CN103539809B - Two silicic acid dichloro propyl ester compound of fire retardant second dioxy support and preparation method thereof - Google Patents

Abstract

The invention relates to a flame retardant ethylenedioxyethylene disilicate dichloropropyl compound and a preparation method thereof. The structure of the compound is shown in the following formula: The preparation method is: below 30°C, dropwise add 2 times mole of epichlorohydrin relative to silicon tetrachloride to the organic solution of silicon tetrachloride, react at 50°C for 2 hours; then drop into the organic solution of silicon tetrachloride 0.5 Doubling moles of ethylene glycol, then react at 65-80°C for 7-10h; then drop below 50°C, then dropwise add 1-1.5 times moles of epichlorohydrin relative to silicon tetrachloride, and react at 70-85°C 5-8h, after purification treatment, the flame retardant ethylenedioxyethylene bisilicate dichloropropyl ester is obtained; the compound of the present invention contains two kinds of flame retardant elements silicon and chlorine, and the synergistic flame retardant effect is high, and is suitable for use as polyvinyl chloride, A flame retardant for materials such as polyurethane, epoxy resin and unsaturated resin; the preparation process is simple, the cost is low, and industrial production is easy to realize.

Description

Flame retardant ethylenedioxyethylene disilicate dichloropropyl ester compound and preparation method thereof

technical field

The invention relates to a flame retardant ethylenedioxyethylene bisilicate dichloropropyl ester compound and a preparation method thereof, in particular to a flame retardant bis[tri(dichloropropoxy)silyloxy]ethane compound According to the preparation method thereof, the compound has high synergistic flame retardant effect of silicon and chlorine dual elements, and is suitable for being used as a flame retardant for materials such as polyvinyl chloride, polyurethane, epoxy resin and unsaturated resin.

Background technique

Due to the rapid development of science, technology and economy, people's safety awareness has been continuously enhanced, which has promoted the rapid development of the flame retardant industry. Since the European Union announced in 1986 that polybrominated diphenyl ether flame retardants produced harmful substances when they burned, the use of halogenated flame retardants has been restricted. However, due to the excellent overall cost performance of halogenated flame retardants, it is still difficult to find ideal alternatives. Therefore, the non-halogenation process will not be too fast, but research and development of high-efficiency halogenated flame retardants to reduce the amount of flame retardants added, thereby reducing the toxicity during combustion, has become an important research direction for flame retardants. The synergistic flame retardant effect produced by the compounding of various flame retardants can improve the flame retardant performance, and the designed molecular structure contains a variety of flame retardant elements, and through the synergistic flame retardant and synergistic effect of various flame retardant elements in the molecule, the flame retardant performance can be improved. It is a more effective way to achieve high-efficiency flame retardants.

The present invention uses silicon tetrachloride, a by-product of the photovoltaic industry, as a raw material to prepare silicon and chlorine two-element synergistic flame retardant ethylenedioxyethylene bisilicate dichloropropyl ester, and both silicon and chlorine in silicon tetrachloride are excellent Flame retardant element, silicon-based flame retardant itself has excellent thermal stability, silicon can form a dense silicon carbon layer during combustion, effective in preventing melt dripping and flame retardant and smoke suppression, and is currently a low-smoke, low-toxicity One of the key points in the development of flame retardant materials. Designing two excellent flame retardant elements in the same molecular structure produces a synergistic flame retardant effect and can exert an ideal flame retardant effect. The compound of the invention has a symmetrical polyester structure and has excellent flame retardancy and plasticizing properties.

Contents of the invention

One of the purposes of the present invention is to propose to prepare a kind of flame retardant bis[three (dichloropropoxy) silyloxy] ethane compound with silicon tetrachloride, its flame retardancy is good, can overcome the existing technology lack of.

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

Flame retardant bis[tri(dichloropropoxy)silyloxy]ethane 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 method for preparing a flame retardant bis[tri(dichloropropoxy)silyloxy]ethane, the raw material of which is cheap and easy to obtain, the process is simple, the investment in equipment is small, and it is easy to scale up production, the method is:

Replace the air in the reaction vessel with nitrogen, add an organic solvent and silicon tetrachloride, cool with a cold water bath under stirring, reduce the temperature of the reaction system to below 30°C, and add dropwise 2 times the molar amount of silicon tetrachloride For epichlorohydrin, the dropwise addition process controls the reaction temperature not to be higher than 40°C. After the drop is completed, the temperature is raised to 50°C, and the temperature is kept for 2 hours; Control the reaction temperature not to be higher than 55°C, raise the temperature to 65-80°C after dropping, and react for 7-10 hours; after the HCl gas is released, cool the system down to below 50°C, and add dropwise the relative silicon tetrachloride 1- 1.5 times the mole of epichlorohydrin, control the reaction temperature not higher than 60°C at the rate of addition, after the drop, raise the temperature of the system to 70-85°C, keep the temperature for 5-8 hours, and test the solution pH=5-6 as the reaction end point . After purification, the flame retardant bis[tri(dichloropropoxy)silyloxy]ethane was obtained.

The above-mentioned organic solvent is acetonitrile, dioxane, ethylene dichloride, carbon tetrachloride or ethylene glycol dimethyl ether, and the amount of its organic solvent volume (ml) is the amount of silicon tetrachloride quality (g) 3-4 times.

After the above-mentioned purification process, it is cooled to 30°C, and then the solvent, excess epichlorohydrin (recycled) and a small amount of low boiling point are removed by distillation under reduced pressure, and then the temperature is lowered to 60°C, and then the theoretical mass of the product (g) is added. Wash with 2-3 times the volume (ml) of petroleum ether, stir for 0.5 h, transfer to a separatory funnel to stand for stratification, separate the lower layer material liquid, and distill under reduced pressure to remove a small amount of petroleum ether.

The petroleum ether mentioned above is petroleum ether with a boiling range of 60-90°C or 90-120°C.

In the research of the inventor, it was found that ethylene glycol and silicon tetrachloride were difficult to dissolve and react, and it was difficult to diffuse in a jelly shape, and the volatilization of silicon tetrachloride would increase when the reaction temperature was increased. Silicon reacts with 2 times the mole of epichlorohydrin to form a silicate diester, and then reacts with ethylene glycol, which overcomes the difficulty of ethylene glycol and silicon tetrachloride being difficult to dissolve, and also overcomes the high-temperature volatility of silicon tetrachloride The problem.

The flame retardant bis[tri(dichloropropoxy)silyloxy]ethane of the present invention is a yellow transparent liquid with a yield of 89.3% to 93.4%, its flash point (open cup): 198±5°C, refraction Ratio: n _D ²⁵ =1.4158, density (25°C): 1.3549 g/cm ³ . It is suitable as a flame retardant for materials such as polyvinyl chloride, polyvinyl alcohol, epoxy resin, unsaturated resin and polyurethane.

The preparation process principle of flame retardant bis[tri(dichloropropoxy)silyloxy]ethane is shown in the following formula:

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

①The flame retardant bis[tri(dichloropropoxy)silyloxy]ethane compound of the present invention contains two flame retardant elements of silicon and chlorine, and its synergistic flame retardant efficiency is high, and the silicon element has a carbon-forming effect, which can effectively prevent The secondary combustion caused by the material being heated, melted and dripped.

2. The flame retardant bis[tri(dichloropropoxy)silyloxy]ethane compound of the present invention is a diester structure with large molecular weight, low volatility, good plasticity and good symmetry, and its physical and chemical properties are stable. It has good compatibility with polymer materials and can adapt to high temperature processing of engineering plastics.

③The present invention uses the by-product silicon tetrachloride of polysilicon industry as raw material to prepare silicon and chlorine synergistic flame retardant bis[tri(dichloropropoxy)silyloxy]ethane, in order to solve the problem of comprehensive utilization of silicon tetrachloride Puzzles provide an effective way.

4. The preparation method of the present invention first allows silicon tetrachloride and epichlorohydrin to react to generate silicate diester, and then reacts with ethylene glycol, which overcomes the insoluble problem of ethylene glycol in silicon tetrachloride, and is also conducive to The directional reaction of ethylene glycol and silicon tetrachloride also overcomes the problem that silicon tetrachloride is easily volatile under high temperature.

5. The solvent and excess epichlorohydrin in the process of the present invention can be directly recycled, and its raw materials are easy to get, the production cost is low, the equipment investment is small, and it is easy to scale production, and has good application and development prospects.

Description of drawings

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

1. For the infrared spectrogram of bis[tri(dichloropropoxy)silyloxy]ethane, see Figure 1 of the accompanying drawing for details;

Figure 1 shows that 2960cm ^-1 (stretching vibration of CH with chlorine group); 2882cm ^-1 (stretching vibration of CH); 1460cm ^-1 (bending vibration of CH ⁾ ; bending vibration); 1111cm ^-1 and 783cm ^-1 (stretching vibration and bending vibration of Si-OC); 1047cm ^-1 and 968cm ^-1 (double peak of stretching vibration of CO); 665cm ^-1 (stretching vibration of C-Cl ).

2. For the NMR spectrum of bis[tri(dichloropropoxy)silyloxy]ethane, see Figure 2 of the accompanying drawing for details;

Figure 2 shows that deuterated chloroform is used as a solvent, and δ4.46-4.50 is the hydrogen peak of the methylene connected to oxygen in -SiOCH _{2 CHClCH 2} Cl _; The hydrogen peak of the methine linked by oxygen; δ4.04-4.10 is the hydrogen peak of the methylene in -SiOCH ₂ CH ₂ OSi-; δ3.96-4.01 is the hydrogen of the chloromethylene in -SiOCH ₂ CHClCH ₂ Cl Peak; δ3.65-3.76 is the hydrogen peak of chloromethyl in -SiOCH ₂ CHClCH ₂ Cl and -SiOCH(CH ₂ Cl) ₂ ; δ7.26 is the proton peak of deuterated chloroform exchange.

detailed description

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

Example 1 In a 250ml four-neck flask equipped with a stirrer, a thermometer and a high-efficiency reflux condenser, and an extremely expandable sealing sleeve is installed on the upper mouth of the condenser, replace the air in the bottle with nitrogen, and add 60ml of dioxane ring and 17g (11.47ml, 0.1mol) of silicon tetrachloride, under stirring, cooled with a cold water bath, the temperature of the reaction system was reduced to below 30°C, and 18.504g (15.68ml, 0.2mol) of epichlorohydrin was added dropwise, During the dropwise addition process, the reaction temperature should not be higher than 40°C. After the dropwise addition, the temperature was raised to 50°C, and the temperature was kept for 2 hours; then, the upper port of the reflux condenser tube was replaced with a drying tube, and 3.1g (2.78ml, 0.05mol) of ethylene di Drop the alcohol into the four-necked flask, control the reaction temperature not higher than 55°C with the dropping speed, raise the temperature to 75°C after the drop, and react for 8 hours; after the HCl gas is released, cool the system down to below 50°C, drop 11.10g (9.41ml, 0.12mol) epichlorohydrin, control the reaction temperature not higher than 60°C at the rate of addition, after the drop, raise the temperature of the system to 80°C, react for 5 hours, and detect that the pH of the reaction solution is 5-6 The end of the reaction: Dioxane, excess epichlorohydrin (recycled) and a small amount of low boiling point are removed by vacuum distillation, then cooled to 60°C, then 90ml of petroleum ether is added for washing, stirred for 0.5h, and transferred to a separatory funnel Stand in the middle and separate the layers, separate the lower layer material liquid, and distill off a small amount of petroleum ether under reduced pressure to obtain the product bis[tris(dichloropropoxy)silyloxy]ethane. Its yield is 93.4%, flash point (open cup): 198±5°C, refractive index: n _D ²⁵ =1.4158, density (25°C): 1.3549 g/cm ³ .

Example 2 In a 250ml four-neck flask equipped with an agitator, a thermometer and a high-efficiency reflux condenser, and an extremely expandable sealing sleeve at the upper mouth of the condenser, replace the air in the bottle with nitrogen, and add 60ml tetrachloride Carbon and 17g (11.47ml, 0.1mol) of silicon tetrachloride, under stirring, cooled with a cold water bath, the temperature of the reaction system was reduced to below 30°C, and 18.504g (15.68ml, 0.2mol) of epichlorohydrin was added dropwise, During the dropwise addition process, the reaction temperature should not be higher than 40°C. After the dropwise addition, the temperature was raised to 50°C, and the temperature was kept for 2 hours; then, the upper port of the reflux condenser tube was replaced with a drying tube, and 3.1g (2.78ml, 0.05mol) of ethylene di Drop the alcohol into the four-necked flask, control the reaction temperature not higher than 55°C with the dropping speed, raise the temperature to 70°C after dropping, and react for 9 hours; after the HCl gas is released, cool the system down to below 50°C, drop 9.34g (7.92ml, 0.101mol) epichlorohydrin, control the reaction temperature not higher than 60°C at the rate of addition, after the drop, raise the temperature of the system to 75°C, react for 8 hours, and detect that the pH of the reaction solution is 5-6 The end of the reaction: carbon tetrachloride, excess epichlorohydrin (recycling) and a small amount of low boiling point are removed by distillation under reduced pressure, then the temperature is lowered to 60°C, then 90ml of petroleum ether is added for washing, stirred for 0.5h, and transferred to a separatory funnel Stand in the middle and separate the layers, separate the lower layer material liquid, and distill off a small amount of petroleum ether under reduced pressure to obtain the product bis[tris(dichloropropoxy)silyloxy]ethane. Its yield is 89.3%, flash point (open cup): 198±5°C, refractive index: n _D ²⁵ =1.4158, density (25°C): 1.3549 g/cm ³ .

Example 3 In a 250ml four-necked flask equipped with an agitator, a thermometer and a high-efficiency reflux condenser, and an extremely expandable seal at the top of the condenser, replace the air in the bottle with nitrogen, and add 60ml of ethylene glycol Dimethyl ether and 17g (11.47ml, 0.1mol) of silicon tetrachloride, under stirring, cooled with a cold water bath, the temperature of the reaction system was reduced to below 30°C, and 18.504g (15.68ml, 0.2mol) of epoxy chloride was added dropwise Propane, the dropwise addition process controls the reaction temperature not to be higher than 40°C. After the drop, the temperature is raised to 50°C, and the heat preservation reaction is carried out for 2 hours; then the upper port of the reflux condenser is replaced with a drying tube, and 3.1g (2.78ml, 0.05mol) Ethylene glycol was dropped into the four-necked flask, and the reaction temperature was controlled by the dropping speed to not be higher than 60°C. After the drop, the temperature was raised to 80°C, and the reaction was carried out for 7 hours; after the HCl gas was released, the temperature of the system was lowered to below 55°C. Add 10.18g (8.62ml, 0.11mol) of epichlorohydrin dropwise, and control the reaction temperature at a rate not higher than 50°C. After the drop, raise the temperature of the system to 85°C, react for 6 hours, and check that the pH of the reaction solution is 5- 6 is the end point of the reaction; ethylene glycol dimethyl ether, excess epichlorohydrin (recycled) and a small amount of low boiling point are removed by distillation under reduced pressure, then the temperature is lowered to 60°C, and 90ml of petroleum ether is added for washing, stirred for 0.5h, and transferred to Put it into a separatory funnel and let it stand for stratification, separate the lower layer material liquid, and distill off a small amount of petroleum ether under reduced pressure to obtain the product bis[tris(dichloropropoxy)silyloxy]ethane. Its yield is 90.7%, flash point (open cup): 198±5°C, refractive index: n _D ²⁵ =1.4158, density (25°C): 1.3549 g/cm ³ .

Example 4 In a 250ml four-neck flask equipped with a stirrer, a thermometer and a high-efficiency reflux condenser, and an extremely expandable sealing sleeve is installed at the upper mouth of the condenser, replace the air in the bottle with nitrogen, and add 60ml of dichloroethylene Alkane and 17g (11.47ml, 0.1mol) of silicon tetrachloride, under stirring, cooled with a cold water bath, the temperature of the reaction system was reduced to below 30°C, and 18.504g (15.68ml, 0.2mol) of epichlorohydrin was added dropwise, During the dropwise addition process, the reaction temperature should not be higher than 40°C. After the dropwise addition, the temperature was raised to 50°C, and the temperature was kept for 2 hours; then, the upper port of the reflux condenser tube was replaced with a drying tube, and 3.1g (2.78ml, 0.05mol) of ethylene di Alcohol was dropped into the four-necked flask, and the reaction temperature was controlled by the dropping speed to not be higher than 55°C. After the drop, the temperature was raised to 65°C, and the reaction was carried out for 10 hours; after the HCl gas was released, the system was cooled down to below 50°C, and added dropwise 12.03g (10.19ml, 0.13mol) epichlorohydrin, control the reaction temperature not higher than 60°C at the rate of addition, after the drop, raise the temperature of the system to 70°C, react for 7 hours, and detect that the pH of the reaction solution is 5-6 Reaction end point; Dichloroethane, excess epichlorohydrin (recycled) and a small amount of low boiling point are removed by vacuum distillation, then cooled to 60°C, then 90ml of petroleum ether is added for washing, stirred for 0.5h, and transferred to a separatory funnel Stand in the middle and separate the layers, separate the lower layer material liquid, and distill off a small amount of petroleum ether under reduced pressure to obtain the product bis[tris(dichloropropoxy)silyloxy]ethane. Its yield is 91.5%, flash point (open cup): 198±5°C, refractive index: n _D ²⁵ =1.4158, density (25°C): 1.3549 g/cm ³ .

Example 5 In a 250ml four-neck flask equipped with an agitator, a thermometer and a high-efficiency reflux condenser, and an extremely expandable seal at the top of the condenser, replace the air in the bottle with nitrogen, and add 60ml of acetonitrile and 17g (11.47ml, 0.1mol) of silicon tetrachloride, under stirring, cooled with a cold water bath to lower the temperature of the reaction system below 30°C, and dropwise added 18.504g (15.68ml, 0.2mol) of epichlorohydrin, and the dropwise addition process Control the reaction temperature not to be higher than 40°C. After dripping, raise the temperature to 50°C and keep it warm for 2 hours; then replace the top of the reflux condenser tube with a drying tube, and drop 3.1g (2.78ml, 0.05mol) of ethylene glycol into the In a four-necked flask, the reaction temperature is controlled at a rate of addition not higher than 55°C. After the drop, the temperature is raised to 75°C and reacted for 8 hours; after the HCl gas is released, the temperature of the system is lowered to below 50°C, and 12.95g ( 10.97ml, 0.14mol) of epichlorohydrin, the reaction temperature is controlled by the rate of addition to not be higher than 60°C, after the drop, the temperature of the system is raised to 80°C for 6 hours, and the pH of the reaction solution is detected to be 5-6 as the end point of the reaction; Remove acetonitrile, excess epichlorohydrin (recycled for use) and a small amount of low-boiling matter by distillation under pressure, then cool down to 60°C, add 90ml of petroleum ether to wash, stir at constant temperature 60°C for 0.5h, transfer to a separatory funnel to stand and separate , Separate the lower layer material liquid, and distill off a small amount of petroleum ether under reduced pressure to obtain the product bis[tri(dichloropropoxy)silyloxy]ethane. Its yield is 92.6%, flash point (open cup): 198±5°C, refractive index: n _D ²⁵ =1.4158, density (25°C): 1.3549 g/cm ³ .

Table 1 The main process parameters of the preparation example of ethylenedioxyethylene disilicate dichloropropyl

The inventor of this case also applied the above-mentioned prepared ethylenedioxyethylene disilicate dichloropropyl to polyvinyl chloride. Reference: GB/T2406-2008 "Test Method for Combustion Performance of Plastics - Oxygen Index Method" to measure the limiting oxygen index of the sample. The flame retardant ethylenedioxyethylene disilicate dichloropropyl ester, the plasticizer dioctyl phthalate (DOP), the synergistic flame retardant antimony trioxide (Sb ₂ O ₃ ) and polyvinyl chloride ( PVC) was mixed evenly in different proportions, extruded with an extruder to make a sample with a diameter of 3mm, and its flame retardancy was tested, and some test results were listed as shown in Table 2:

Table 2 Flame retardant performance data of ethylenedioxyethylene disilicate dichloropropyl

Experiments show that the flame retardant ethylenedioxyethylene disilicate dichloropropyl has good compatibility with polyvinyl _chloride , has good flame retardancy synergy with _Sb2O3 , and has good flame retardancy , Charcoal anti-dripping performance and plasticizing performance.

Claims (5)

1. a preparation method for fire retardant two [three (compound) silicon acyloxy] ethane, it is characterized in that, the method is:

The air in reaction vessel is fallen with nitrogen replacement, add organic solvent and silicon tetrachloride, under agitation, with cooling bath cooling, make temperature of reaction system be reduced to less than 30 DEG C, drip the epoxy chloropropane relative to silicon tetrachloride 2 times moles, drip process control temperature of reaction not higher than 40 DEG C, after dripping off, be warming up to 50 DEG C, insulation reaction 2h; Instill the ethylene glycol relative to silicon tetrachloride 0.5 times mole again, control temperature of reaction not higher than 55 DEG C with rate of addition, after dripping off, be warming up to 65-80 DEG C, reaction 7-10h; After HCl gas discharges, again system is cooled to less than 50 DEG C, drip relative to silicon tetrachloride 1-1.5 times moles of epichlorohydrin, temperature of reaction is controlled not higher than 60 DEG C with rate of addition, after dripping off, system temperature is risen to 70-85 DEG C, insulation reaction 5-8h, detecting pH value of solution=5-6 is reaction end; Purifiedly process to obtain product fire retardant two [three (compound) silicon acyloxy] ethane, the structure of this compound is shown below:

In its formula, m is the integer of 0-3.

2. the preparation method of fire retardant two [three (compound) silicon acyloxy] ethane according to claim 1, it is characterized in that: described organic solvent is acetonitrile, dioxane, ethylene dichloride, tetracol phenixin or glycol dimethyl ether, its organic solvent volume milliliter number is 3-4 times of silicon tetrachloride quality grams.

3. the preparation method of fire retardant two [three (compound) silicon acyloxy] ethane according to claim 1, it is characterized in that: described purified process is that underpressure distillation removes desolventizing and excessive epoxy chloropropane and a small amount of low boilers, then cool to 60 DEG C, add the petroleum ether of product Theoretical Mass grams 2-3 times of volume milliliter number again, stir 0.5h, be transferred to stratification in separating funnel, separate lower floor's feed liquid, underpressure distillation removes a small amount of sherwood oil.

4. the preparation method of fire retardant two [three (compound) silicon acyloxy] ethane according to claim 3, is characterized in that: the boiling range of described sherwood oil is 60-90 DEG C or 90-120 DEG C.

5. the preparation method of fire retardant two [three (compound) silicon acyloxy] ethane according to claim 3, is characterized in that: described underpressure distillation removes desolventizing and excessive epoxy chloropropane is the solvent or epoxy chloropropane recovery use collected.