CN103554147B - Fire retardant match gram three silicic acid bromine propyl ester compounds and preparation method thereof - Google Patents
Fire retardant match gram three silicic acid bromine propyl ester compounds and preparation method thereof Download PDFInfo
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- -1 silicic acid bromine propyl ester compounds Chemical class 0.000 title claims abstract description 50
- 239000003063 flame retardant Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 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 29
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 29
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 21
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 15
- 238000009413 insulation Methods 0.000 claims description 15
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 12
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- 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
- 238000004886 process control Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000013517 stratification Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 abstract description 11
- UFZSAEITPLBPGV-UHFFFAOYSA-N [Br].[Si](O)(O)(O)O Chemical compound [Br].[Si](O)(O)(O)O UFZSAEITPLBPGV-UHFFFAOYSA-N 0.000 abstract description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 7
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920006305 unsaturated polyester Polymers 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 238000009835 boiling Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000011160 research Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 239000002994 raw material 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
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-DYCDLGHISA-N Deuterium chloride Chemical compound [2H]Cl VEXZGXHMUGYJMC-DYCDLGHISA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
The present invention relates to a kind of fire retardant match gram three silicic acid bromine propyl ester compounds and preparation method thereof, the structure of this compound is shown below:
-OC in its formula
3h
6br is the mixture of 2-bromo-1-propoxy-or 1-bromo-2-propoxy-or 2-bromo-1-propoxy-and the bromo-2-propoxy-of 1-.Preparation method is: below 25 DEG C, in the organic solution of silicon tetrachloride, the mole bromine propyl alcohol such as to drip, in 45 DEG C of reaction 2h; Instill the organic solution relative to silicon tetrachloride 1/3 times of mole of trihydroxyethyl isocyanuric ester again, at 80-95 DEG C of reaction 9-12h; Be cooled to less than 55 DEG C again, then drip relative to silicon tetrachloride 2-3 times of mole bromine propyl alcohol, at 80-90 DEG C of reaction 8-10h, then add acid binding agent, insulated and stirred 1h, purified process, obtain fire retardant match gram three silicic acid bromine propyl ester; The compounds of this invention is suitable as the fire retardant of polyvinyl chloride, urethane, epoxy resin and unsaturated polyester etc., and preparation technology is simple, and cost is low, is easy to realize suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of fire retardant match gram three silicic acid bromine propyl ester compounds and preparation method thereof, be specifically related to a kind of fire retardant three [2-tri-(bromine propoxy-) silicon trimethylammonium] isocyanurate compounds and preparation method thereof, this compound can be used as the fire retardant of the materials such as polyvinyl chloride, unsaturated polyester, urethane and epoxy resin.
Background technology
Current organic synthesis macromolecular material is applied widely, and it has inflammableness mostly.According to statistics, the fire occurred for many years is mostly directly or indirectly relevant with inflammable material, therefore facilitates the research of fire retardant or fire retardant material.Adding fire retardant is in the material a kind of effective ways realizing fire-retardant fireproof, and traditional halogenated flame retardant can discharge obnoxious flavour when material combustion.Along with the enhancing of environmental consciousness, halogenated flame retardant enjoys pressure, but uses the field of halogenated flame retardant at some, is also difficult to find suitable substitute time near.Research halogenated flame retardant, improves the usefulness of halogenated flame retardant, the toxicity produced during by reducing fire retardant add-on in the material to reduce burning, one of important directions becoming research.By the composite usefulness that can improve halogenated flame retardant of fire retardant, in same a part, embed multiple ignition-proof element cooperative flame retardant is also the more effective approach realizing highly effective flame-retardant.The development research of thus working in coordination with halogenated flame retardant to multielement has become the heat subject of research.
Fire retardant match gram three silicic acid bromine propyl ester of the present invention contain silicon, nitrogen and bromine three kinds of ignition-proof elements, when material combustion, element silicon in molecular structure can generate fine and close silicon layer of charcoal, nitrogen element plays expansion heat-blocking action, bromo element and auxiliary flame retardant antimonous oxide cooperative flame retardant effect are multiplied, comprehensive cooperative flame retardant synergism highly significant.Fire retardant raw materials of the present invention make use of the silicon tetrachloride as by-product of polysilicon, for the pollution problem solving silicon tetrachloride opens an effective way.Synthesis technique environmental friendliness of the present invention, meets the developing direction of fire retardant, and its product flame-retarded efficiency is high, has very wide application and development prospect.
Summary of the invention
An object of the present invention is that a kind of fire retardant match gram three silicic acid bromine propyl ester compounds prepared by proposition silicon tetrachloride.Its physical and chemical performance is stablized, and good heat resistance is good with macromolecular material consistency, and has plasticising and become the anti-drip effect of charcoal, can overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme:
Fire retardant match gram three silicic acid bromine propyl ester compounds, it is characterized in that, this compound structure is shown below:
-OC in its formula
3h
6br is the mixture of 2-bromo-1-propoxy-or 1-bromo-2-propoxy-or 2-bromo-1-propoxy-and the bromo-2-propoxy-of 1-.
Another object of the present invention is to the preparation method proposing a kind of fire retardant match gram three silicic acid bromine propyl ester, its cheaper starting materials is easy to get, and technique is simple, and facility investment is few, is easy to large-scale production, and the method is:
The air in reaction vessel is fallen with nitrogen replacement, add organic solvent and silicon tetrachloride, under agitation, with cooling bath cooling, make temperature of reaction system be reduced to less than 25 DEG C, drip and the equimolar bromopropyl alcohol of silicon tetrachloride, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, then instill the organic solution of the trihydroxyethyl isocyanuric ester (Sai Ke) relative to silicon tetrachloride 1/3 times mole, control temperature of reaction system not higher than 65 DEG C with rate of addition, after dripping off, be warming up to 80-95 DEG C, reaction 9-12h; After HCl gas discharges, then system is cooled to less than 55 DEG C, drips the bromopropyl alcohol relative to silicon tetrachloride 2-3 times mole, control temperature of reaction not higher than 70 DEG C with rate of addition, after dripping off, system temperature is risen to 80-90 DEG C, insulation reaction 8-10h; After HCl gas discharges, then add the acid binding agent of product Theoretical Mass (g) 2%-6%, insulated and stirred 1h, detecting solution PH=5-6 is reaction end.Purified process, obtains fire retardant three [2-tri-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates.
Bromopropyl alcohol as above is the mixture of 2-bromopropyl alcohol, 1-bromo-2-propyl alcohol or 2-bromopropyl alcohol and the bromo-2-propyl alcohol of 1-.
Organic solvent as above is ethylene dichloride, dioxane, acetonitrile, tetrachloroethane or 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 bromopropyl alcohol (reclaim and use) and a small amount of low boilers, then cool to 60 DEG C, add the hexanaphthene washing of product Theoretical Mass (g) 2-4 times volume (ml) again, stir 0.5h, be transferred to stratification in separating funnel, separate lower floor's feed liquid, underpressure distillation removes a small amount of hexanaphthene.
Match gram solid bad dispersibility in the organic solution of silicon tetrachloride is found in contriver's research, reactive behavior is low, improve the volatile quantity that temperature of reaction can increase again silicon tetrachloride, therefore selected first allow silicon tetrachloride with etc. mole bromine propyl alcohol react, generate silicic acid monoesters, then react with match gram, the dispersiveness to match gram can be improved, and can react at a higher temperature, overcome the easy volatile of silicon tetrachloride.
Fire retardant match gram three silicic acid bromine propyl ester disclosed by the invention are yellow transparent liquid, and its productive rate is 87.8% ~ 93.7%.Its flash-point (open cup): 194 ± 5 DEG C, density: 1.798g/cm
3(25 DEG C), refractive index: n
d 25=1.4132; It is suitable as the use of the fire retardant of the materials such as polyvinyl chloride, unsaturated polyester, urethane and epoxy resin.
Preparation technology's principle of fire retardant match gram three silicic acid bromine propyl ester is shown below:
-OC in its formula
3h
6br is the mixture of 2-bromo-1-propoxy-or 1-bromo-2-propoxy-or 2-bromo-1-propoxy-and the bromo-2-propoxy-of 1-.
Compared with prior art, beneficial effect of the present invention is:
1. fire retardant match gram three silicic acid bromine propyl ester compounds of the present invention contain silicon, nitrogen and bromine element, its cooperative flame retardant usefulness is high, element silicon has into charcoal effect, and 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 match gram three silicic acid bromine propyl ester compounds of the present invention are polyester structures, and molecular weight is large, volatility is low, plasticity is good, symmetry is good, and its physical and chemical performance is stablized, good with macromolecular material consistency, can be adapted to the high temperature process of engineering plastics.
3. the present invention with the silicon tetrachloride as by-product of polysilicon industry be Material synthesis silicon, nitrogen and bromine synergistic fire retardant match gram three silicic acid bromine propyl ester, for solve silicon tetrachloride comprehensive utilization a difficult problem provide an effective way.
4. preparation method of the present invention first allows silicon tetrachloride and bromopropyl alcohol 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 bromopropyl alcohol can directly be recycled, and its raw material is cheap and easy to get, and production cost is low, and facility investment is few, is easy to large-scale production, have well application and DEVELOPMENT PROSPECT.
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-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates, refers to Figure of description Fig. 1;
Fig. 1 shows, 2977cm
-1(stretching vibration with the C-H of bromo); 2884cm
-1(stretching vibration of C-H); 1441cm
-1(flexural vibration of C-H); 1695cm
-1(stretching vibration of C=O); 1387cm
-1(stretching vibration of C-N); 1093cm
-1and 869cm
-1(stretching vibration of Si-O-C and flexural vibration); 1038cm
-1and 986cm
-1(stretching vibration of C-O); 632cm
-1(stretching vibration of C-Br).
2, the nuclear magnetic spectrum figure of three [2-tri-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates, refers to Figure of description Fig. 2;
Fig. 2 shows, δ 1.27-1.33 is-SiOCH (CH
2br) CH
3the hydrogen peak of middle methyl; δ 1.53-1.58 is-SiOCH
2cHBrCH
3the hydrogen peak of middle methyl; δ 3.39-3.47 is-NCH
2cH
2the hydrogen peak of the methylene radical be connected with nitrogen in OSi-; δ 3.48-3.51 is-SiOCH (CH
2br) CH
3the hydrogen peak of middle brooethyl; δ 3.66-3.77 is-SiOCH
2cHBrCH
3in the hydrogen peak of bromine methylene radical and-SiOCH (CH
2br) CH
3in the hydrogen peak of methylene radical that is connected with oxygen; δ 3.97-4.08 is-NCH
2cH
2the hydrogen peak of the methylene radical be connected with oxygen in OSi-; δ 4.15-4.27 is-SiOCH
2cHBrCH
3in the hydrogen peak of methylene radical that is connected with oxygen; 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 ethylene dichloride and 8.5g (5.67ml, 0.05mol) silicon tetrachloride, under agitation, cool with cooling bath, make temperature of reaction system be reduced to less than 25 DEG C, drip 6.95g (4.46ml, 0.05mol) bromopropyl alcohol, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, the solution that 4.358g (0.0167mol) Sai Ke is dissolved in 50ml ethylene dichloride 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 80 DEG C, reaction 12h; After HCl gas discharges, then system is cooled to less than 55 DEG C, drips 14.039g (9.01ml, 0.101mol) bromopropyl alcohol, control temperature of reaction not higher than 70 DEG C with rate of addition, after dripping off, system temperature is risen to 83 DEG C, insulation reaction 10h; After HCl gas discharges, then add 0.7g trimeric cyanamide, insulated and stirred 1h, detecting solution PH=5-6 is reaction end.Be cooled to 35 DEG C, filter, filtrate is underpressure distillation removing ethylene dichloride and excessive bromopropyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, then add the washing of 60ml hexanaphthene, 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-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 87.8%, flash-point (open cup): 194 ± 5 DEG C, density: 1.798g/cm
3(25 DEG C), refractive index: n
d 25=1.4132.
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, cool with cooling bath, make temperature of reaction system be reduced to less than 25 DEG C, drip 6.95g (4.46ml, 0.05mol) bromopropyl alcohol, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, the solution that 4.358g (0.0167mol) Sai Ke is dissolved in 50ml dioxane is added dropwise in four-hole boiling flask, controls temperature of reaction not higher than 65 DEG C with rate of addition, 90 DEG C are warming up to after dripping off, reaction 9h, after HCl gas discharges, then is cooled to less than 55 DEG C by system, drip 15.29g (9.81ml, 0.11mol) bromopropyl alcohol, controls temperature of reaction not higher than 70 DEG C, after dripping off with rate of addition, 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 solution PH=5-6 is reaction end.Be cooled to 35 DEG C, filter, filtrate is underpressure distillation removing dioxane and excessive bromopropyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, then add the washing of 60ml hexanaphthene, 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-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 93.7%, flash-point (open cup): 194 ± 5 DEG C, density: 1.798g/cm
3(25 DEG C), refractive index: n
d 25=1.4132.
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, cool with cooling bath, make temperature of reaction system be reduced to less than 25 DEG C, drip 6.95g (4.46ml, 0.05mol) bromopropyl alcohol, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, the solution that 4.358g (0.0167mol) Sai Ke is dissolved in 50ml acetonitrile 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 80 DEG C, reaction 11h; After HCl gas discharges, then system is cooled to less than 55 DEG C, drips 16.68g (10.71ml, 0.12mol) bromopropyl alcohol, control temperature of reaction not higher than 70 DEG C with rate of addition, after dripping off, system temperature is risen to 80 DEG C, insulation reaction 9h; After HCl gas discharges, then add 0.8g trimeric cyanamide, insulated and stirred 1h, detecting solution PH=5-6 is reaction end.Be cooled to 35 DEG C, filter, filtrate is underpressure distillation removing acetonitrile and excessive bromopropyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, then add the washing of 60ml hexanaphthene, 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-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 89.5%, flash-point (open cup): 194 ± 5 DEG C, density: 1.798g/cm
3(25 DEG C), refractive index: n
d 25=1.4132.
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 tetrachloroethane and 8.5g (5.67ml, 0.05mol) silicon tetrachloride, under agitation, cool with cooling bath, make temperature of reaction system be reduced to less than 25 DEG C, drip 6.95g (4.46ml, 0.05mol) bromopropyl alcohol, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, the solution that 4.358g (0.0167mol) Sai Ke is dissolved in 50ml tetrachloroethane is added dropwise in four-hole boiling flask, controls temperature of reaction not higher than 65 DEG C with rate of addition, 95 DEG C are warming up to after dripping off, reaction 9h, after HCl gas discharges, then is cooled to less than 55 DEG C by system, drip 18.07g (11.60ml, 0.13mol) bromopropyl alcohol, controls temperature of reaction not higher than 70 DEG C, after dripping off with rate of addition, system temperature is risen to 90 DEG C, insulation reaction 8h; After HCl gas discharges, then add 0.9g trimeric cyanamide, insulated and stirred 1h, detecting solution PH=5-6 is reaction end.Be cooled to 35 DEG C, filter, filtrate is underpressure distillation removing tetrachloroethane and excessive bromopropyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, then add the washing of 60ml hexanaphthene, 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-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 91.3%, flash-point (open cup): 194 ± 5 DEG C, density: 1.798g/cm
3(25 DEG C), refractive index: n
d 25=1.4132.
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 glycol dimethyl ether and 8.5g (5.67ml, 0.05mol) silicon tetrachloride, under agitation, cool with cooling bath, make temperature of reaction system be reduced to less than 25 DEG C, drip 6.95g (4.46ml, 0.05mol) bromopropyl alcohol, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, the solution that 4.358g (0.0167mol) Sai Ke is dissolved in 50ml glycol dimethyl ether 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 10h, after HCl gas discharges, again system is cooled to less than 55 DEG C, drip 19.46g (12.49ml, 0.14mol) bromopropyl alcohol, controls temperature of reaction not higher than 70 DEG C, after dripping off with rate of addition, system temperature is risen to 85 DEG C, insulation reaction 9h; After HCl gas discharges, then add 1.3g trimeric cyanamide, insulated and stirred 1h, detecting solution PH=5-6 is reaction end.Be cooled to 35 DEG C, filter, filtrate is underpressure distillation removing glycol dimethyl ether and excessive bromopropyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, then add the washing of 60ml hexanaphthene, 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-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 90.6%, flash-point (open cup): 194 ± 5 DEG C, density: 1.798g/cm
3(25 DEG C), refractive index: n
d 25=1.4132.
The preparation example main technologic parameters of gram three silicic acid bromine propyl ester matched by table 1
The match of above-mentioned synthesis gram three silicic acid bromine propyl ester are also applied in polyvinyl chloride by inventor.Reference: GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " surveys the flame retardant properties of product in polyvinyl chloride.Get fire retardant match gram three silicic acid bromine propyl ester, dioctyl phthalate (DOP) (DOP), synergistic flame retardant antimonous oxide (Sb
2o
3) and polyvinyl chloride (PVC) mix rear forcing machine in varing proportions and extrude, and make long 15cm, diameter be 3mm batten and to it fire-retardant and physicals test, it is as shown in the table for test-results:
The flame retardant properties data of gram three silicic acid bromine propyl ester matched by table 2
Experiment shows, fire retardant match gram three silicic acid bromine propyl ester 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 (7)
1. a preparation method for fire retardant three [2-tri-(bromine propoxy-) 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, make temperature of reaction system be reduced to less than 25 DEG C, drip and the equimolar bromopropyl alcohol of silicon tetrachloride, drip process control temperature of reaction not higher than 30 DEG C, after dripping off, be warming up to 45 DEG C, insulation reaction 2h; After HCl gas discharges, instill the organic solution of the trihydroxyethyl isocyanuric ester relative to silicon tetrachloride 1/3 times mole again, control temperature of reaction system not higher than 65 DEG C with rate of addition, after dripping off, be warming up to 80-95 DEG C, reaction 9-12h, after HCl gas discharges, then system is cooled to less than 55 DEG C, drips the bromopropyl alcohol relative to silicon tetrachloride 2-3 times mole, temperature of reaction is controlled not higher than 70 DEG C with rate of addition, after dripping off, system temperature is risen to 80-90 DEG C, insulation reaction 8-10h; 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-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates, the structure of this compound is shown below:
-OC in its formula
3h
6br is the mixture of 2-bromo-1-propoxy-or 1-bromo-2-propoxy-or 2-bromo-1-propoxy-and the bromo-2-propoxy-of 1-.
2. the preparation method of three [2-tri-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates according to claim 1, is characterized in that: described bromopropyl alcohol is the mixture of 2-bromopropyl alcohol, 1-bromo-2-propyl alcohol or 2-bromopropyl alcohol and the bromo-2-propyl alcohol of 1-.
3. the preparation method of fire retardant three [2-tri-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates according to claim 1, it is characterized in that: described organic solvent is ethylene dichloride, dioxane, acetonitrile, tetrachloroethane or glycol dimethyl ether, its organic solvent volume milliliter number is 2-3 times of silicon tetrachloride quality grams.
4. the preparation method of fire retardant three [2-tri-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates according to claim 2, 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.
5. the preparation method of fire retardant three [2-tri-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates according to claim 1, is characterized in that: described acid binding agent is trimeric cyanamide.
6. the preparation method of fire retardant three [2-tri-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates according to claim 1, 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 bromopropyl alcohol 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.
7. the preparation method of fire retardant three [2-tri-(bromine propoxy-) silicon trimethylammonium] chlorinated isocyanurates according to claim 6, is characterized in that: described filtrate decompression distillation removes desolventizing and excessive bromopropyl alcohol is the solvent or bromopropyl alcohol recovery use collected.
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| CN102731549A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Triazinetri-tri(chloropropyl) silicate compound and preparation method thereof |
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