CN103360418A - Flame retardant di(tribromophenyl)di(dichloropropyl)silicate compound and preparation method thereof - Google Patents
Flame retardant di(tribromophenyl)di(dichloropropyl)silicate compound and preparation method thereof Download PDFInfo
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- CN103360418A CN103360418A CN2013102968169A CN201310296816A CN103360418A CN 103360418 A CN103360418 A CN 103360418A CN 2013102968169 A CN2013102968169 A CN 2013102968169A CN 201310296816 A CN201310296816 A CN 201310296816A CN 103360418 A CN103360418 A CN 103360418A
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- epoxy chloropropane
- chloropropyls
- silicic acid
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- tribromo phenyl
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Abstract
The invention relates to a flame retardant di(tribromophenyl)di(dichloropropyl)silicate compound and a preparation method thereof. The structure of the compound is disclosed as the following formula, wherein n is a whole number ranging from 0 to 2. The preparation method comprises the following steps: dropwisely adding equal mole of epoxy chloropropane into a silicon tetrachloride organic solution at 25 DEG C, keeping the temperature at 50 DEG C to react for 1 hour, adding twice mole of tribromophenol, keeping the temperature at 70-100 DEG C to react for 3-6 hours, dropwisely adding a certain mole ratio of epoxy chloropropane, keeping the temperature at 100-120 DEG C to react for 6-8 hours, and distilling under reduced pressure to remove excessive epoxy chloropropane, solvent and small amounts of low-boiling-point substances, thereby obtaining the productdi(tribromophenyl)di(dichloropropyl)silicate. The di(tribromophenyl)di(dichloropropyl)silicate is an excellent flame-retardant plasticizer, has the effects of charring and dripping prevention, and can be used as a flame retardant for polyvinyl chloride, unsaturated polyester, polyurethane, epoxy resin and other materials. The invention has the advantages of cheap and accessible raw materials, low production cost, low equipment investment and simple production technique, and can easily implement large-scale production.
Description
Technical field
The present invention relates to a kind of fire retardant silicic acid two (tribromo phenyl) two (two chloropropyls) ester cpds and preparation method thereof, this compound can be used as the fire retardant of the materials such as polyvinyl chloride, unsaturated polyester, urethane and Resins, epoxy.
Background technology
China's fire retardant industry has welcome fast-developing opportunity along with domestic economy fast development and international trade increase.In recent years China's fire retardant consumption increase is very fast, from now on will be with higher speed sustainable growth, but along with the raising of people to the fire retardant environmental requirement, its development trend is when improving flame retardant properties, more pays attention to environmental protection and ecological safety.No matter China's fire retardant exists larger gap with developed country on the kind or on the consumption at present, and along with promulgation and the mandatory regulation of country to flame retardant regulation, wide prospect will appear in the development and application of China's fire retardant.Wherein the exploitation of multielement synergy efficient flame-retarding agent is one of emphasis direction of development.
Fire retardant silicic acid two of the present invention (tribromo phenyl) two (two chloropropyls) ester molecule is bromine, silicon, chlorine element synergy efficient flame-retarding agent; Wherein used raw material silicon tetrachloride is the by product of polysilicon industry, and the solution polysilicon by-product problem of complex utilization that is disclosed as of the present invention has been opened up a new approach, has good environmental benefit; Fragrant bromine structure in the molecule have electronic structure polytropism and with the isostructural similarity of polyvinyl chloride, thereby can increase the consistency of the macromolecular materials such as this fire retardant and polyvinyl chloride, and wherein the content of bromine is higher, makes the flame-retarded efficiency increase; This compound flame-retarded efficiency is high, purposes is wide, is easy to Industry Promotion, can produce preferably economic benefit.
Summary of the invention
One of purpose of the present invention is to propose a kind of fire retardant silicic acid two (tribromo phenyl) two (two chloropropyls) ester cpds.Its physical and chemical performance is stable, silicon, bromine, chlorine element cooperative flame retardant usefulness height, and good heat resistance, good with the macromolecular material consistency, and have plasticising and become the charcoal effect, can overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of fire retardant silicic acid two (tribromo phenyl) two (two chloropropyls) ester cpds is characterized in that this compound structure is shown below:
N is the integer of 0-2 in its formula.
Another object of the present invention is to propose the preparation method of a kind of fire retardant silicic acid two (tribromo phenyl) two (two chloropropyls) ester, its raw material is cheap and easy to get, and technique is simple, is easy to large-scale production, and technical scheme is as follows:
Under agitation; under 25 ℃ of temperature; under nitrogen protection; in the organic solution of silicon tetrachloride, drip equimolar epoxy chloropropane; after dripping off; 40min is warming up to 50 ℃; insulation reaction 1h; the tribromophenol that adds again the twice mole is warming up to 70-100 ℃, insulation reaction 3-6h; after hydrogen to be chlorinated discharges; be cooled to below 50 ℃, drip the epoxy chloropropane of certain mol proportion again, then 1h is warming up to 100-120 ℃; insulation reaction 6-8h; make the pH value of reaction solution reach 5～6, excessive epoxy chloropropane (reclaim and use) is removed in underpressure distillation; solvent (reclaim and use) and a small amount of low boilers get product silicic acid two (tribromo phenyl) two (two chloropropyls) ester.
Aforesaid certain mol proportion is silicon tetrachloride: epoxy chloropropane (dripping for the first time): tribromophenol: the mol ratio of epoxy chloropropane (dripping for the second time) is 1: 1: 2: 1-1: 1: 2: 2.
Its organic solvent of the organic solution of aforesaid silicon tetrachloride is dioxane, toluene, dimethylbenzene, chlorobenzene, tetrachloroethane or diethylene glycol dimethyl ether.
Find solid tribromophenol bad dispersibility in the organic solution of silicon tetrachloride in contriver's research, reactive behavior is low, improving temperature of reaction can increase again the volatile quantity of silicon tetrachloride, therefore selected and allowed first the epoxy chloropropane of 1mol and the silicon tetrachloride of 1mol react, generate the silicic acid monoesters, again with the reaction of 2mol tribromophenol, improved the dispersiveness of tribromophenol, and can under higher temperature, react, overcome the volatility of silicon tetrachloride.
Silicic acid two of the present invention (tribromo phenyl) two (two chloropropyls) ester is yellow thick liquid, and its productive rate is 97.0%～98.6%, flash-point (open cup): 270 ± 5 ℃, and decomposition temperature: 305 ± 5 ℃, density: 2.221g/cm
3(25 ℃), refractive index: n
D 25=1.6632.It is suitable as the usefulness of the fire retardant of the materials such as polyvinyl chloride, unsaturated polyester, urethane and Resins, epoxy, and this silicic acid two (tribromo phenyl) two (two chloropropyls) ester synthesis technological principle is shown below:
M is the integer of 0-1 in its formula, and n is the integer of 0-2.
Compared with prior art, beneficial effect of the present invention is:
1. silicic acid two of the present invention (tribromo phenyl) two (two chloropropyls) ester cpds, its physical and chemical performance is stable, and decomposition temperature is high, and is good with the macromolecular material consistency, can be adapted to the high temperature process of engineering plastics.
2. contain silicon, bromine, three kinds of ignition-proof elements of chlorine in the compounds of this invention molecule, element cooperative flame retardant usefulness is high, wherein element silicon has into the charcoal effect, thereby the secondary combustion that effectively prevents material melted by heating drippage and produce, and compound also has certain plastification, can reduce the addition of softening agent.
3. the present invention is take the silicon tetrachloride as by-product of polysilicon industry as raw material synthetic silicic acid two (tribromo phenyl) two (two chloropropyls) ester, for a difficult problem that solves the silicon tetrachloride comprehensive utilization provides an effective way, the fire retardant new variety that cost performance is good have been opened up again.
4. preparation method of the present invention allows first silicon tetrachloride and epichlorohydrin reaction generate the silicic acid monoesters, and then and the tribromophenol reaction, it is active low and be difficult for the shortcoming of disperseing to have overcome tribromophenol, has also overcome the volatile characteristics of reaction under the silicon tetrachloride high temperature.
5. solvent and excessive epoxy chloropropane during the present invention synthesizes can directly be recycled, and its raw material is cheap and easy to get, and production cost is low, and facility investment is few, is easy to large-scale production, has good application, DEVELOPMENT PROSPECT.
Description of drawings
For structure and the performance spy who further specifies product provides following accompanying drawing.
1, silicic acid two (tribromo phenyl) two (two chloropropyls) IR of dodecyl stearate figure sees Figure of description Fig. 1 for details;
Fig. 1 shows, 3071cm
-1The place is c h bond stretching vibration peak on the phenyl ring, 2962cm
-1The place is with chloro c h bond stretching vibration peak, 2916cm
-1The place is c h bond stretching vibration peak on the Oxymethylene, 1553cm
-1The place is the stretching vibration peak of phenyl ring skeleton, 1457cm
-1The place is-CH
2-the flexural vibration peak, 1265cm
-1The place is the stretching vibration peak of C-O key, 1113cm
-1The place is the stretching vibration peak of C-Br key, 1081cm
-1The place is the stretching vibration peak of Si-O-C key, 736cm
-1The place is the stretching vibration peak of C-Cl key.
2, the nuclear magnetic spectrum figure of silicic acid two (tribromo phenyl) two (two chloropropyls) ester sees Figure of description Fig. 2 for details;
Fig. 2 shows that δ 3.502-3.666 is-OCH
2CHClCH
2H peak on the methylene radical that Cl is upper with chlorine links to each other; δ 3.681-3.714 is-OCH
2CHClCH
2H peak on the upper chloromethyl of Cl; δ 3.720-3.783 is-OCH (CH
2Cl)
2H peak on the upper chloromethyl; δ 3.998-4.174 is-OCH
2CHClCH
2H peak on the methylene radical that Cl is upper with oxygen links to each other; δ 4.211-4.502 is-OCH (CH
2Cl)
2H peak on upper and the methyne that oxygen links to each other; δ 7.502-7.801 is H peak on the phenyl ring; δ 7.265 is the proton peak of solvent deuterochloroform exchange.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further.
Embodiment 2 is being equipped with agitator, thermometer, dropping funnel and efficient backflow prolong and in the prolong 150ml four-hole boiling flask that drying tube is housed suitable for reading, behind the air in the nitrogen replacement bottle falling, add 70ml toluene and 8.50g (0.05mol) silicon tetrachloride, open and stir, under 25 ℃ of temperature, drip 4.63g (0.05mol) epoxy chloropropane, after dripping off, 40min is warming up to 50 ℃, insulation reaction 1h adds 33.08g (0.1mol) tribromophenol again, is warming up to 80 ℃, insulation reaction 4.5h, after hydrogen to be chlorinated discharges, be cooled to 50 ℃, drip again 9.25g (0.1mol) epoxy chloropropane, after dripping off, 1h is warming up to 105 ℃, and insulation reaction 7.5h makes the pH value of reaction solution reach 5～6, excessive epoxy chloropropane (reclaim and use) and solvent (reclaim and use) and a small amount of low boilers are removed in underpressure distillation, get silicic acid two (tribromo phenyl) two (two chloropropyls) ester.Its productive rate is 98.6%, flash-point (open cup): 270 ± 5 ℃, and decomposition temperature: 305 ± 5 ℃, refractive index: n
D 25=1.6632, density: 2.221g/cm
3(25 ℃).
Embodiment 3 is being equipped with agitator, thermometer, dropping funnel and efficient backflow prolong and in the prolong 150ml four-hole boiling flask that drying tube is housed suitable for reading, behind the air in the nitrogen replacement bottle falling, add 70ml dimethylbenzene and 8.50g (0.05mol) silicon tetrachloride, open and stir, under 25 ℃ of temperature, drip 4.63g (0.05mol) epoxy chloropropane, after dripping off, 40min is warming up to 50 ℃, insulation reaction 1h adds 33.08g (0.1mol) tribromophenol again, is warming up to 85 ℃, insulation reaction 4h, after hydrogen to be chlorinated discharges, be cooled to 50 ℃, drip again 4.63g (0.05mol) epoxy chloropropane, after dripping off, 1h is warming up to 110 ℃, and insulation reaction 7h makes the pH value of reaction solution reach 5～6, excessive epoxy chloropropane (reclaim and use) and solvent (reclaim and use) and a small amount of low boilers are removed in underpressure distillation, get silicic acid two (tribromo phenyl) two (two chloropropyls) ester.Its productive rate is 97.7%, flash-point (open cup): 270 ± 5 ℃, and decomposition temperature: 305 ± 5 ℃, refractive index: n
D 25=1.6632, density: 2.221g/cm
3(25 ℃).
Embodiment 4 is being equipped with agitator, thermometer, dropping funnel and efficient backflow prolong and in the prolong 150ml four-hole boiling flask that drying tube is housed suitable for reading, behind the air in the nitrogen replacement bottle falling, add 70ml chlorobenzene and 8.50g (0.05mol) silicon tetrachloride, open and stir, under 25 ℃ of temperature, drip 4.63g (0.05mol) epoxy chloropropane, after dripping off, 40min is warming up to 50 ℃, insulation reaction 1h adds 33.08g (0.1mol) tribromophenol again, is warming up to 75 ℃, insulation reaction 5h, after hydrogen to be chlorinated discharges, be cooled to 50 ℃, drip again 6.48g (0.07mol) epoxy chloropropane, after dripping off, 1h is warming up to 115 ℃, and insulation reaction 6.5h makes the pH value of reaction solution reach 5～6, excessive epoxy chloropropane (reclaim and use) and solvent (reclaim and use) and a small amount of low boilers are removed in underpressure distillation, get silicic acid two (tribromo phenyl) two (two chloropropyls) ester.Its productive rate is 98.1%, flash-point (open cup): 270 ± 5 ℃, and decomposition temperature: 305 ± 5 ℃, refractive index: n
D 25=1.6632, density: 2.221g/cm
3(25 ℃).
Embodiment 5 is being equipped with agitator, thermometer, dropping funnel and efficient backflow prolong and in the prolong 150ml four-hole boiling flask that drying tube is housed suitable for reading, behind the air in the nitrogen replacement bottle falling, add 70ml tetrachloroethane and 8.50g (0.05mol) silicon tetrachloride, open and stir, under 25 ℃ of temperature, drip 4.63g (0.05mol) epoxy chloropropane, after dripping off, 40min is warming up to 50 ℃, insulation reaction 1h adds 33.08g (0.1mol) tribromophenol again, is warming up to 100 ℃, insulation reaction 3h, after hydrogen to be chlorinated discharges, be cooled to 50 ℃, drip again 8.33g (0.09mol) epoxy chloropropane, after dripping off, 1h is warming up to 120 ℃, and insulation reaction 6h makes the pH value of reaction solution reach 5～6, excessive epoxy chloropropane (reclaim and use) and solvent (reclaim and use) and a small amount of low boilers are removed in underpressure distillation, get silicic acid two (tribromo phenyl) two (two chloropropyls) ester.Its productive rate is 98.3%, flash-point (open cup): 270 ± 5 ℃, and decomposition temperature: 305 ± 5 ℃, density: 2.221g/cm
3(25 ℃), refractive index: n
D 25=1.6632.
Embodiment 6 is being equipped with agitator, thermometer, dropping funnel and efficient backflow prolong and in the prolong 150ml four-hole boiling flask that drying tube is housed suitable for reading, behind the air in the nitrogen replacement bottle falling, add 70ml diethylene glycol dimethyl ether and 8.50g (0.05mol) silicon tetrachloride, open and stir, under 25 ℃ of temperature, drip 4.63g (0.05mol) epoxy chloropropane, after dripping off, 40min is warming up to 50 ℃, insulation reaction 1h adds 33.08g (0.1mol) tribromophenol again, is warming up to 95 ℃, insulation reaction 3.5h, after hydrogen to be chlorinated discharges, be cooled to 50 ℃, drip again 7.40g (0.08mol) epoxy chloropropane, after dripping off, 1h is warming up to 120 ℃, and insulation reaction 6h makes the pH value of reaction solution reach 5～6, excessive epoxy chloropropane (reclaim and use) and solvent (reclaim and use) and a small amount of low boilers are removed in underpressure distillation, get silicic acid two (tribromo phenyl) two (two chloropropyls) ester.Its productive rate is 98.0%, density: 2.221g/cm
3(25 ℃), refractive index: n
D 25=1.6632, flash-point (open cup): 270 ± 5 ℃, decomposition temperature: 305 ± 5 ℃.
The preparation example main technologic parameters of table 1 silicic acid two (tribromo phenyl) two (two chloropropyls) ester
Annotate: EPC is epoxy chloropropane in the table 1.
This case contriver also is applied to above-mentioned synthetic silicic acid two (tribromo phenyl) two (two chloropropyls) ester in the polyvinyl chloride.Reference: GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " surveys the flame retardant properties of product in polyvinyl chloride.Get product silicic acid two (tribromo phenyl) two (two chloropropyls) ester, dibutyl phthalate (DBP), Sb
2O
3And polyvinyl chloride (PVC) mixes in varing proportions and extrudes with forcing machine afterwards, and makes long 15cm, diameter be the batten of 3mm and to it fire-retardant and physicals test, test-results is as shown in table 2:
Table 2 silicic acid two (tribromo phenyl) two (two chloropropyls) ester is fire-retardant and quantitative measurement data to polyvinyl chloride
As shown in Table 2, silicic acid two (tribromo phenyl) two (two chloropropyls) esters and polyvinyl chloride have good consistency, with Sb
2O
3Good fire-retardant synergistic is arranged, have good flame retardant properties, become charcoal anti-drippage performance and plasticising performance.Silicic acid two (tribromo phenyl) two (two chloropropyls) ester is excellent fire retardant.
Claims (6)
1. a fire retardant silicic acid two (tribromo phenyl) two (two chloropropyls) ester cpds is characterized in that the structure of this compound is shown below:
N is the integer of 0-2 in its formula.
2. the preparation method of described silicic acid two (tribromo phenyl) two (two chloropropyls) ester according to claim 1; it is characterized in that; the method is: under agitation; under nitrogen protection; under 25 ℃ of temperature; drip equimolar epoxy chloropropane in the organic solution of silicon tetrachloride, after dripping off, 40min is warming up to 50 ℃; insulation reaction 1h; the tribromophenol that adds again the twice mole is warming up to 70-100 ℃, insulation reaction 3-6h; after hydrogen to be chlorinated discharges; be cooled to below 50 ℃, drip the epoxy chloropropane of certain mol proportion again, then 1h is warming up to 100-120 ℃; insulation reaction 6-8h; make the pH value of reaction solution reach 5～6, excessive epoxy chloropropane and solvent and a small amount of low boilers are removed in underpressure distillation, get product silicic acid two (tribromo phenyl) two (two chloropropyls) ester.
3. the preparation method of described silicic acid two (tribromo phenyl) two (two chloropropyls) ester according to claim 2, it is characterized in that: described certain mol proportion is silicon tetrachloride: epoxy chloropropane (dripping for the first time): tribromophenol: the mol ratio of epoxy chloropropane (dripping for the second time) is 1: 1: 2: 1-1: 1: 2: 2.
4. the preparation method of described silicic acid two (tribromo phenyl) two (two chloropropyls) ester according to claim 2, it is characterized in that: described dropping epoxy chloropropane is twice dropping.
5. the preparation method of described silicic acid two (tribromo phenyl) two (two chloropropyls) ester according to claim 2, it is characterized in that: its organic solvent of the organic solution of described silicon tetrachloride is dioxane, toluene, dimethylbenzene, chlorobenzene, tetrachloroethane or diethylene glycol dimethyl ether.
6. the preparation method of described silicic acid two (tribromo phenyl) two (two chloropropyls) ester according to claim 2, it is characterized in that: excessive epoxy chloropropane is removed in described underpressure distillation and solvent uses for epoxy chloropropane and the solvent recuperation of collecting.
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Citations (3)
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|---|---|---|---|---|
| US4476267A (en) * | 1983-11-02 | 1984-10-09 | Ethyl Corporation | High impact polystyrene containing halophenoxyalkylsilane flame retardant |
| CN102050961A (en) * | 2010-11-01 | 2011-05-11 | 苏州科技学院 | Aryl silicate ester flame retardant plasticizer and preparation method thereof |
| CN103333189A (en) * | 2013-07-16 | 2013-10-02 | 苏州科技学院 | 2-(3-broMopropoxy)-2(2-dicholoropropoxy) silane compound used as fire retardant and preparation method thereof |
-
2013
- 2013-07-16 CN CN201310296816.9A patent/CN103360418B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4476267A (en) * | 1983-11-02 | 1984-10-09 | Ethyl Corporation | High impact polystyrene containing halophenoxyalkylsilane flame retardant |
| CN102050961A (en) * | 2010-11-01 | 2011-05-11 | 苏州科技学院 | Aryl silicate ester flame retardant plasticizer and preparation method thereof |
| CN103333189A (en) * | 2013-07-16 | 2013-10-02 | 苏州科技学院 | 2-(3-broMopropoxy)-2(2-dicholoropropoxy) silane compound used as fire retardant and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张雨山等: "溴系阻燃剂的应用研究及发展趋势", 《化学工业与工程》 * |
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