CN103665016B - Fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane compounds and preparation method thereof - Google Patents
Fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane compounds and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 41
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 39
- 239000010703 silicon Substances 0.000 title claims abstract description 39
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 38
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 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 32
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 32
- -1 3-bromopropyl alcohol Chemical compound 0.000 claims abstract description 29
- 238000009413 insulation Methods 0.000 claims abstract description 16
- 238000010792 warming Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 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
- 239000000047 product Substances 0.000 claims description 13
- 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
- 238000001816 cooling Methods 0.000 claims description 9
- 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
- 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
- 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
- 239000002904 solvent Substances 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 8
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920006305 unsaturated polyester Polymers 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 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 class 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 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 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
- 238000011161 development Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 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
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-DYCDLGHISA-N Deuterium chloride Chemical compound [2H]Cl VEXZGXHMUGYJMC-DYCDLGHISA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
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Abstract
The present invention relates to a kind of fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane compounds and preparation method thereof, the structure of this compound is shown below:
Description
Technical field
The present invention relates to a kind of fire retardant two [three (3-bromine propoxy-) 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
Along with the standard of living of people improves constantly, fire safety consciousness constantly strengthens, and facilitates the fast development of fire retardant industry.Carcinogens Er Evil is produced silent when European Union announces and finds polybrominated diphenyl ether retardant burning for 1986, the use of halogenated flame retardant is restricted, but because the comprehensive cost performance of halogenated flame retardant is excellent, flame-retarded efficiency is high, little on the machining property impact of material, and be difficult to find desirable surrogate, though the cry of halogen-free environment-friendlyflame flame retardant is high, but non-halogen is still a very long process, thus develops efficient halogenated flame retardant and reduce to reduce the consumption of fire retardant the important research direction that its toxicity has become halogenated flame retardant.Being wherein one of method realizing fire-resistant synergistic by the composite raising flame retardant effect of multiple fire retardant, containing multiple ignition-proof element in design molecular structure, and by intramolecular ignition-proof element synergy, is the more efficiently method realizing retardant synergist.
Embedded in silicon and the excellent ignition-proof element of bromine two kinds in fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane molecule of the present invention simultaneously, the basis that efficient bromine system is fire-retardant turn increases the fire retardation of element silicon, dual element is worked in coordination with and is produced synergistic function from different fire retardant mechanisms, silicon forms fine and close silicon layer of charcoal when burning, thus can show higher flame-retarded efficiency; Raw material silicon tetrachloride wherein used is again the by product of polysilicon industry, for the problem of complex utilization solving silicon tetrachloride as by-product of polysilicon opens up a new way, has good environmental benefit; Two silicate structure in molecule can increase the consistency with macromolecular materials such as polyvinyl chloride; This compound flame-retarded efficiency is high, purposes wide, can produce good economic benefit.
Summary of the invention
An object of the present invention is that a kind of fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane compounds prepared by proposition silicon tetrachloride.Its physical and chemical performance is stablized, 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, present invention employs following technical scheme:
Fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane compounds, it is characterized in that, this compound structure is shown below:
(BrCH
2CH
2CH
2O
SiOCH
2CH
2OSi
OCH
2CH
2CH
2Br)
3。
Another object of the present invention is to the preparation method proposing a kind of fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane, its cheaper starting materials is easy to get, and technique is simple, and facility investment is few, is easy to large-scale production, and 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 25 DEG C, drip relative to the equimolar 3-bromopropyl alcohol of silicon tetrachloride, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, then instill the ethylene glycol relative to silicon tetrachloride 0.5 times mole, control temperature of reaction not higher than 50 DEG C with rate of addition, after dripping off, be warming up to 55-75 DEG C, reaction 6-10h; After HCl gas discharges, then system is cooled to less than 40 DEG C, drips relative to silicon tetrachloride 2-3 doubly mole 3-bromopropyl alcohol, control temperature of reaction not higher than 55 DEG C with rate of addition, after dripping off, system temperature is risen to 65-85 DEG C, insulation reaction 7-10h; After HCl gas discharges, then add the acid binding agent of product Theoretical Mass (g) 2%-5%, stir 1h, detecting solution PH=5-6 is reaction end.Purified process, obtains product fire retardant two [three (3-bromine propoxy-) 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 process as above is for being cooled to 30 DEG C, filter, filtrate decompression distillation is except desolventizing and excessive 3-bromopropyl alcohol (reclaim and use) and a small amount of low boilers, then cool to 60 DEG C, add the petroleum ether of product Theoretical Mass (g) 2-3 times volume (ml) 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.
Sherwood oil as above is that the boiling range of sherwood oil is at 60-90 DEG C or 90-120 DEG C.
Find in contriver's research that ethylene glycol and silicon tetrachloride are difficult to fused reaction, not easily spread in g., jelly-like, and the volatile quantity improving temperature of reaction silicon tetrachloride can increase again, therefore selected and first allowed silicon tetrachloride react with a mole 3-bromopropyl alcohol such as grade, after generating silicic acid monoesters, again with glycol reaction, overcome the difficult problem that ethylene glycol and silicon tetrachloride not easily fuse, also overcome the volatile problem of silicon tetrachloride high temperature.
Fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane disclosed by the invention is light yellow liquid, and its productive rate is 86.6% ~ 95.2%.Its flash-point (open cup): 200 ± 5 DEG C, density: 1.638g/cm
3(25 DEG C), refractive index: n
d 25=1.4027; It is suitable as the use of the fire retardant of the materials such as polyvinyl chloride, unsaturated polyester, urethane and epoxy resin.
Fire retardant two [preparation technology's principle of three (3-bromine propoxy-) silicon acyloxy ethylene ester is shown below:
Compared with prior art, beneficial effect of the present invention is:
1. fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane compounds siliceous bromine two ignition-proof element of the present invention, its cooperative flame retardant usefulness is high, element silicon has into charcoal effect, can effectively prevent material melted by heating from dripping and the secondary combustion of generation.
2. fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane compounds of the present invention is dibasic acid esters structure, molecular weight is large, volatility is low, plasticity is good, symmetry is good, its physical and chemical performance is stablized, good with macromolecular material consistency, the high temperature process of engineering plastics can be adapted to.
3. the present invention is with the silicon tetrachloride as by-product of polysilicon industry for raw material prepares silicon and bromine synergistic fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane, and the difficult problem fully utilized for solving silicon tetrachloride provides an effective way.
4. preparation method of the present invention first allows silicon tetrachloride and 3-bromopropyl alcohol react and generates silicic acid monoesters, and then and glycol reaction, overcome the problem of ethylene glycol indissoluble in silicon tetrachloride, also be conducive to the orientation response of ethylene glycol and silicon tetrachloride, under also overcoming silicon tetrachloride high temperature, react a volatile difficult problem.
5. the solvent in present invention process and excessive 3-bromopropyl alcohol 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, have well application and DEVELOPMENT PROSPECT.
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 high performance reflux condenser, and be equipped with in the 250ml four-hole boiling flask of drying tube prolong is 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, cool with cooling bath, make temperature of reaction system be reduced to less than 25 DEG C, drip 13.9g (8.88ml, 0.1mol) 3-bromopropyl alcohol, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, 3.1g (2.78ml, 0.05mol) ethylene glycol is added dropwise in four-hole boiling flask, controls temperature of reaction not higher than 50 DEG C with rate of addition, after dripping off, be warming up to 55 DEG C, reaction 10h; After HCl gas discharges, then system is cooled to less than 40 DEG C, drips 27.939g (17.84ml, 0.20lmol) 3-bromopropyl alcohol, control temperature of reaction not higher than 55 DEG C with rate of addition, after dripping off, system temperature is risen to 65 DEG C, insulation reaction 10h; After HCl gas discharges, then add 1.2g trimeric cyanamide, stir 1h, detecting solution PH=5-6 is reaction end.Be cooled to 30 DEG C, filter, filtrate is underpressure distillation removing ethylene dichloride and excessive 3-bromopropyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, then add 90ml petroleum ether, 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, obtains product two [three (3-bromine propoxy-) silicon acyloxy] ethane.Its productive rate is 86.6%, flash-point (open cup): 200 ± 5 DEG C, density: 1.638g/cm
3(25 DEG C), refractive index: n
d 25=1.4027.
Embodiment 2 is being equipped with agitator, thermometer and high performance reflux condenser, and be equipped with in the 250ml four-hole boiling flask of drying tube prolong is 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, cool with cooling bath, make temperature of reaction system be reduced to less than 25 DEG C, drip 13.9g (8.88ml, 0.1mo1) 3-bromopropyl alcohol, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, 3.1g (2.78ml, 0.05mol) ethylene glycol is added dropwise in four-hole boiling flask, controls temperature of reaction not higher than 50 DEG C with rate of addition, after dripping off, be warming up to 65 DEG C, reaction 8h; After HCl gas discharges, then system is cooled to less than 40 DEG C, drips 29.19g (18.64ml, 0.21mol) 3-bromopropyl alcohol, control temperature of reaction not higher than 55 DEG C with rate of addition, after dripping off, system temperature is risen to 75 DEG C, insulation reaction 8h; After HCl gas discharges, then add 1.5g trimeric cyanamide, stir 1h, detecting solution PH=5-6 is reaction end.Be cooled to 30 DEG C, filter, filtrate is underpressure distillation removing tetracol phenixin and excessive 3-bromopropyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, then add 90ml petroleum ether, 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, obtains product two [three (3-bromine propoxy-) silicon acyloxy] ethane.Its productive rate is 88.7%, flash-point (open cup): 200 ± 5 DEG C, density: 1.638g/cm
3(25 DEG C), refractive index: n
d 25=1.4027.
Embodiment 3 is being equipped with agitator, thermometer and high performance reflux condenser, and be equipped with in the 250ml four-hole boiling flask of drying tube prolong is suitable for reading, with the air in nitrogen replacement bottle falling, add 60ml dioxane and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, cool with cooling bath, make temperature of reaction system be reduced to less than 25 DEG C, drip 13.9g (8.88ml, 0.1mol) 3-bromopropyl alcohol, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, 3.1g (2.78ml, 0.05mol) ethylene glycol is added dropwise in four-hole boiling flask, controls temperature of reaction not higher than 50 DEG C with rate of addition, after dripping off, be warming up to 70 DEG C, reaction 7h; After HCl gas discharges, then system is cooled to less than 40 DEG C, drips 30.58g (19.53ml, 0.22mol) 3-bromopropyl alcohol, control temperature of reaction not higher than 55 DEG C with rate of addition, after dripping off, system temperature is risen to 80 DEG C, insulation reaction 7h; After HCl gas discharges, then add 1.6g trimeric cyanamide, stir 1h, detecting solution PH=5-6 is reaction end.Be cooled to 30 DEG C, filter, filtrate is underpressure distillation removing dioxane and excessive 3-bromopropyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, then add 90ml petroleum ether, 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, obtains product two [three (3-bromine propoxy-) silicon acyloxy] ethane.Its productive rate is 95.2%, flash-point (open cup): 200 ± 5 DEG C, density: 1.638g/cm
3(25 DEG C), refractive index: n
d 25=1.4027.
Embodiment 4 is being equipped with agitator, thermometer and high performance reflux condenser, and be equipped with in the 250ml four-hole boiling flask of drying tube prolong is 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, cool with cooling bath, make temperature of reaction system be reduced to less than 25 DEG C, drip 13.9g (8.88ml, 0.1mol) 3-bromopropyl alcohol, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, 3.1g (2.78ml, 0.05mol) ethylene glycol is added dropwise in four-hole boiling flask, controls temperature of reaction not higher than 50 DEG C with rate of addition, after dripping off, be warming up to 75 DEG C, reaction 6h; After HCl gas discharges, then system is cooled to less than 40 DEG C, drips 31.97g (20.42ml, 0.23mol) 3-bromopropyl alcohol, control temperature of reaction not higher than 55 DEG C with rate of addition, after dripping off, system temperature is risen to 85 DEG C, insulation reaction 7h; After HCl gas discharges, then add 1.9g trimeric cyanamide, stir 1h, detecting solution PH=5-6 is reaction end.Be cooled to 30 DEG C, filter, filtrate is underpressure distillation removing glycol dimethyl ether and excessive 3-bromopropyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, then add 90ml petroleum ether, 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, obtains product two [three (3-bromine propoxy-) silicon acyloxy] ethane.Its productive rate is 93.5%, flash-point (open cup): 200 ± 5 DEG C, density: 1.638g/cm
3(25 DEG C), refractive index: n
d 25=1.4027.
Embodiment 5 is being equipped with agitator, thermometer and high performance reflux condenser, and be equipped with in the 250ml four-hole boiling flask of drying tube prolong is suitable for reading, with the air in nitrogen replacement bottle falling, add 60ml acetonitrile and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, cool with cooling bath, make temperature of reaction system be reduced to less than 25 DEG C, drip 13.9g (8.88ml, 0.1mol) 3-bromopropyl alcohol, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, 3.1g (2.78ml, 0.05mol) ethylene glycol is added dropwise in four-hole boiling flask, controls temperature of reaction not higher than 50 DEG C with rate of addition, after dripping off, be warming up to 60 DEG C, reaction 9h; After HCl gas discharges, then system is cooled to less than 40 DEG C, drips 33.36g (21.30ml, 0.24mol) 3-bromopropyl alcohol, control temperature of reaction not higher than 55 DEG C with rate of addition, after dripping off, system temperature is risen to 70 DEG C, insulation reaction 9h; After HCl gas discharges, then add 2.1g trimeric cyanamide, stir 1h, detecting solution PH=5-6 is reaction end.Be cooled to 30 DEG C, filter, filtrate is underpressure distillation removing acetonitrile and excessive 3-bromopropyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, then add 90ml petroleum ether, 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, obtains product two [three (3-bromine propoxy-) silicon acyloxy] ethane.Its productive rate is 91.3%, flash-point (open cup): 200 ± 5 DEG C, density (25 DEG C): 1.638g/cm
3, refractive index: n
d 25=1.4027.
The preparation example main technologic parameters of table 1 two [three (3-bromine propoxy-) silicon acyloxy] ethane
Two [three (3-bromine propoxy-) silicon acyloxy] ethane of above-mentioned preparation is also applied in polyvinyl chloride by inventor.Reference: GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " surveys the flame retardant properties of product in polyvinyl chloride.Get fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane, dioctyl phthalate (DOP) (DOP), synergistic flame retardant antimonous oxide (Sb
2o
3) and polyvinyl chloride (PVC) mix rear forcing machine in varing proportions and extrude, and make long 15cm, diameter be 3mm batten and to it fire-retardant and physicals test, test-results is as shown in table 2:
The flame retardant properties data of table 2 two [three (3-bromine propoxy-) silicon acyloxy] ethane
Experiment shows, fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane 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.
The ir data of product two [three (3-bromine propoxy-) silicon acyloxy] ethane of the present invention is as follows: 2961cm
-1(stretching vibration with the C-H of bromo); 2895cm
-1(stretching vibration of C-H); 1460cm
-1(flexural vibration of C-H); 1425cm
-1(flexural vibration with the C-H of bromo); 1108cm
-1and 801cm
-1(stretching vibration of Si-O-C and flexural vibration); 1042cm
-1and 976cm
-1(the stretching vibration doublet of C-O); 631cm
-1(stretching vibration of C-Br).
The nuclear magnetic spectrum data (making solvent with deuterochloroform) of product two [three (3-bromine propoxy-) silicon acyloxy] ethane of the present invention are as follows: δ 3.95-4.02 is-SiOCH
2cH
2the hydrogen peak of the upper methylene radical of OSi-; δ 3.76-3.82 is-Si (OCH
2cH
2cH
2br)
3the hydrogen peak of the upper methylene radical near oxygen; δ 3.23-3.37 is-Si (OCH
2cH
2cH
2br)
3the hydrogen peak of upper brooethyl; δ 1.62-1.74 is-Si (OCH
2cH
2cH
2br)
3the hydrogen peak of the methylene radical of upper centre; The proton peak that δ 7.26 exchanges for solvent carbon deuterium chloride.
Claims (6)
1. a preparation method for fire retardant two [three (3-bromine propoxy-) 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 25 DEG C, drip relative to the equimolar 3-bromopropyl alcohol of silicon tetrachloride, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, then instill the ethylene glycol relative to silicon tetrachloride 0.5 times mole, control temperature of reaction not higher than 50 DEG C with rate of addition, after dripping off, be warming up to 55-75 DEG C, reaction 6-10h; After HCl gas discharges, then system is cooled to less than 40 DEG C, drips relative to silicon tetrachloride 2-3 doubly mole 3-bromopropyl alcohol, control temperature of reaction not higher than 55 DEG C with rate of addition, after dripping off, system temperature is risen to 65-85 DEG C, insulation reaction 7-10h; After HCl gas discharges, then add the acid binding agent of product Theoretical Mass 2%-5%, insulated and stirred 1h, detecting pH value of solution=5-6 is reaction end; Purified process, obtain fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane, the structure of this compound is shown below:
2. the preparation method of fire retardant two [three (3-bromine propoxy-) 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, the volume milliliter number of its organic solvent is 3-4 times of silicon tetrachloride quality grams.
3. the preparation method of fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane according to claim 1, is characterized in that: described acid binding agent is trimeric cyanamide.
4. the preparation method of fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane according to claim 1, it is characterized in that: described purified process is for being cooled to 30 DEG C, filter, filtrate decompression distillation is except desolventizing and excessive 3-bromopropyl alcohol 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.
5. the preparation method of fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane according to claim 4, is characterized in that: described sherwood oil is that the boiling range of sherwood oil is at 60-90 DEG C or 90-120 DEG C.
6. the preparation method of fire retardant two [three (3-bromine propoxy-) silicon acyloxy] ethane according to claim 4, is characterized in that: described underpressure distillation is the solvent or 3-bromopropyl alcohol recovery use collected.
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| WO2009126207A1 (en) * | 2008-04-08 | 2009-10-15 | Waters Technologies Corporation | Composite materials containing nanoparticles and their use in chromatography |
| CN102731828A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Chlorine and bromine-containing bisilicate fire retardant 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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|---|---|---|---|---|
| WO2009126207A1 (en) * | 2008-04-08 | 2009-10-15 | Waters Technologies Corporation | Composite materials containing nanoparticles and their use in chromatography |
| CN102731828A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Chlorine and bromine-containing bisilicate fire retardant 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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