CN103333191A - Flame retardant tri-(tribromophenoxy) dichloro propoxy silane compound and preparation method thereof - Google Patents

Flame retardant tri-(tribromophenoxy) dichloro propoxy silane compound and preparation method thereof Download PDF

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CN103333191A
CN103333191A CN2013102967096A CN201310296709A CN103333191A CN 103333191 A CN103333191 A CN 103333191A CN 2013102967096 A CN2013102967096 A CN 2013102967096A CN 201310296709 A CN201310296709 A CN 201310296709A CN 103333191 A CN103333191 A CN 103333191A
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tribromophenoxy
silane
dichloro propoxy
preparation
dichloro
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CN103333191B (en
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王彦林
王玉霞
孟凡一
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Zhangjiagang Leyu Science And Technology Innovation Park Investment Development Co Ltd
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Suzhou University of Science and Technology
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Abstract

The invention relates to a flame retardant tri-(tribromophenoxy) dichloro propoxy silane compound and a preparation method thereof. A structural formula of the compound is as follows as shown in the specification, wherein when R1 is H, R2 is CH2Cl, and when R1 is CH2Cl, R2 is H. The preparation method comprises the steps that equimolar dichloropropanol is dropwise added to an organic solution of silicon tetrachloride, and reacts at 35 DEG C for 1h; three times of mole of tribromphenol is added, and reacts at 80-110 DEG C for 7-9h; a solvent is removed by reduced pressure distillation; and tri-(tribromophenoxy) dichloro propoxy silane is obtained. Tri-(tribromophenoxy) dichloro propoxy silane is an excellent antiflaming plasticizer, has charring and dripping prevention functions, has good compatibility with a high polymer material, and can serve as a flame retardant of polyvinyl chloride, unsaturated polyester, polyurethane, epoxy resin and the like, raw materials of tri-(tribromophenoxy) dichloro propoxy silane are low in cost and easy to obtain, the production cost is low, the equipment investment is low, a production technology is simple, and the scale production is facilitated.

Description

A kind of fire retardant three (tribromophenoxy) dichloro propoxy-silane compound and preparation method thereof
Technical field
The present invention relates to a kind of fire retardant three (tribromophenoxy) dichloro propoxy-silane compound and preparation method thereof, this compound can be used as the fire retardant of materials such as polyvinyl chloride, unsaturated polyester, urethane and Resins, epoxy.
Background technology
Along with progress of science and technology, people's standard of living improves constantly, and fire safety consciousness constantly strengthens, and has promoted the fast development of fire retardant industry.From European Union 1986 announce produce when finding the polybrominated diphenyl ether retardant burning carcinogens Er Evil silent after, the use of halogenated flame retardant is restricted, but because the comprehensive price ratio of halogenated flame retardant is good, and be difficult to find desirable surrogate, reduce the important research direction that its toxicity has become halogenated flame retardant thereby research and develop efficient halogenated flame retardant with the consumption that reduces fire retardant.Wherein be one of method that realizes fire-resistant synergistic by the composite raising flame retardant effect of multiple fire retardant, contain multiple ignition-proof element in the design molecular structure, and by intramolecular ignition-proof element synergy, be the more efficiently method that realizes fire retardant synergy.
Silicon, bromine, three kinds of ignition-proof elements of chlorine have been embedded simultaneously in the present invention three (tribromophenoxy) dichloro propoxy-silane flame retardant molecule, element produces synergistic function from different fire retardant mechanisms, silicon can form fine and close silicon carbon layer when burning, on efficient halogen is fire-retardant basis, increase the fire retardation of element silicon again, thereby can show higher flame-retarded efficiency; Wherein used raw material silicon tetrachloride is the by product of polysilicon industry, thereby of the present invention being disclosed as solve the polysilicon byproduct comprehensive and utilize problem to open up a new approach, has good environmental benefit; The polytropism that fragrant bromine structure in the molecule has electronic structure reaches and the isostructural similarity of polyvinyl chloride, thereby can increase the consistency of macromolecular materials such as this fire retardant and polyvinyl chloride; Again for market has increased efficient flame-retarding agent new variety, this compound flame-retarded efficiency height, purposes are wide, can produce favorable economic benefit.
Summary of the invention
One of purpose of the present invention is to propose a kind of fire retardant three (tribromophenoxy) dichloro propoxy-silane compound.Its physical and chemical performance is stable, the flame-retarded efficiency height, and good heat resistance, good with the macromolecular material consistency, and have plasticising and become charcoal to prevent the drippage 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 three (tribromophenoxy) dichloro propoxy-silane compound is characterized in that, this change meeting thing structure is shown below:
R in its formula 1R during=H 2=CH 2Cl; R 1=CH 2R during Cl 2=H.
Another object of the present invention is to propose the preparation method of a kind of fire retardant three (tribromophenoxy) dichloro propoxy-silane, its raw material is cheap and easy to get, and technology is simple, is easy to large-scale production, and technical scheme is as follows:
Under agitation; under nitrogen protection; with the ice-water bath cooling, make temperature of reaction system be reduced to 0 ℃, in the organic solution of silicon tetrachloride, drip equimolar dichlorohydrine; drip process control temp below 8 ℃; after dripping off, 1h is warmed up to 35 ℃, insulation reaction 1h; after hydrogenchloride has been put; the tribromophenol that adds three times of moles again is warming up to 80-110 ℃, insulation reaction 7-9h; after hydrogenchloride has been put; being cooled to below 40 ℃, feeding the acid that oxyethane is removed trace in the reaction solution under the liquid level, is terminal point during check reaction solution pH=5-6; underpressure distillation desolventizing (reclaim and use) and a small amount of low boilers get product three (tribromophenoxy) dichloro propoxy-silane.
Aforesaid dichlorohydrine is 2,3-, two trimethylewne chlorohydrin 3-s or 1,3-, two chloro-2-propyl alcohol.
Its organic solvent of the organic solution of aforesaid silicon tetrachloride is diethylene glycol dimethyl ether, glycol dimethyl ether, dioxane, acetonitrile, tetrachloroethane or chlorobenzene.
Feeding oxyethane under the aforesaid liquid level is that oxyethane is acid binding agent.
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 the volatile quantity of silicon tetrachloride again, therefore selected for use and allowed the dichlorohydrine of 1mol and the silicon tetrachloride of 1mol react earlier, generate the silicic acid monoesters, again with the reaction of 3mol tribromophenol, improved the dispersiveness of tribromophenol, can under higher temperature, react, overcome the volatility of silicon tetrachloride.
Fire retardant three of the present invention (tribromophenoxy) dichloro propoxy-silane is faint yellow solid, and its productive rate is 97.2%～98.5%, and it is suitable as the usefulness of the fire retardant of materials such as polyvinyl chloride, unsaturated polyester, urethane and Resins, epoxy.Three (tribromophenoxy)-2,3-two chloro-1-propoxy-silane: its fusing point: 185 ℃, flash-point (open cup): 228 ± 5 ℃, decomposition temperature: 270 ± 5 ℃; Three (tribromophenoxy)-1,3-two chloro-2-propoxy-silane: its fusing point: 179 ℃, flash-point (open cup): 224 ± 5 ℃, decomposition temperature: 272 ± 5 ℃.
The synthesis technique principle of this three (tribromophenoxy) dichloro propoxy-silane is shown below:
Figure BSA00000925597000031
R wherein 1R during=H 2=CH 2Cl; R 1=CH 2R during Cl 2=H.
Compared with prior art, beneficial effect of the present invention is:
1. the present invention three (tribromophenoxy) dichloro propoxy-silane compound, its physical and chemical performance is stable, and the decomposition temperature height 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 The compounds of this invention molecule, element cooperative flame retardant usefulness height, 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 synthetic three (tribromophenoxy) dichloro propoxy-silane of raw material with the silicon tetrachloride as by-product of polysilicon industry, 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 silicon tetrachloride and the reaction of equimolar dichlorohydrine generate the silicic acid monoesters earlier, and then and tribromophenol reaction, overcome the active low and difficult shortcoming of disperseing of tribromophenol, also overcome the volatile characteristics of reaction under the silicon tetrachloride high temperature.
5. to make acid binding agent with oxyethane simple to operate in the present invention, is easy to purify separate.
6. the solvent 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, three (tribromophenoxy)-2, the nuclear magnetic spectrum figure of 3-two chloro-1-propoxy-silane sees Figure of description Fig. 1 for details;
Fig. 1 shows that δ 3.658-3.697 is-OCH 2CHClCH 2H peak on the methylene radical that Cl is last with chlorine links to each other; δ 3.708-3.715 is-OCH 2CHClCH 2H peak on the last chloromethyl of Cl; δ 4.078-4.246 is-OCH 2CHClCH 2H peak on the methylene radical that Cl is last with oxygen links to each other; δ 7.558-7.862 is H peak on the phenyl ring; δ 7.265 is the proton peak of solvent deuterochloroform exchange.
2, three (tribromophenoxy)-1, the nuclear magnetic spectrum figure of 3-two chloro-2-propoxy-silane, see Figure of description Fig. 2 for details:
Fig. 2 shows that δ 3.718-3.744 is-OCH (CH 2Cl) 2H peak on the last chloromethyl; δ 4.383-4.451 is-OCH (CH 2Cl) 2With the H peak on the methyne that oxygen links to each other; δ 7.558-7.862 is the 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 1 is being equipped with agitator, thermometer, dropping funnel and efficient reflux condensing tube and in the 500ml four-hole boiling flask of the prolong hydrogen chloride absorption device that the series connection drying tube is housed suitable for reading, behind the air in the nitrogen replacement bottle falling, add 180ml diethylene glycol dimethyl ether and 16.99g (0.1mol) silicon tetrachloride, under agitation, cool off with ice-water bath, make temperature of reaction system be reduced to 0 ℃, in the organic solution of silicon tetrachloride, drip 12.90g (0.1mol) 2,3-two trimethylewne chlorohydrin 3-s, drip process control temp below 8 ℃, after dripping off, 1h is warmed up to 35 ℃, insulation reaction 1h, after hydrogenchloride has been put, add 99.24g (0.3mol) tribromophenol again, be warming up to 110 ℃, insulation reaction 7h, after hydrogenchloride has been put, be cooled to below 40 ℃, load onto a soft seal cover that can extremely stretch in that prolong is suitable for reading, feed the acid that oxyethane is removed trace in the reaction solution under the liquid level, be terminal point during check reaction solution pH=5-6, underpressure distillation desolventizing (reclaim and use) and a small amount of low boilers get three (tribromophenoxy)-2,3-two chloro-1-propoxy-silane.Its productive rate is 97.7%, fusing point: 185 ℃, and flash-point (open cup): 228 ± 5 ℃, decomposition temperature: 270 ± 5 ℃.
Embodiment 2 is being equipped with agitator, thermometer, dropping funnel and efficient reflux condensing tube and in the 500ml four-hole boiling flask of the prolong hydrogen chloride absorption device that the series connection drying tube is housed suitable for reading, behind the air in the nitrogen replacement bottle falling, add 180ml glycol dimethyl ether and 16.99g (0.1mol) silicon tetrachloride, under agitation, cool off with ice-water bath, make temperature of reaction system be reduced to 0 ℃, in the organic solution of silicon tetrachloride, drip 12.90g (0.1mol) 2,3-two trimethylewne chlorohydrin 3-s, drip process control temp below 8 ℃, after dripping off, 1h is warmed up to 35 ℃, insulation reaction 1h, after hydrogenchloride has been put, add 99.24g (0.3mol) tribromophenol again, be warming up to 80 ℃, insulation reaction 9h, after hydrogenchloride has been put, be cooled to below 40 ℃, load onto a soft seal cover that can extremely stretch in that prolong is suitable for reading, feed the acid that oxyethane is removed trace in the reaction solution under the liquid level, be terminal point during check reaction solution pH=5-6, underpressure distillation desolventizing (reclaim and use) and a small amount of low boilers get three (tribromophenoxy)-2,3-two chloro-1-propoxy-silane.Its productive rate is 98.2%, fusing point: 185 ℃, and flash-point (open cup): 228 ± 5 ℃, decomposition temperature: 270 ± 5 ℃.
Embodiment 3 is being equipped with agitator, thermometer, dropping funnel and efficient reflux condensing tube and in the 500ml four-hole boiling flask of the prolong hydrogen chloride absorption device that the series connection drying tube is housed suitable for reading, behind the air in the nitrogen replacement bottle falling, add 180ml dioxane and 16.99g (0.1mol) silicon tetrachloride, under agitation, cool off with ice-water bath, make temperature of reaction system be reduced to 0 ℃, in the organic solution of silicon tetrachloride, drip 12.90g (0.1mol) 2,3-two trimethylewne chlorohydrin 3-s, drip process control temp below 8 ℃, after dripping off, 1h is warmed up to 35 ℃, insulation reaction 1h, after hydrogenchloride has been put, add 99.24g (0.3mol) tribromophenol again, be warming up to 90 ℃, insulation reaction 8h, after hydrogenchloride has been put, be cooled to below 40 ℃, load onto a soft seal cover that can extremely stretch in that prolong is suitable for reading, feed the acid that oxyethane is removed trace in the reaction solution under the liquid level, be terminal point during check reaction solution pH=5-6, underpressure distillation desolventizing (reclaim and use) and a small amount of low boilers get three (tribromophenoxy)-2,3-two chloro-1-propoxy-silane.Its productive rate is 98.5%, fusing point: 185 ℃, and flash-point (open cup): 228 ± 5 ℃, decomposition temperature: 270 ± 5 ℃.
Embodiment 4 is being equipped with agitator, thermometer, dropping funnel and efficient reflux condensing tube and in the 500ml four-hole boiling flask of the prolong hydrogen chloride absorption device that the series connection drying tube is housed suitable for reading, behind the air in the nitrogen replacement bottle falling, add 180ml acetonitrile and 16.99g (0.1mol) silicon tetrachloride, under agitation, cool off with ice-water bath, make temperature of reaction system be reduced to 0 ℃, in the organic solution of silicon tetrachloride, drip 12.90g (0.1mol) 1,3-two chloro-2-propyl alcohol, drip process control temp below 8 ℃, after dripping off, 1h is warmed up to 35 ℃, insulation reaction 1h, after hydrogenchloride has been put, add 99.24g (0.3mol) tribromophenol again, be warming up to 80 ℃, insulation reaction 9h, after hydrogenchloride has been put, be cooled to below 40 ℃, load onto a soft seal cover that can extremely stretch in that prolong is suitable for reading, feed the acid that oxyethane is removed trace in the reaction solution under the liquid level, be terminal point during check reaction solution pH=5-6, underpressure distillation desolventizing (reclaim and use) and a small amount of low boilers get three (tribromophenoxy)-1,3-two chloro-2-propoxy-silane.Its productive rate is 97.5%, fusing point: 179 ℃, and flash-point (open cup): 224 ± 5 ℃, decomposition temperature: 272 ± 5 ℃.
Embodiment 5 is being equipped with agitator, thermometer, dropping funnel and efficient reflux condensing tube and in the 500ml four-hole boiling flask of the prolong hydrogen chloride absorption device that the series connection drying tube is housed suitable for reading, behind the air in the nitrogen replacement bottle falling, add 180ml tetrachloroethane and 16.99g (0.1mol) silicon tetrachloride, under agitation, cool off with ice-water bath, make temperature of reaction system be reduced to 0 ℃, in the organic solution of silicon tetrachloride, drip 12.90g (0.1mol) 1,3-two chloro-2-propyl alcohol, drip process control temp below 8 ℃, after dripping off, 1h is warmed up to 35 ℃, insulation reaction 1h, after hydrogenchloride has been put, add 99.24g (0.3mol) tribromophenol again, be warming up to 100 ℃, insulation reaction 7h, after hydrogenchloride has been put, be cooled to below 40 ℃, load onto a soft seal cover that can extremely stretch in that prolong is suitable for reading, feed the acid that oxyethane is removed trace in the reaction solution under the liquid level, be terminal point during check reaction solution pH=5-6, underpressure distillation desolventizing (reclaim and use) and a small amount of low boilers get three (tribromophenoxy)-1,3-two chloro-2-propoxy-silane.Its productive rate is 98.5%, fusing point: 179 ℃, and flash-point (open cup): 224 ± 5 ℃, decomposition temperature: 272 ± 5 ℃.
Embodiment 6 is being equipped with agitator, thermometer, dropping funnel and efficient reflux condensing tube and in the 500ml four-hole boiling flask of the prolong hydrogen chloride absorption device that the series connection drying tube is housed suitable for reading, behind the air in the nitrogen replacement bottle falling, add 180ml chlorobenzene and 16.99g (0.1mol) silicon tetrachloride, under agitation, cool off with ice-water bath, make temperature of reaction system be reduced to 0 ℃, in the organic solution of silicon tetrachloride, drip 12.90g (0.1mol) 1,3-two chloro-2-propyl alcohol, drip process control temp below 8 ℃, after dripping off, 1h is warmed up to 35 ℃, insulation reaction 1h, after hydrogenchloride has been put, add 99.24g (0.3mol) tribromophenol again, be warming up to 90 ℃, insulation reaction 8h, after hydrogenchloride has been put, be cooled to below 40 ℃, load onto a soft seal cover that can extremely stretch in that prolong is suitable for reading, feed the acid that oxyethane is removed trace in the reaction solution under the liquid level, be terminal point during check reaction solution pH=5-6, underpressure distillation desolventizing (reclaim and use) and a small amount of low boilers get three (tribromophenoxy)-1,3-two chloro-2-propoxy-silane.Its productive rate is 97.2%, fusing point: 179 ℃, and flash-point (open cup): 224 ± 5 ℃, decomposition temperature: 272 ± 5 ℃.
The preparation example main technologic parameters of table 1 three (tribromophenoxy) dichloro propoxy-silane
Figure BSA00000925597000071
This case contriver also is applied to above-mentioned synthetic three (tribromophenoxy) dichloro propoxy-silane in the polyvinyl chloride.Reference: GB/T2406-2008 " plastics combustibility test method-oxygen index method " surveys the flame retardant properties of product in polyvinyl chloride.Get product three (tribromophenoxy) dichloro propoxy-silane, dibutyl phthalate (DBP), Sb 2O 3And polyvinyl chloride (PVC) mixes the back in varing proportions and extrudes with forcing machine, 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 three (tribromophenoxy) dichloro propoxy-silane is fire-retardant and physicals test data to PVC
Figure BSA00000925597000081
Annotate: because flame retardant properties is identical between the isomer of three (tribromophenoxy) dichloro propoxy-silane, repeats statement one by one less than the flame retardant properties with each concrete isomer and list.
As shown in Table 2, three (tribromophenoxy) dichloro propoxy-silane and polyvinyl chloride have good intermiscibility, with Sb 2O 3The good flame synergistic is arranged, polyvinyl chloride is had good flame retardancy, becomes charcoal anti-drippage performance and plasticising performance.Three (tribromophenoxy) dichloro propoxy-silane is the excellent fire retardant agent.

Claims (6)

1. a fire retardant three (tribromophenoxy) dichloro propoxy-silane compound is characterized in that the structure of this compound is shown below:
Figure FSA00000925596900011
R in its formula 1R during=H 2=CH 2Cl; R 1=CH 2R during Cl 2=H.
2. according to the preparation method of claim 1 described three (tribromophenoxy) dichloro propoxy-silane; it is characterized in that; this method is: under agitation; under nitrogen protection; with the ice-water bath cooling, make temperature of reaction system be reduced to 0 ℃, in the organic solution of silicon tetrachloride, drip equimolar dichlorohydrine; drip process control temp below 8 ℃; after dripping off, 1h is warmed up to 35 ℃, insulation reaction 1h; after hydrogenchloride has been put; the tribromophenol that adds three times of moles again is warming up to 80-110 ℃, insulation reaction 7-9h; after hydrogenchloride has been put; being cooled to below 40 ℃, feeding the acid that oxyethane is removed trace in the reaction solution under the liquid level, is terminal point during check reaction solution pH=5-6; underpressure distillation desolventizing (reclaim and use) and a small amount of low boilers get product three (tribromophenoxy) dichloro propoxy-silane.
3. according to the preparation method of claim 2 described three (tribromophenoxy) dichloro propoxy-silane, it is characterized in that: described dihalo-propyl alcohol is 2,3-, two trimethylewne chlorohydrin 3-s or 1,3-, two chloro-2-propyl alcohol.
4. according to the preparation method of claim 2 described three (tribromophenoxy) dichloro propoxy-silane, it is characterized in that: its organic solvent of the organic solution of described silicon tetrachloride is diethylene glycol dimethyl ether, glycol dimethyl ether, dioxane, acetonitrile, tetrachloroethane or chlorobenzene.
5. according to the preparation method of claim 2 described three (tribromophenoxy) dichloro propoxy-silane, it is characterized in that: feeding oxyethane under the described liquid level is that oxyethane is acid binding agent.
6. according to the preparation method of claim 2 described three (tribromophenoxy) dichloro propoxy-silane, it is characterized in that: described underpressure distillation desolventizing is used for the solvent recuperation of collecting.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3492328A (en) * 1965-12-07 1970-01-27 Dynamit Nobel Ag Production of halogenated tetraphenoxysilanes
CN102731552A (en) * 2012-07-17 2012-10-17 苏州科技学院 Flame retardant tribromophenoxychloropropoxytri(chloropropyl) silicate compound and preparation method thereof
CN102731553A (en) * 2012-07-17 2012-10-17 苏州科技学院 Tris(dichloropropyl) tribromophenoxy chloropropyl silicate compound and preparation method thereof
CN102731826A (en) * 2012-07-17 2012-10-17 苏州科技学院 Halogenated tetra-aryl silicic acid ester compound serving as flame retardant and preparation method thereof
CN102731825A (en) * 2012-07-17 2012-10-17 苏州科技学院 Chloro- and bromo-containing silicate flame retardant compound and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3492328A (en) * 1965-12-07 1970-01-27 Dynamit Nobel Ag Production of halogenated tetraphenoxysilanes
CN102731552A (en) * 2012-07-17 2012-10-17 苏州科技学院 Flame retardant tribromophenoxychloropropoxytri(chloropropyl) silicate compound and preparation method thereof
CN102731553A (en) * 2012-07-17 2012-10-17 苏州科技学院 Tris(dichloropropyl) tribromophenoxy chloropropyl silicate compound and preparation method thereof
CN102731826A (en) * 2012-07-17 2012-10-17 苏州科技学院 Halogenated tetra-aryl silicic acid ester compound serving as flame retardant and preparation method thereof
CN102731825A (en) * 2012-07-17 2012-10-17 苏州科技学院 Chloro- and bromo-containing silicate flame retardant compound and preparation method thereof

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