CN105254676B - Double (phosphorus heterocycle methoxyl group) silane compounds of aminomethyl phenyl and preparation method thereof - Google Patents

Abstract

The present invention relates to double (phosphorus heterocycle methoxyl group) silane compounds of a kind of fire retardant aminomethyl phenyl and preparation method thereof, the structure of the compound is shown below：

Description

Methylphenylbis(phosphacyclomethoxy)silane compound and preparation method thereof

technical field

The invention relates to a flame retardant methylphenyl bis(phosphacyclomethoxy)silane compound and a preparation method thereof, in particular to a flame retardant methylphenyl bis(1-oxo-1-methyl- 4-Ethyl-1-phospha-2,6-dioxa-cyclohexyl-<4>-methoxy)silane compound and its preparation method, the compound contains phosphorus and silicon double flame retardant elements, phosphorus Silicon Synergy has a high flame retardant performance, suitable for use as a flame retardant for polyester PBT, PET, nylon, PC, polyurethane, furan resin and other materials.

Background technique

In the development trend of non-halogenated flame retardants, phosphorus-based flame retardants are favored because of their high efficiency, environmental protection, and low toxicity. However, because the addition of such flame retardants will cause changes in the mechanical properties of materials, people hope that Improve the deficiencies of phosphorus-based flame retardants by introducing other excellent flame-retardant elements into the molecule. Silicone-based flame retardant is a new type of halogen-free flame retardant, and it is also a char-forming smoke suppressant. It is also a good dispersant, which can increase the compatibility between flame retardants and polymer materials. Experimental studies have shown that the flame retardant synergy between phosphorus and organosilicon groups can not only improve the flame retardant properties of the material, but also improve the processing performance of the substrate. Therefore, the research and application of phosphorus and silicon synergistic flame retardants have received more and more attention.

The invention discloses a flame retardant methylphenyl bis(phosphacyclomethoxy)silane compound and a preparation method thereof. The compound molecule contains two flame retardant elements, phosphorus and silicon. Phosphorus and silicon synergistically have a good flame retardant effect, and it has the advantages of silicon-based flame retardants and phosphorus-based flame retardants, and shows good char formation And friendly processing performance, is a high-efficiency, smoke-suppressing, non-toxic flame retardant, has a good application and development prospects.

Contents of the invention

One of the objectives of the present invention is to propose a phosphorus-silicon synergistic flame retardant methylphenylbis(phosphacyclomethoxy)silane compound. It has stable physical and chemical properties, good heat resistance, good compatibility with macromolecular materials, and has the effect of charring and anti-dripping, which can overcome the shortcomings in the prior art.

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

A kind of methylphenyl bis (phosphacyclomethoxy) silane compound, it is characterized in that, the structure of this compound is as shown in the following formula:

Another object of the present invention is to propose a method for preparing methylphenylbis(phosphacyclomethoxy)silane as described above, which has simple technology, low equipment investment, is suitable for large-scale production, and has good development and application prospects , the method is:

Under nitrogen protection, control methylphenyldimethoxysilane and 4-ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane (abbreviation: caged phosphate) The molar ratio is 1:2-1:2.5, then add catalyst and organic solvent, heat up to 120-160°C, keep warm for 14-19h, remove the organic solvent by distillation under reduced pressure, and obtain the product methylphenyl bis (phosphacyclomethoxy)silane.

The method can also be:

Under nitrogen protection, control methylphenyldimethoxysilane and 4-ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane (abbreviation: caged phosphate) The molar ratio is 1:2-1:2.5, then add the catalyst, raise the temperature to 130-180°C, keep the temperature for 13-18h, and purify to obtain the product methylphenylbis(phosphacyclomethoxy)silane.

The above-mentioned organic solvent is diglyme, anisole or dimethylformamide (DMF), and its consumption is that the volume of organic solvent in milliliters is the mass of methylphenyldimethoxysilane in grams. 1-5 times.

The catalyst mentioned above is dimethyl sulfate, methyl p-toluenesulfonate or ethyl p-toluenesulfonate, and the amount thereof is 3%-6% of the mass of methylphenyldimethoxysilane.

The above-mentioned purification treatment method is to add distilled water whose theoretical mass in grams is 1-2 times the volume in milliliters of the product, stir to disperse the solid in water, suction filter and dry.

The methylphenylbis(phosphacyclomethoxy)silane of the present invention is a white solid, its yield is 82.6%-90.5%, melting point: 160±2°C, decomposition temperature: 328±5°C, suitable for use as polyester Flame retardant for PBT, PET, nylon, PC, polyurethane, furan resin and other materials.

The preparation technology principle of methylphenyl bis(phosphacyclomethoxy)silane is shown in the following formula:

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

①The methylphenylbis(phosphacyclomethoxy)silane compound of the present invention contains two kinds of flame retardant elements, silicon and phosphorus. Under high temperature, the phosphorus element is converted into phosphoric acid or polyphosphoric acid, which can catalyze the formation of charcoal, and the formed polyphosphoric acid The film has the function of heat and oxygen insulation; silicon and carbon form a dense silicon carbon layer, which can effectively prevent the occurrence of molten dripping. Silicon and phosphorus synergistically flame-retardant from different mechanisms can exert high flame-retardant performance.

2. The phenyl contained in the molecular structure of the methylphenyl bis(phosphacyclomethoxy)silane compound of the present invention has the multidirectionality of the electronic structure, which can increase its compatibility with materials, and its dispersibility is good, and it is not easy to The precipitation has little effect on the mechanical properties of the material, thus promoting the improvement of the flame retardant effect.

3. The molecular structure of the methylphenyl bis(phosphacyclomethoxy) silane compound of the present invention contains a C-P bond, a C-Si bond and two six-membered ring structures. These structural characteristics make the physical and chemical properties of the compound stable, and the decomposition temperature High, can adapt to high temperature processing of engineering plastics.

4. The preparation of the methylphenyl bis(phosphacyclomethoxy) silane compound of the present invention is to convert the inorganic phosphorus compound into an organic phosphine compound through a bimolecular rearrangement reaction, so that its thermal stability and flame retardancy have been greatly improved. Big improvement.

⑤ The preparation method of the methylphenylbis(phosphacyclomethoxy)silane compound of the present invention does not have any shrinkage of small molecules, has a high atom utilization rate, and is easy to industrialized transformation and production.

Description of drawings

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

Fig. 1 is the infrared spectrogram of methylphenylbis(phosphacyclomethoxy) silane; Fig. 1 shows: 3175cm ^-1 (stretch vibration of CH bond on the benzene ring); 2998cm ^-1 and 2946cm ^-1 (CH bond 1478cm ^-1 (bending vibration of CH bond); 1250cm ^-1 (stretching vibration of P=O bond); 1000cm ^-1 (stretching vibration of Si-OC bond); 926cm ^-1 (stretching vibration of Si-OC bond Bending vibration); 874cm ^-1 (stretching vibration of POC bond); 740cm ^-1 (stretching vibration of Si-C bond).

Fig. 2 is the NMR spectrogram of methylphenylbis(phosphacyclomethoxy) silane; Fig. 2 shows: deuterated chloroform is solvent, and δ0.78-0.87 is the methyl hydrogen that links to silicon on Si _- CH peak; δ0.87-1.00 is the peak of methyl hydrogen linked to carbon on C- _CH2CH3 ; _δ1.20-1.34 is the peak of methylene hydrogen linked to carbon on C- _{CH2CH3 ;} δ1.56 -1.73 is the methyl hydrogen peak connected with phosphorus oxygen on O=P-CH ₃ ; δ4.21-4.32 is the methylene hydrogen peak connected with oxygen on Si-OCH ₂ C; δ4.48-4.62 is (CH ₂ O) ₂ -P=O(-CH ₃ ) The hydrogen peak of methylene oxide connected to oxygen on the phosphine ring; δ7.24-7.47 is the hydrogen peak on the benzene ring.

detailed description

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

Example 1 In a 200ml four-neck flask equipped with a stirrer, a thermometer, and a high-efficiency reflux condenser, replace the air in the bottle with nitrogen, and add 37.28g (0.23mol) of cage-like phosphate ester and 90ml of diethylene glycol dimethyl ether , 18.23g (0.10mol) methylphenyldimethoxysilane and 0.85g dimethyl sulfate, heat up to 160 ° C, keep the temperature for 14 hours, remove diethylene glycol dimethyl ether (recycled) by distillation under reduced pressure, and then Add 80ml of distilled water, stir to disperse the solid in water, suction filter and dry to obtain white solid methylphenylbis(phosphacyclomethoxy)silane, the product yield is 87.4%, melting point: 160±2°C, decompose Temperature: 328±5°C.

Example 2 In a 150ml four-neck flask equipped with a stirrer, a thermometer, and a high-efficiency reflux condenser, replace the air in the bottle with nitrogen, and add 38.90g (0.24mol) of caged phosphate, 18.23g (0.10mol) of methyl Phenyldimethoxysilane and 0.55g dimethyl sulfate, heat up to 130°C, keep warm for 18h, cool to 60°C, add 60ml of distilled water, stir to disperse the solid in the water, filter and dry to obtain a white solid Methylphenylbis(phosphacyclomethoxy)silane, product yield 88.7%, melting point: 160±2°C, decomposition temperature: 328±5°C.

Example 3 In a 200ml four-neck flask equipped with a stirrer, a thermometer, and a high-efficiency reflux condenser, replace the air in the bottle with nitrogen, and add 34.04g (0.21mol) of caged phosphate ester, 60mlDMF, and 18.23g (0.10mol) Methylphenyldimethoxysilane and 0.65g methyl p-toluenesulfonate, heat up to 140°C, keep warm for 16 hours, distill off DMF under reduced pressure (for recycling), then add 100ml of distilled water, stir to disperse the solid in water , suction filtration, and drying to obtain white solid methylphenylbis(phosphacyclomethoxy)silane with a product yield of 84.0%, melting point: 160±2°C, and decomposition temperature: 328±5°C.

Example 4 In a 200ml four-neck flask equipped with a stirrer, a thermometer, and a high-efficiency reflux condenser, replace the air in the bottle with nitrogen, and add 35.66g (0.22mol) of caged phosphate, 30ml of anisole solution, and 18.23g (0.10mol) methylphenyldimethoxysilane and 0.75g ethyl p-toluenesulfonate, heat up to 120°C, keep warm for 19h, remove anisole (recycled) by distillation under reduced pressure, then add 70ml of distilled water, Stir to disperse the solid in water, filter with suction and dry to obtain white solid methylphenylbis(phosphacyclomethoxy)silane, the product yield is 85.2%, melting point: 160±2°C, decomposition temperature: 328±5 ℃.

Example 5 In a 200ml four-neck flask equipped with a stirrer, a thermometer, and a high-efficiency reflux condenser, replace the air in the bottle with nitrogen, and add 32.42g (0.20mol) of caged phosphate, 18.23g (0.10mol) of methyl Phenyldimethoxysilane and 1.10g of ethyl p-toluenesulfonate, heat up to 180°C, keep warm for 13h, cool to 60°C, add 70ml of distilled water, stir to disperse the solid in water, filter with suction and dry to obtain White solid methylphenylbis(phosphacyclomethoxy)silane, product yield 82.6%, melting point: 160±2°C, decomposition temperature: 328±5°C.

Example 6 In a 200ml four-neck flask equipped with a stirrer, a thermometer, and a high-efficiency reflux condenser, replace the air in the bottle with nitrogen, and add 40.52g (0.25mol) of caged phosphate ester and 90ml of diethylene glycol dimethyl ether , 18.23g (0.10mol) methylphenyldimethoxysilane and 0.80g methyl p-toluenesulfonate, heated up to 150 ° C, kept the temperature for 15 hours, diethylene glycol dimethyl ether was removed by vacuum distillation (recycled use) , then add 80ml of distilled water, stir to disperse the solid in water, filter with suction and dry to obtain white solid methylphenylbis(phosphacyclomethoxy)silane, product yield 90.5%, melting point: 160±2°C , Decomposition temperature: 328±5℃.

Table 1 The main process parameters of the preparation example

The inventors of the present case also applied the methylphenylbis(phosphacyclomethoxy)silane prepared above to polyester PBT. Reference: GB/T2406-2008 "Test Method for Combustion Performance of Plastics - Oxygen Index Method" to measure the limiting oxygen index of the sample. Take the product phospho-silicon synergistic flame retardant methylphenylbis(phosphacyclomethoxy)silane and polyester PBT in different weight percentages and mix them uniformly, then extrude them with an extruder at 230°C to make a diameter of 3mm The spline, and its flame retardant performance was tested, the test results are shown in Table 2:

Table 2 Flame retardant performance data of methylphenylbis(phosphacyclomethoxy)silane used in PBT

As can be seen from Table 2, when the addition amount of the flame retardant methylphenylbis(phosphacyclomethoxy)silane of the present invention reaches 20%, the limiting oxygen index of the flame retardant PBT system reaches 30%, which has good flame retardancy Combustion effect, and the defect that the material is easy to melt and drip when heated or burned is improved. Therefore, the flame retardant of the present invention has good flame retardant performance and charring anti-dripping performance, and the application prospect is very broad.

Claims (3)

1. a preparation method of flame retardant methylphenyl bis(phosphacyclomethoxy) silane, is characterized in that, the method is: Under nitrogen protection, control the molar ratio of methylphenyldimethoxysilane to 4-ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane to be 1:2- 1:2.5, then add organic solvent and catalyst dimethyl sulfate, methyl p-toluenesulfonate or ethyl p-toluenesulfonate, the amount of catalyst used is 3%-6% of the mass of methylphenyldimethoxysilane , heat up to 120-160°C, keep warm for 14-19h, distill off the organic solvent under reduced pressure, add distilled water with the theoretical mass of the product in grams 1-2 times the volume in milliliters, stir to disperse the solid in water, filter with suction, and dry. Obtain product methylphenyl bis(phosphacyclomethoxy) silane, the structure of this compound is shown in the following formula: 2. the preparation method of methylphenyl bis(phosphacyclomethoxy) silane as claimed in claim 1, is characterized in that: described organic solvent is diglyme, anisole or dimethyl Dimethoxyformamide (DMF), the amount of which is 1-5 times that the volume of organic solvent in milliliters is 1-5 times the mass of methylphenyldimethoxysilane in grams. 3. a preparation method of flame retardant methylphenyl bis(phosphacyclomethoxy) silane, is characterized in that, the method is: Under nitrogen protection, control the molar ratio of methylphenyldimethoxysilane to 4-ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane to be 1:2- 1: 2.5, then add catalyst dimethyl sulfate, methyl p-toluenesulfonate or ethyl p-toluenesulfonate, the consumption of its catalyst is 3%-6% of the quality of methylphenyldimethoxysilane, and the temperature is raised to 130-180°C, heat preservation reaction for 13-18h, add distilled water with 1-2 times the theoretical mass of the product in milliliters, stir to disperse the solid in the water, filter with suction, and dry to obtain the product methylphenylbis(phosphora Cyclomethoxy) silane, the structure of this compound is shown in the following formula: