CN103539807B - Three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] isocyanurate compounds and preparation method thereof - Google Patents
Three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] isocyanurate compounds and preparation method thereof Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 41
- 239000010703 silicon Substances 0.000 title claims abstract description 41
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000003063 flame retardant Substances 0.000 claims abstract description 39
- -1 chloro-2-propyl Chemical group 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 28
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 28
- 238000009413 insulation Methods 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical group ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 238000004886 process control Methods 0.000 claims description 7
- 238000013517 stratification Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 2
- 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
- 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
- 229920006305 unsaturated polyester Polymers 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 32
- 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 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 description 12
- 238000009835 boiling Methods 0.000 description 10
- 230000002195 synergetic effect Effects 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 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 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000009970 fire resistant effect Effects 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
- 229920000728 polyester Polymers 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
- 125000006414 CCl Chemical group ClC* 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
- 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
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000002301 combined effect Effects 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
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 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
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Abstract
The present invention relates to a kind of fire retardant three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] isocyanurate 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 three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] isocyanurate compounds and preparation method thereof, this compound silicon, nitrogen and chlorine element cooperative flame retardant usefulness are high, are 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 more has urgency to the demand of new and effective fire retardant.After silent from generation carcinogens Er Evil during European Union's announcement discovery polybrominated diphenyl ether retardant burning in 1986, the use of halogenated flame retardant is restricted, but because the comprehensive cost performance of halogenated flame retardant is excellent, and be difficult to find desirable surrogate, thus research and develop 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.
Fire retardant three [2-tri-(1 of the present invention, 3-dichloro isopropoxy) silicon trimethylammonium] embedded in silicon, nitrogen and chlorine three kinds of ignition-proof elements in tricarbimide ester molecule simultaneously, element is worked in coordination with and is produced synergistic function from different fire retardant mechanisms, silicon can form fine and close silicon layer of charcoal when burning, nitrogen element can play expansion thermal-insulation function, chlorine and auxiliary flame retardant antimonous oxide can produce fire-resistant synergistic effect at double, and combined effect can show higher flame-retarded efficiency; Raw material silicon tetrachloride wherein used is the by product of polysilicon industry, and thus of the present invention being disclosed as solves polysilicon by-product problem of complex utilization and open a new approach, has good environmental benefit; Polyester many chlorine structure in molecule can increase the consistency of this macromolecular material such as fire retardant and polyvinyl chloride; Again for market adds efficient flame-retarding agent new variety, 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 silicon, nitrogen and chlorine synergistic fire retardant three [2-tri-(1 prepared by proposition silicon tetrachloride, 3-dichloro isopropoxy) silicon trimethylammonium] isocyanurate compounds, its good flame resistance, can overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme:
Fire retardant three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] isocyanurate 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 three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates, its technique is simple; be easy to large-scale production, and raw material is easy to get, with low cost; facility investment is few, 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, temperature of reaction system is made to be reduced to less than 25 DEG C, drip and silicon tetrachloride equimolar 1, the chloro-2-propyl alcohol of 3-bis-, 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 organic solution of the trihydroxyethyl isocyanuric ester (Sai Ke) relative to silicon tetrachloride 1/3 times mole, control temperature of reaction not higher than 65 DEG C with rate of addition, after dripping off, be warming up to 80-95 DEG C, reaction 9-13h; After HCl gas discharges, then system is cooled to less than 50 DEG C, drips 1 relative to silicon tetrachloride 2-3 times mole, the chloro-2-propyl alcohol of 3-bis-, controls temperature of reaction not higher than 65 DEG C, after dripping off with rate of addition, system temperature is risen to 80-95 DEG C, insulation reaction 7-10h; After HCl gas discharges, then add the acid binding agent of product Theoretical Mass (g) 2%-6%, insulated and stirred 1h, detecting pH value of solution=5-6 is reaction end.Purified process, obtains product three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates.
Organic solvent as above is tetrachloroethane, dioxane, acetonitrile, toluene or diethylene glycol dimethyl ether, and the amount of its organic solvent volume (ml) is 2-3 times of silicon tetrachloride quality (g).
The organic solution of trihydroxyethyl isocyanuric ester as above (Sai Ke) is the solution that match gram is dissolved in described organic solvent, and the amount of its organic solvent volume (ml) is 10-15 times of match gram mass (g).
Acid binding agent as above is trimeric cyanamide.
Purified process as above is for being cooled to 35 DEG C, 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 DEG C, then add the hexanaphthene washing of product Theoretical Mass (g) 2-4 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 hexanaphthene.
Contriver finds match gram solid bad dispersibility in the organic solution of silicon tetrachloride under study for action, reactive behavior is low, improve the volatile quantity that temperature of reaction can increase again silicon tetrachloride, therefore selected and first allowed silicon tetrachloride react with waiting mole 1,3-bis-chloro-2-propyl alcohol, generated silicic acid monoesters, react with match gram again, the dispersiveness of match gram can be improved, and to react at a higher temperature, to overcome the easy volatile of silicon tetrachloride.
Fire retardant three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates disclosed by the invention is yellow transparent liquid, and productive rate is 88.4% ~ 93.2%, its flash-point (open cup): 207 ± 5 DEG C, refractive index: n
d 25=1.5135, density (25 DEG C): 1.489g/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 three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates is shown below:
Compared with prior art, beneficial effect of the present invention is:
1. fire retardant three [2-tri-(1 of the present invention, 3-dichloro isopropoxy) silicon trimethylammonium] isocyanurate compounds contains silicon, nitrogen and chlorine element, 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, nitrogen element has the heat insulation effect that expands.
2. fire retardant three [2-tri-(1 of the present invention, 3-dichloro isopropoxy) silicon trimethylammonium] isocyanurate compounds is polyester 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 silicon, nitrogen and chlorine synergistic fire retardant three [2-tri-(1 prepared by raw material, 3-dichloro isopropoxy) silicon trimethylammonium] isocyanurate 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 the chloro-2-propyl alcohol of 1,3-bis-react and generates silicic acid monoesters, and then reacts with match gram, improves Sai Ke and not easily disperses the shortcoming low with activity, react a volatile difficult problem under overcoming silicon tetrachloride high temperature.
5. the solvent in present invention process and excessive 1,3-bis-chloro-2-propyl 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.
Accompanying drawing explanation
In order to the stuctures and properties spy further illustrating product provides following accompanying drawing.
1, the infrared spectrogram of three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates, refers to Figure of description Fig. 1;
Fig. 1 shows, 1095cm
-1and 872cm
-1(stretching vibration of Si-O-C and flexural vibration); 2980cm
-1(stretching vibration with the C-H of chloro); 2935cm
-1and 2893cm
-1(stretching vibration of C-H); 1436cm
-1(CH
2the flexural vibration of-middle C-H); 1698cm
-1(stretching vibration of C=O); 763cm
-1(stretching vibration of C-Cl); 1027cm
-1and 986cm
-1(stretching vibration of C-O); 1382cm
-1(stretching vibration of C-N).
2, the nuclear magnetic spectrum figure of three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates, refers to Figure of description Fig. 2;
Fig. 2 shows, deuterochloroform makes solvent, and δ 4.08-4.19 is-OCH (CH
2cl)
2in to be connected with oxygen the hydrogen peak of methyne; δ 3.97-4.08 is-NCH
2cH
2the hydrogen peak of the methylene radical be connected with oxygen in OSi-; δ 3.52-3.77 is-OCH (CH
2cl)
2the hydrogen peak of middle chloromethyl; δ 3.17-3.27 is-NCH
2cH
2the hydrogen peak of the methylene radical be connected with nitrogen in OSi-; 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 20ml tetrachloroethane and 8.5g (5.67ml, 0.05mol) silicon tetrachloride, under agitation, with cooling bath cooling, make temperature of reaction system be reduced to less than 25 DEG C, drip 6.45g (4.78ml, 0.05mol) 1, the chloro-2-propyl alcohol of 3-bis-, 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, the solution that 4.358g (0.0167mol) Sai Ke is dissolved in 50ml tetrachloroethane is added dropwise in four-hole boiling flask, temperature of reaction is controlled not higher than 65 DEG C with rate of addition, 90 DEG C are warming up to after dripping off, reaction 11h, after HCl gas discharges, again system is cooled to less than 50 DEG C, drip the chloro-2-propyl alcohol of 13.029g (9.65ml, 0.101mol) 1,3-bis-, temperature of reaction is controlled not higher than 65 DEG C with rate of addition, after dripping off, system temperature is risen to 95 DEG C, insulation reaction 8h; After HCl gas discharges, then add 0.8g trimeric cyanamide, insulated and stirred 1h, detecting pH value of solution=5-6 is reaction end.Be cooled to 35 DEG C, filter, filtrate is underpressure distillation removing tetrachloroethane and excessive 1,3-bis-chloro-2-propyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add the washing of 50ml hexanaphthene again, stir 0.5h, be transferred to stratification in separating funnel, separate lower floor's feed liquid, underpressure distillation removes a small amount of hexanaphthene, obtains product three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 88.4%, flash-point (open cup): 207 ± 5 DEG C, refractive index: n
d 25=1.5135, density (25 DEG C): 1.489g/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 20ml dioxane and 8.5g (5.67ml, 0.05mol) silicon tetrachloride, under agitation, with cooling bath cooling, make temperature of reaction system be reduced to less than 25 DEG C, drip 6.45g (4.78ml, 0.05mol) 1, the chloro-2-propyl alcohol of 3-bis-, 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, the solution that 4.358g (0.0167mol) Sai Ke is dissolved in 50ml dioxane is added dropwise in four-hole boiling flask, temperature of reaction is controlled not higher than 65 DEG C with rate of addition, 90 DEG C are warming up to after dripping off, reaction 10h, after HCl gas discharges, again system is cooled to less than 50 DEG C, drip the chloro-2-propyl alcohol of 14.19g (10.51ml, 0.11mol) 1,3-bis-, temperature of reaction is controlled not higher than 65 DEG C with rate of addition, after dripping off, system temperature is risen to 90 DEG C, insulation reaction 8h; After HCl gas discharges, then add 0.6g trimeric cyanamide, insulated and stirred 1h, detecting pH value of solution=5-6 is reaction end.Be cooled to 35 DEG C, filter, filtrate is underpressure distillation removing dioxane and excessive 1,3-bis-chloro-2-propyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add the washing of 50ml hexanaphthene again, stir 0.5h, be transferred to stratification in separating funnel, separate lower floor's feed liquid, underpressure distillation removes a small amount of hexanaphthene, obtains product three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 93.2%, flash-point (open cup): 207 ± 5 DEG C, refractive index: n
d 25=1.5135, density (25 DEG C): 1.489g/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 20ml acetonitrile and 8.5g (5.67ml, 0.05mol) silicon tetrachloride, under agitation, with cooling bath cooling, make temperature of reaction system be reduced to less than 25 DEG C, drip 6.45g (4.78ml, 0.05mol) 1, the chloro-2-propyl alcohol of 3-bis-, 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, the solution that 4.358g (0.0167mol) Sai Ke is dissolved in 50ml acetonitrile is added dropwise in four-hole boiling flask, temperature of reaction is controlled not higher than 65 DEG C with rate of addition, 80 DEG C are warming up to after dripping off, reaction 13h, after HCl gas discharges, again system is cooled to less than 50 DEG C, drip the chloro-2-propyl alcohol of 15.48g (11.46ml, 0.12mol) 1,3-bis-, temperature of reaction is controlled not higher than 65 DEG C with rate of addition, after dripping off, system temperature is risen to 80 DEG C, insulation reaction 10h; After HCl gas discharges, then add 0.8g trimeric cyanamide, insulated and stirred 1h, detecting pH value of solution=5-6 is reaction end.Be cooled to 35 DEG C, filter, filtrate is underpressure distillation removing acetonitrile and excessive 1,3-bis-chloro-2-propyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add the washing of 50ml hexanaphthene again, stir 0.5h, be transferred to stratification in separating funnel, separate lower floor's feed liquid, underpressure distillation removes a small amount of hexanaphthene, obtains product three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 89.8%, flash-point (open cup): 207 ± 5 DEG C, refractive index: n
d 25=1.5135, density (25 DEG C): 1.489g/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 20ml toluene and 8.5g (5.67ml, 0.05mol) silicon tetrachloride, under agitation, with cooling bath cooling, make temperature of reaction system be reduced to less than 25 DEG C, drip 6.45g (4.78ml, 0.05mol) 1, the chloro-2-propyl alcohol of 3-bis-, 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, the solution that 4.358g (0.0167mol) Sai Ke is dissolved in 50ml toluene is added dropwise in four-hole boiling flask, temperature of reaction is controlled not higher than 65 DEG C with rate of addition, 85 DEG C are warming up to after dripping off, reaction 12h, after HCl gas discharges, again system is cooled to less than 50 DEG C, drip the chloro-2-propyl alcohol of 16.77g (12.42ml, 0.13mol) 1,3-bis-, temperature of reaction is controlled not higher than 65 DEG C with rate of addition, after dripping off, system temperature is risen to 85 DEG C, insulation reaction 9h; After HCl gas discharges, then add 0.7g trimeric cyanamide, insulated and stirred 1h, detecting pH value of solution=5-6 is reaction end.Be cooled to 35 DEG C, filter, filtrate is underpressure distillation removing toluene and excessive 1,3-bis-chloro-2-propyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add the washing of 50ml hexanaphthene again, stir 0.5h, be transferred to stratification in separating funnel, separate lower floor's feed liquid, underpressure distillation removes a small amount of hexanaphthene, obtains product three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 90.6%, flash-point (open cup): 207 ± 5 DEG C, refractive index: n
d 25=1.5135, density (25 DEG C): 1.489g/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 20ml diethylene glycol dimethyl ether and 8.5g (5.67ml, 0.05mol) silicon tetrachloride, under agitation, with cooling bath cooling, make temperature of reaction system be reduced to less than 25 DEG C, drip 6.45g (4.78ml, 0.05mol) 1, the chloro-2-propyl alcohol of 3-bis-, 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, the solution that 4.358g (0.0167mol) Sai Ke is dissolved in 50ml diethylene glycol dimethyl ether is added dropwise in four-hole boiling flask, controls temperature of reaction not higher than 65 DEG C with rate of addition, after dripping off, be warming up to 95 DEG C, reaction 9h; After HCl gas discharges, then system is cooled to less than 50 DEG C, drips 18.06g (13.37ml, 0.14mol) 1,3-bis-chloro-2-propyl alcohol, controls temperature of reaction not higher than 65 DEG C with rate of addition, after dripping off, system temperature is risen to 90 DEG C, insulation reaction 7h; After HCl gas discharges, then add 1g trimeric cyanamide, insulated and stirred 1h, detecting pH value of solution=5-6 is reaction end.Be cooled to 35 DEG C, filter, filtrate is underpressure distillation removing diethylene glycol dimethyl ether and excessive 1,3-bis-chloro-2-propyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add the washing of 50ml hexanaphthene again, stir 0.5h, be transferred to stratification in separating funnel, separate lower floor's feed liquid, underpressure distillation removes a small amount of hexanaphthene, obtains product three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 91.4%, flash-point (open cup): 207 ± 5 DEG C, refractive index: n
d 25=1.5135, density (25 DEG C): 1.489g/cm
3.
Table 1 three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates preparation example main technologic parameters
Fire retardant three [2-tri-(1, the 3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates 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 three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates, 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 three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates
Experiment shows, fire retardant three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates 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 (5)
1. the preparation method of fire retardant three [2-tri-(1, a 3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates, 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 1, the chloro-2-propyl alcohol of 3-bis-, 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 organic solution of the trihydroxyethyl isocyanuric ester relative to silicon tetrachloride 1/3 times mole, control temperature of reaction not higher than 65 DEG C with rate of addition, after dripping off, be warming up to 80-95 DEG C, reaction 9-13h; After HCl gas discharges, then system is cooled to less than 50 DEG C, drips 1 relative to silicon tetrachloride 2-3 times mole, the chloro-2-propyl alcohol of 3-bis-, controls temperature of reaction not higher than 65 DEG C, after dripping off with rate of addition, system temperature is risen to 80-95 DEG C, insulation reaction 7-10h; After HCl gas discharges, then add the acid binding agent of product Theoretical Mass 2%-6%, insulated and stirred 1h, detecting pH value of solution=5-6 is reaction end; Purified process, obtain fire retardant three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates, the structure of this compound is shown below:
2. fire retardant three [2-tri-(1 according to claim 1,3-dichloro isopropoxy) silicon trimethylammonium] preparation method of chlorinated isocyanurates, it is characterized in that: described organic solvent is tetrachloroethane, dioxane, acetonitrile, toluene or diethylene glycol dimethyl ether, its organic solvent volume milliliter number is 2-3 times of silicon tetrachloride quality grams.
3. fire retardant three [2-tri-(1 according to claim 1,3-dichloro isopropoxy) silicon trimethylammonium] preparation method of chlorinated isocyanurates, it is characterized in that: the organic solution of described trihydroxyethyl isocyanuric ester is the solution that trihydroxyethyl isocyanuric ester is dissolved in described organic solvent, its organic solvent volume milliliter number is 10-15 times of trihydroxyethyl isocyanuric ester quality grams.
4. the preparation method of fire retardant three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] chlorinated isocyanurates according to claim 1, is characterized in that: described acid binding agent is trimeric cyanamide.
5. fire retardant three [2-tri-(1 according to claim 1,3-dichloro isopropoxy) silicon trimethylammonium] preparation method of chlorinated isocyanurates, it is characterized in that: described purified process is for being cooled to 35 DEG C, 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 DEG C, add the hexanaphthene washing of product Theoretical Mass grams 2-4 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 hexanaphthene.
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| CN102050961A (en) * | 2010-11-01 | 2011-05-11 | 苏州科技学院 | Aryl silicate ester flame retardant plasticizer and preparation method thereof |
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