of nickel acetate, nickel chloride, nickel fluoride, nickel bromide, nickel trifluoromethanesulfonate, nickel acetylacetonate and bis (triphenylphosphine) nickel dichloride.

The preparation method of the novel nitrogen-containing organic antimony flame retardant is characterized in that the reaction conditions for preparing the novel nitrogen-containing organic antimony flame retardant are as follows: reacting for 8-12h under the protection of nitrogen.

The preparation method of the novel nitrogen-containing organic antimony flame retardant is characterized in that in the preparation of the novel nitrogen-containing organic antimony flame retardant, a solvent used for recrystallization is one or more of dichloromethane, ethyl acetate, n-hexane, petroleum ether and ethanol.

The novel nitrogen-containing organic antimony flame retardant provided by the invention has the advantages of no halogen, low toxicity, small addition amount, good compatibility with polymer materials and the like. The novel nitrogen-containing organic antimony flame retardant and the epoxy resin provided by the invention have the following advantages in the combustion process: good appearance, good anti-dripping performance and good stability.

[ description of the drawings ]

FIG. 1 shows a preparation method of a novel nitrogen-containing organic antimony flame retardant provided by the invention.

[ detailed description ] embodiments

The synthesis route of the novel nitrogen-containing organic antimony flame retardant provided by the invention is shown in figure 1.

Adding diphenyl antimony chloride containing a bridged nitrogen atom ligand, arylboronic acid, a nickel catalyst and an accelerant into a reactor, vacuumizing and backfilling nitrogen for 3 times, then adding a solvent into the reactor, and reacting for 8-12 h. And (4) after the reaction is finished, decompressing to remove the solvent, and recrystallizing to obtain the target product.

The invention is further illustrated below with reference to specific preparation examples:

example 1

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃Radical hydrogen), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₆、R₁₇、R₁₈The group is hydrogen), 5mol percent nickel acetate and 2 equivalents of sodium carbonate, vacuumizing and backfilling nitrogen for three times, adding 40ml of toluene under the nitrogen atmosphere, and reacting for 12 hours at 120 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 90%.

The nitrogen-containing organic antimony flame retardant obtained in example 1 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the test result shows that the novel nitrogen-containing organic antimony flame retardant achieves the national standard in the aspects of two important flame retardant performance indexes of limited oxygen index and vertical combustion, obtains good flame retardant effect, has small dosage and is worthy of further popularization and application.

Example 2

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃Radical hydrogen), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 120 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 92%.

The nitrogen-containing organic antimony flame retardant obtained in example 2 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	21.92	24.89	27.87	29.89	32.99	34.69	37.25
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 3

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃Radical hydrogen), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Ethyl group), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 8h at 120 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 93%.

The nitrogen-containing organic antimony flame retardant obtained in example 3 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.03	25.23	27.87	29.91	32.91	34.74	36.89
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 4

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃Radical hydrogen), 9mmol of arylboronic acid (R)₁₅、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₄Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 8h at 120 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 95%.

The nitrogen-containing organic antimony flame retardant obtained in example 4 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

Example 5

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃Radical hydrogen), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Tert-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen backfilling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 8h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 94%.

The nitrogen-containing organic antimony flame retardant obtained in example 5 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.13	25.07	28.02	29.99	32.95	34.69	36.59
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 6

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃Radical hydrogen), 9mmol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₆Methoxy group), 5 mol% nickel acetate, 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen three times, adding 40ml toluene under nitrogen atmosphere, and reacting at 120 ℃ for 10 h. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 85%.

The nitrogen-containing organic antimony flame retardant obtained in example 6 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	21.92	25.09	28.11	29.79	32.97	34.78	36.36
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 7

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃Group is hydrogen) 9mmol of arylboronic acid (R)₁₅、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₄Ethyl group), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 120 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 75%.

The nitrogen-containing organic antimony flame retardant obtained in example 7 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

Example 8

0.6mol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 500mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃Radical hydrogen), 0.9mol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₆Isopropyl), 3 mol% nickel acetate, 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen three times, adding 200ml toluene under nitrogen atmosphere, and reacting for 8h at 120 ℃. After the reaction is finished, the toluene is removed under reduced pressure,recrystallizing with ethyl acetate and n-hexane to obtain the target product with a yield of 97%.

The nitrogen-containing organic antimony flame retardant obtained in example 8 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	21.96	25.15	28.20	29.83	32.96	34.91	36.65
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 9

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃Radical hydrogen), 9mmol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₆Acetyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 120 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 78%.

The nitrogen-containing organic antimony flame retardant obtained in example 9 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	21.90	25.18	28.20	29.91	32.96	34.92	36.52
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 10

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃Radical hydrogen), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆N-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen for three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 8h at 120 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with dichloromethane and n-hexane, wherein the yield is 88%.

The nitrogen-containing organic antimony flame retardant obtained in example 10 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

Example 11

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃Radical hydrogen), 9mmol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₆Vinyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 8h at 120 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 77%.

The nitrogen-containing organic antimony flame retardant obtained in example 11 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	21.97	25.53	28.01	29.88	33.02	34.81	36.51
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 12

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₃Is methyl) 9mmol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₆Ethynyl group), 5 mol% nickel acetate, 2 equivalents of carbonic acidSodium, vacuum-pumping and backfilling with nitrogen for three times, adding 40ml of toluene under the nitrogen atmosphere, and reacting for 8 hours at 120 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 80%.

The nitrogen-containing organic antimony flame retardant obtained in example 12 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	21.93	25.02	27.63	29.87	33.05	34.77	36.31
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 13

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₃Tert-butyl), 9mmol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₆Phenyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen backfilling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 8h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 85%.

The nitrogen-containing organic antimony flame retardant obtained in example 13 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	21.94	25.12	27.65	29.78	33.04	34.73	36.32
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 14

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₃Methoxy), 9mmol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₆Formyl), 5mol percent nickel acetate, 2 equivalents of sodium carbonate, vacuumizing, backfilling with nitrogen for three times, adding 40ml of toluene under the nitrogen atmosphere, and reacting for 8 hours at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 83%.

The nitrogen-containing organic antimony flame retardant obtained in example 14 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.03	25.22	27.68	29.81	32.99	34.69	36.29
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 15

Into a 100mL reaction tube6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand₁、R₂、R₃、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₄Methyl), 9mmol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₅Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with dichloromethane and n-hexane, wherein the yield is 88%.

The nitrogen-containing organic antimony flame retardant prepared in example 15 above was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the specimens were 100mm × 6.5mm × 3mm in size measured by an oxygen index meter according to GB/T2406-1993 standard and 125mm × 13mm × 3mm in size measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.05	25.02	27.66	29.73	33.07	34.69	36.32
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 16

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₄Ethyl), 9mmol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₅Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 8h at 100 ℃. Inverse directionAfter the reaction, toluene was removed under reduced pressure, and the product was recrystallized from dichloromethane and n-hexane to give the desired product in a yield of 90%.

The nitrogen-containing organic antimony flame retardant obtained in example 16 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

Example 17

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₅Ethyl), 9mmol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₅Methoxy), 5 mol% nickel acetate, 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 8h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with dichloromethane and n-hexane, wherein the yield is 92%.

The nitrogen-containing organic antimony flame retardant obtained in example 17 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.13	25.05	27.71	29.83	33.17	34.88	36.44
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 18

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₅Methyl), 9mmol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₅Isopropyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 8h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with dichloromethane and n-hexane, wherein the yield is 85%.

The nitrogen-containing organic antimony flame retardant obtained in example 18 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.06	25.12	27.77	29.74	33.14	34.75	36.33
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 19

6mmol of diphenylantimony chloride (R) containing bridged nitrogen atom ligand is added into a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃Radical hydrogen), 9mmol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₅N-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen for three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 8h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with dichloromethane and n-hexane, wherein the yield is 86%.

The nitrogen-containing organic antimony flame retardant obtained in example 19 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.10	25.07	27.65	29.86	33.21	34.69	36.31
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 20

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃Radical hydrogen), 9mmol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₅Acetyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with dichloromethane and n-hexane, wherein the yield is 87%.

The nitrogen-containing organic antimony flame retardant obtained in example 20 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.12	25.08	27.66	29.68	33.02	34.71	36.51
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 21

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₅Methyl), 9mmol of arylboronic acid (R)₁₄、R₁₆、R₁₇、R₁₈The radical being hydrogen, R₁₅Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with dichloromethane and n-hexane, wherein the yield is 78%.

The nitrogen-containing organic antimony flame retardant obtained in example 21 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.23	25.18	27.76	29.78	33.12	34.81	36.61
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 22

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₆Methyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₆、R₁₈The radical being hydrogen, R₁₇Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 83%.

The nitrogen-containing organic antimony flame retardant obtained in example 22 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.22	25.19	27.78	29.75	33.13	34.82	36.68
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 23

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₇Methyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₆、R₁₈The radical being hydrogen, R₁₇Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 88%.

The nitrogen-containing organic antimony flame retardant obtained in example 23 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.24	25.21	27.79	29.77	33.15	34.83	36.78
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 24

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₇Ethyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₆、R₁₈The radical being hydrogen, R₁₇Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 92%.

The nitrogen-containing organic antimony flame retardant obtained in example 24 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.27	25.23	27.74	29.79	33.17	34.86	36.71
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 25

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₇Isopropyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₆、R₁₈The radical being hydrogen, R₁₇Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 90%.

The nitrogen-containing organic antimony flame retardant obtained in example 25 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.28	25.25	27.78	29.81	33.19	34.83	36.74
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 26

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₇Tert-butyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₆、R₁₈The radical being hydrogen, R₁₇Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 87%.

The nitrogen-containing organic antimony flame retardant obtained in example 26 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. Limiting oxygen

The addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.31	25.15	27.81	29.83	33.21	34.85	36.80
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 27

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₈Isopropyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₆、R₁₈The radical being hydrogen, R₁₇Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 84%.

The nitrogen-containing organic antimony flame retardant obtained in example 27 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.11	25.19	27.84	29.85	33.11	34.95	36.83
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 28

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R_4、R₅、R₆、R₇、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₈Methyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₆、R₁₈The radical being hydrogen, R₁₇Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 85%.

The nitrogen-containing organic antimony flame retardant obtained in example 28 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.18	25.13	27.86	29.75	33.14	34.97	36.66
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 29

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₈Ethyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₆、R₁₈The radical being hydrogen, R₁₇Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 91%.

The nitrogen-containing organic antimony flame retardant obtained in example 29 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the specimens were 100mm × 6.5mm × 3mm in size measured by an oxygen index meter according to GB/T2406.1-2008 standard and 125mm × 13mm × 3mm in size measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.15	25.23	27.76	29.78	33.16	34.92	36.71
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 30

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₈Ethyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Tert-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen backfilling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 86%.

The nitrogen-containing organic antimony flame retardant obtained in example 30 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.17	25.25	27.66	29.88	33.18	34.72	36.61
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 31

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₈Isopropyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Is tertiary butyl), 5mol percent nickel acetate, 2 equivalent sodium carbonate, vacuumizing and backfilling nitrogen for three times, wherein the nitrogen is40ml of toluene were added under an atmosphere and reacted at 100 ℃ for 10 hours. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 91%.

The nitrogen-containing organic antimony flame retardant obtained in example 31 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.19	25.35	27.76	29.78	33.28	34.82	36.32
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 32

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₇、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₈Methyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Tert-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen backfilling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 93%.

The nitrogen-containing organic antimony flame retardant obtained in example 32 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.23	25.38	27.79	29.75	33.24	34.86	36.52
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 33

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₇Methyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Tert-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen backfilling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 88%.

The nitrogen-containing organic antimony flame retardant obtained in example 33 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

Example 34

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₆、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₇Ethyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Tert-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen backfilling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 86%.

The nitrogen-containing organic antimony flame retardant obtained in example 34 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.35	25.49	27.68	29.79	33.35	34.78	36.33
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 35

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₆Ethyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Tert-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen backfilling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 86%.

The nitrogen-containing organic antimony flame retardant obtained in example 35 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.45	25.69	27.78	29.99	33.75	34.88	37.03
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 36

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₆Methyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Tert-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen backfilling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 84%.

The nitrogen-containing organic antimony flame retardant obtained in example 36 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.41	25.62	27.74	29.92	33.76	34.81	37.01
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 37

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₆Isopropyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Tert-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen backfilling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 88%.

The nitrogen-containing organic antimony flame retardant obtained in example 37 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.43	25.52	27.71	29.93	33.56	34.81	37.07
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 38

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₄、R₅、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₆Isopropyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Tert-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen backfilling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 85%.

The nitrogen-containing organic antimony flame retardant obtained in example 38 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.45	25.72	27.81	29.96	33.59	34.85	37.17
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 39

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₃Methyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Is a tertiary butyl group),5 mol% nickel acetate and 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen for three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 88%.

The nitrogen-containing organic antimony flame retardant obtained in example 39 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.47	25.52	27.84	29.97	33.19	34.75	36.97
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 40

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₃Ethyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Tert-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen backfilling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 93%.

The nitrogen-containing organic antimony flame retardant obtained in example 40 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.41	25.57	27.94	29.98	33.29	34.79	36.98
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

EXAMPLE 41

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₃Methoxy), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Tert-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen backfilling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 90%.

The nitrogen-containing organic antimony flame retardant obtained in example 41 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.31	25.58	27.97	30.08	33.39	34.89	36.99
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 42

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₃Methoxy), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 90%.

The nitrogen-containing organic antimony flame retardant obtained in example 42 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.39	25.68	27.99	30.28	33.49	34.99	37.29
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 43

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₃Methoxy), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Acetyl), 5 mol% nickel acetate, 2 equivalent sodium carbonate, vacuumizing and backfilling with nitrogen for three times in the presence of nitrogen40ml of toluene were added under an atmosphere and reacted at 100 ℃ for 10 hours. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 78%.

The nitrogen-containing organic antimony flame retardant obtained in example 43 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.49	25.67	27.96	30.29	33.46	34.91	37.20
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 44

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₃Methoxy), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆N-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen for three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 84%.

The nitrogen-containing organic antimony flame retardant obtained in example 44 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.59	25.77	27.99	30.39	33.56	34.98	37.22
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 45

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₄、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₃Methoxy), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Isopropyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 89%.

The nitrogen-containing organic antimony flame retardant obtained in example 45 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.55	25.72	27.91	30.37	33.52	34.93	37.21
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 46

6mmol of diphenyl antimony containing bridged nitrogen atom ligand is added into a 100mL reaction tubeChlorine (R)₁、R₂、R₃、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₄Methoxy), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Isopropyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 89%.

The nitrogen-containing organic antimony flame retardant obtained in example 46 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. Limiting oxygen

The addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.56	25.74	27.93	30.39	33.54	34.96	37.26
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 47

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₄Ethyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Isopropyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 87 percent。

The nitrogen-containing organic antimony flame retardant obtained in example 47 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.57	25.72	27.95	30.42	33.56	34.97	37.28
Burning or the likeStage V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 48

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₄Tert-butyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Isopropyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, vacuumizing and backfilling with nitrogen three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 87%.

The nitrogen-containing organic antimony flame retardant obtained in example 48 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.59	25.62	28.28	30.72	33.88	35.28	37.67
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 49

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₄Tert-butyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Methyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen back-filling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 87%.

The nitrogen-containing organic antimony flame retardant obtained in example 49 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.52	25.60	28.21	30.63	33.81	35.10	37.27
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

Example 50

6mmol of diphenylantimony chloride (R) containing a bridged nitrogen ligand was added to a 100mL reaction tube₁、R₂、R₃、R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The radical being hydrogen, R₄Tert-butyl), 9mmol of arylboronic acid (R)₁₄、R₁₅、R₁₇、R₁₈The radical being hydrogen, R₁₆Tert-butyl), 5 mol% nickel acetate, 2 equivalents sodium carbonate, evacuation and nitrogen backfilling three times, adding 40ml toluene under nitrogen atmosphere, and reacting for 10h at 100 ℃. After the reaction is finished, the toluene is removed under reduced pressure, and the target product is obtained by recrystallization with ethyl acetate and n-hexane, wherein the yield is 95%.

The nitrogen-containing organic antimony flame retardant obtained in example 50 was added to an epoxy resin to conduct an oxygen index test and a vertical flame rating test, and the sample bar size was 100mm × 6.5mm × 3mm as measured by an oxygen index meter according to GB/T2406.1-2008 standard, and was 125mm × 13mm × 3mm as measured by a vertical flame meter according to UL94 standard. The specific experimental results of the performance tests of the limiting oxygen index and the vertical burning grade are as follows:

the addition amount of	0.01	0.05	0.10	0.15	0.20	0.25	0.30
								Oxygen index%	22.50	25.23	28.25	30.33	33.71	35.13	37.57
Combustion class V	V-1	V-1	V-1	V-0	V-0	V-0	V-0

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. A nitrogen-containing organoantimony flame retardant having the following structural formula (I):

the substituents shown in the structural formula (I) are characterized in that R is₁、R₂、R₃、R₄、R₅The group is one or more of hydrogen, methyl, methoxy, ethyl, tert-butyl, ethoxy, isopropyl, cyano, n-butyl and phenyl; the R is₆、R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃The group is one or more of hydrogen, methyl, ethyl, isopropyl and tert-butyl; the R is₁₄、R₁₅、R₁₆、R₁₇、R₁₈The group is one or more of hydrogen, methyl, methoxy, ethyl, tert-butyl, ethoxy, isopropyl, cyano, formyl, acetyl, n-butyl, phenyl, vinyl and ethynyl.

2. The nitrogen-containing organic antimony flame retardant of claim 1, wherein the nitrogen-containing organic antimony is prepared by the following method: the organic antimony flame retardant (I) containing nitrogen is obtained by reacting diphenyl antimony chloride and aryl boric acid containing a bridged nitrogen atom ligand as raw materials, a common organic solvent as a preparation solvent, a common inorganic salt as a reaction promoter and a Ni (II) complex as a catalyst at the temperature of 100-120 ℃ for 8-12 h.

3. The nitrogen-containing organic antimony flame retardant of claim 2, wherein the preparation solvent of the nitrogen-containing organic antimony flame retardant is selected from Tetrahydrofuran (THF), Toluene (Toluene), Acetone (Acetone), acetonitrile (CH)₃CN), N-Dimethylformamide (DMF).

4. The nitrogen-containing organic antimony flame retardant of claim 2, wherein the catalyst used for preparing the nitrogen-containing organic antimony flame retardant is one of nickel acetate, nickel chloride, nickel fluoride, nickel trifluoromethanesulfonate, nickel acetylacetonate and bis (triphenylphosphine) nickel dichloride.

5. The nitrogen-containing organic antimony flame retardant of claim 2, wherein the accelerator used for preparing the nitrogen-containing organic antimony flame retardant is one of potassium nitrate, potassium acetate, potassium carbonate, sodium carbonate, cesium carbonate, sodium bicarbonate, potassium hydrogen phosphate, potassium dihydrogen phosphate, potassium tert-butoxide, sodium tert-butoxide and sodium acetate.