CN102731545B - Isocyanurate chloropropyl chloroethyl silicate and preparation method thereof - Google Patents
Isocyanurate chloropropyl chloroethyl silicate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nitrogen, silicon and chlorine thee-element synergic flame retardant tri{2-chloro-3-[tri(chloroethoxy)silicon acyloxy]propyl}isocyanurate compound and a preparation method thereof. The structure of the compound is shown as a formula in the specification. The preparation method comprises the following steps: dripping organic solvent solution of triglycidyl Isocyanurate into silicon tetrachloride, and reacting for 4 to 6 hours at a temperature of between 50 and 70 DEG C; and cooling to 30 DEG C, introducing ethylene oxide under the liquid surface, reacting for 2 to 3 hours at a temperature of between 45 and 55 DEG C, and purifying to obtain the tri{2-chlor-3-[tri(chloroethoxy)silicon acyloxy]propyl}isocyanurate. The compound has good flame retardant plasticization, and is suitable for flame retardant plasticizer such as polyvinyl chloride, polyurethane, epoxy resin, unsaturated resin and the like; and the method has simple production process and low cost, and is easy for industrial production.
Description
Technical field
The present invention relates to a kind of nitrogen, silicon, chlorine element synergistic fire retardant tricarbimide chlorine propoxy-tetra-(chloroethyl) silicate compound and preparation method thereof, be specifically related to a kind of three { the chloro-3-[tri-of 2-(chloroethoxy) silicon acyloxy] propyl group } tricarbimide ester cpds and preparation method thereof, this compound is suitable for the flame-retardant plasticizer of polyvinyl chloride, urethane, epoxy resin, unsaturated polyester etc.
Background technology
Along with the development of national economy and the raising of living standards of the people, the macromolecular materials such as synthon, plastics, rubber are more and more widely used in the every field such as communications and transportation, material of construction, electronic apparatus, household furniture, interior decoration.But these macromolecular materials generally all have inflammableness, easy initiation fire accident, for solve synthetic materials resistance to combustion, press down the problems such as cigarette, guarantee the security that synthetic materials is used, effective means is to add fire retardant.Because halogenated flame retardant addition is few, cheap and good with synthetic materials consistency, do not change the original machining property of fire retardant goods, thereby be the organic fire-retardant of current production rate and usage quantity maximum.But because it can decompose problems such as producing hydrogen halide when burning, halogenated flame retardant is restricted.Along with day by day strengthening of fire-retardant awareness of the importance of fire prevention in world wide and being gradually improved of flame retardant regulation, promoted the research and development application of environment friendly flame retardant, especially novel, efficient, low toxicity type fire retardant faces more urgent demand.The addition of simultaneously developing efficient halogenated flame retardant minimizing fire retardant is the important directions of research to reach the amount of the hydrogen halide of being emitted when minimizing is burnt and to reduce the impact of material mechanical processing characteristics.The excellent properties that press down cigarette because silicon-type flame-retardant plasticizer has, promotes into carbon obtains people's attention.But silicon-type product price general charged is expensive, use range is narrow, and use is restricted.
The invention discloses that to take the silicon tetrachloride as by-product of polysilicon industry be main raw material synthetic nitrogen, silicon, chlorine element cooperative flame retardant immunomodulator compounds and preparation method thereof, the present invention combines nitrogenated flame retardant expandable flame retardant, silicon-series five-retardant can generate fine and close silicon carbon layer, the meteorological fire-retardant mechanism of halogenated flame retardant, developed the nitrogen of Cheap highly effective, silicon, chlorine element synergistic fire retardant tricarbimide chlorine propoxy-tetra-(chloroethyl) silicate compound, the research of this product has successfully been opened up an effective way to the comprehensive utilization of contaminated solution thing silicon tetrachloride, increased again a new and effective fire retardant kind to market, to promoting the fast development of China's Fire Retardant Industry, the safety that ensures people's lives and properties all has an important significance.
Summary of the invention
One of object of the present invention is to propose a kind of silicon tetrachloride as by-product synthetic nitrogen by polysilicon industry, silicon, chlorine cooperative flame retardant softening agent three { the chloro-3-[tri-of 2-(chlorine propoxy-) silicon acyloxy] propyl group } tricarbimide ester cpds, its flame-retarded efficiency is high, can overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
Three the chloro-3-[tri-of 2-(chloroethoxy) silicon acyloxy] and propyl group } tricarbimide ester cpds, it is characterized in that, the structure of this compound is shown below:
Another object of the present invention is to propose the synthetic method of a kind of three { the chloro-3-[tri-of 2-(chloroethoxy) silicon acyloxy] propyl group } tricarbimide ester cpds; its technique is simple, be easy to large-scale production, and raw material is cheap and easy to get, and facility investment is few; with low cost, the method is:
Under 20 ℃ of conditions, the organic solvent solution of certain density isocyanuric acid three-glycidyl ester is added drop-wise in the silicon tetrachloride of 3 times moles, be then warming up to 50 ℃～70 ℃ sustained reaction 4～6h; Cool to again 30 ℃, under liquid level, pass into the oxyethane of certain mol proportion, then be warming up to 45 ℃～55 ℃ sustained reaction 2～3h, when reaction solution PH=5-6, excessive oxyethane and organic solvent and a small amount of low boilers are removed in distillation, obtain three the chloro-3-[tri-of 2-(chloroethoxy) silicon acyloxy] and propyl group } chlorinated isocyanurates.
Finite concentration is that the quality of isocyanuric acid three-glycidyl ester and the volume ratio of organic solvent are 1 as mentioned above: 5-1: 15.
The oxyethane of certain mol proportion is isocyanuric acid three-glycidyl ester as mentioned above: silicon tetrachloride: oxyethane mol ratio is 1: 3: 9-1: 3: 12.
Organic solvent as above is for being dioxane, tetrahydrofuran (THF), acetonitrile or ethylene dichloride.
Tricarbimide chlorine propoxy-silicic acid chloroethene ester of the present invention is colourless or light yellow liquid, and product yield is 94.6%～97.3%, flash-point (open cup): 214 ± 5 ℃, and decomposition temperature: (278 ± 5) ℃, refractive index: n
d 20=1.6648, density (25 ℃): 1.383g/cm
3, it is suitable as the fire-retardant use of the materials such as polyvinyl chloride, urethane, epoxy resin, unsaturated polyester, and the synthesis technique principle of this tricarbimide chlorine propoxy-silicic acid chloroethene ester is shown below:
Compared with prior art, beneficial effect of the present invention is:
1. because tricarbimide chlorine propoxy-silicic acid chloroethene ester of the present invention is nitrogen, silicon, the agent of chlorine element collaborative type flame-retardant, cooperative flame retardant usefulness is high, and structural symmetry is good, product is stable, decomposition temperature is high, and has the intermiscibility of polyester structure and macromolecular material good, and plasticity is good.
2. the silicon tetrachloride problem of complex utilization that the solution polysilicon industry that is developed as of tricarbimide chlorine propoxy-tetra-(chloroethyl) silicate compound of the present invention gives off has searched out effective ways, and building-up process atom utilization 100%, more be conducive to environmental protection, there is good environmental benefit, there is again good economic benefit.
3. the synthesis technique equipment of tricarbimide chlorine propoxy-silicic acid chloroethene ester of the present invention is simple and easy to control, with low cost, is suitable for most chemical enterprise and carries out large-scale production.
Accompanying drawing explanation
In order to further illustrate structure and the performance spy of product, provide following accompanying drawing.
1, three the infrared spectrogram of { the chloro-3-[tri-of 2-(chloroethoxy) silicon acyloxy] propyl group } chlorinated isocyanurates, refers to Figure of description Fig. 1;
Fig. 1 shows, at 2964cm
-1-2884cm
-1place is c h bond stretching vibration peak, 2820-2780cm
-1place is the stretching vibration peak of C-N key, 1690-1700cm
-1place is the stretching vibration peak of ketonic linkage, 1464cm
-1place is-CH
2-flexural vibration peak, 1264cm
-1place is the stretching vibration peak of C-O key, 1114cm
-1place is the stretching vibration peak of Si-O key, 762cm
-1place is the stretching vibration peak of C-Cl key.
2, three the nuclear magnetic spectrum figure of { the chloro-3-[tri-of 2-(chloroethoxy) silicon acyloxy] propyl group } chlorinated isocyanurates, refers to Figure of description Fig. 2;
Fig. 2 shows, deuterochloroform is made solvent, and δ 3.58-3.65 place is-NCH
2cH (Cl) CH
2the upper methylene radical 2H peak being connected with oxygen of O-; δ 3.66-3.70 is-OCH
2cH
2the upper methylene radical 6H peak being connected with oxygen of Cl; δ 3.90-4.10 is-OCH
2cH
2the upper methylene radical 6H peak being connected with chlorine of Cl; δ 4.15-4.32 place is-NCH
2cH (Cl) CH
2the upper methylene radical 2H peak being connected with nitrogen of O-; δ 4.47-4.63 is-NCH
2cH (Cl) CH
2the upper chlorine substituted methylene 1H of O-peak; δ 7.29-7.30 place is the H peak of deuterochloroform solvent.
Specific embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further.
Embodiment 1, in the 100ml there-necked flask of agitator, thermometer and efficient backflow prolong is housed, adds 10ml acetonitrile, with nitrogen, catches up with the air in most bottle, accurately draws 3.40ml (0.03mol) SiCl
4be placed in there-necked flask.Taking 3.00g (0.01mol) isocyanuric acid three-glycidyl ester is dissolved in 40ml acetonitrile, at 20 ℃, will in the about 0.5h of this solution, be added drop-wise in there-necked flask, after dropwising, be warming up to 50 ℃ of insulation reaction 6h, be cooled to again 30 ℃, fill the expansion soft seal cover that can extremely stretch efficient backflow prolong is suitable for reading, under liquid level, pass into 3.96g (0.09mol) oxyethane, pass into process control temp not higher than 40 ℃, then be warming up to 55 ℃ of insulation reaction 3h, check reaction solution pH is terminal at 5-6, after reaction finishes, underpressure distillation goes out solvent and low boilers and obtains product three { the chloro-3-[tri-of 2-(chlorine propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates, productive rate is 94.6%, flash-point (open cup): 214 ± 5 ℃, decomposition temperature: 278 ± 5 ℃, refractive index: n
d 20=1.6648, density (25 ℃): 1.383g/cm
3.
Embodiment 2, in the 100ml there-necked flask of agitator, thermometer and efficient backflow prolong is housed, adds 10ml tetrahydrofuran (THF), with nitrogen, catches up with the air in most bottle, accurately draws 3.40ml (0.03mol) SiCl
4be placed in there-necked flask.Taking 3.00g (0.01mol) isocyanuric acid three-glycidyl ester is dissolved in 40ml tetrahydrofuran (THF), at 20 ℃, will in the about 0.5h of this solution, be added drop-wise in there-necked flask, after dropwising, be warming up to 50 ℃ of insulation reaction 4h, be cooled to again 30 ℃, fill the expansion soft seal cover that can extremely stretch efficient backflow prolong is suitable for reading, under liquid level, pass into 4.40g (0.10mol) oxyethane, pass into process control temp not higher than 40 ℃, then be warming up to 50 ℃ of insulation reaction 3h, check reaction solution pH is terminal at 5-6, after reaction finishes, underpressure distillation goes out solvent and low boilers and obtains product three { the chloro-3-[tri-of 2-(chlorine propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates, productive rate is 95.5%, flash-point (open cup): 214 ± 5 ℃, decomposition temperature: 278 ± 5 ℃, refractive index: n
d 20=1.6648, density (25 ℃): 1.383g/cm
3.
Embodiment 3, in the 100ml there-necked flask of agitator, thermometer and efficient backflow prolong is housed, adds 10ml dioxane, with nitrogen, catches up with the air in most bottle, accurately draws 3.40ml (0.03mol) SiCl
4be placed in there-necked flask.Take 3.00g (0.01mol) isocyanuric acid three-glycidyl ester and be dissolved in 40ml dioxane, at 20 ℃, will in the about 0.5h of this solution, be added drop-wise in there-necked flask, after dropwising, be warming up to 60 ℃ of insulation reaction 5h, be cooled to again 30 ℃, fill the expansion soft seal cover that can extremely stretch efficient backflow prolong is suitable for reading, under liquid level, pass into 4.84g (0.11mol) oxyethane, pass into process control temp not higher than 40 ℃, then be warming up to 45 ℃ of insulation reaction 2h, check reaction solution pH is terminal at 5-6, after reaction finishes, underpressure distillation goes out solvent and low boilers and obtains product three { the chloro-3-[tri-of 2-(chlorine propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates, productive rate is 96.3%, flash-point (open cup): 214 ± 5 ℃, decomposition temperature: 278 ± 5 ℃, refractive index: n
d 20=1.6648, density (25 ℃): 1.383g/cm
3.
Embodiment 4, in the 100ml there-necked flask of agitator, thermometer and efficient backflow prolong is housed, adds 10ml ethylene dichloride, with nitrogen, catches up with the air in most bottle, accurately draws 3.40ml (0.03mol) SiCl
4be placed in there-necked flask.Take 3.00g (0.01mol) isocyanuric acid three-glycidyl ester and be dissolved in 40ml ethylene dichloride, at 20 ℃, will in the about 0.5h of this solution, be added drop-wise in there-necked flask, after dropwising, be warming up to 70 ℃ of insulation reaction 5h, be cooled to again 30 ℃, fill the expansion soft seal cover that can extremely stretch efficient backflow prolong is suitable for reading, under liquid level, pass into 5.28g (0.12mol) oxyethane, pass into process control temp not higher than 40 ℃, then be warming up to 45 ℃ of insulation reaction 2h, check reaction solution pH is terminal at 5-6, after reaction finishes, underpressure distillation goes out solvent and low boilers and obtains product three { the chloro-3-[tri-of 2-(chlorine propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates, productive rate is 97.3%, flash-point (open cup): 214 ± 5 ℃, decomposition temperature: 278 ± 5 ℃, refractive index: n
d 20=1.6648, density (25 ℃): 1.383g/cm
3.
Table 1 preparation example main technologic parameters
This case contriver is also applied to above-mentioned synthetic cyanuric acid chlorine propoxy-silicic acid chloroethene ester in polyvinyl chloride.Reference: the limiting oxygen index(LOI) of GB/T2406-2008 < < Plastics Combustion method for testing performance-oxygen index method > > test sample product.After getting product three { the chloro-3-[tri-of 2-(chlorine propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates, plasticizer phthalic acid dioctyl ester, synergistic flame retardant antimonous oxide and polyvinyl chloride and mixing in varing proportions, with forcing machine, extrude, make the batten that diameter is 3mm, and its flame retardant properties is tested, listed part test result as shown in the table:
The flame retardant properties data of table 2 three { the chloro-3-[tri-of 2-(chlorine propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates
Claims (2)
1. a preparation method for nitrogen, silicon, chlorine element synergistic fire retardant three { the chloro-3-[tri-of 2-(chloroethoxy) silicon acyloxy] propyl group } chlorinated isocyanurates, is characterized in that, the method is:
Under 20 ℃ of conditions, control isocyanuric acid three-glycidyl ester: silicon tetrachloride: the mol ratio of oxyethane is 1: 3: 9-1: 3: 12, it is 1 that isocyanuric acid three-glycidyl ester quality grams and organic solvent volume milliliter are counted to ratio: 5-1: 15 solution is added drop-wise in silicon tetrachloride, is then warming up to 50 ℃～70 ℃ sustained reaction 4～6h; Cool to again 30 ℃, under liquid level, pass into oxyethane, then be warming up to 45 ℃～55 ℃ sustained reaction 2～3h, when reaction solution pH=5-6, excessive oxyethane and organic solvent and a small amount of low boilers are removed in distillation, three { the chloro-3-[tri-of 2-(chloroethoxy) silicon acyloxy] propyl group } chlorinated isocyanurates, the structure of this compound is shown below:
2. according to claim 1 three the preparation method of { the chloro-3-[tri-of 2-(chloroethoxy) silicon acyloxy] propyl group } chlorinated isocyanurates, is characterized in that: described organic solvent is for being dioxane, tetrahydrofuran (THF), acetonitrile or ethylene dichloride.
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| CN102731544B (en) * | 2012-07-17 | 2014-12-10 | 苏州科技学院 | Triazine trichloropropoxy tris(chloroethyl) silicate compound and preparation method thereof |
| CN103554148B (en) * | 2013-11-08 | 2015-11-25 | 苏州科技学院相城研究院 | Fire retardant match gram three silicic acid bromine ethyl ester compounds and preparation method thereof |
| CN103554155B (en) * | 2013-11-08 | 2015-12-30 | 苏州科技学院相城研究院 | Fire retardant match gram three tetra-(chloroethyl) silicate compounds and preparation method thereof |
| CN103554149B (en) * | 2013-11-08 | 2015-11-25 | 苏州科技学院相城研究院 | Three [2-tri-(1,3-dibromo isopropoxy) silicon trimethylammonium] isocyanurate compounds and preparation method thereof |
| CN103554146B (en) * | 2013-11-08 | 2015-12-30 | 苏州科技学院相城研究院 | Fire retardant match gram three silicic acid chlorine bromine propyl ester compounds and preparation method thereof |
| CN103539807B (en) * | 2013-11-08 | 2016-04-06 | 苏州科技学院相城研究院 | Three [2-tri-(1,3-dichloro isopropoxy) silicon trimethylammonium] isocyanurate compounds and preparation method thereof |
| CN104672267B (en) * | 2015-03-06 | 2019-04-16 | 苏州阳桥化工科技有限公司 | The preparation method of fire retardant match gram dimethyl halo ethyoxyl silicate ester compound |
| CN104744504B (en) * | 2015-03-06 | 2017-10-17 | 湖州睿高新材料有限公司 | A kind of silicon, nitrogen, the preparation method of halogen multielement cooperative flame retardant immunomodulator compounds |
| CN104710468B (en) * | 2015-03-06 | 2018-05-04 | 苏州阳桥化工科技有限公司 | Isocyanuric acid three (dimethyl dihalo- propoxyl group silicon acyloxy halogen propyl group) ester compounds and preparation method thereof |
| CN104672270B (en) * | 2015-03-06 | 2018-05-04 | 苏州阳桥化工科技有限公司 | Isocyanuric acid three (dimethyl halogen propoxyl group silicon acyloxy halogen propyl group) ester compounds and preparation method thereof |
| CN104693230B (en) * | 2015-03-06 | 2018-08-21 | 湖州睿高新材料有限公司 | A kind of preparation method of silicon, nitrogen, halogen cooperative flame retardant plasticizer |
| CN104672271B (en) * | 2015-03-06 | 2018-05-04 | 苏州阳桥化工科技有限公司 | Isocyanuric acid three (dimethyl halogen ethyoxyl silicon acyloxy halogen propyl group) ester compounds and preparation method thereof |
| CN107474220B (en) * | 2017-08-21 | 2019-05-10 | 成都纺织高等专科学校 | A kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin and preparation method thereof |
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