CN103554157A - Flame retardant ethylenedioxy bromoethyl bisilicate compound and preparation method thereof - Google Patents
Flame retardant ethylenedioxy bromoethyl bisilicate compound and preparation method thereof Download PDFInfo
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- CN103554157A CN103554157A CN201310557186.6A CN201310557186A CN103554157A CN 103554157 A CN103554157 A CN 103554157A CN 201310557186 A CN201310557186 A CN 201310557186A CN 103554157 A CN103554157 A CN 103554157A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 39
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- 239000010703 silicon Substances 0.000 claims abstract description 29
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 26
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 26
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 21
- 238000004821 distillation Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000009413 insulation Methods 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 8
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000004886 process control Methods 0.000 claims description 7
- 238000013517 stratification Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- VUBFDPHDHBTRIR-UHFFFAOYSA-N [Br].CCO Chemical compound [Br].CCO VUBFDPHDHBTRIR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 8
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- 239000011347 resin Substances 0.000 abstract 1
- 230000000979 retarding effect Effects 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 241000790917 Dioxys <bee> Species 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
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- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
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- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a flame retardant ethylenedioxy bromoethyl bisilicate compound and a preparation method thereof. The structure of the compound is represented by a formula shown in a drawing. The preparation method comprises the steps of reacting silicon tetrachloride with bromoethanol of a mole which is equal to that of silicon tetrachloride in an organic solvent at the temperature below 20 DEG C, then, dropwise adding glycol of a mole which is 0.5 times that of silicon tetrachloride, heating to the temperature of 50-65 DEG C after completing dripping, and reacting for 6-9 hours; then, dropwise adding bromoethanol of a mole which is 2-3 times that of silicon tetrachloride, and carrying out heat-preservation reaction for 6-9 hours at the temperature of 60-75 DEG C; then, adding an acid binding agent, and carrying out heat preservation for 1 hour while stirring; purifying, thereby obtaining the flame retardant ethylenedioxy bromoethyl bisilicate. The compound disclosed by the invention has high flame retarding efficacy due to the synergism of silicon and bromine and is suitable for serving as a flame retardant for materials, such as polyvinyl chloride, polyurethane, epoxy resin, unsaturated resin and the like, and the preparation method is simple and is low in cost, so that the industrial production is easy to realize.
Description
Technical field
The present invention relates to two silicic acid bromine ethyl ester compounds of a kind of fire retardant second dioxy support and preparation method thereof, be specifically related to a kind of fire retardant two [three (bromine oxethyl) silicon acyloxy] ethane compounds and preparation method thereof, this compound can be used as the fire retardant of the materials such as polyvinyl chloride, unsaturated polyester, urethane and epoxy resin.
Background technology
The application in daily life of organic polymer synthetic materials is more and more extensive, but synthesized polymer material is inflammable mostly, often cause fire, people's the security of the lives and property is caused to serious threat, therefore promoted the development of fire retardant material and flame-retarded technology.Along with the raising of people's living standard and the continuous enhancing of environmental consciousness, in recent years halogenated flame retardant has been proposed again to stricter requirement, towards the future development of efficient, low cigarette and low toxicity.Because silicon ignition-proof element has into charcoal effect, siliceous and research and development halogen dual element synergistic fire retardant are more subject to people's attention.Organosilicon halogen synergistic fire retardant has the advantages such as usefulness is high, good processability, can effectively prevent material melted by heating drippage and the secondary combustion of generation.Thereby the research of organosilicon halogen synergistic fire retardant has importance very much.
The two silicic acid bromine ethyl ester raw materials of fire retardant second dioxy support of the present invention have utilized the silicon tetrachloride as by-product of polysilicon, for solving the pollution problem of silicon tetrachloride, have opened up an effective way; It contains silicon and two kinds of ignition-proof elements of bromine, has good cooperative flame retardant synergism, can form fine and close silicon charcoal layer when element silicon makes material combustion, can effectively solve a difficult problem for material melted by heating drippage.The comprehensive cost performance of this fire retardant is high, has a wide range of applications DEVELOPMENT PROSPECT.
Summary of the invention
One of object of the present invention is to propose to prepare a kind of fire retardant two [three (bromine oxethyl) silicon acyloxy] ethane compounds with silicon tetrachloride.Its physical and chemical performance is stable, and good heat resistance is good with macromolecular material consistency, and has plasticising and become the anti-drip effect of charcoal, can overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
Fire retardant two [three (bromine oxethyl) silicon acyloxy] ethane compounds, is characterized in that, this compound structure is shown below:
The preparation method who another object of the present invention is to propose a kind of fire retardant two [three (bromine oxethyl) silicon acyloxy] ethane, its raw material is cheap and easy to get, and technique is simple, and facility investment is few, is easy to large-scale production, and the method is:
With nitrogen replacement, fall the air in reaction vessel, add organic solvent and silicon tetrachloride, under agitation, cooling with cooling bath, temperature of reaction system is reduced to below 20 ℃, drip with respect to the equimolar bromoethanol of silicon tetrachloride, drip process control temperature of reaction not higher than 30 ℃, after dripping off, be warming up to 40 ℃, insulation reaction 2h; After HCl gas discharges, then splash into the ethylene glycol with respect to 0.5 times mole of silicon tetrachloride, with rate of addition, control temperature of reaction not higher than 45 ℃, after dripping off, be warming up to 50-65 ℃, reaction 6-9h; After HCl gas discharges, then system is cooled to below 40 ℃, drips with respect to silicon tetrachloride 2-3 times of mole bromine ethanol, with rate of addition, control temperature of reaction not higher than 55 ℃, after dripping off, temperature is risen to 60-75 ℃, insulation reaction 6-9h; After HCl gas discharges, then add the acid binding agent of product Theoretical Mass (g) 2%-5%, insulated and stirred 1h, detection solution PH=5-6 is reaction end.Purified processing, obtains fire retardant two [three (bromine oxethyl) silicon acyloxy] ethane.
Organic solvent as above is acetonitrile, dioxane, ethylene dichloride, tetracol phenixin or glycol dimethyl ether, and the amount of its organic solvent volume (ml) is 3-4 times of silicon tetrachloride quality (g).
Acid binding agent as above is trimeric cyanamide.
Purified being treated to as above is cooled to 30 ℃, filter, filtrate decompression distillation is except desolventizing and excessive bromoethanol (reclaim and use) and a small amount of low boilers, then cool to 60 ℃, the petroleum ether that adds again 2-3 times of volume of product Theoretical Mass (g) (ml), stirs 0.5h, is transferred to stratification in separating funnel, separate lower floor's feed liquid, a small amount of sherwood oil is removed in underpressure distillation.
Sherwood oil as above is that the boiling range of sherwood oil is at 60-90 ℃ or 90-120 ℃.
In contriver's research, find that ethylene glycol and silicon tetrachloride are difficult to fused reaction, be jelly shape and be difficult for diffusion, and the volatile quantity that improves temperature of reaction silicon tetrachloride can increase again, therefore selected first allow silicon tetrachloride with etc. mole bromine ethanol synthesis, generate after silicic acid monoesters, with glycol reaction, overcome ethylene glycol and silicon tetrachloride and be difficult for a fused difficult problem again, also overcome the volatile problem of silicon tetrachloride high temperature.
Fire retardant two disclosed by the invention [three (bromine oxethyl) silicon acyloxy] ethane is yellow transparent liquid, and its productive rate is 88.4%～95.5%.Its flash-point (open cup): 198 ± 5 ℃, refractive index: n
d 25=1.4152, density (25 ℃): 1.847g/cm
3; It is suitable as the use of the fire retardant of the materials such as polyvinyl chloride, unsaturated polyester, urethane and epoxy resin.
Preparation technology's principle of fire retardant two [three (bromine oxethyl) silicon acyloxy] ethane is shown below:
Compared with prior art, beneficial effect of the present invention is:
1. fire retardant second dioxy of the present invention supports two dual ignition-proof elements of the siliceous bromine of silicic acid bromine ethyl ester compound, and its cooperative flame retardant usefulness is high, and element silicon has into charcoal effect, can effectively prevent material melted by heating drippage and the secondary combustion of generation.
2. the two silicic acid bromine ethyl ester compounds of fire retardant second dioxy support of the present invention are dibasic acid esters structures, and molecular weight is large, volatility is low, plasticity is good, symmetry is good, and its physical and chemical performance is stable, good with macromolecular material consistency, can be adapted to the high temperature process of engineering plastics.
3. the preparation of the two silicic acid bromine ethyl esters of fire retardant second dioxy support of the present invention be take silicon tetrachloride as raw material, for solving a difficult problem for silicon tetrachloride comprehensive utilization, provides an effective way.
4. preparation method of the present invention first allows silicon tetrachloride react with bromoethanol and generates silicic acid monoesters, and then and glycol reaction, overcome the problem of ethylene glycol indissoluble in silicon tetrachloride, also the orientation response that is conducive to ethylene glycol and silicon tetrachloride, has also overcome and under silicon tetrachloride high temperature, has reacted a volatile difficult problem.
5. the solvent in technique of the present invention and excessive bromoethanol 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 and DEVELOPMENT PROSPECT.
Accompanying drawing explanation
In order to further illustrate structure and the performance spy of product, provide following accompanying drawing.
1, the infrared spectrogram of two [three (bromine oxethyl) silicon acyloxy] ethane, refers to Figure of description Fig. 1;
Fig. 1 shows, 2954cm
-1(with the stretching vibration of the C-H of bromo); 2878cm
-1(stretching vibration of C-H); 1108cm
-1and 795cm
-1(stretching vibration of Si-O-C and flexural vibration); 1456cm
-1(flexural vibration of C-H); 1426cm
-1(with the flexural vibration of the C-H of bromo); 1041cm
-1and 972cm
-1(the stretching vibration doublet of C-O); 627cm
-1(stretching vibration of C-Br).
2, the nuclear magnetic spectrum figure of two [three (bromine oxethyl) silicon acyloxy] ethane, refers to Figure of description Fig. 2;
Fig. 2 shows, δ 4.00-4.09 is-Si (OCH
2cH
2br)
3in hydrogen peak on the methylene radical that is connected with oxygen; δ 3.89-3.95 is-SiOCH
2cH
2hydrogen peak on methylene radical in OSi-; δ 3.58-3.64 is-Si (OCH
2cH
2br)
3hydrogen peak on middle brooethyl; δ 7.26 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 and efficient backflow prolong, and in the prolong 250ml four-hole boiling flask that drying tube is housed suitable for reading, with the air in nitrogen replacement bottle falling, add 60ml ethylene dichloride and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, cooling with cooling bath, temperature of reaction system is reduced to below 20 ℃, drips 12.5g (7.09ml, 0.1mol) bromoethanol, drip process control temperature of reaction not higher than 30 ℃, after dripping off, be warming up to 40 ℃, insulation reaction 2h; After HCl gas discharges, 3.1g (2.78ml, 0.05mol) ethylene glycol is splashed in four-hole boiling flask, with rate of addition, control temperature of reaction not higher than 45 ℃, after dripping off, be warming up to 50 ℃, reaction 9h; After HCl gas discharges, then system is cooled to below 40 ℃, drips 25.125g (14.25ml, 0.201mol) bromoethanol, with rate of addition, control temperature of reaction not higher than 55 ℃, after dripping off, system temperature is risen to 60 ℃, insulation reaction 9h; After HCl gas discharges, then add 1g trimeric cyanamide, insulated and stirred 1h, detection solution PH=5-6 is reaction end.Be cooled to 30 ℃, filter, filtrate again underpressure distillation is removed ethylene dichloride and excessive bromoethanol (reclaim and use) and a small amount of low boilers, then cool to 60 ℃, add again 85ml petroleum ether, stir 0.5h, be transferred to stratification in separating funnel, separate lower floor's feed liquid, underpressure distillation is removed a small amount of sherwood oil and is obtained product two [three (bromine oxethyl) silicon acyloxy] ethane.Its productive rate is 88.4%, flash-point (open cup): 198 ± 5 ℃, and refractive index: n
d 25=1.4152, density (25 ℃): 1.847g/cm
3.
Embodiment 2 is being equipped with agitator, thermometer and efficient backflow prolong, and in the prolong 250ml four-hole boiling flask that drying tube is housed suitable for reading, with the air in nitrogen replacement bottle falling, add 60ml dioxane and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, cooling with cooling bath, temperature of reaction system is reduced to below 20 ℃, drips 12.5g (7.09ml, 0.1mo1) bromoethanol, drip process control temperature of reaction not higher than 30 ℃, after dripping off, be warming up to 40 ℃, insulation reaction 2h; After HCl gas discharges, 3.1g (2.78ml, 0.05mol) ethylene glycol is splashed in four-hole boiling flask, with rate of addition, control temperature of reaction not higher than 45 ℃, after dripping off, be warming up to 65 ℃, reaction 6h; After HC l gas discharges, then system is cooled to below 40 ℃, drips 26.25g (14.89ml, 0.21mol) bromoethanol, with rate of addition, control temperature of reaction not higher than 55 ℃, after dripping off, system temperature is risen to 70 ℃, insulation reaction 8h; After HCl gas discharges, then add 1.2g trimeric cyanamide, insulated and stirred 1h, detection solution PH=5-6 is reaction end.Be cooled to 30 ℃, filter, filtrate again underpressure distillation is removed dioxane and excessive bromoethanol (reclaim and use) and a small amount of low boilers, then cool to 60 ℃, then add 85ml petroleum ether, stir 0.5h, be transferred to stratification in separating funnel, separate lower floor's feed liquid, a small amount of sherwood oil is removed in underpressure distillation, obtains product two [three (bromine oxethyl) silicon acyloxy] ethane.Its productive rate is 95.5%, flash-point (open cup): 198 ± 5 ℃, and refractive index: n
d 25=1.4152, density (25 ℃): 1.847g/cm
3.
Embodiment 3 is being equipped with agitator, thermometer and efficient backflow prolong, and in the prolong 250ml four-hole boiling flask that drying tube is housed suitable for reading, with the air in nitrogen replacement bottle falling, add 60ml acetonitrile and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, cooling with cooling bath, temperature of reaction system is reduced to below 20 ℃, drips 12.5g (7.09ml, 0.1mol) bromoethanol, drip process control temperature of reaction not higher than 30 ℃, after dripping off, be warming up to 40 ℃, insulation reaction 2h; After HCl gas discharges, 3.1g (2.78ml, 0.05mol) ethylene glycol is splashed in four-hole boiling flask, with rate of addition, control temperature of reaction not higher than 45 ℃, after dripping off, be warming up to 55 ℃, reaction 8h; After HCl gas discharges, then system is cooled to below 40 ℃, drips 27.5g (15.60ml, 0.22mol) bromoethanol, with rate of addition, control temperature of reaction not higher than 55 ℃, after dripping off, system temperature is risen to 65 ℃, insulation reaction 8h; After HCl gas discharges, then add 1.5g trimeric cyanamide, insulated and stirred 1h, detection solution PH=5-6 is reaction end.Be cooled to 30 ℃, filter, filtrate again underpressure distillation is removed acetonitrile and excessive bromoethanol (reclaim and use) and a small amount of low boilers, then cool to 60 ℃, then add 85ml petroleum ether, stir 0.5h, be transferred to stratification in separating funnel, separate lower floor's feed liquid, a small amount of sherwood oil is removed in underpressure distillation, obtains product two [three (bromine oxethyl) silicon acyloxy] ethane.Its productive rate is 94.6%, flash-point (open cup): 198 ± 5 ℃, and refractive index: n
d 25=1.4152, density (25 ℃): 1.847g/cm
3.
Embodiment 4 is being equipped with agitator, thermometer and efficient backflow prolong, and in the prolong 250ml four-hole boiling flask that drying tube is housed suitable for reading, with the air in nitrogen replacement bottle falling, add 60ml tetracol phenixin and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, cooling with cooling bath, temperature of reaction system is reduced to below 20 ℃, drips 12.5g (7.09ml, 0.1mol) bromoethanol, drip process control temperature of reaction not higher than 30 ℃, after dripping off, be warming up to 40 ℃, insulation reaction 2h; After HCl gas discharges, 3.1g (2.78ml, 0.05mol) ethylene glycol is splashed in four-hole boiling flask, with rate of addition, control temperature of reaction not higher than 45 ℃, after dripping off, be warming up to 55 ℃, reaction 8h; After HCl gas discharges, then system is cooled to below 40 ℃, drips 28.75g (16.31ml, 0.23mol) bromoethanol, with rate of addition, control temperature of reaction not higher than 55 ℃, after dripping off, system temperature is risen to 65 ℃, insulation reaction 7h; After HCl gas discharges, then add 1.7g trimeric cyanamide, insulated and stirred 1h, detection solution PH=5-6 is reaction end.Be cooled to 30 ℃, filter, filtrate again underpressure distillation is removed tetracol phenixin and excessive bromoethanol (reclaim and use) and a small amount of low boilers, then cool to 60 ℃, then add 85ml petroleum ether, stir 0.5h, be transferred to stratification in separating funnel, separate lower floor's feed liquid, a small amount of sherwood oil is removed in underpressure distillation, obtains product two [three (bromine oxethyl) silicon acyloxy] ethane.Its productive rate is 89.3%, flash-point (open cup): 198 ± 5 ℃, and refractive index: n
d 25=1.4152, density (25 ℃): 1.847g/cm
3.
Embodiment 5 is being equipped with agitator, thermometer and efficient backflow prolong, and in the prolong 250ml four-hole boiling flask that drying tube is housed suitable for reading, with the air in nitrogen replacement bottle falling, add 60ml glycol dimethyl ether and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, cooling with cooling bath, temperature of reaction system is reduced to below 20 ℃, drips 12.5g (7.09ml, 0.1mol) bromoethanol, drip process control temperature of reaction not higher than 30 ℃, after dripping off, be warming up to 40 ℃, insulation reaction 2h; After HCl gas discharges, 3.1g (2.78ml, 0.05mol) ethylene glycol is splashed in four-hole boiling flask, with rate of addition, control temperature of reaction not higher than 45 ℃, after dripping off, be warming up to 60 ℃, reaction 7h; After HCl gas discharges, then system is cooled to below 40 ℃, drips 30.00g (17.02ml, 0.24mol) bromoethanol, with rate of addition, control temperature of reaction not higher than 55 ℃, after dripping off, system temperature is risen to 75 ℃, insulation reaction 6h; After HCl gas discharges, then add 1g trimeric cyanamide, insulated and stirred 1h, detection solution PH=5-6 is reaction end.Be cooled to 30 ℃, filter, filtrate again underpressure distillation is removed glycol dimethyl ether and excessive bromoethanol (reclaim and use) and a small amount of low boilers, then cool to 60 ℃, then add 85ml petroleum ether, stir 0.5h, be transferred to stratification in separating funnel, separate lower floor's feed liquid, a small amount of sherwood oil is removed in underpressure distillation, obtains product two [three (bromine oxethyl) silicon acyloxy] ethane.Its productive rate is 92.2%, flash-point (open cup): 198 ± 5 ℃, and refractive index: n
d 25=1.4152, density (25 ℃): 1.847g/cm
3.
The preparation example main technologic parameters of the two silicic acid bromine ethyl esters of table 1 fire retardant second dioxy support
This case contriver is also applied to the two silicic acid bromine ethyl esters of second dioxy support of above-mentioned preparation in 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 the two silicic acid bromine ethyl esters of fire retardant second dioxy support, dioctyl phthalate (DOP) (DOP), synergistic flame retardant antimonous oxide (Sb
2o
3) and polyvinyl chloride (PVC) mix in varing proportions and with forcing machine, extrude afterwards, and make long 15cm, the batten that diameter is 3mm and to it fire-retardant and physicals test, it is as shown in the table for test-results:
The flame retardant properties data of the two silicic acid bromine ethyl esters of table 2 fire retardant second dioxy support
Experiment shows, the two silicic acid bromine ethyl esters of fire retardant second dioxy support and polyvinyl chloride have good consistency, with Sb
2o
3there is good fire-retardant synergistic, there is good flame retardant properties, become the anti-dropping performance of charcoal and plasticising performance.
Claims (8)
1. fire retardant two [three (bromine oxethyl) silicon acyloxy] ethane compounds, is characterized in that, the structure of this compound is shown below:
2. the preparation method of fire retardant two according to claim 1 [three (bromine oxethyl) silicon acyloxy] ethane, is characterized in that, the method is:
With nitrogen replacement, fall the air in reaction vessel, add organic solvent and silicon tetrachloride, under agitation, cooling with cooling bath, temperature of reaction system is reduced to below 20 ℃, drip with respect to the equimolar bromoethanol of silicon tetrachloride, drip process control temperature of reaction not higher than 30 ℃, after dripping off, be warming up to 40 ℃, insulation reaction 2h; After HCl gas discharges, then splash into the ethylene glycol with respect to 0.5 times mole of silicon tetrachloride, with rate of addition, control temperature of reaction not higher than 45 ℃, after dripping off, be warming up to 50-65 ℃, reaction 6-9h; After HCl gas discharges, then system is cooled to below 40 ℃, drips with respect to silicon tetrachloride 2-3 times of mole bromine ethanol, with rate of addition, control temperature of reaction not higher than 55 ℃, after dripping off, temperature is risen to 60-75 ℃, insulation reaction 6-9h; After HCl gas discharges, then add the acid binding agent of product Theoretical Mass (g) 2%-5%, insulated and stirred 1h, detection solution PH=5-6 is reaction end; Purified processing, obtains fire retardant two [three (bromine oxethyl) silicon acyloxy] ethane.
3. the preparation method of fire retardant two according to claim 2 [three (bromine oxethyl) silicon acyloxy] ethane, it is characterized in that: described organic solvent is acetonitrile, dioxane, ethylene dichloride, tetracol phenixin or glycol dimethyl ether, the amount of its organic solvent volume (ml) is 3-4 times of silicon tetrachloride quality (g).
4. the preparation method of fire retardant two according to claim 2 [three (bromine oxethyl) silicon acyloxy] ethane, is characterized in that: described dropping bromoethanol is divided into twice dropping.
5. the preparation method of fire retardant two according to claim 2 [three (bromine oxethyl) silicon acyloxy] ethane, is characterized in that: described acid binding agent is trimeric cyanamide.
6. the preparation method of fire retardant two according to claim 2 [three (bromine oxethyl) silicon acyloxy] ethane, it is characterized in that: described purified being treated to is cooled to 30 ℃, filter, filtrate decompression distillation is except desolventizing and excessive bromoethanol and a small amount of low boilers, then cool to 60 ℃, the petroleum ether that adds again 2-3 times of volume of product Theoretical Mass (g) (ml), stir 0.5h, be transferred to stratification in separating funnel, separate lower floor's feed liquid, a small amount of sherwood oil is removed in underpressure distillation.
7. the preparation method of fire retardant two according to claim 6 [three (bromine oxethyl) silicon acyloxy] ethane, is characterized in that: the boiling range that described sherwood oil is sherwood oil is at 60-90 ℃ or 90-120 ℃.
8. the preparation method of fire retardant two according to claim 6 [three (bromine oxethyl) silicon acyloxy] ethane, is characterized in that: solvent and the bromoethanol recovery use of described underpressure distillation for collecting.
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| US20090060815A1 (en) * | 2007-08-27 | 2009-03-05 | The Research Foundation Of State University Of New York | Silylated carbon nanotubes and methods of making same |
| CN102140114A (en) * | 2011-02-23 | 2011-08-03 | 苏州科技学院 | Methyl silicic acid tri(2,3-dichloropropyl) ester compound and preparation method thereof |
| CN102775431A (en) * | 2012-07-17 | 2012-11-14 | 苏州科技学院 | Novel coordinate flame retardant compound of three elements silicon, chlorine and bromine, and preparation method thereof |
| CN102898450A (en) * | 2012-07-17 | 2013-01-30 | 苏州科技学院 | Novel chlorine and bromine-containing bisilicate fire retardant compound and preparation method thereof |
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| US20090060815A1 (en) * | 2007-08-27 | 2009-03-05 | The Research Foundation Of State University Of New York | Silylated carbon nanotubes and methods of making same |
| CN102140114A (en) * | 2011-02-23 | 2011-08-03 | 苏州科技学院 | Methyl silicic acid tri(2,3-dichloropropyl) ester compound and preparation method thereof |
| CN102775431A (en) * | 2012-07-17 | 2012-11-14 | 苏州科技学院 | Novel coordinate flame retardant compound of three elements silicon, chlorine and bromine, and preparation method thereof |
| CN102898450A (en) * | 2012-07-17 | 2013-01-30 | 苏州科技学院 | Novel chlorine and bromine-containing bisilicate fire retardant compound and preparation method thereof |
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