CN103554161B - Fire retardant two [three (2,3-compound) silicon acyloxy] ethane compounds and preparation method thereof - Google Patents
Fire retardant two [three (2,3-compound) silicon acyloxy] ethane compounds and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 40
- 239000010703 silicon Substances 0.000 title claims abstract description 40
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 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
- 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 11
- 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
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 21
- 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
- 238000004821 distillation Methods 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound 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
- 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 2
- 125000000532 dioxanyl group Chemical group 0.000 claims description 2
- 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 16
- 239000000463 material Substances 0.000 abstract description 6
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 6
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 229920006305 unsaturated polyester Polymers 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000694 effects Effects 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
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000003340 retarding agent Substances 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
- 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 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
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Abstract
The present invention relates to a kind of fire retardant two [three (2,3-compound) 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 (2,3-compound) silicon acyloxy] ethane compounds and preparation method thereof, this compound silicon and chlorine dual element are worked in coordination with good flame retardant properties, is suitable as the fire retardant of the materials such as polyvinyl chloride, urethane, epoxy resin and unsaturated polyester.
Background technology
The market requirement of global fire retardant presented a rapidly rising trend always in recent years, especially more urgent to demand that is novel, efficient and environment friendly flame retardant.The current situation of current fire retardant is; along with the fire-retardant legislation of global increasingly stringent; fire safety standard; the cry of appearance and the environment protection in succession of industry instruction is more and more higher; due to can toxic gas be produced when halogenated flame retardant burns, be restricted in a lot, but due to the comprehensive cost performance of halogenated flame retardant excellent; also be difficult to find suitable substitute in a lot, researching and developing efficient halogenated flame retardant has become one of important research direction.Wherein multielement cooperative flame retardant is the effective way realizing highly effective flame-retardant.
Silicon-containing compound is the up-and-coming youngster in flame retardant area, enjoys favor with the flame retardant resistance of excellence, good processibility and satisfied mechanical property.Material usually and one or more synergists be used as fire retardant and more can play good fire retardation.Important topic one of that fire retardant study to obtain efficient flame-retarding agent by silicon and halogen element design in same molecule.
Fire retardant two [three (2 of the present invention, 3-compound) silicon acyloxy] ethane, its molecular structure belongs to symmetrical two silicate structure, containing silicon and chlorine two kinds of ignition-proof elements, cooperative flame retardant effect can be produced, promoting the generation of layer of charcoal, overcome melting drippage, is a kind of fire retardant efficiently; Raw materials make use of the silicon tetrachloride as by-product of photovoltaic industry, for the pollution problem solving silicon tetrachloride provides an effective way; Fire retardant applied range of the present invention, comprehensive cost performance is high, preparation technology's environmental friendliness, meets the developing direction of efficient flame-retarding agent.
Summary of the invention
An object of the present invention is that a kind of fire retardant two [three (2,3-compound) silicon acyloxy] ethane compounds prepared by proposition silicon tetrachloride, and its fire-retardant plasticity is good, can overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme:
Fire retardant two [three (2,3-compound) silicon acyloxy] ethane compounds, it is characterized in that, the structure of this compound is shown below:
Another object of the present invention is to the preparation method proposing fire retardant two [three (2,3-compound) 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:
Fall the air in reaction vessel 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 and equimolar 2, the 3-dichlorohydrines of silicon tetrachloride, drip process control temperature of reaction not higher than 35 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 55 DEG C with rate of addition, after dripping off, be warming up to 65-80 DEG C, reaction 7-10h; After HCl gas discharges, then system is cooled to less than 50 DEG C, drips 2, the 3-dichlorohydrines relative to silicon tetrachloride 2-3 times mole, control temperature of reaction not higher than 60 DEG C with rate of addition, after dripping off, system temperature is risen to 70-90 DEG C, 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, detecting solution PH=5-6 is reaction end.Purified process, obtains fire retardant two [three (2,3-compound) silicon acyloxy] ethane.
Organic solvent as above is dioxane, ethylene dichloride, tetracol phenixin, glycol dimethyl ether or acetonitrile, 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 2,3-dichlorohydrine (reclaim and use) and a small amount of low boilers, then cool to 60 DEG C, then add the petroleum ether of product Theoretical Mass (g) 2-3 times volume (ml), 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 first allow silicon tetrachloride with wait moles 2,3-dichlorohydrine reacts, after generating silicic acid monoesters, then 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.
Two [three (2,3-compound) silicon acyloxy] disclosed by the invention ethane is yellow transparent liquid, and its productive rate is 87.8% ~ 96.6%, its flash-point (open cup): 200 ± 5 DEG C, refractive index: n
d 25=1.4068, density (25 DEG C): 1.3483g/cm
3.It is suitable as the use of the fire retardant of the materials such as polyvinyl chloride, polyvinyl alcohol, epoxy resin, unsaturated polyester and urethane.
Preparation technology's principle of fire retardant two [three (2,3-compound) silicon acyloxy] ethane is shown below:
Compared with prior art, beneficial effect of the present invention is:
1. fire retardant two [three (2 of the present invention, 3-compound) silicon acyloxy] ethane compounds contains silicon and chlorine two ignition-proof element, its cooperative flame retardant usefulness is high, and 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 (2 of the present invention, 3-compound) silicon acyloxy] ethane compounds 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 with the silicon tetrachloride as by-product of polysilicon industry for raw material prepares silicon and chlorine synergistic fire retardant two [three (2,3-compound) silicon acyloxy] ethane compounds, for the difficult problem solving silicon tetrachloride comprehensive utilization provides an effective way.
4. preparation method of the present invention first allows silicon tetrachloride and 2, the reaction of 3-dichlorohydrine 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 2,3-excessive dichlorohydrines 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.
Accompanying drawing explanation
In order to the stuctures and properties spy further illustrating product provides following accompanying drawing.
1, the infrared spectrogram of two [three (2,3-compound) silicon acyloxy] ethane, refers to Figure of description Fig. 1;
Fig. 1 shows, 2958cm
-1(stretching vibration with the C-H of chloro); 2885cm
-1(stretching vibration of C-H); 1461cm
-1(flexural vibration of C-H); 1430cm
-1(flexural vibration with the C-H of chloro); 1109cm
-1and 786cm
-1(stretching vibration of Si-O-C and flexural vibration); 1043cm
-1and 970cm
-1(the stretching vibration doublet of C-O); 719cm
-1(stretching vibration of C-C1).
2, the nuclear magnetic spectrum figure of two [three (2,3-compound) silicon acyloxy] ethane, refers to Figure of description Fig. 2;
Fig. 2 shows, deuterochloroform makes solvent, and δ 4.05-4.13 is-Si (OCH
2cHClCH
2cl)
3in the hydrogen peak of methylene radical that is connected with oxygen; δ 3.90-3.97 is-SiOCH
2cH
2the hydrogen peak of OSi-methylene; δ 3.74-3.81 is-Si (OCH
2cHClCH
2cl)
3the hydrogen peak of middle chlorine methylene radical; δ 3.55-3.62 is-Si (OCH
2cHClCH
2cl)
3the hydrogen peak of middle chloromethyl; The proton peak that δ 7.26 exchanges for solvent carbon deuterium chloride.
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 tetracol phenixin and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, with cooling bath cooling, make temperature of reaction system be reduced to less than 25 DEG C, drip 12.9g (9.47ml, 0.1mol) 2,3-dichlorohydrine, drips process control temperature of reaction not higher than 35 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 55 DEG C with rate of addition, after dripping off, be warming up to 65 DEG C, reaction 10h; After HCl gas discharges, then system is cooled to less than 50 DEG C, drips 25.929g (19.04ml, 0.201mol) 2,3-dichlorohydrines, control temperature of reaction not higher than 60 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 1g trimeric cyanamide, insulated and stirred 1h, detecting solution PH=5-6 is reaction end.Be cooled to 30 DEG C, filter, filtrate is underpressure distillation removing tetracol phenixin and 2,3-excessive dichlorohydrines (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add 90ml petroleum ether 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, obtains product two [three (2,3-compound) silicon acyloxy] ethane.Its productive rate is 87.8%, flash-point (open cup): 200 ± 5 DEG C, refractive index: n
d 25=1.4068, density (25 DEG C): 1.3483g/cm
3.
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 acetonitrile and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, with cooling bath cooling, make temperature of reaction system be reduced to less than 25 DEG C, drip 12.9g (9.47ml, 0.1mol) 2,3-dichlorohydrine, drips process control temperature of reaction not higher than 35 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, control temperature of reaction not higher than 55 DEG C with rate of addition, after dripping off, be warming up to 70 DEG C, reaction 9h, after HC1 gas discharges, then system is cooled to less than 50 DEG C, drips 27.09g (19.90ml, 0.21mol) 2,3-dichlorohydrine, controls temperature of reaction not higher than 60 DEG C, after dripping off with rate of addition, system temperature is risen to 75 DEG C, insulation reaction 9h; After HCl gas discharges, then add 1.2g trimeric cyanamide, insulated and stirred 1h, detecting solution PH=5-6 is reaction end.Be cooled to 30 DEG C, filter, filtrate is underpressure distillation removing acetonitrile and 2,3-excessive dichlorohydrines (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add 90ml petroleum ether 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, obtains product two [three (2,3-compound) silicon acyloxy] ethane.Its productive rate is 89.5%, flash-point (open cup): 200 ± 5 DEG C, refractive index: n
d 25=1.4068, density (25 DEG C): 1.3483g/cm
3.
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 glycol dimethyl ether and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, with cooling bath cooling, make temperature of reaction system be reduced to less than 25 DEG C, drip 12.9g (9.47ml, 0.1mol) 2,3-dichlorohydrine, drips process control temperature of reaction not higher than 35 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, control temperature of reaction not higher than 55 DEG C with rate of addition, after dripping off, be warming up to 80 DEG C, reaction 7h, after HCl gas discharges, then system is cooled to less than 50 DEG C, drips 28.38g (20.84ml, 0.22mol) 2,3-dichlorohydrine, controls temperature of reaction not higher than 60 DEG C, after dripping off with rate of addition, system temperature is risen to 85 DEG C, insulation reaction 8h; After HCl gas discharges, then add 0.6g trimeric cyanamide, insulated and stirred 1.4h, detecting solution PH=5-6 is reaction end.Be cooled to 30 DEG C, filter, filtrate is underpressure distillation removing glycol dimethyl ether and 2,3-excessive dichlorohydrines (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add 90ml petroleum ether 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, obtains product two [three (2,3-compound) silicon acyloxy] ethane.Its productive rate is 94.4%, flash-point (open cup): 200 ± 5 DEG C, refractive index: n
d 25=1.4068, density (25 DEG C): 1.3483g/cm
3.
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 dioxane and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, with cooling bath cooling, make temperature of reaction system be reduced to less than 25 DEG C, drip 12.9g (9.47ml, 0.1mol) 2,3-dichlorohydrine, drips process control temperature of reaction not higher than 35 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 55 DEG C with rate of addition, after dripping off, be warming up to 80 DEG C, reaction 7h; After HCl gas discharges, then system is cooled to less than 50 DEG C, drips 29.67g (21.79ml, 0.23mol) 2,3-dichlorohydrine, control temperature of reaction not higher than 60 DEG C with rate of addition, after dripping off, system temperature is risen to 90 DEG C, insulation reaction 6h; After HCl gas discharges, then add 1.6g trimeric cyanamide, insulated and stirred 1h, detecting solution PH=5-6 is reaction end.Be cooled to 30 DEG C, filter, filtrate is underpressure distillation removing dioxane and 2,3-excessive dichlorohydrines (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add 90ml petroleum ether 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, obtains product two [three (2,3-compound) silicon acyloxy] ethane.Its productive rate is 96.6%, flash-point (open cup): 200 ± 5 DEG C, refractive index: n
d 25=1.4068, density (25 DEG C): 1.3483g/cm
3.
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 ethylene dichloride and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, with cooling bath cooling, make temperature of reaction system be reduced to less than 25 DEG C, drip 12.9g (9.47ml, 0.1mol) 2,3-dichlorohydrine, drips process control temperature of reaction not higher than 35 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 55 DEG C with rate of addition, after dripping off, be warming up to 75 DEG C, reaction 8h; After HCl gas discharges, then system is cooled to less than 50 DEG C, drips 30.96g (22.74ml, 0.24mol) 2,3-dichlorohydrine, control temperature of reaction not higher than 60 DEG C with rate of addition, after dripping off, system temperature is risen to 83 DEG C, insulation reaction 7h; After HCl gas discharges, then add 1.5g trimeric cyanamide, insulated and stirred 1h, detecting solution PH=5-6 is reaction end.Be cooled to 30 DEG C, filter, filtrate is underpressure distillation removing ethylene dichloride and 2,3-excessive dichlorohydrines (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add 90ml petroleum ether 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, obtains product two [three (2,3-compound) silicon acyloxy] ethane.Its productive rate is 91.3%, flash-point (open cup): 200 ± 5 DEG C, refractive index: n
d 25=1.4068, density (25 DEG C): 1.3483g/cm
3.
Table 1 two [three (2,3-compound) silicon acyloxy] ethane preparation example main technologic parameters
Two [three (2,3-compound) silicon acyloxy] ethane of above-mentioned preparation is also applied in polyvinyl chloride by inventor.The limiting oxygen index(LOI) of reference: GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " test sample product.Get fire retardant two [three (2,3-compound) silicon acyloxy] ethane, plasticizer phthalic acid dioctyl ester (DOP), synergistic flame retardant antimonous oxide (Sb
2o
3) and after polyvinyl chloride (PVC) mixes in varing proportions, extrude with forcing machine, make the batten that diameter is 3mm, and its flame retardant properties is tested, list part test result as shown in table 2:
The flame retardant properties data of table 2 two [three (2,3-compound) silicon acyloxy] ethane
Experiment shows, two [three (2,3-compound) 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.
Claims (6)
1. fire retardant two [three (2, a 3-compound) silicon acyloxy] ethane compounds, it is characterized in that, the structure of this compound is shown below:
2. the preparation method of two [three (2,3-compound) silicon acyloxy] ethane as claimed in claim 1, 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, temperature of reaction system is made to be reduced to less than 25 DEG C, drip and silicon tetrachloride equimolar 2,3-dichlorohydrine, drips process control temperature of reaction not higher than 35 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 55 DEG C with rate of addition, after dripping off, be warming up to 65-80 DEG C, reaction 7-10h; After HCl gas discharges, then system is cooled to less than 50 DEG C, drips 2, the 3-dichlorohydrines relative to silicon tetrachloride 2-3 times mole, control temperature of reaction not higher than 60 DEG C with rate of addition, after dripping off, system temperature is risen to 70-90 DEG C, insulation reaction 6-9h; 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, obtains fire retardant two [three (2,3-compound) silicon acyloxy] ethane.
3. fire retardant two [three (2 according to claim 2,3-compound) silicon acyloxy] preparation method of ethane, it is characterized in that: described organic solvent is dioxane, ethylene dichloride, tetracol phenixin, acetonitrile or glycol dimethyl ether, its organic solvent volume milliliter number is 3-4 times of silicon tetrachloride quality grams.
4. the preparation method of fire retardant two [three (2,3-compound) silicon acyloxy] ethane according to claim 2, is characterized in that: described acid binding agent is trimeric cyanamide.
5. fire retardant two [three (2 according to claim 2,3-compound) silicon acyloxy] preparation method of ethane, 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 2,3-dichlorohydrine 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.
6. the preparation method of fire retardant two [three (2,3-compound) silicon acyloxy] ethane according to claim 5, 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.
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