CN106243385B - A kind of DOPO based flameproofings and preparation method thereof - Google Patents

Abstract

The invention discloses a DOPO-based flame retardant and a preparation method thereof. The method uses 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and paraformaldehyde as raw materials to synthesize the precursor І through substitution reaction. Utilize the active hydroxyl group of І, and then substitute/esterify it with phenyl phosphate dichloride and hydroxyethyl acrylate to prepare a flame retardant with high phosphorus content and its own active double bond. The flame retardant is applied to an unsaturated polyester resin matrix to form a flame retardant unsaturated polyester resin composite material. The flame retardant of the invention can improve the flame retardant performance of the unsaturated resin matrix material through the gas phase and the condensed phase, and overcomes the disadvantages of poor compatibility between the existing additive flame retardant and the polymer matrix, easy migration and low flame retardant efficiency. When the flame retardant is used to flame-retardant unsaturated polyester resin, the vertical combustion level of the material can reach V-0 level at a relatively low addition amount, and the flame-retardant effect is good. The product of the invention has high purity, high yield and convenient aftertreatment.

Description

A kind of DOPO-based flame retardant and preparation method thereof

technical field

The invention belongs to the technical field of flame retardant design and preparation, and in particular relates to a DOPO-based flame retardant and a preparation method thereof.

Background technique

Due to many excellent properties such as good chemical stability, easy processing, and low cost, polymer materials have been widely used in many fields such as electronic communications, biomedicine, aerospace, automobile industry, and construction. However, most polymer materials are easy to decompose and burn at high temperatures, and release a lot of heat and toxic gases at the same time, endangering human life and property safety. In order to realize the full potential of these polymer materials in industrial applications, it has become necessary to improve their flame retardancy. At present, it is widely used to add flame retardants to various polymers to improve their flame retardant properties. Phosphorus-containing flame retardants have attracted the attention of many scholars at home and abroad because of their advantages of "environmental friendliness" and high-efficiency flame retardant.

9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is an intermediate of a new type of environmentally friendly flame retardant, because its molecular structure contains biphenyl ring and phenanthrene ring structure , At the same time, it also contains active phosphorus-hydrogen bonds, which can react with olefins, epoxy bonds and carbonyl compounds to form derivatives with unique properties. However, the degradation temperature of DOPO and its derivatives is relatively low, and its thermal stability is poor. It is easy to be heated and melted and degraded during high-temperature processing, which cannot meet the processing temperature of most polymer materials.

Chinese Patent Publication No. CN104086751A reports a DOPO-based s-triazine ring hydrogenated benzimidazole epoxy curing agent and a preparation method thereof. First, take cyanuric chloride and p-hydroxybenzaldehyde as raw materials to obtain intermediate I 2,4,6-three (4-formylphenoxy)-1,3,5-s-triazine ring; then intermediate I React with DOPO to get the intermediate IIDOPO-based 2,4,6-tris(4-formylphenoxy)-1,3,5-s-triazine ring; finally react the intermediate II with o-phenylenediamine to get the final hindered Combustion agent DOPO-based s-triazine ring hydrogenated benzimidazole epoxy curing agent, the vertical combustion level of the curing agent has passed UL-94V-0 level, and the flame retardant effect is good. However, a catalyst must be used in the preparation process of the flame retardant, which causes great pollution to the environment.

Chinese Patent Publication No. CN103881134A reports a DOPO-derived phosphorus-nitrogen flame retardant and a preparation method thereof. Under the condition of solution reflux and azeotropic water removal, the target product DOPO-HAM can be synthesized by adding the N-methylolacrylamide solution dropwise into the DOPO solution. The flame retardant has high thermal stability, phosphorus and nitrogen synergistic retardation Good combustion effect and other advantages. However, although the azeotropic water removal method is used in the reaction process, the partial hydrolysis and ring-opening reaction of DOPO cannot be completely avoided, resulting in incomplete reaction. Moreover, in the flame retardant test of cotton, when the mass fraction of phosphorus in the cotton cloth is 1.09%, it can only reach the UL-94V-1 level.

Chinese Patent Publication No. 104193967A reports a bisphenol A-monobenzoxazine/epoxy resin copolymer containing double DOPO. First, use DOPO and bisphenol A-bisbenzoxazine as raw materials to prepare intermediate I bisphenol A containing double DOPO, and then react intermediate I with aniline and paraformaldehyde to obtain flame retardant bisphenol containing double DOPO A-Monobenzoxazine. The prepared flame retardant is mixed with the epoxy resin in proportion to obtain the flame retardant material after temperature raising and ring-opening copolymerization. However, the flame retardant material can only reach the V-0 level when the flame retardant is added in an amount of 50 wt%, and the flame retardant is added in a relatively large amount.

Taking DOPO-based flame retardants as an example, the application status of flame retardants in polymer materials is briefly described and analyzed, and many problems still exist in the application of flame retardants are pointed out.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the prior art, to provide a DOPO-based flame retardant, which is a reactive phosphorus-containing halogen-free DOPO-based flame retardant, when applied to epoxy acrylic resin, unsaturated When used in a variety of polymer matrices containing unsaturated double bonds, such as resins, it can significantly improve the flame retardancy of the material.

Another object of the present invention is to provide a simple preparation method of the above-mentioned DOPO-based flame retardant.

In order to solve the above technical problems, the present invention adopts the following technical solutions.

A DOPO-based flame retardant. The appearance of the flame retardant is a yellow viscous liquid. The specific chemical structure of the flame retardant is as follows, including three parts, one part is the dehydroxyl part of the DOPO-based modified monoalcohol, It has the effect of gas phase flame retardancy; one part is a phosphate ester part containing phosphorus elements, which has a condensed phase flame retardancy effect; the other part is a hydroxyethyl acrylate part with active double bonds.

Wherein, R ₁ is methyl, methoxy, ethyl, ethoxy, phenyl or phenoxy; R ₂ is H atom or methyl.

Preferably, R ₁ is methyl, methoxy, phenyl or phenoxy.

A kind of preparation method of DOPO-based flame retardant described above, this method is with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and paraformaldehyde as raw material, by The phosphorus-containing compound precursor I was synthesized by the substitution reaction. Utilize the active hydroxyl group of the precursor I, and then substitute/esterify it with phosphoryl dichloride and acrylate hydroxyethyl esters to prepare a reactive flame retardant monomer II with high phosphorus content and active double bonds. The specific preparation Proceed as follows:

(1) First, DOPO is dissolved in solvent 1 according to the reaction molar ratio, and the temperature is raised to reaction temperature 1 for a period of time under the protection of an inert gas; after DOPO is completely dissolved, paraformaldehyde enters the reaction system, and the temperature rises to To the reaction temperature 2, keep the solution in the reflux state and keep the reaction for a period of time; after the reaction is completed, cool to room temperature, filter, and wash the precipitate with solvent 1; put the precipitate in a vacuum oven for vacuum drying, heat and hold for a period of time time; after that, cool to room temperature to obtain precursor I, and the specific synthetic route is as follows:

(2) Dissolve phosphorus oxydichloride in solvent 2, stir and react for a period of time under ice bath temperature; slowly add acid-binding agent and solvent 2 into the reaction system in a certain molar ratio for ice bath reaction; then slowly add acrylate hydroxyl Ethyl ester compound and solvent 2 react in ice bath for 4-6 hours; then slowly add the mixture of precursor I and solvent 2 to the reaction system, react in ice bath for 4-6 hours, then warm up to room temperature and react for 8-12 hours; After the end, remove the acid-binding agent salt by filtration, and remove the unreacted monomer and solvent by rotary evaporation to obtain pure DOPO-based flame retardant II. The specific synthesis route is as follows:

Preferably, the general structural formula of the phosphoryl dichloride is Cl ₂ POR ₁ ,

Further preferably, the phosphoryl dichloride is phenyl phosphate dichloride, phenyl phosphoryl dichloride, methyl phosphoryl dichloride, methoxy phosphoryl dichloride, ethyl phosphoryl dichloride and ethoxy One of phosphoryl dichloride.

Preferably, the hydroxyethyl acrylate compound is one of hydroxyethyl acrylate and hydroxyethyl methacrylate.

Preferably, in step (1), the solvent 1 is selected from toluene or xylene.

Preferably, in step (1), the inert gas is selected from nitrogen, helium or argon.

Preferably, in step (1), the reaction temperature 1 is 75-85°C.

Preferably, in step (1), the reaction temperature 2 is 90-100°C.

Preferably, in step (1), the reaction reflux time is 6-10 hours.

Preferably, in step (1), the washing is performed 2 to 3 times with toluene.

Preferably, in step (1), the vacuum drying temperature is 60-80° C., and the vacuum drying time is 8-12 hours.

Preferably, in step (1), the paraformaldehyde is in an equimolar ratio to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Preferably, in step (2), the precursor I is in an equimolar ratio to the hydroxyethyl acrylate compound.

Preferably, in step (2), the solvent 2 is selected from tetrahydrofuran, dichloromethane or chloroform.

Preferably, in step (2), the molar ratio of the phosphoric acid dichloride to the acid-binding agent is 1: (1-4), and the molar ratio of the phosphoryl dichloride to the hydroxyethyl acrylate compound is 1: (1~2).

Preferably, in step (2), the acid-binding agent is triethylamine.

Preferably, in step (2), the temperature of the ice bath is -10 to 5°C;

Preferably, in step (2), the room temperature is 25°C.

Preferably, in step (2), the rotary evaporation temperature is 40-60°C.

One of the uses of the flame retardant obtained in the present invention is to apply it in unsaturated polyester resin (UPR) or epoxy acrylic resin (EA) to improve flame retardancy.

Compared with prior art, the present invention has following advantage:

The present invention synthesizes the phosphorus-containing compound precursor I through a substitution reaction. The reactive DOPO-based flame retardant II with high phosphorus content and active double bonds is prepared by using the active hydroxyl group of I, and then substituting/esterifying it with phosphoryl dichloride and hydroxyethyl acrylate. The flame retardant monomer of the present invention has a high molecular weight, can improve the flame retardant performance of the material through the gas phase and the condensed phase, and overcomes the low thermal decomposition temperature, poor compatibility with the polymer matrix, and easy migration of the existing small molecular phosphorus flame retardants. Disadvantages such as low flame retardant efficiency. When the flame retardant is flame retardant unsaturated polyester resin, the vertical burning level of the material can reach V-0 level at a relatively low addition amount, and the flame retardant effect is good. The product of the invention has high purity and yield, and the post-treatment process is simple and convenient.

Detailed ways

The present invention will be described in further detail below in conjunction with specific examples, but not limited to these examples.

The parts in the following examples refer to parts by weight and percentage by weight unless otherwise specified.

Example 1:

In the first step, add 0.5mol (108g) DOPO (9,10-di Hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide) and 200mL toluene, stirred and heated to 80°C under nitrogen protection, after stirring until DOPO was completely dissolved, added 15g of paraformaldehyde, and then heated to Reflux reaction at 95°C for 8 hours, white precipitate will be produced during the reaction. When the reaction was complete, the reaction was stopped, and the precipitate was filtered and washed with toluene and vacuum-dried at 70° C. for 10 h to obtain dry product I.

In the second step, phenyl dichlorinated phosphate (PDCP) (21.1g, 0.1mol) and 80mL tetrahydrofuran (THF) were added into a 250mL three-necked flask equipped with a mechanical stirrer, and the temperature of the system was controlled at 0°C; Triethylamine (TEA) (21.3g, 0.21mol) was added to the system; then hydroxyethyl acrylate (HEA) (11.6g, 0.1mol) and 20mL THF were added dropwise, and the process continued for 2 hours; after the reaction continued for 4 hours, Add product I (0.1mol, 24.6g) and 20mL tetrahydrofuran, and this process lasts for 2 hours; then, after 4 hours of reaction, the system is raised to room temperature for reaction, and after 10 hours of reaction, the triethylamine salt is removed by filtration, and the final product is obtained by rotary evaporation at 40°C. The product is yellow viscous liquid DOPO-based flame retardant II. Yield 80%.

Product structure characterization:

FTIR (KBr, cm ^-1 ): 3071 (ν _{= CH} ), 2961-2922 (ν _-CH ), 1953 (ν _benzene ), 1730 (ν _{C = O} ), 1638 (ν _{C = C} ), 1480-1405 (δ _CH ),1280(ν _P=O ),1200(ν _cc ),1080(ν _PO ). ¹ H-NMR(400MHz,CDCl ₃ -d,ppm):7.95-7.01(m,13H),6.27 (dd,1H), 6.05(m,1H), 5.59(t,1H), 4.88(dd,2H), 4.47(t,2H), 4.31(dd,2H).

Example 2

In the first step, add 0.5mol (108g) DOPO and 200mL toluene to a 500mL three-necked flask equipped with a thermometer, a nitrogen inlet tube and a reflux condenser (the tail end is connected to an anhydrous calcium chloride drying tube), and the Under protection, stir and heat up to 75°C. After stirring until DOPO is completely dissolved, add 15g of paraformaldehyde, then heat up to 90°C and reflux for 10 hours. White precipitate will appear during the reaction. When the reaction was complete, the reaction was stopped, and the precipitate was filtered and washed with toluene and vacuum-dried at 80° C. for 10 h to obtain dry product I.

In the second step, phenyl dichlorinated phosphate (PDCP) (21.1g, 0.1mol) and 80mL of dichloromethane were added into a 250mL three-necked flask equipped with a mechanical stirrer, and the temperature of the system was controlled at -10°C; Add triethylamine (TEA) (21.3g, 0.21mol) in the system; Then drop into hydroxyethyl methacrylate (HEMA) (13.0g, 0.1mol) and 20mL tetrahydrofuran, this process continues 2 hours; Add product I (0.1mol, 24.6g) and 20mL tetrahydrofuran after 1 hour, and this process lasts for 2 hours; after 4 hours of reaction, the system is raised to room temperature for reaction, after 12 hours of reaction, remove triethylamine salt by filtration, and rotate at 40°C The final product was yellow viscous liquid DOPO-based flame retardant II. Yield 82%.

Product structure characterization:

FTIR (KBr, cm ^-1 ): 3071 (ν _{= CH} ), 2961-2922 (ν _-CH ), 1953 (ν _benzene ), 1730 (ν _{C = O} ), 1638 (ν _{C = C} ), 1480-1405 (δ _CH ),1280(ν _P=O ),1200(ν _cc ),1080(ν _PO ). ¹ H-NMR(400MHz,CDCl ₃ -d,ppm):7.95-7.01(m,13H),6.48 (d,1H), 6.40(d,1H), 4.88(t,2H), 4.47(t,2H), 4.31(dd,2H), 2.01(d,1H).

Example 3:

In the first step, add 0.5mol (108g) DOPO and 200mL toluene to a 500mL three-necked flask equipped with a thermometer, a nitrogen inlet tube and a reflux condenser (the tail end is connected to an anhydrous calcium chloride drying tube), and the Under protection, stir and heat up to 80°C. After stirring until DOPO is completely dissolved, add 15g of paraformaldehyde, then heat up to 95°C and reflux for 8 hours. White precipitate will appear during the reaction. When the reaction was complete, the reaction was stopped, and the precipitate was filtered and washed with toluene and vacuum-dried at 70° C. for 12 h to obtain dry product I.

In the second step, add phenyl dichlorinated phosphate (PDCP) (21.1g, 0.1mol) and 80mL chloroform into a 250mL three-necked flask equipped with a mechanical stirrer, and control the temperature of the system at 5°C; after 30 minutes, add Triethylamine (TEA) (21.3g, 0.21mol); Add hydroxyethyl acrylate (HEA) (11.6g, 0.1mol) and 20mL of chloroform dropwise, this process continues for 2 hours; After the reaction continues for 3 hours, add product I (0.1mol, 24.6g) and 20mL chloroform, this process continued for 2 hours; then the system was raised to room temperature for reaction after 5 hours of reaction, the reaction was continued for 10 hours, and the triethylamine salt was removed by filtration, and the final product was yellow viscous Thick liquid DOPO-based flame retardant II. Yield 78%.

Product structure characterization:

FTIR (KBr, cm ^-1 ): 3071 (ν _{= CH} ), 2961-2922 (ν _-CH ), 1953 (ν _benzene ), 1730 (ν _{C = O} ), 1638 (ν _{C = C} ), 1480-1405 (δ _CH ),1280(ν _P=O ),1200(ν _cc ),1080(ν _PO ). ¹ H-NMR(400MHz,CDCl ₃ -d,ppm):7.95-7.01(m,13H),6.27 (dd,1H), 6.05(m,1H), 5.59(t,1H), 4.88(dd,2H), 4.47(t,2H), 4.31(dd,2H).

Example 4:

In the first step, add 0.5mol (108g) DOPO and 200mL toluene to a 500mL three-necked flask equipped with a thermometer, a nitrogen inlet tube and a reflux condenser (the tail end is connected to an anhydrous calcium chloride drying tube), and the Under protection, stir and heat up to 85°C. After stirring until DOPO is completely dissolved, add 15g of paraformaldehyde, then heat up to 100°C and reflux for 6 hours. White precipitate will appear during the reaction. When the reaction was complete, the reaction was stopped, and the precipitate was filtered and washed with toluene and vacuum-dried at 80° C. for 10 h to obtain dry product I.

In the second step, add phenylphosphoryl dichloride (19.5g, 0.1mol) and 80mL tetrahydrofuran (THF) into a 250mL three-necked flask equipped with a mechanical stirrer, and control the temperature of the system at 0°C; after 30 minutes, add Triethylamine (TEA) (21.3g, 0.21mol); Then hydroxyethyl acrylate (HEA) (11.6g, 0.1mol) and 20mL THF were added dropwise, and this process continued for 2 hours; after the reaction continued for 4 hours, product I was added (0.1mol, 24.6g) and 20mL tetrahydrofuran, the process continued for 2 hours; then the system was raised to room temperature for reaction after 4 hours of reaction, and the reaction was continued for 10 hours. After the reaction was continued for 10 hours, the triethylamine salt was removed by filtration, and the final product was yellow viscous Thick liquid DOPO-based flame retardant II. Yield 80%.

Product structure characterization:

FTIR (KBr, cm ^-1 ): 3071 (ν _{= CH} ), 2961-2922 (ν _-CH ), 1953 (ν _benzene ), 1730 (ν _{C = O} ), 1638 (ν _{C = C} ), 1480-1405 (δ _CH ),1280(ν _P=O ),1200(ν _cc ),1080(ν _PO ). ¹ H-NMR(400MHz,CDCl ₃ -d,ppm):7.95-7.01(m,13H),6.27 (dd,1H), 6.05(m,1H), 5.59(t,1H), 4.88(dd,2H), 4.47(t,2H), 4.31(dd,2H).

Example 5:

In the first step, add 0.5mol (108g) DOPO and 200mL toluene to a 500mL three-necked flask equipped with a thermometer, a nitrogen inlet tube and a reflux condenser (the tail end is connected to an anhydrous calcium chloride drying tube), and the Under protection, stir and heat up to 75°C. After stirring until DOPO is completely dissolved, add 15g of paraformaldehyde, then heat up to 90°C and reflux for 10 hours. White precipitate will appear during the reaction. When the reaction was complete, the reaction was stopped, and the precipitate was filtered and washed with toluene and vacuum-dried at 60° C. for 12 h to obtain dry product I.

In the second step, add phenylphosphoryl dichloride (19.5g, 0.1mol) and 80mL tetrahydrofuran (THF) into a 250mL three-necked flask equipped with a mechanical stirrer, and control the temperature of the system at 0°C; after 30 minutes, add Triethylamine (TEA) (21.3g, 0.21mol); then dropwise into hydroxyethyl methacrylate (HEMA) (13.0g, 0.1mol) and 20mL THF, this process continued for 2 hours; after the reaction continued for 4 hours, add Product I (0.1mol, 24.6g) and 20mL tetrahydrofuran, the process continued for 2 hours; then reacted for 4 hours and raised the system to room temperature for reaction, continued for 10 hours after the reaction was filtered to remove triethylamine salt, and the final product was obtained by rotary evaporation at 40°C Yellow viscous liquid DOPO-based flame retardant II. Yield 80%.

Product structure characterization:

FTIR (KBr, cm ^-1 ): 3071 (ν _{= CH} ), 2961-2922 (ν _-CH ), 1953 (ν _benzene ), 1730 (ν _{C = O} ), 1638 (ν _{C = C} ), 1480-1405 (δ _CH ),1280(ν _P=O ),1200(ν _cc ),1080(ν _PO ). ¹ H-NMR(400MHz,CDCl ₃ -d,ppm):7.95-7.01(m,13H),6.48 (d,1H), 6.40(d,1H), 4.88(t,2H), 4.47(t,2H), 4.31(dd,2H), 2.01(d,1H).

Embodiment 6:

In the first step, add 0.5mol (108g) DOPO and 200mL toluene to a 500mL three-necked flask equipped with a thermometer, a nitrogen inlet tube and a reflux condenser (the tail end is connected to an anhydrous calcium chloride drying tube), and the Under protection, stir and heat up to 80°C. After stirring until DOPO is completely dissolved, add 15g of paraformaldehyde, then heat up to 95°C and reflux for 10 hours. White precipitate will appear during the reaction. When the reaction was complete, the reaction was stopped, and the precipitate was filtered and washed with toluene and vacuum-dried at 80° C. for 8 h to obtain dry product I.

In the second step, add methylphosphoryl dichloride (13.2g, 0.1mol) and 80mL tetrahydrofuran (THF) into a 250mL three-necked flask equipped with a mechanical stirrer, and control the temperature of the system at 0°C; after 30 minutes, add Triethylamine (TEA) (21.3g, 0.21mol); Then hydroxyethyl acrylate (HEA) (11.6g, 0.1mol) and 20mL THF were added dropwise, and this process continued for 2 hours; after the reaction continued for 6 hours, product I was added (0.1mol, 24.6g) and 20mL tetrahydrofuran, the process continued for 2 hours; then the system was raised to room temperature after 6 hours of reaction, and the reaction was continued for 12 hours. After the reaction was continued for 12 hours, the triethylamine salt was removed by filtration, and the final product was yellow viscous Thick liquid DOPO-based flame retardant II. Yield 73%.

Product structure characterization:

FTIR (KBr, cm ^-1 ): 3071 (ν _{= CH} ), 2961-2922 (ν _-CH ), 1953 (ν _benzene ), 1730 (ν _{C = O} ), 1638 (ν _{C = C} ), 1480-1405 (δ _CH ),1280(ν _P=O ),1200(ν _cc ),1080(ν _PO ). ¹ H-NMR(400MHz,CDCl ₃ -d,ppm):7.95-7.01(m,8H),6.27 (dd,1H), 6.05(m,1H), 5.59(t,1H), 4.88(dd,2H), 4.47(t,2H), 4.31(dd,2H), 1.43(d,3H).

Embodiment 7:

In order to investigate the flame retardancy of the DOPO-based reactive phosphorus-containing halogen-free flame retardant II of the present invention, a flammable unsaturated polyester resin (UPR) was selected as the matrix in this embodiment, and the The obtained flame retardant was added into UPR according to the following formula (see Table 1), mixed uniformly, poured into a mold, cured at 90°C for 24 hours, and then cured at room temperature to prepare a standard sample. The flame retardant properties of these standard samples (UL94 reference standard: ASTM D3801-10; LOI reference standard: ASTM D2863-06A), the test results are shown in Table 1.

Table 1

It can be seen from Table 1 that when the amount of flame retardant added is greater than or equal to 20wt%, the flame retardancy of unsaturated polyester resin is better, and can reach V-0 level, and the limiting oxygen index can reach 34%.

Embodiment 8:

In order to investigate the flame-retardant effect of DOPO-based flame retardant II of the present invention in epoxy acrylic resin, the present embodiment selects a kind of flammable epoxy acrylic resin (EA) as matrix, and the obtained Flame retardant II was added to EA according to the following formula (see Table 2), mixed uniformly, poured into a mold, and prepared a standard sample by UV curing. The flame retardant performance of these standard samples (UL94 reference standard: ASTM D3801-10; LOI reference standard: ASTM D2863-06A), the test results are shown in Table 2.

Table 2

It can be seen from Table 2 that when the amount of flame retardant added is greater than or equal to 25wt%, the flame retardancy of epoxy acrylic resin is better, and can reach V-0 level, and the limiting oxygen index can reach 32%.

It can be seen from the above examples that the reaction conditions for the preparation of DOPO-based phosphorus-containing reactive halogen-free flame retardants in the present invention are easy to realize, and the operation is simple. Flame retardant properties.

The present invention has been described in detail above, and its purpose is to allow those familiar with this field to understand the content of the present invention and implement it, and can not limit the scope of protection of the present invention. Effect changes or modifications should be covered within the protection scope of the present invention.

Claims (10)

1. a kind of DOPO based flameproofings, which is characterized in that the fire retardant is clear yellow viscous type liquid, including three parts, a part The monohydric alcohol being modified for DOPO bases removes hydroxylic moiety, has gas phase fire-retardant effectiveness；A part is the phosphoric acid ester of phosphorus element-containing Part has condensed phase fire retardation；Another part is then the hydroxy-ethyl acrylate class part of active double bond, described fire-retardant The chemical constitution of agent is as follows：

Wherein, R₁For methyl, methoxyl group, ethyl, ethyoxyl, phenyl or phenoxy group；R₂For H atom or methyl.

2. the method for preparing a kind of DOPO based flameproofings described in claim 1, which is characterized in that this method is with 9,10- dihydros- 9- oxa- -10- phospho hetero phenanthrene -10- oxides and paraformaldehyde are raw material, synthesize phosphorus-containing compound presoma by substitution reaction I recycles the active hydroxyl groups of presoma I and phosphinylidyne dichloro, acrylate hydroxyl ethyl ester class compound that substitution/esterification system occurs For the response type DOPO based flameproofings II of phosphorous and activity double key is gone out, specific preparation process is as follows：

(1) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dissolved in solvent 1 first, in inert gas shielding It is lower that temperature is risen into reaction temperature 1；It again will be more after the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies are completely dissolved Polyformaldehyde is put into reaction system, and temperature, which is risen to reaction temperature 2, makes solution be in reflux state；It waits after the completion of reacting, it is cooling To room temperature, filtering, with 1 washing precipitate of solvent；The sediment is put into vacuum drying oven and is dried in vacuo；Later, it is cooled to room Temperature, obtains presoma I, and specific synthetic route is as follows：

(2) phosphinylidyne dichloro is dissolved in solvent 2, is stirred under ice bath；Add the reaction of acid binding agent ice bath；Acrylic acid is added dropwise later Ester hydroxyl ethyl ester class compound and 2 ice bath of solvent react 4~6 hours；The mixture of presoma I and solvent 2 are added later, ice bath is anti- It is warmed to room temperature reaction 8~12 hours after answering 4~6 hours；It waits for after reaction, being filtered to remove acid binding agent salt, revolving removes not anti- Answer monomer and solvent, you can obtain pure DOPO based flameproofings II, specific synthetic route is as follows：

3. a kind of preparation method of DOPO based flameproofings according to claim 2, it is characterised in that：The phosphinylidyne dichloro General structure is Cl₂POR₁。

4. a kind of preparation method of DOPO based flameproofings according to claim 2, it is characterised in that：The phosphinylidyne dichloro is PhosphorodichloridicAcid Acid Phenyl Ester, diphenylphosphoryl dichloro, methyl phosphinylidyne dichloro, methoxyl group phosphinylidyne dichloro, ethyl phosphinylidyne dichloro and ethyoxyl One kind in phosphinylidyne dichloro；The acrylate hydroxyl ethyl ester class compound is in hydroxy-ethyl acrylate and hydroxyethyl methacrylate One kind.

5. a kind of preparation method of DOPO based flameproofings according to claim 2, it is characterised in that：It is described in step (1) Solvent 1 is toluene or dimethylbenzene；The inert gas is nitrogen, helium or argon gas.

6. a kind of preparation method of DOPO based flameproofings according to claim 2, it is characterised in that：It is described in step (1) Reaction temperature 1 is 75~85 DEG C；The reaction temperature 2 is 90~100 DEG C；The time of the reflux is 6~10 hours；It is described to wash It washs and is washed 2~3 times using toluene；The vacuum drying temperature is 60~80 DEG C, and the vacuum drying time is 8~12h.

7. a kind of preparation method of DOPO based flameproofings according to claim 2, it is characterised in that：It is described in step (1) Paraformaldehyde and the miscellaneous -10- phospho hetero phenanthrenes -10- oxides equimolar ratio of 9,10- dihydro-9-oxies.

8. a kind of preparation method of DOPO based flameproofings according to claim 2, it is characterised in that：It is described in step (2) Solvent 2 is tetrahydrofuran, dichloromethane or chloroform；The acid binding agent is triethylamine.

9. a kind of preparation method of DOPO based flameproofings according to claim 2, it is characterised in that：It is described in step (2) The molar ratio of phosphinylidyne dichloro and acid binding agent is 1:(1~4)；Mole of the phosphinylidyne dichloro and acrylate hydroxyl ethyl ester class compound Than being 1:(1~2)；The presoma I and acrylate hydroxyl ethyl ester class compound equimolar ratio.

10. a kind of preparation method of DOPO based flameproofings according to claim 2, it is characterised in that：In step (2), institute The temperature for stating ice bath is -10~5 DEG C；The room temperature is 25 DEG C；The temperature of the revolving is 40~60 DEG C.