CN103554149B - Three [2-tri-(1,3-dibromo isopropoxy) silicon trimethylammonium] isocyanurate compounds and preparation method thereof - Google Patents
Three [2-tri-(1,3-dibromo 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 42
- 239000010703 silicon Substances 0.000 title claims abstract description 42
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 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 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000003063 flame retardant Substances 0.000 claims abstract description 42
- -1 bromo-2-propyl Chemical group 0.000 claims abstract description 36
- 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
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 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 30
- 239000007789 gas Substances 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 15
- 238000009413 insulation Methods 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
- 238000010792 warming Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 238000000034 method Methods 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
- 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
- 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 6
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 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
- 238000005516 engineering 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 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
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 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
- 238000003786 synthesis reaction Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 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
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 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
- 239000002574 poison Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 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
- 239000000126 substance Substances 0.000 description 1
Abstract
The present invention relates to a kind of fire retardant three [2-tri-(1,3-dibromo 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-dibromo isopropoxy) silicon trimethylammonium] isocyanurate compounds and preparation method thereof, this compound silicon, nitrogen and bromine 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 the fast development of China's synthesized polymer material industry, macromolecular material is widely used in every field such as building materials, electronic apparatus, communications and transportation, space flight and aviation, household furniture, upholstery and clothing, food, lodging and transportion--basic necessities of life.Because it has inflammableness mostly, often cause fire, facilitate the research of fire retardant and the application of fire retardant material.The production and supplyment main halogen system product of China's fire retardant, in halogen system, bromide fire retardant effect is best.But after sending RoHS instruction from European Union in 1986, first Poly Brominated Diphenyl Ethers is restricted, the halogenated flame retardant of broad sense all receives restriction subsequently, halogenated flame retardant is had higher requirement, exploitation high-efficiency low-toxicity halogenated flame retardant has become the important topic of research, be wherein effective means by the composite raising flame-retarded efficiency of multiple fire retardant, and be the approach realizing efficient flame-retarding agent by designing in molecule that multielement works in coordination with.Silicon system hinders right agent and itself has excellent thermostability, effective anti-melt drippage and smoke suppressing, it is one of the emphasis of current low cigarette, low-poison and combustion-resisting developing material, nitrogenated flame retardant has excellent expansion heat-blocking action, and exploitation nitrogen, silicon and bromine element synergistic fire retardant are one of important research directions.
Containing the ignition-proof element that silicon, nitrogen and bromine three kinds is excellent in fire retardant three [2-tri-(1,3-dibromo isopropoxy) silicon trimethylammonium] tricarbimide ester molecule of the present invention, good cooperative flame retardant effect can be produced.Its raw materials make use of the silicon tetrachloride as by-product of polysilicon, for the pollution problem solving silicon tetrachloride opens an effective way; Product application scope is wide, and comprehensive cost performance is high, synthesis technique environmental friendliness, meets the researchdevelopment direction of fire retardant, has very wide DEVELOPMENT PROSPECT.
Summary of the invention
An object of the present invention is that a kind of fire retardant three [2-tri-(1 prepared by proposition silicon tetrachloride, 3-dibromo isopropoxy) silicon trimethylammonium] isocyanurate compounds, its silicon, nitrogen and bromine cooperative flame retardant usefulness are high, Stability Analysis of Structures, good with material compatibility, deficiency of the prior art can be overcome.
For achieving the above object, present invention employs following technical scheme:
Fire retardant three [2-tri-(1,3-dibromo 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-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates, its cheaper starting materials is easy to get; technique is simple; 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, temperature of reaction system is made to be reduced to less than 30 DEG C, drip and silicon tetrachloride equimolar 1, the bromo-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 40 DEG C, after dripping off, be warming up to 50 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 70 DEG C with rate of addition, after dripping off, be warming up to 85-95 DEG C, reaction 9-12h; 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 bromo-2-propyl alcohol of 3-bis-, control temperature of reaction not higher than 65 DEG C with rate of addition, after dripping off, system temperature is risen to 85-95 DEG C of 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-(1,3-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates.
Organic solvent as above is tetrachloroethane, dioxane, glycol dimethyl ether, 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 bromo-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 first allow silicon tetrachloride with react relative to mole 1,3-bis-bromo-2-propyl alcohol such as silicon tetrachlorides, generation 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-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates disclosed by the invention is yellow transparent liquid, and productive rate is 87.4% ~ 93.5%, its flash-point (open cup): 209 ± 5 DEG C, refractive index: n
d 25=1.5431, density (25 DEG C): 2.252g/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.
The synthesis technique principle of fire retardant three [2-tri-(1,3-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates is shown below:
SiCl
4+HOCH(CH
2Br)
2→Cl
3Si-OCH(CH
2Br)
2
Compared with prior art, beneficial effect of the present invention is:
1. fire retardant three [2-tri-(1 of the present invention, 3-dibromo isopropoxy) silicon trimethylammonium] isocyanurate compounds contains silicon, nitrogen and bromine three kinds of elements, 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-dibromo 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 bromine synergistic fire retardant three [2-tri-(1 prepared by raw material, 3-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates, 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 bromo-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-bromo-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-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates, refers to Figure of description Fig. 1;
Fig. 1 shows, 2981cm
-1(stretching vibration with the C-H of bromo); 2938cm
-1and 2887cm
-1(stretching vibration of C-H); 1698cm
-1(stretching vibration of C=O); 1089cm
-1and 874cm
-1(stretching vibration of Si-O-C and flexural vibration); 1437cm
-1(flexural vibration of C-H); 1024cm
-1and 972cm
-1(stretching vibration of C-O); 1379cm
-1(stretching vibration of C-N); 631cm
-1(stretching vibration of C-Br).
2, the nuclear magnetic spectrum figure of three [2-tri-(1,3-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates, refers to Figure of description Fig. 2;
Fig. 2 shows, deuterochloroform makes solvent, and δ 4.13-4.23 is-OCH (CH
2br)
2in hydrogen peak on the methyne that is connected with oxygen; δ 3.96-4.05 is-NCH
2cH
2hydrogen peak on the methylene radical be connected with oxygen in OSi-; δ 3.47-3.70 is-OCH (CH
2br)
2the hydrogen peak of middle brooethyl; δ 3.21-3.26 is-NCH
2cH
2hydrogen peak on 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 30 DEG C, drip 10.89g (5.14ml, 0.05mol) 1, the bromo-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 40 DEG C, after dripping off, be warming up to 50 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 70 DEG C with rate of addition, 95 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 bromo-2-propyl alcohol of 22.007g (10.38ml, 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 10h; 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 1,3-bis-bromo-2-propyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add the washing of 80ml 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-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 87.4%, flash-point (open cup): 209 ± 5 DEG C, refractive index: n
d 25=1.5431, density (25 DEG C): 2.252g/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 30 DEG C, drip 10.89g (5.14ml, 0.05mol) 1, the bromo-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 40 DEG C, after dripping off, be warming up to 50 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 70 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 bromo-2-propyl alcohol of 23.969g (11.31ml, 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 9h; After HCl gas discharges, then add 1.2g trimeric cyanamide, insulated and stirred 1h, detecting solution PH=5-6 is reaction end.Be cooled to 35 DEG C, filter, filtrate is underpressure distillation removing dioxane and excessive 1,3-bis-bromo-2-propyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add the washing of 80ml 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-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 93.5%, flash-point (open cup): 209 ± 5 DEG C, refractive index: n
d 25=1.5431, density (25 DEG C): 2.252g/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 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 30 DEG C, drip 10.89g (5.14ml, 0.05mol) 1, the bromo-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 40 DEG C, after dripping off, be warming up to 50 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 70 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 bromo-2-propyl alcohol of 26.148g (12.33ml, 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 85 DEG C, insulation reaction 10h; After HCl gas discharges, then add 1g 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 1,3-bis-bromo-2-propyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add the washing of 80ml 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-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 88.6%, flash-point (open cup): 209 ± 5 DEG C, refractive index: n
d 25=1.5431, density (25 DEG C): 2.252g/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 30 DEG C, drip 10.89g (5.14ml, 0.05mol) 1, the bromo-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 40 DEG C, after dripping off, be warming up to 50 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, controls temperature of reaction not higher than 70 DEG C with rate of addition, after dripping off, be warming up to 90 DEG C, reaction 11h; After HCl gas discharges, then system is cooled to less than 50 DEG C, drips 28.327g (13.36ml, 0.13mol) 1,3-bis-bromo-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 95 DEG C, insulation reaction 8h; After HCl gas discharges, then add 1.5g trimeric cyanamide, insulated and stirred 1h, detecting solution PH=5-6 is reaction end.Be cooled to 35 DEG C, filter, filtrate is underpressure distillation removing toluene and excessive 1,3-bis-bromo-2-propyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add the washing of 80ml 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-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 91.4%, flash-point (open cup): 209 ± 5 DEG C, refractive index: n
d 25=1.5431, density (25 DEG C): 2.252g/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 30 DEG C, drip 10.89g (5.14ml, 0.05mol) 1, the bromo-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 40 DEG C, after dripping off, be warming up to 50 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, temperature of reaction is controlled not higher than 70 DEG C with rate of addition, 95 DEG C are warming up to after dripping off, reaction 9h, after HCl gas discharges, again system is cooled to less than 50 DEG C, drip the bromo-2-propyl alcohol of 30.506g (14.39ml, 0.14mol) 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 1.8g 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 diethylene glycol dimethyl ether and excessive 1,3-bis-bromo-2-propyl alcohol (reclaim use) and a small amount of low boilers again, then cool to 60 DEG C, add the washing of 80ml 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-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates.Its productive rate is 92.7%, flash-point (open cup): 209 ± 5 DEG C, refractive index: n
d 25=1.5431, density (25 DEG C): 2.252g/cm
3.
Table 1 three [2-tri-(1,3-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates preparation example main technologic parameters
Three [2-tri-(1,3-dibromo 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-dibromo 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-dibromo isopropoxy) silicon trimethylammonium] chlorinated isocyanurates
Experiment shows, fire retardant three [2-tri-(1,3-dibromo 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 (6)
1. the preparation method of fire retardant three [2-tri-(1, a 3-dibromo 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 30 DEG C, drip and silicon tetrachloride equimolar 1, the bromo-2-propyl alcohol of 3-bis-, drips process control temperature of reaction not higher than 40 DEG C, after dripping off, be warming up to 50 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 system not higher than 70 DEG C with rate of addition, after dripping off, be warming up to 85-95 DEG C, reaction 9-12h; 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 bromo-2-propyl alcohol of 3-bis-, control temperature of reaction not higher than 65 DEG C with rate of addition, after dripping off, system temperature is risen to 85-95 DEG C of 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, the structure obtaining fire retardant three [2-tri-(1,3-dibromo isopropoxy) silicon trimethylammonium] this compound of chlorinated isocyanurates is shown below:
2. fire retardant three [2-tri-(1 according to claim 1,3-dibromo isopropoxy) silicon trimethylammonium] preparation method of chlorinated isocyanurates, it is characterized in that: described organic solvent is tetrachloroethane, dioxane, glycol dimethyl ether, 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-dibromo 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-dibromo 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-dibromo 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 bromo-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.
6. fire retardant three [2-tri-(1 according to claim 5,3-dibromo isopropoxy) silicon trimethylammonium] preparation method of chlorinated isocyanurates, it is characterized in that: described filtrate decompression distillation is except desolventizing and excessive 1,3-bis-bromo-2-propyl alcohol is the solvent or 1,3-bis-bromo-2-propyl alcohol recovery use collected.
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| CN102731545A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Isocyanurate chloropropyl chloroethyl silicate and preparation method thereof |
| CN102731549A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Triazinetri-tri(chloropropyl) silicate compound and preparation method thereof |
| CN102731830A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Nitrogen-containing chloro-polysilicate compound and preparation method thereof |
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| CN102731545A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Isocyanurate chloropropyl chloroethyl silicate and preparation method thereof |
| CN102731549A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Triazinetri-tri(chloropropyl) silicate compound and preparation method thereof |
| CN102731830A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Nitrogen-containing chloro-polysilicate compound and preparation method thereof |
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