CN103554160A - Flame retardant bis[tris(1,3-dichloro-2-propoxy)silicon-acyloxy]ethane compound and preparation method thereof - Google Patents
Flame retardant bis[tris(1,3-dichloro-2-propoxy)silicon-acyloxy]ethane compound and preparation method thereof Download PDFInfo
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- CN103554160A CN103554160A CN201310557190.2A CN201310557190A CN103554160A CN 103554160 A CN103554160 A CN 103554160A CN 201310557190 A CN201310557190 A CN 201310557190A CN 103554160 A CN103554160 A CN 103554160A
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- -1 ethane compound Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract 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 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 title abstract description 16
- 239000007983 Tris buffer Substances 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 42
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 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
- 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
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 5
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- 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
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- 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
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- 239000000047 product Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000034 method Methods 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
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- 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
- 238000012545 processing Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 239000000460 chlorine Substances 0.000 abstract description 7
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 6
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 abstract 2
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 abstract 2
- 238000004321 preservation Methods 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
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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 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 230000002195 synergetic effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
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- 239000003610 charcoal Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-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
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
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- 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
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- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a flame retardant bis[tris(1,3-dichloro-2-propoxy)silicon-acyloxy]ethane 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 1,3-dichloro-2-propanol of a mole which is equal to that of silicon tetrachloride in an organic solvent at the temperature below 25 DEG C, then, dropwise adding glycol of a mole which is 0.5 times that of silicon tetrachloride, heating to the temperature of 65-80 DEG C after completing dripping, and reacting for 7-10 hours; then, dropwise adding 1,3-dichloro-2-propanol of a mole which is 2-3 times that of silicon tetrachloride, and carrying out heat-preservation reaction for 6-10 hours at the temperature of 70-90 DEG C; then, adding an acid binding agent, and carrying out heat preservation for 1 hour while stirring; purifying, thereby obtaining the flame retardant bis[tris(1,3-dichloro-2-propoxy)silicon-acyloxy]ethane. The compound disclosed by the invention has high flame retarding efficacy due to the synergism of silicon and chlorine 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 facilitated.
Description
Technical field
The present invention relates to a kind of fire retardant two [three (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane compounds and preparation method thereof, this compound is suitable as the fire retardant of the materials such as polyvinyl chloride, urethane, epoxy resin and unsaturated polyester.
Background technology
Along with improving constantly and the enhancing of fire safety consciousness of the fast development of world economy and people's living standard, fire retardant industry is developed rapidly, and particularly the research of new and effective fire retardant is more had to urgency.From European Union 1986 announce produce while finding polybrominated diphenyl ether retardant burning carcinogens Er Evil silent after, the use of halogenated flame retardant is restricted, but because the comprehensive cost performance of halogenated flame retardant is good, and be difficult to find desirable surrogate, thereby research and develop efficient halogenated flame retardant, to reduce the consumption of fire retardant, reduce its toxicity, become the important research direction of halogenated flame retardant.By the composite raising flame retardant effect of multiple fire retardant, be wherein one of method realizing fire-resistant synergistic, in design molecular structure, contain multiple ignition-proof element, and by intramolecular ignition-proof element synergy, be the more efficiently method that realizes fire retardant synergy.
Fire retardant two [three (1 of the present invention, the chloro-2-propoxy-of 3-bis-) silicon acyloxy] embedded silicon and two kinds of ignition-proof elements of chlorine in ethane molecule simultaneously, two elements are collaborative produces synergistic function from different fire retardant mechanisms, silicon can form fine and close silicon charcoal layer when burning, chlorine and auxiliary flame retardant antimonous oxide can produce fire-resistant synergistic effect at double, and combined effect can show higher flame-retarded efficiency; Wherein raw material silicon tetrachloride used is the by product of polysilicon industry, thereby of the present invention being disclosed as solve polysilicon by-product problem of complex utilization and opened up a new approach, has good environmental benefit; Two many chlorine of silicon ester structures in molecule can increase the consistency of the macromolecular materials such as this fire retardant and polyvinyl chloride; This compound flame-retarded efficiency is high, purposes is wide, can produce good economic benefit.
Summary of the invention
One of object of the present invention is to propose to prepare a kind of silicon and chlorine cooperative flame retardant fire retardant two [three (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane compounds with silicon tetrachloride, and its good flame resistance, can overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
Fire retardant two [three (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane compounds, is characterized in that, the structure of this compound is shown below:
The preparation method who another object of the present invention is to propose fire retardant two [three (the chloro-2-propoxy-of 1,3-bis-) 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 25 ℃, drip and silicon tetrachloride equimolar 1, the chloro-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 35 ℃, after dripping off, be warming up to 45 ℃, 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 55 ℃, after dripping off, be warming up to 65-80 ℃, reaction 7-10h; After HCl gas discharges, then system is cooled to below 50 ℃, drips with respect to silicon tetrachloride 2-3 times mole 1, the chloro-2-propyl alcohol of 3-bis-, controls temperature of reaction not higher than 60 ℃ with rate of addition, after dripping off, system temperature is risen to 70-90 ℃, insulation reaction 6-10h; 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 (the chloro-2-propoxy-of 1,3-bis-) 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 1, the chloro-2-propyl alcohol of 3-bis-(reclaim and use) and a small amount of low boilers, then cool to 60 ℃, then add the petroleum ether of 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.
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 wait mole 1, the reaction of the chloro-2-propyl alcohol of 3-bis-, generates after silicic acid monoesters, then with glycol reaction, overcome ethylene glycol and silicon tetrachloride and be difficult for a fused difficult problem, also overcome the volatile problem of silicon tetrachloride high temperature.
Fire retardant two of the present invention [three (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane is yellow transparent liquid, and productive rate is 88.6%～95.8%, its flash-point (open cup): 202 ± 5 ℃, and refractive index: n
d 25=1.4163, density (25 ℃): 1.3378g/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 (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane is shown below:
Compared with prior art, beneficial effect of the present invention is:
1. fire retardant two of the present invention [three (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane compounds contains silicon and chlorine two elements, 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. fire retardant two [three (1 of the present invention, the chloro-2-propoxy-of 3-bis-) 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 stable, good with macromolecular material consistency, can be adapted to the high temperature process of engineering plastics.
3. the present invention be take the silicon tetrachloride as by-product of polysilicon industry and is prepared silicon and chlorine synergistic fire retardant two [three (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane 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 and 1, the chloro-2-propyl alcohol reaction of 3-bis-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 1, the chloro-2-propyl alcohol of 3-bis-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 (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane, refers to Figure of description Fig. 1;
Fig. 1 shows, 2961cm
-1(with the stretching vibration of the C-H of chloro); 2882cm
-1(stretching vibration of C-H); 1458cm
-1(flexural vibration of C-H); 1428cm
-1(with the flexural vibration of the C-H of chloro); 1091cm
-1and 784cm
-1(stretching vibration of Si-O-C and flexural vibration); 1041cm
-1and 971cm
-1(the stretching vibration doublet of C-O); 723cm
-1(stretching vibration of C-C1).
2, the nuclear magnetic spectrum figure of two [three (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane, refers to Figure of description Fig. 2;
Fig. 2 shows, deuterochloroform is made solvent, and δ 3.47-3.58 is-OCH (CH
2cl)
2the hydrogen peak of upper chloromethyl; δ 3.92-3.97 is-SiOCH
2cH
2the hydrogen peak of methylene radical in OSi-; δ 3.75-3.83 is-OCH (CH
2cl)
2hydrogen peak on the connected methyne of upper oxygen; 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 acetonitrile and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, cooling with cooling bath, temperature of reaction system is reduced to below 25 ℃, drip 12.9g (9.55ml, 0.1mol) 1, the chloro-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 35 ℃, after dripping off, be warming up to 45 ℃, 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 55 ℃, after dripping off, be warming up to 65 ℃, reaction 10h; After HCl gas discharges, then system is cooled to below 50 ℃, drips 25.929g (19.20ml, 0.201mol) 1, the chloro-2-propyl alcohol of 3-bis-, controls temperature of reaction not higher than 60 ℃ with rate of addition, after dripping off, system temperature is risen to 70 ℃, insulation reaction 10h; 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 acetonitrile and excessive 1, the chloro-2-propyl alcohol of 3-bis-(reclaim and use) and a small amount of low boilers, then cool to 60 ℃, add again 90ml 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 (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane.Its productive rate is 88.6%, flash-point (open cup): 202 ± 5 ℃, and refractive index: n
d 25=1.4163, density (25 ℃): 1.3378g/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 tetracol phenixin and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, cooling with cooling bath, temperature of reaction system is reduced to below 25 ℃, drip 12.9g (9.55ml, 0.1mol) 1, the chloro-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 35 ℃, after dripping off, be warming up to 45 ℃, 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 55 ℃, after dripping off, be warming up to 70 ℃, reaction 9h; After HCl gas discharges, then system is cooled to below 50 ℃, drips 27.09g (20.06ml, 0.21mol) 1, the chloro-2-propyl alcohol of 3-bis-, controls temperature of reaction not higher than 60 ℃ with rate of addition, after dripping off, system temperature is risen to 75 ℃, insulation reaction 9h; 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 tetracol phenixin and excessive 1, the chloro-2-propyl alcohol of 3-bis-(reclaim and use) and a small amount of low boilers, then cool to 60 ℃, add again 90ml 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 (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane.Its productive rate is 90.2%, flash-point (open cup): 202 ± 5 ℃, and refractive index: n
d 25=1.4163, density (25 ℃): 1.3378g/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 dioxane and 17g (11.47ml, 0.1mol) silicon tetrachloride, under agitation, cooling with cooling bath, temperature of reaction system is reduced to below 25 ℃, drip 12.9g (9.55ml, 0.1mol) 1, the chloro-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 35 ℃, after dripping off, be warming up to 45 ℃, 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 55 ℃, after dripping off, be warming up to 80 ℃, reaction 7h; After HCl gas discharges, then system is cooled to below 50 ℃, drips 28.38g (21.01ml, 0.22mol) 1, the chloro-2-propyl alcohol of 3-bis-, controls temperature of reaction not higher than 60 ℃ with rate of addition, after dripping off, system temperature is risen to 90 ℃, insulation reaction 6h; 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 dioxane and excessive 1, the chloro-2-propyl alcohol of 3-bis-(reclaim and use) and a small amount of low boilers, then cool to 60 ℃, add again 90ml 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 (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane.Its productive rate is 95.8%, flash-point (open cup): 202 ± 5 ℃, and refractive index: n
d 25=1.4163, density (25 ℃): 1.3378g/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 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 ℃, drip 12.9g (9.55ml, 0.1mol) 1, the chloro-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 35 ℃, after dripping off, be warming up to 45 ℃, 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 55 ℃, after dripping off, be warming up to 75 ℃, reaction 8h; After HCl gas discharges, then system is cooled to below 50 ℃, drips 29.67g (21.97ml, 0.23mol) 1, the chloro-2-propyl alcohol of 3-bis-, controls temperature of reaction not higher than 60 ℃ with rate of addition, after dripping off, system temperature is risen to 83 ℃, insulation reaction 8h; 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 ethylene dichloride and excessive 1, the chloro-2-propyl alcohol of 3-bis-(reclaim and use) and a small amount of low boilers, then cool to 60 ℃, add again 90ml 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 (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane.Its productive rate is 92.7%, flash-point (open cup): 202 ± 5 ℃, and refractive index: n
d 25=1.4163, density (25 ℃): 1.3378g/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 25 ℃, drip 12.9g (9.55ml, 0.1mol) 1, the chloro-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 35 ℃, after dripping off, be warming up to 45 ℃, 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 55 ℃, after dripping off, be warming up to 80 ℃, reaction 7h, after HCl gas discharges, then system is cooled to below 50 ℃, drips 30.96g (22.92ml, 0.24mol) 1, the chloro-2-propyl alcohol of 3-bis-, controls temperature of reaction not higher than 60 ℃, after dripping off with rate of addition, system temperature is risen to 85 ℃, insulation reaction 7h; After HCl gas discharges, then add 1.6g 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 1, the chloro-2-propyl alcohol of 3-bis-(reclaim and use) and a small amount of low boilers, then cool to 60 ℃, add again 90ml 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 (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane.Its productive rate is 93.5%, flash-point (open cup): 202 ± 5 ℃, and refractive index: n
d 25=1.4163, density (25 ℃): 1.3378g/cm
3.
Table 1 two [three (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane preparation example main technologic parameters
This case contriver is also applied to two [three (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane of above-mentioned preparation in polyvinyl chloride.Reference: the limiting oxygen index(LOI) of GB/T2406-2008 < < Plastics Combustion method for testing performance-oxygen index method > > test sample product.Get fire retardant two [three (the chloro-2-propoxy-of 1,3-bis-) 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, with forcing machine, extrude, make the batten that diameter is 3mm, and its flame retardant properties is tested, listed part test result as shown in table 2:
The flame retardant properties data of table 2 two [three (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane
Experiment shows, two [three (the chloro-2-propoxy-of 1,3-bis-) 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 (8)
1. a fire retardant two [three (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane compounds, is characterized in that, the structure of this compound is shown below:
2. the preparation method of two [three (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane as claimed in claim 1, 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 25 ℃, drip and silicon tetrachloride equimolar 1, the chloro-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 35 ℃, after dripping off, be warming up to 45 ℃, 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 55 ℃, after dripping off, be warming up to 65-80 ℃, reaction 7-10h; After HCl gas discharges, then system is cooled to below 50 ℃, drips with respect to silicon tetrachloride 2-3 times mole 1, the chloro-2-propyl alcohol of 3-bis-, controls temperature of reaction not higher than 60 ℃ with rate of addition, after dripping off, system temperature is risen to 70-90 ℃, insulation reaction 6-10h; 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 (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane.
3. fire retardant two [three (1 according to claim 2, the chloro-2-propoxy-of 3-bis-) silicon acyloxy] preparation method of 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 (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane, is characterized in that: described dropping 1, the chloro-2-propyl alcohol of 3-bis-is divided into twice dropping.
5. the preparation method of fire retardant two according to claim 2 [three (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane, is characterized in that: described acid binding agent is trimeric cyanamide.
6. fire retardant two [three (1 according to claim 2, the chloro-2-propoxy-of 3-bis-) silicon acyloxy] preparation method of ethane, it is characterized in that: described purified being treated to is cooled to 30 ℃, filter, filtrate decompression distillation is except desolventizing and excessive 1, the chloro-2-propyl alcohol of 3-bis-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 (the chloro-2-propoxy-of 1,3-bis-) 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 (the chloro-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane, is characterized in that: the solvent or 1 of described underpressure distillation for collecting, the chloro-2-propyl alcohol of 3-bis-reclaims and uses.
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| 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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| 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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