CN104926875A - Flame retardant hydroxymethyl phosphonyl heterocyclic phenylphosphonate compound and preparation method therefor - Google Patents

Abstract

The invention relates to a flame retardant hydroxymethylphosphono heterocyclic phenylphosphonate compound and a preparation method thereof. The structure of the compound is shown in the following formula: The preparation method is: under the protection of nitrogen, at 20°C, mix equimolar phenylphosphonic dichloride and trihydroxymethylphosphine oxide well, raise the temperature to 85°C for 2 hours, then raise the temperature to 110-140°C to react 4- After 8h, hydrogen chloride was exhausted, and after purification, hydroxymethylphosphonoheterocyclic phenylphosphonate was obtained. The compound of the invention has high phosphorus content and excellent flame retardant performance, and is suitable for use as a flame retardant for unsaturated resin, polyvinyl alcohol, polyurethane, epoxy resin and the like. And the preparation method is one-step reaction, the process is simple, the equipment investment is small, and the industrialized production is easy to realize.

Description

Flame retardant hydroxymethylphosphonoheterocyclic phenylphosphonate compound and preparation method thereof

technical field

The invention relates to an organic phosphine flame retardant hydroxymethylphosphono heterocyclic phenyl phosphonate compound and a preparation method thereof, in particular to a 1,4-dioxo-1-phenyl-4-hydroxymethyl - 2,6-dioxa-1,4-diphosphorinane compound and its preparation method, the compound is suitable as a flame retardant for unsaturated resin, polyvinyl alcohol, epoxy resin, etc.; for polyurethane It is used as a reactive flame retardant; it can also be used as an intermediate in organic synthesis.

Background technique

With the rapid development of polymer materials, the application of flame retardant polymer materials is very extensive. Due to the enhancement of people's awareness of safety and environmental protection, there is a higher demand for flame retardant materials and flame retardants. When flame retardant materials are required to have good In addition to the flame retardant performance, it is also required to be friendly to the environment, so the development direction of non-halogenated flame retardants is proposed, thereby promoting the development of environmentally friendly flame retardants such as phosphorus and nitrogen. Among them, organic phosphine flame retardants are more popular. These flame retardants contain C-P bonds, have enhanced chemical stability, low smoke, low toxicity, high flame retardant efficiency, and little impact on the mechanical and physical properties of materials. , Therefore, organic phosphine flame retardants have become one of the most promising flame retardant varieties in recent years.

The invention discloses an organic phosphine flame retardant hydroxymethylphosphono heterocyclic phenylphosphonate compound and a preparation method thereof. The product of the invention has a ring structure, high phosphorus content, good stability, excellent flame retardant performance and good compatibility with materials. The organic phosphine bond (C-P bond) in the molecule will bring stability to the compound. At the same time, the structure also contains an active hydroxyl functional group, which can be used as a reactive flame retardant to prepare bulk flame retardant materials. The reaction of the invention is a one-step method, the process is simple, the equipment investment is small, the cost is low, and the development prospect is very good.

Contents of the invention

One of the objectives of the present invention is to provide an organic phosphine flame retardant hydroxymethylphosphonoheterocyclic phenylphosphonate compound, which has high flame retardant efficiency and wide application range, and can overcome the deficiencies in the prior art.

In order to realize the above-mentioned purpose of the invention, the present invention has adopted following technical scheme:

An organic phosphine flame retardant hydroxymethylphosphono heterocyclic phenyl phosphonate compound is characterized in that the structure of the compound is shown in the following formula:

Another object of the present invention is to propose a preparation method of organic phosphine flame retardant hydroxymethylphosphono heterocyclic phenylphosphonate compound, which has simple process, low equipment investment, easy large-scale production, and cheap and easy raw materials. Yes, the cost is low, the method is:

In a reactor equipped with a stirrer, a thermometer, a high-efficiency reflux condenser and a hydrogen chloride absorption device, under the protection of nitrogen, at 20 ° C, fully mix equimolar phenylphosphonic dichloride and trimethylolphosphine oxide, When the temperature is raised to 60°C, hydrogen chloride begins to be released obviously, and the temperature is raised to 85°C for 2 hours, then the temperature is raised to 110-140°C for 4-8 hours, until no hydrogen chloride is produced, and the hydrogen chloride is exhausted in a vacuum, the temperature is lowered to below 30°C, and after purification, The product hydroxymethylphosphonoheterocyclic phenylphosphonate was obtained.

The method can also be:

In a reactor equipped with a stirrer, a thermometer, a high-efficiency reflux condenser and a hydrogen chloride absorption device, under the protection of nitrogen, add an organic solvent and trimethylolphosphine oxide, and add dropwise with trimethylol phosphine oxide at 20°C under stirring Phenylphosphonic dichloride with the same mole of phosphine oxide, mixed well, heated up to 60°C and began to release hydrogen chloride obviously, raised the temperature to 85°C for 2 hours, then raised the temperature to 110-140°C for 4-8 hours, until no hydrogen chloride was produced, reduced The solvent was removed by distillation under pressure, the temperature was lowered to below 30°C, and the product was purified to obtain the product hydroxymethylphosphonoheterocyclic phenylphosphonate.

The aforementioned organic solvents are xylene, chlorobenzene, ethylene glycol diethyl ether, and toluene, and the amount in milliliters is 2-5 times the mass of trishydroxymethylphosphine oxide in grams.

The above-mentioned purification process is to add ice water whose theoretical mass is 1-2 times the volume in milliliters, and add 5% sodium carbonate solution dropwise under stirring to make the pH of the reaction system = 7. Lower floor feed liquid, decompression distillation removes a small amount of water in the material.

The organic phosphine flame retardant of the present invention is a colorless viscous liquid, the product yield is 84.7%-95.3%, the refractive index: n _D ²⁰ =1.4988, and the density (25°C) : 1.667g/cm ³ , decomposition temperature: 236±5°C. It is suitable as a flame retardant for unsaturated resins, polyvinyl alcohol, epoxy resin, etc. It is used as an additive reactive flame retardant for polyurethane, and can also be used as an intermediate in organic synthesis. The organic phosphine flame retardant hydroxymethylphosphine The synthesis process principle of acyl heterocyclic phenyl phosphonate is shown in the following formula:

Compared with prior art, the beneficial effect of the present invention is:

① The organic phosphine flame retardant of the present invention, the hydroxymethylphosphono heterocyclic phenyl phosphonate compound, has a phosphorus content of 23.7%, high flame retardant efficiency, and a good symmetry in its ring structure, which also contains an active hydroxyl group The functional group can be used as a reactive flame retardant to prepare bulk flame retardant materials.

② The raw material trimethylolphosphine oxide used in the organic phosphine flame retardant of the present invention, which is a hydroxymethylphosphono heterocyclic phenylphosphonate compound, is itself an excellent reactive organic phosphine flame retardant. The dichlorination reaction increases the content of phosphorus, and introduces an aromatic ring with diester structure and electronic structure, which endows the product with better compatibility with polymer materials.

③ The preparation method of the organic phosphine flame retardant hydroxymethylphosphonoheterocyclic phenylphosphonate compound of the present invention is a one-step reaction, the process is simple, the equipment investment is small, the operation is convenient, the cost is low, and it is easy for large-scale transformation and production.

Description of drawings

In order to further illustrate the structure and performance of the product, the following drawings are given.

1. The infrared spectrum of hydroxymethylphosphonoheterocyclic phenylphosphonate, please refer to Figure 1 of the accompanying drawing for details;

Figure 1 shows that at 3407cm ^-1 is the stretching vibration peak of hydroxyl OH bond; at 3032cm ^-1 is the stretching vibration peak of CH bond on the benzene ring; at 2929cm ^-1 is the stretching vibration peak of methylene CH bond, and at 1474cm ^{- 1} is the bending vibration peak of methylene CH bond; 1312cm ^-1 is the stretching vibration peak of P=O double bond; 1108cm ^-1 and 1067cm ^-1 are the stretching vibration peaks of CO bond; 996cm ^-1 is PO The stretching vibration peak of the bond; 778cm ^-1 is the stretching vibration peak of the CP bond.

2. For the NMR spectrum of hydroxymethylphosphonoheterocyclic phenylphosphonate, see Figure 2 of the accompanying drawing for details;

Figure 2 shows that with deuterated water as the solvent, the H peak at δ3.18-3.23 is the H peak of hydroxyl; the H peak at δ3.95-4.02 is the methylene connected to the oxygen heteroatom; The H peak of the methylene group connected to the hydroxyl group; the H peak of the phenyl group at δ7.22-7.45; the H peak of the deuterated water solvent at δ4.70.

3. The differential heat map of hydroxymethylphosphonoheterocyclic phenylphosphonate, see Figure 3 of the accompanying drawing for details;

Figure 3 shows that the temperature begins to lose weight at 236°C, and when the weight loss rate is 50%, the temperature is 348°C; there is still 24% residue when the end temperature is 800°C, indicating that the product has better thermal stability.

specific embodiment

The technical solution of the present invention will be further described below in combination with specific embodiments.

Example 1 In a 100ml four-necked flask equipped with a stirrer, a thermometer, a high-efficiency reflux condenser and connected to a hydrogen chloride absorption device on the condenser, the air in the bottle was driven away with nitrogen, and 30ml xylene was added, and 14.00g ( 0.1mol) trishydroxymethyl phosphine oxide, under stirring, at 20°C, add 19.50g (0.1mol) phenylphosphonic dichloride dropwise, make it fully mixed, heat up to 60°C, hydrogen chloride begins to be released, heat up to Insulate at 85°C for 2 hours, then raise the temperature to 140°C for 4 hours, wait until no hydrogen chloride is released, remove xylene (recycled) by distillation under reduced pressure, cool down to below 30°C, add 50ml of ice water, and add 5% of Sodium carbonate solution, make the reaction system pH=7, let stand to separate layers, separate the lower layer material liquid, and distill off a small amount of water under reduced pressure to obtain a colorless viscous liquid hydroxymethylphosphonoheterocyclic phenylphosphonate, producing The ratio is 95.3%, the refractive index: n _D ²⁰ =1.4988, the density (25°C): 1.667g/cm ³ , and the decomposition temperature: 236±5°C.

Example 2 In a 100ml four-necked flask equipped with a stirrer, a thermometer, a high-efficiency reflux condenser and connected to a hydrogen chloride absorption device on the condenser, the air in the bottle was driven away with nitrogen, and 40ml of chlorobenzene was added, 14.00g ( 0.1mol) trishydroxymethyl phosphine oxide, under stirring, at 20°C, add 19.50g (0.1mol) phenylphosphonic dichloride dropwise, make it fully mixed, heat up to 60°C, hydrogen chloride begins to be released, heat up to Insulate at 85°C for 2 hours, then heat up to 130°C for 5 hours, wait until no hydrogen chloride is released, remove chlorobenzene (recycled) by distillation under reduced pressure, cool down to below 30°C, add 45ml of ice water, and add 5% of Sodium carbonate solution, make the reaction system pH=7, let stand to separate layers, separate the lower layer material liquid, and distill off a small amount of water under reduced pressure to obtain a colorless viscous liquid hydroxymethylphosphonoheterocyclic phenylphosphonate, producing The rate is 94.1%, the refractive index: n _D ²⁰ =1.4988, the density (25°C): 1.667g/cm ³ , the decomposition temperature: 236±5°C.

Example 3 In a 150ml four-neck flask equipped with a stirrer, a thermometer, a high-efficiency reflux condenser and a hydrogen chloride absorption device connected to the upper mouth of the condenser, the air in the bottle was driven away with nitrogen, and 50ml of ethylene glycol diethyl ether was added. 14.00g (0.1mol) of trishydroxymethylphosphine oxide, under stirring, at 20°C, add dropwise 19.50g (0.1mol) of phenylphosphonic dichloride, make it fully mixed, heat up to 60°C, hydrogen chloride begins to be released , heat up to 85°C for 2 hours, then heat up to 120°C for 6 hours, wait until no hydrogen chloride is released, remove ethylene glycol diethyl ether (recycled) by distillation under reduced pressure, cool down to below 30°C, add 40ml of ice water, and stir , add 5% sodium carbonate solution dropwise to make the reaction system pH=7, let it stand for stratification, separate the lower layer material liquid, and distill off a small amount of water under reduced pressure to obtain a colorless viscous liquid hydroxymethylphosphonoheterocyclic benzene Phosphonic acid ester, the yield is 93.5%, the refractive index: n _D ²⁰ =1.4988, the density (25°C): 1.667g/cm ³ , the decomposition temperature: 236±5°C.

Example 4 In a 150ml four-necked flask equipped with a stirrer, a thermometer, a high-efficiency reflux condenser and connected to a hydrogen chloride absorption device on the condenser, the air in the bottle was driven away with nitrogen, and 60ml of toluene was added, and 14.00g (0.1 mol) trihydroxymethyl phosphine oxide, under stirring, at 20°C, add 19.50g (0.1mol) phenylphosphonic dichloride dropwise, make it fully mixed, heat up to 60°C, hydrogen chloride begins to be released, heat up to 85 Keep warm at ℃ for 2 hours, then raise the temperature to 110℃ and keep it warm for 7 hours. After no hydrogen chloride is released, toluene is removed by distillation under reduced pressure (recycling), and the temperature is lowered to below 30℃. Then add 30ml of ice water, and add 5% sodium carbonate dropwise under stirring. Solution, make the reaction system pH=7, leave to stand for stratification, separate the lower layer feed liquid, and remove a small amount of water by distillation under reduced pressure to obtain a colorless viscous liquid hydroxymethylphosphonoheterocyclic phenylphosphonate, the yield is 92.6%, refractive index: n _D ²⁰ =1.4988, density (25°C): 1.667g/cm ³ , decomposition temperature: 236±5°C.

Example 5 In a 100ml four-neck flask equipped with a stirrer, a thermometer, a high-efficiency reflux condenser and a hydrogen chloride absorbing device connected to the upper mouth of the condenser, the air in the bottle was driven away with nitrogen, and 14.00g (0.1mol) of three Hydroxymethylphosphine oxide, under stirring, add 19.50g (0.1mol) phenylphosphonic dichloride dropwise at 20°C, make it fully mixed, heat up to 60°C, hydrogen chloride begins to be released, heat up to 85°C and keep for 2 hours , and then heated up to 140°C for 5 hours of heat preservation reaction. After no hydrogen chloride was released, the hydrogen chloride was exhausted in a vacuum. After cooling down to below 30°C, 50ml of ice water was added, and under stirring, 5% sodium carbonate solution was added dropwise to make the reaction system pH=7, standing for stratification, separating the lower layer material liquid, and removing a small amount of water by distillation under reduced pressure to obtain a colorless viscous liquid hydroxymethylphosphonoheterocyclic phenylphosphonate, the yield was 86.3%, the refractive index : n _D ²⁰ =1.4988, density (25°C): 1.667g/cm ³ , decomposition temperature: 236±5°C.

Example 6 In a 100ml four-necked flask equipped with a stirrer, a thermometer, a high-efficiency reflux condenser and a hydrogen chloride absorbing device connected to the upper mouth of the condenser, the air in the bottle was driven away with nitrogen, and 14.00g (0.1mol) of three Hydroxymethylphosphine oxide, under stirring, add 19.50g (0.1mol) phenylphosphonic dichloride dropwise at 20°C, make it fully mixed, heat up to 60°C, hydrogen chloride begins to be released, heat up to 85°C and keep for 2 hours , and then heated up to 120°C for 8 hours of heat preservation reaction. After no hydrogen chloride was released, the hydrogen chloride was exhausted in a vacuum. The temperature was lowered to below 30°C, and 40ml of ice water was added. Under stirring, 5% sodium carbonate solution was added dropwise to make the reaction system pH=7, standing for stratification, separating the lower layer material liquid, and distilling off a small amount of water under reduced pressure to obtain a colorless viscous liquid hydroxymethylphosphonoheterocyclic phenylphosphonate, the yield was 84.7%, the refractive index : n _D ²⁰ =1.4988, density (25°C): 1.667g/cm ³ , decomposition temperature: 236±5°C.

Table 1 Preparation Example Main Process Parameters

The inventors of the present case also applied the product hydroxymethylphosphono heterocyclic phenylphosphonate prepared above to unsaturated resins. Reference: GB/T2406-2008 "Test Method for Combustion Performance of Plastics - Oxygen Index Method" to measure the limiting oxygen index of the sample. After mixing the product with unsaturated resin, cyclohexanone peroxide and cobalt naphthenate in different proportions, pour it into a mold to make a 15cm-long, 0.7cm-wide, and 0.3cm-thick specimen, and test its flame retardancy. Test, the measured LOI results are shown in Table 2:

Table 2 Flame retardant data of hydroxymethylphosphonoheterocyclic phenylphosphonate in unsaturated resin

It can be seen from Table 2 that without adding any flame retardant, the limiting oxygen index of the unsaturated resin can only be 18%, which belongs to the extremely flammable range. When the addition amount of the unsaturated resin material accounts for 20%, its oxygen index has reached the flame-retardant level of 27%, which shows that the product of the present invention, hydroxymethylphosphonoheterocyclic phenylphosphonate, has a good effect on unsaturated resins. flame retardant effect.

Claims (5)

1. an organic phosphine fire retardant methylol phosphono heterocycle shape phenyl-phosphonic acid ester cpds, it is characterized in that, the structure of this compound is shown below:

2. a preparation method for organic phosphine fire retardant methylol phosphono heterocycle shape phenyl-phosphonic acid ester cpds, it is characterized in that, the method is:

In the reactor that agitator, thermometer, high performance reflux condenser and hydrogen chloride absorption device are housed; under nitrogen protection, in 20 DEG C, equimolar phenyl phosphonyl chloride and trishydroxymethyl phosphine oxide are fully mixed; be warming up to 60 DEG C of beginnings and obviously release hydrogenchloride; be warming up to 85 DEG C of insulation 2h, then be warming up to 110-140 DEG C of reaction 4-8h, to producing without hydrogenchloride; vacuum makes hydrogenchloride drain again; be cooled to less than 30 DEG C, purified process, obtain product methylol phosphono heterocycle shape phenyl phosphonic acid esters.

3. a preparation method for organic phosphine fire retardant methylol phosphono heterocycle shape phenyl-phosphonic acid ester cpds, it is characterized in that, the method is:

Agitator is being housed, thermometer, in the reactor of high performance reflux condenser and hydrogen chloride absorption device, under nitrogen protection, add organic solvent and trishydroxymethyl phosphine oxide, under stirring, in 20 DEG C, drip the phenyl phosphonyl chloride of identical with trishydroxymethyl phosphine oxide mole, fully mix, be warming up to 60 DEG C of beginnings and obviously release hydrogenchloride, be warming up to 85 DEG C of insulation 2h, be warming up to 110-140 DEG C of reaction 4-8h again, to producing without hydrogenchloride, underpressure distillation is except desolventizing, be cooled to less than 30 DEG C, purified process, obtain product methylol phosphono heterocycle shape phenyl phosphonic acid esters.

4. the preparation method of methylol phosphono heterocycle shape phenyl-phosphonic acid ester cpds as claimed in claim 3, it is characterized in that: described organic solvent is dimethylbenzene, chlorobenzene, ethylene glycol diethyl ether, toluene, its consumption volume milliliter number is 2-5 times of trishydroxymethyl phosphine oxide quality grams.

5. the preparation method of methylol phosphono heterocycle shape phenyl-phosphonic acid ester cpds as described in claim 2 and 3, it is characterized in that: described purification process is the frozen water adding product Theoretical Mass grams 1-2 times of volume milliliter number, under stirring, drip the sodium carbonate solution of 5%, make reaction system pH=7, stratification, separates lower floor's feed liquid, water a small amount of in underpressure distillation removing material.