JP6964762B2 - Phosphorus-containing silicone active ester, its preparation method, flame-retardant resin composition, prepreg, and metal-clad laminate - Google Patents

Description

The present invention relates to the technical field of flame retardants, and more particularly to flame-retardant phosphorus-containing silicone active esters, methods of preparing them, and their use.

With the development of the synthetic materials industry and the development of application fields, flame retardants are expected to be widely applied in various fields such as chemical building materials, electronic and electrical equipment, traffic transportation, aerospace, daily furniture, interior interiors, clothing, food and housing. doing.

Research and development of new flame retardants are the development from low molecular flame retardants to oligomer flame retardants, the development from a single flame retardant to a flame retardant system in which multiple flame retardants "synergize", and the addition type. There are three trends: the development of flame retardants to reactive flame retardants.

Organophosphorus flame retardants are flame retardants with good flame retardancy, can replace halogenated flame retardants, and are environmentally friendly flame retardants. Here, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (abbreviated as DOPO), 1,8-dinaphthyl-1,3,2-dioxanephosphine (abbreviated as NDPO), 9,10-Dihydro-9-oxa-10-acrydophosphine-10-oxide (abbreviated as DPPO), 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10 -Phosphorus-containing flame retardants typified by oxide (abbreviated as DOPO-HQ) and 2- (diphenylphosphinyl) hydroquinone (abbreviated as DPPQ) are widely used as epoxy resin flame retardants due to their good flame retardant performance. in use. Silicon flame retardant is a new type of non-halogen flame retardant that is highly efficient, low toxicity, prevents droplets and is environmentally friendly, and is also a carbonized layer-forming smoke suppressant. The silicon flame retardant can impart excellent flame retardant performance to the base material, and can further improve the processing performance, heat resistance performance, etc. of the base material. Therefore, it has been rapidly developed as a new flame retardant since the 1980s in the 20th century.

In the technical field of copper-clad laminates, the flame retardants currently adopted are mainly bromine-containing and non-halogen phosphorus-containing systems, and generally, in the bromine-containing system, the flame retardant performance is V-0 level. The bromine content must reach 15% or higher, and a high bromine content reduces the heat resistance of the system and produces hydrogen bromide gas. Further, in recent years, since carcinogens such as dioxin and dibenzofuran have been detected in the combustion products of wastes of electronic and electrical equipment containing halogens such as bromine and chlorine, the application of brominated epoxy resins is restricted. In order to reduce the bromine content in the system, a resin with a special structure having a flame retardant effect can be added, but the cost is significantly increased. Non-halogen phosphorus-containing systems need to have a phosphorus content of at least 2.5% in order for flame retardancy to reach V-0. Since a large amount of phosphorus-containing resin is added, the material is highly brittle, the processability is poor, the phosphorus-containing resin is expensive, and the product cost is high.

According to the research of the inventor, the main chain phosphorus-containing silicon active ester can not only be used as a curing agent for thermosetting resins (for example, epoxy resins), but can also exert the effect of a non-halogen flame retardant, and has a low phosphorus content. It was found that the flame retardant effect of UL94 V-0 can be achieved by the content. Since the flame retardant has a reactive group, it does not migrate and precipitate in the later use process and affect the use performance, and the main chain structure contains silicon segments, so that it has good process processability. And complete the present invention.

The object of the present invention can be realized by the following technical proposals.

In one aspect of the present invention, a phosphorus-containing silicon active ester having a structure represented by the formula (I) is provided.

(However, Ar is a C6-C18 aryl group, preferably a phenyl group.
n = an integer of 1 to 5,
R1 and R2 are independently C6-C18 aryl groups, C6-C18 aryloxy groups, C1-C6 aliphatic groups, C1-C6 alkoxy groups, or C2-C6 alkenyl groups, respectively.
A is

It is one of the
B is

Any one of them. )
In some embodiments, R1 and R2 are independently phenyl groups, C1-C5 alkyl groups or vinyl groups, respectively.

In another aspect of the invention
(1) Reaction of 9,10-dihydro-9-oxa-10-phosphineanthrene-10-oxide (abbreviated as DOPO) derivative or diphenylphosphine oxide (DPO) derivative with dihalosilane in the presence of a catalyst. When,

(2) The product obtained in step (1) is subjected to an esterification reaction with an aryl halide to obtain a phosphorus-containing silicon active ester having a structure represented by the formula (I).
Including

The DOPO derivatives are the reaction products of DOPO and benzoquinone (10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ)) and DOPO and 1 , 4-Naphthoquinone reaction product (DOPO-NQ), the DPO derivative is a reaction product of DPO and benzoquinone (DPO-HQ) and a reaction product of DPO and 1,4-naphthoquinone (DPO-NQ). Provided is a method for preparing the above phosphorus-containing silicon active ester selected from DPO-NQ).

In some embodiments, the ratio of the number of moles of the DOPO or DPO derivative to dihalosilane is 1: (0.5-5), preferably 1: (0.5-1).
In some embodiments, the dihalosilane is of formula

It has the structure shown by, where R1 and R2 are as defined above, where X is a halogen, preferably chlorine, and

In some embodiments, the catalyst is selected from triethylamine, pyridine, sodium hydroxide, potassium hydroxide, anhydrous sodium carbonate, anhydrous potassium carbonate, and sodium methoxydo, more preferably the catalyst is triethylamine.

In some embodiments, the amount of the catalyst used is 2 to 4 times, preferably 2.2 to 3 times, the number of moles of the DOPO or DPO derivative.

In some embodiments, step (1) is carried out in a solvent system, said solvent system selected from dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP), preferably. When DMAc is used as a solvent, the concentration of the reaction system in step (1) is 15% to 30%, and when DMAc is used as a solvent, the concentration of the reaction system is 18 to 25%.

In some embodiments, the reaction temperature of step (1) is room temperature to 120 ° C. and the reaction time is 5 to 20 hours, more preferably the reaction temperature is 50 to 120 ° C. and the reaction time is 7. ~ 12 hours,

In some embodiments, the reaction in step (1) is carried out in the presence of a protective gas, the preferred protective gas being nitrogen gas.

In some embodiments, the ratio of the number of moles of the aryl halide to the product obtained in step (1) in step (2) is 1: 0.5-2, preferably 1: 0.8-. 1.2

In some embodiments, the aryl halide is an aryl chloride, more preferably a benzoyl chloride.

In some embodiments, step (2) is performed in the same system as step (1).

In some embodiments, a post-reaction post-treatment step further comprises, said post-treatment comprising filtration and distillation of optionally optional low boiling point material, further including subsequent washing and drying.

Preferably, the reagent used for the washing is selected from an alcohol solvent, an ester solvent, and deionized water, and more preferably deionized water.

In another aspect of the present invention, there is provided a flame-retardant resin composition containing a thermosetting resin, a curing agent, the phosphorus-containing silicone active ester described above, an optional filler, and a curing accelerator.

In some embodiments, the phosphorus-containing silicone active ester accounts for 5-30%, preferably 5-20% of the total weight of the flame-retardant resin composition.

In some embodiments, the weight content of phosphorus in the flame retardant resin composition is less than 2.5%, preferably less than 1%.

In some embodiments, the weight content of phosphorus in the flame retardant resin composition is greater than 0.7%.

In some embodiments, the weight content of silicon in the flame retardant resin composition is greater than 0.5%.

In some embodiments, the weight content of phosphorus in the flame retardant resin composition is greater than 0.7% and the weight content of silicon is greater than 0.5%.

In some embodiments, the thermosetting resin is one or more selected from epoxy resins, polyurethane resins, cyanate resins, and benzoxazine resins, and the total amount of organic solids in the flame-retardant resin composition. Calculated based on 100 parts by weight, the content of the thermosetting resin may be 30 to 95 parts by weight, preferably 30 to 60 parts by weight.

In some embodiments, the curing agent is one or more selected from phenol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, active ester curing agents, and radical initiators, and is difficult. The total amount of organic solids in the flammable resin composition is calculated in 100 parts by weight, and the content of the curing agent may be 5 to 50 parts by weight, preferably 10 to 30 parts by weight.

In some embodiments, the active ester curing agent is obtained by reacting a phenolic compound linked by an alicyclic hydrocarbon structure, a bifunctional carboxylic acid aromatic compound or an acid halide, and a monohydroxy compound. Be done. The amount of the bifunctional carboxylic acid aromatic compound or acid halide used is 1 mol, the amount of the phenol compound linked by the alicyclic hydrocarbon structure is 0.05 to 0.75 mol, and the amount is monohydroxy. The amount of the compound used is 0.25 to 0.95 mol. The active ester curing agent may contain an active ester having the following structural formula.

However, X in the formula is a benzene ring or a naphthalene ring, j is 0 or 1, k is 0 or 1, and n indicates that the average repeating unit is 0.25 to 1.25. ..

In some embodiments, the filler is selected from aluminum hydroxide, boehmite, silica, talc, mica, barium sulphate, lithopone, calcium carbonate, wollastonite, kaolin, bluesite, diatomaceous earth, bentonite, or pebbles powder. The total amount of organic solids in the flame-retardant resin composition is calculated in 100 parts by weight, and the filler content may be 0 to 100 parts by weight, preferably 10 ~ 50 parts by weight.

In some embodiments, the curing accelerator is one or a mixture of any one or at least two of an imidazole-based curing accelerator, an organic phosphine curing accelerator, or a tertiary amine curing accelerator, and is flame-retardant. The total amount of the organic solid content in the sex resin composition is calculated in 100 parts by weight, and the content of the curing accelerator may be 0.01 to 2 parts by weight, preferably 0.05 to 1.5 parts by weight. ..

In another aspect of the invention, there is provided a prepreg comprising a substrate and the flame-retardant resin composition described above attached to the substrate by immersion or coating.

In some embodiments, the substrate is glass cloth and the material is inorganic fibers (eg, glass fibers such as E glass, D glass, L glass, M glass, S glass, T glass, NE glass, quartz). Alternatively, it may be an organic fiber (for example, polyimide, polyamide, polyester, polyphenylene ether, liquid crystal polymer, etc.), and is preferably E glass cloth.

In some embodiments, the prepreg is formed of a semi-cured epoxy-modified acrylate resin composition and substrate. The process of forming the prepreg may be to infiltrate the base material with an epoxy-modified acrylate resin composition in a varnish state, volatilize the solvent by heating, and convert the prepreg into a semi-cured state.

Another aspect of the present invention further provides a metal-clad laminate comprising at least one of the above-mentioned prepregs and a metal foil coated on one or both sides of the prepreg.

The present invention has at least one of the following technical effects.

(1) In the present invention, V-0 can be realized with a low phosphorus content and silicon content by constructing a DOPO structure or a DPO structure and a silane structure in a main chain structure of the same molecule, and The main chain structure of the flame retardant contains a silicon segment, which has good process processability, and improves defects such as brittle phosphorus-containing compounds and inferior heat resistance to moisture and heat.

(2) The flame retardant of the present invention has a reactive active ester group, does not migrate and precipitate in the later use process and does not affect the use performance, and further, the active ester group is an epoxy resin. After the reaction, it has low dielectric properties and can be applied to the formulation of non-halogen low dielectric constant (Dk) resins.

(3) Compared with the conventional phosphoric acid ester-structured phosphoric acid flame retardant, the flame retardant of the present invention contains a Si—OC structure in the main chain and has lower heat resistance and lower polarity. Moreover, since the DOPO or DPO structure has better flame retardancy efficiency with respect to the phosphoric acid ester structure, the resin composition and the copper-clad laminate produced by the resin composition have excellent heat resistance and flame retardancy. ..

(4) The ratio of P and Si in the phosphorus-containing silicon active ester can be controlled or adjusted to be adapted for use in different materials.

The DSC reaction curve when the phosphor silicon flame retardant of this invention and an epoxy resin are combined is shown.

Hereinafter, some embodiments of the present invention will be described with specific embodiments, but the embodiments of the present invention are not limited to these examples.

<Preparation Example 1 (blending ratio 5: 4)>
After stirring 240 g of DOPO-HQ and 1200 g of DMAc in a four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermometer for 20 to 30 minutes, nitrogen gas was introduced and sufficiently dispersed. 150 g of diphenyldichlorosilane is added at a time, the triethylamine catalyst is slowly added dropwise, 164 g of triethylamine is controlled to be added dropwise for about 1 h, the temperature is raised to 70 ° C. and the reaction is carried out for about 2 hours, and then benzoyl chloride is added once. In addition, the reaction was continued for 10 hours, filtered, washed with water, dried, and 377 g of the product was obtained. According to the GPC test, the Mn = 1200, the P content in the flame retardant was 6.15%, and the Si content was contained. The amount was 4.4% and the number was PBS-54.

<Preparation Example 2 (blending ratio 4: 3)>
After stirring 256 g of DOPO-HQ and 1200 g of DMAc in a four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermometer for 20 to 30 minutes, nitrogen gas was introduced and sufficiently dispersed. 150 g of diphenyldichlorosilane is added at a time, the triethylamine catalyst is slowly added dropwise, and 176 g of triethylamine is controlled to be added dropwise for about 1 h, then the temperature is raised to 100 ° C. and the reaction is carried out for about 12 hours, and then benzoyl chloride is added. Add at once, continue to react for 10 hours, filter, wash with water, dry to obtain 377 g of product, Mn = 860 by GPC test, P content in its flame retardant is 6.14%, Si The content was 4.1% and the number was PBS-43.

<Preparation Example 3 (blending ratio 3: 2)>
After stirring 288 g of DOPO-NQ and 1200 g of DMAc in a four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermometer for 20 to 30 minutes, nitrogen gas was introduced and sufficiently dispersed. 150 g of dimethyldichlorosilane is added at a time, the triethylamine catalyst is slowly added dropwise, and 198 g of triethylamine is controlled to be added dropwise for about 1 h, then the temperature is raised to 90 ° C. for about 12 hours of reaction, and then benzoyl chloride is added. Add at once, continue to react for 10 hours, filter, wash with water, dry to obtain 377 g of product, Mn = 601 by GPC test, P content in its flame retardant is 6.1%, Si The content was 3.64% and the number was PBS-32.

<Preparation Example 4 (blending ratio 2: 1)>
After stirring 384 g of DOPO-HQ and 1200 g of DMAc in a four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermometer for 20 to 30 minutes, nitrogen gas was introduced and sufficiently dispersed. 150 g of diphenyldichlorosilane is added at a time, the triethylamine catalyst is slowly added dropwise, and 264 g of triethylamine is controlled to be added dropwise for about 1 h, then the temperature is raised to 90 ° C. for about 12 hours of reaction, and then benzoyl chloride is added. Add at once, continue to react for 10 hours, filter, wash with water, dry to obtain 377 g of product, Mn = 473 by GPC test, P content in its flame retardant is 6.05%, Si The content was 2.7% and the number was PBS-21.

FIG. 1 shows a DSC reaction curve in which the prepared phosphorus silicon flame retardant and an epoxy resin (Hongchang 128E) are combined, and the curve is suitable with a mass ratio of the epoxy resin and the phosphorus silicon flame retardant of 1: 1. It is obtained by adding the solvent methyl ethyl ketone (MEK) and an appropriate amount of a curing accelerator, mixing them uniformly, preparing an adhesive solution, and measuring the temperature using a DSC device under a temperature rising condition of 10 ° C./min. As can be seen from the figure, there is a strong reaction exothermic peak between 160 and 180 ° C., and the phosphorus silicon flame retardant can react with the epoxy resin to form a crosslinked network, that is, the flame retardant of the present invention. It was found that it is not present in the plate in free form and there is no risk of flame retardant precipitation during late use.

<Example 1>
When 100 g of bisphenol A epoxy resin (brand: Hongchang 128E) and 10 g of flame retardant PSi-54 are placed in a beaker and stirred while heating, the flame retardant is sufficiently melt-mixed with the epoxy resin to make the system transparent and uniform. , 34 g of the curing agent DDS (4,4-diaminodiphenylsulfone) was added, and the mixture was melt-mixed so as to be uniform and transparent in the same manner. A cast product was prepared by heating and curing by a program of / 1h-200 ° C./1h-220 ° C./1h, allowed to cool naturally, and after demolding, the cast product was pale yellow and transparent. The P content in the cast product is 0.427%, the Si content is 0.306%, the cast product is flame retardant, Tg and Td 5% are shown in Table 1, and the cast product numbers are PSi. It was -54-10.

<Examples 2 to 12>
A cast product was prepared using the same method as in Example 1, and for example, 20 g of the flame retardant PSi-54 was added to the combination of 128 + DDS and marked as PSi-54-20. Thus, PSi-54-20, PSi-54-30, PSi-43-10, PSi-43-20, PSi-43-30, PSi-32-10, PSi-32-20, PSi-32, respectively. They were numbered -30, PSi-21-10, PSi-21-20, and PSi-21-30.

<Example 13>
Put 70 g of bisphenol A epoxy resin (brand: Hongchang 128E), 30 g cyanate (brand: Yangshu Tenkei CE01PS), and 20 g of flame retardant PSi-43 in a beaker and stir while heating to sufficiently add the flame retardant to the epoxy resin. After melt-mixing, when the system becomes transparent and uniform, 24 g of the curing agent DDS (4,4-diaminodiphenylsulfone) is added, melt-mixed so that it becomes uniform and transparent in the same manner, and then placed in a mold to 100. Vacuum defoaming is performed at ° C for 30 minutes, and the cast product is prepared by heating and curing with a program of 160 ° C / 1h-200 ° C / 1h-220 ° C / 1h, allowed to cool naturally, and after demolding, the cast product is light. It was transparent yellow. The P content in the cast product is 0.810%, the Si content is 0.561%, the cast product is flame retardant, Tg and Td 5% are shown in Table 1, and the cast product number is CE. It was 433-20.

<Example 14>
Put 70 g of bisphenol A epoxy resin (brand: Hongchang 128E), 30 g of benzoxazine (brand: HUNTSMAN 8290), and 20 g of flame retardant PSi-43 in a beaker and stir while heating to make the flame retardant sufficient for the epoxy resin. When the system becomes transparent and uniform, 24 g of the curing agent DDS (4,4-diaminodiphenylsulfone) is added, and the mixture is melt-mixed so that it becomes uniform and transparent in the same manner, and then placed in a mold. Vacuum defoaming is performed at 100 ° C. for 30 minutes, and the cast product is prepared by heating and curing with a program of 160 ° C./1h-200 ° C./1h-220 ° C./1h to prepare a cast product. It was pale yellow and transparent. The P content in the cast product is 0.810%, the Si content is 0.561%, the cast product is flame retardant, Tg and Td 5% are shown in Table 1, and the cast product number is BOZ. It was 433-20.

<Comparative example 1>
100 g of bisphenol A epoxy resin (brand: Hongchang 128E) and 34 g of curing agent DDS (4,4-diaminodiphenyl sulfone) are placed in a beaker and stirred while heating to sufficiently melt and mix the DDS with the epoxy resin. After that, it was placed in a mold, vacuum defoamed at 100 ° C. for 30 minutes, and heated and cured by a program of 160 ° C. / 1h-200 ° C./1h-220 ° C./1h to prepare a cast product. After allowing to cool naturally and removing the mold, the cast product was pale yellow and transparent. The P content and the Si content in the cast product were both 0, the cast product was flame-retardant, Tg and Td 5% were shown in Table 1, and the cast product number was KB.

<Comparative example 2>
118 g of bisphenol A epoxy resin (brand: Hongchang 128E), 3.8 g of diphenylsilanediol, and 7.2 g of DOPO-HQ are placed in a beaker and stirred while heating to sufficiently melt and mix the flame retardant with the epoxy resin. When the system is transparent and uniform, 34 g of the curing agent DDS (4,4-diaminodiphenylsulfone) is added, melt-mixed so as to be uniform and transparent, and then placed in a mold at 100 ° C. Vacuum defoaming is performed for 30 minutes, and the cast product is prepared by heating and curing with a program of 160 ° C / 1h-200 ° C / 1h-220 ° C / 1h, allowed to cool naturally, and after demolding, the cast product is pale yellow and transparent. Met. Both the P content and the Si content in the cast product are consistent with the cast product number PSi-54-10, that is, the P content is 0.427% and the Si content is 0.306%. The cast product was flame retardant, Tg and Td 5% were shown in Table 1, and the cast product number was FP-54-10.

<Comparative example 3>
137 g of bisphenol A epoxy resin (brand: Hongchang 128E), 8.7 g of diphenylsilanediol, and 16.2 g of DOPO-HQ are placed in a beaker and stirred while heating to sufficiently melt and mix the flame retardant with the epoxy resin. When the system is transparent and uniform, 34 g of the curing agent DDS (4,4-diaminodiphenylsulfone) is added, melt-mixed so as to be uniform and transparent, and then placed in a mold at 100 ° C. Vacuum defoaming is performed for 30 minutes, and the cast product is prepared by heating and curing with a program of 160 ° C / 1h-200 ° C / 1h-220 ° C / 1h, allowed to cool naturally, and after demolding, the cast product is pale yellow and transparent. Met. Both the P content and the Si content in the cast product are consistent with the cast product number PSi-54-20, that is, the P content is 0.799% and the Si content is 0.571%. The cast product was flame retardant, Tg and Td 5% were shown in Table 1, and the cast product number was FP-54-20.

The test method for the above characteristics is as follows.
(1) Glass transition temperature (Tg): Measured according to the DSC test method specified in IPC-TM-650 2.4.24 using the DSC test.
(2) DSC reaction curve: The measurement is performed according to the DSC test method specified in IPC-TM-650 2.4.24 using the DSC test, and the temperature rise condition of the measurement is 10 ° C./min.
(3) Ignition loss Td5%: Using the TGA test, measure according to the TGA test method specified in IPC-TM-650 2.4.24.6.
(4) Flame retardancy: Perform according to the UL 94 standard method.

As can be seen from the comparison of the data in Table 1, the blank KB is a basic resin model to be considered, and there is a phenomenon that it almost burns and the droplets ignite the degreased cotton. It has the same phosphorus content and silicon content as in Example 10, the burning time is reduced from 125.9 seconds at the time of compounding to 75.2 seconds, and Comparative Example 3 has the same phosphorus content and silicon as in Example 11. It has a content and the burning time is reduced from 105.3 seconds at the time of compounding to 32.3 seconds, that is, it directly reaches V-0 from the V-1 level, and the flame retardant effect of the silicon silicon flame retardant of the present invention. Is clearly superior to the formulation.

In Examples 1, 4, 7, and 10, when 10 parts of each of the different polymer phosphorous flame retardants was added, the phosphorus content in the cast product was maintained at about 0.42%, and the silicon content was increased. As a result, the flame retardancy tends to improve, and in Examples 2, 5, 8 and 11, the phosphorus content in the cast product is increased when 20 parts of each of the different polymer phosphor silicon flame retardants is added. It was maintained at about 0.79%, and its flame retardancy was significantly improved as the silicon content increased. Further, in the same number of copies of the same flame retardant PSi-43 added to Examples 8, 13 and 14 of the present invention, cyanate (CE) was added in Example 13, and benzoxazine (in Example 14). After the addition of BOZ), the Tg of each is greatly improved, and it can be found that the groove to which benzoxazine is added is particularly excellent in flame retardancy.

The above can reach V-0 when the silicon content reaches a certain amount when the phosphorus content is the same, that is, the dehydration carbonization of the phosphorus element reaches a certain ratio of the silicon element. The stability of the carbon layer can be increased, i.e., a denser protective layer can be formed and flame retardant synergies can be achieved. Overall, the overall performance of the PSi-43 group is relatively optimal, with a burning time of 34.4 seconds with the addition of 13% wt, i.e. at V-0. There was a good heat resistance expression, Tg was 148 ° C, and Td 5% was 370 ° C.

The above contents are merely preferred embodiments of the present invention, and those skilled in the art can make various other corresponding modifications and modifications based on the technical proposals and technical ideas of the present invention, and these modifications and modifications can be made. Should belong to the scope of claims of the present invention.

Claims (19)

A phosphorus-containing silicon active ester having a structure represented by the formula (I).

(However, Ar is a C6-C18 aryl group, and Ar is a C6-C18 aryl group.
n = an integer of 1 to 5,
R1 and R2 are independently C6-C18 aryl groups, C6-C18 aryloxy groups, C1-C6 aliphatic groups, C1-C6 alkoxy groups, or C2-C6 alkenyl groups, respectively.
A is

It is one of the
B is

Any one of them. ) The phosphorus-containing silicon active ester according to claim 1, wherein R1 and R2 are independently phenyl groups, C1-C5 alkyl groups or vinyl groups, respectively. (1) Reacting DOPO-HQ, DOPO-NQ, DPO-HQ or DPO-NQ with dihalosilane in the presence of a catalyst,
(2) The product obtained in step (1) is subjected to an esterification reaction with an aryl halide to obtain a phosphorus-containing silicon active ester having a structure represented by the formula (I).
Including
The DOPO-HQ is the reaction product of DOPO with benzoquinone, DOPO-NQ is the reaction product of DOPO with 1,4-naphthoquinone, the DPO-HQ, the formation reaction of the DPO and benzoquinone It is those, wherein DPO-NQ is Ru reaction products der the DPO and 1,4-naphthoquinone, a method of preparing the phosphorus-containing silicon active ester according to claim 1, characterized in that. The DOPO-HQ, the number of moles of DOPO-NQ, DPO-HQ or DPO-NQ and dihalosilane 1: (0.5-5) Der Ru method of claim 3, characterized in that .. The dihalosilane is of the formula

Has the structure shown in, however, R1 and R2 are as defined in claim 1, X is Ru halogen der A method according to claim 3 or 4, characterized in that. The catalyst is selected from triethylamine, pyridine, sodium hydroxide, potassium hydroxide, anhydrous sodium carbonate, anhydrous potassium carbonate, and sodium methoxide.
The amount of the catalyst, DOPO-HQ, DOPO-NQ , Ru 2-4 Baidea of moles of DPO-HQ or DPO-NQ, that in any one of claims 3-5, characterized in The method described. Step (1) is carried out in a solvent system, said solvent claim, wherein dimethylformamide (DMF), Ru is selected from dimethylacetamide (DMAc), and N- methylpyrrolidone (NMP), that 3-6 The method according to any one of the above. If the DMAc as a solvent, the concentration of the reaction system Ru 15% to 30% der method of claim 7, characterized in that. Step reaction temperature (1) is a normal temperature to 120 ° C., the reaction time is Ru 5-20 hours der A method according to any one of claims 3-8, characterized in that. The reaction in Step (1) Ru carried out in the presence of a protective gas, the method according to any one of claims 3-9, characterized in that. The ratio of the number of moles of the aryl halide to the product obtained in step (1) in step (2) is 1: 0.5 to 2.
The aryl halide is an aryl chloride and
The method according to any one of claims 3 to 10, wherein step (2) is performed in the same system as step (1). Further comprising a post-treatment step after the reaction, the post-processing includes filtration and evaporation of the low boiling substance, any one of claims 3 to 11, further including the subsequent washing and drying, characterized by The method described in the section. The method according to claim 12 , wherein the reagent used for the washing is selected from an alcohol solvent, an ester solvent, and deionized water. A flame-retardant resin composition comprising a thermosetting resin, a curing agent, the phosphorus-containing silicone active ester according to claim 1 or 2, a filler, and a curing accelerator. The phosphorus-containing silicon active ester, accounting for 5-30% of the total weight of the flame retardant resin composition, the flame retardant resin composition according to claim 14, wherein. The flame-retardant resin composition according to claim 14 or 15 , wherein the phosphorus weight content of the flame-retardant resin composition is less than 2.5%. The thermosetting resin is one or more selected from epoxy resin, polyurethane resin, cyanate resin, and benzoxazine resin.
The curing agent is one or more selected from a phenol-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, an active ester curing agent, and a radical initiator.
The filler may be any one or at least two selected from aluminum hydroxide, boehmite, silica, talc, mica, barium sulfate, lithopone, calcium carbonate, wollastonite, kaolin, bluesite, diatomaceous earth, bentonite, or brucite powder. Is a mixture of
14 to claim 14, wherein the curing accelerator is any one or a mixture of at least two of an imidazole-based curing accelerator, an organic phosphine curing accelerator, and a tertiary amine curing accelerator. The flame-retardant resin composition according to any one of 16. A prepreg comprising a base material and the flame-retardant resin composition according to any one of claims 14 to 17 , which is attached to the base material by immersion or coating. A metal-clad laminate comprising at least one prepreg according to claim 18 and a metal foil coated on one or both sides of the prepreg.

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