CN102731830B - Nitrogen-containing chloro-polysilicate compound and preparation method thereof - Google Patents
Nitrogen-containing chloro-polysilicate compound and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a tri{2-chloro-3-[tri(dichloropropoxy)silicon acyloxy]propyl}isocyanurate compound and a preparation method thereof. The structure of the compound is shown in the specification. The preparation method comprises the steps of adding triglycidyl isocyanurate in a certain molar ratio to silicon tetrachloride, preserving heat at 60 DEG C and reacting for 4-5 hours, then dropwise adding epoxy chloropropane in a certain molar ratio, preserving heat at 70-90 DEG C and reacting for 6-8 hours to obtain tri{2-chloro-3-[tri(dichloropropoxy)silicon acyloxy]propyl}isocyanurate through purification treatment. The compound is an excellent flame-retardant plasticizer; and the preparation method is simple in production process and low in equipment investment and is easy for industrial production.
Description
Technical field
The present invention relates to a kind of nitrogenous chloro multi-silicate ester cpds and preparation method thereof, be specifically related to a kind of three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } tricarbimide ester cpds and preparation method thereof.This compound belongs to nitrogen, silicon, chlorine element cooperative flame retardant softening agent, is suitable as the flame-retardant plasticizer of polyvinyl chloride, urethane, Resins, epoxy and unsaturated polyester etc.
Background technology
Along with the widespread use of macromolecular material, because its inflammable fire that often causes can bring serious threat for people's lives and properties, thereby promoted the research of flame-retarded technology and the fast development of flame-retardant plasticizer industry.Flame-retardant plasticizer is to have the plastic processing additives that anti-flaming function has plastification again, and it can overcome because the adding of softening agent makes the more inflammable problem of macromolecular material.More to organic phosphate flame-retardant softening agent research at present, that people always wish to have is new and effective, low toxicity, cheap flame-retardant plasticizer occur in market.For this exploitation to multielement cooperative flame retardant softening agent has become the hot research problem.Owing to silicon is that flame-retardant plasticizer has the attention that the excellent properties that presses down cigarette, promotes into carbon obtains people, but general silicon-series five-retardant exists price height, use range narrow, is restricted.It is the novel nitrogen of feedstock production, silicon, chlorine cooperative flame retardant softening agent three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates that the inventor has researched and developed out silicon tetrachloride as by-product with the polysilicon industry.The present invention can solve the difficult problem of silicon tetrachloride comprehensive utilization, has opened up cheap good flame-retardant plasticizer new variety again, has good environmental benefit, also has good economic implications.
Summary of the invention
One of purpose of the present invention is that its fire-retardant plasticity is good, can overcome deficiency of the prior art with the synthetic a kind of nitrogen of silicon tetrachloride, silicon, chlorine cooperative flame retardant softening agent three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } tricarbimide ester cpds.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of three 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] and propyl group } the 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 preparation method of a kind of as mentioned above three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates; its technology 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, this method is:
Under 25 ℃, the organic solvent solution of the isocyanuric acid three-glycidyl ester of certain mol proportion is added drop-wise in the mixed solution of silicon tetrachloride and organic solvent, cooling is controlled temperature below 30 ℃ with rate of addition down, after dripping off, in one hour temperature is risen to 60 ℃, insulation reaction 4～5h, after reaction finishes, system temperature is down to 50 ℃, epoxy chloropropane with certain mol proportion, be added drop-wise in the above-mentioned mixed solution, after dripping off system temperature is risen to 70-90 ℃, insulation reaction 6～8h is after reaction finishes, underpressure distillation goes out organic solvent and excessive epoxy chloropropane (reclaim and use) and a spot of low boilers, gets colourless or weak yellow liquid three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates.
Aforesaid certain mol proportion is isocyanuric acid three-glycidyl ester: silicon tetrachloride: the epoxy chloropropane mol ratio is 1: 3: 9～1: 3: 12.
Aforesaid organic solvent is acetonitrile, ethylene dichloride, tetrachloroethane, dioxane or diethylene glycol dimethyl ether.
Of the present invention three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates is colourless or weak yellow liquid, productive rate is 96%～99%, its flash-point (open cup): 240 ± 5 ℃, decomposition temperature: 280 ± 5 ℃, density (25 ℃): 1.413g/cm
3, refractive index: n
D 25=1.5666.It is suitable as the usefulness of the flame-retardant plasticizer of materials such as polyvinyl chloride, polyvinyl alcohol, Resins, epoxy, unsaturated polyester, urethane.
The synthesis technique principle of three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates is shown below:
Compared with prior art, beneficial effect of the present invention is:
1. the structure of { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates has symmetry feature preferably because the present invention three, its physical and chemical performance is stable, good with the macromolecular material intermiscibility, good processability, nitrogen, silicon, chlorine element cooperative flame retardant usefulness height, silicon ester structure plasticity is good.
2. the present invention is raw material synthetic three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates with polysilicon industry silicon tetrachloride as by-product, can solve the difficult problem of silicon tetrachloride comprehensive utilization, open up cheap good flame-retardant plasticizer new variety again, had good environmental benefit.
3. the designed synthetic route of the present invention is addition reaction entirely, and atom utilization reaches 100%, and the yield height meets the green synthesis process requirement.
4. raw material of the present invention is cheap and easy to get, and cost is low, all is addition reaction, does not produce any pollutent, meets the friendly process theory; The preparation method is simple, is easy to large-scale production, has good economic implications.
Description of drawings
For structure and the performance spy who further specifies product provides following accompanying drawing.
1, three the infrared spectrogram of { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates, see Figure of description Fig. 1 for details:
Fig. 1 shows, 760cm
-1(stretching vibration of C-Cl); 1701cm
-1(stretching vibration of C=O); 1096cm
-1And 870cm
-1(stretching vibration of Si-O-C and flexural vibration); 1017cm
-1(stretching vibration of C-O); 2340cm
-1(stretching vibration of O=C-N); 1460cm
-1(stretching vibration of C-N).
2, three the nuclear magnetic spectrum figure of { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates, see Figure of description Fig. 2 for details:
Fig. 2 shows that deuterochloroform is made solvent, and δ 3.675-3.702 place is-OCH
2CH (Cl) CH
2The last chlorine substituent methyl of Cl H peak; δ 3.784-3.800 is-OCH
2CH (Cl) CH
2The last chlorine substituted methylene of Cl H peak; δ 3.705-3.740 is-OCH
2CH (Cl) CH
2The last methylene radical H peak that links to each other with oxygen of Cl; δ 4.031-4.142 is-NCH
2CH (Cl) CH
2The methylene radical H peak that the last oxygen of O-links to each other; δ 3.902-4.053 is-NCH
2CH (Cl) CH
2The last chlorine substituted methylene of O-H peak; δ 4.394-4.503 is-NCH
2CH (Cl) CH
2The last methylene radical H peak that links to each other with nitrogen of O-; δ 7.26 makes solvent H peak for deuterochloroform.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further.
Embodiment 2 is being equipped with agitator, thermometer, add the 10ml ethylene dichloride in the 100ml four-hole reaction flask of efficient reflux condensing tube, 3.40ml (0.03mol) silicon tetrachloride, 25 ℃ drip the dichloroethane solution 50ml that contains 3.00g (0.01mol) isocyanuric acid three-glycidyl ester down, be no more than 30 ℃ with rate of addition hierarchy of control temperature, after dripping off, be warming up to 60 ℃ in the 1h, insulation reaction 5h, then system temperature is down to 50 ℃, drip 9.25 (0.10mol) epoxy chloropropane, after dripping off, be warmed up to 80 ℃, insulation reaction 8h, work as PH=5-6, reaction finishes, underpressure distillation desolventizing and excessive epoxy chloropropane (reuse) and a spot of low boilers, colourless liquid three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates, product yield 97%.Its flash-point (open cup): 240 ± 5 ℃, decomposition temperature: 280 ± 5 ℃, density (25 ℃): 1.413g/cm
3, refractive index: n
D 25=1.5666.
Embodiment 3 is being equipped with agitator, thermometer, add the 10ml tetrachloroethane in the 100ml four-hole reaction flask of efficient reflux condensing tube, 3.40ml (0.03mol) silicon tetrachloride, 25 ℃ drip the tetrachloroethane solution 50ml that contains 3.00g (0.01mol) isocyanuric acid three-glycidyl ester down, be no more than 30 ℃ with rate of addition hierarchy of control temperature, after dripping off, be warming up to 60 ℃ in the 1h, insulation reaction 5h, then system temperature is down to 50 ℃, drip 10.18g (0.11mol) epoxy chloropropane, after dripping off, be warmed up to 90 ℃, insulation reaction 7h, work as PH=5-6, reaction finishes, underpressure distillation desolventizing and excessive epoxy chloropropane (reuse) and a spot of low boilers, colourless liquid three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates, product yield 98%.Its flash-point (open cup): 240 ± 5 ℃, decomposition temperature: 280 ± 5 ℃, density (25 ℃): 1.413g/cm
3, refractive index: n
D 25=1.5666.
Embodiment 4 is being equipped with agitator, thermometer, add the 10ml dioxane in the 100ml four-hole reaction flask of efficient reflux condensing tube, 3.40ml (0.03mol) silicon tetrachloride, 25 ℃ drip the dioxane solution 50ml that contains 3.00g (0.01mol) isocyanuric acid three-glycidyl ester down, be no more than 30 ℃ with rate of addition hierarchy of control temperature, after dripping off, be warming up to 60 ℃ in the 1h, insulation reaction 4h, then system temperature is down to 50 ℃, drip 11.18g (0.12mol) epoxy chloropropane, after dripping off, be warmed up to 80 ℃, insulation reaction 6h, work as PH=5-6, reaction finishes, underpressure distillation desolventizing and excessive epoxy chloropropane (reuse) and a spot of low boilers, colourless liquid three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates, product yield 99%.Its flash-point (open cup): 240 ± 5 ℃, decomposition temperature: 280 ± 5 ℃, density (25 ℃): 1.413g/cm
3, refractive index: n
D 25=1.5666.
Embodiment 5 is being equipped with agitator, thermometer, add the 10ml diethylene glycol dimethyl ether in the 100ml four-hole reaction flask of efficient reflux condensing tube, 3.40ml (0.03mol) silicon tetrachloride, 25 ℃ drip the diethylene glycol dimethyl ether solution 50ml that contains 3.00g (0.01mol) isocyanuric acid three-glycidyl ester down, be no more than 30 ℃ with rate of addition hierarchy of control temperature, after dripping off, be warming up to 60 ℃ in the 1h, insulation reaction 4h, then system temperature is down to 50 ℃, drip 11.18g (0.12mol) epoxy chloropropane, after dripping off, be warmed up to 90 ℃, insulation reaction 6h, work as PH=5-6, reaction finishes, underpressure distillation desolventizing and excessive epoxy chloropropane (reuse) and a spot of low boilers, colourless liquid three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates, product yield 98%.Its flash-point (open cup): 240 ± 5 ℃, decomposition temperature: 280 ± 5 ℃, density (25 ℃): 1.413g/cm
3, refractive index: n
D 25=1.5666.
Table 1 preparation example main technologic parameters
This case contriver also is applied to above-mentioned synthetic three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates in the polyvinyl chloride.The limiting oxygen index(LOI) of reference: GB/T2406-2008 " plastics combustibility test method-oxygen index method " test sample product.After getting product silicon halogen cooperative flame retardant softening agent methyl three (2-chlorine propoxy-) silane, plasticizer phthalic acid dioctyl ester, synergistic flame retardant antimonous oxide and polyvinyl chloride and mixing in varing proportions, extrude with forcing machine, make the batten that diameter is 3mm, and its flame retardant properties tested, it is as shown in table 2 to have listed the part test result:
The flame retardant properties data of table 2 three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates
Claims (3)
1. nitrogenous chloro multi-silicate ester flame retardant compound is specifically related to a kind of three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } tricarbimide ester cpds, it is characterized in that the structure of this compound is shown below:
2. the preparation method of { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates according to claim 1 three is characterized in that this method is:
Under 25 ℃, control raw material isocyanuric acid three-glycidyl ester: silicon tetrachloride: the epoxy chloropropane mol ratio is 1: 3: 9-1: 3: 12, the organic solvent solution of isocyanuric acid three-glycidyl ester is added drop-wise in the mixed solution of silicon tetrachloride and organic solvent, control temperature below 30 ℃ with rate of addition, after dripping off, in one hour temperature risen to 60 ℃ of insulation reaction 4-5h, after reaction finishes, system temperature is down to 50 ℃, with epoxy chloropropane, be added drop-wise in the above-mentioned mixed solution, after dripping off system temperature risen to 70-90 ℃ of insulation reaction 6-8h, after reaction finished, underpressure distillation went out organic solvent and excessive epoxy chloropropane and a spot of low boilers, got colourless or weak yellow liquid three { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates.
3. as the preparation method of { 2-chloro-3-[three (dichloro propoxy-) silicon acyloxy] propyl group } chlorinated isocyanurates as described in the claim 2 three, it is characterized in that: described organic solvent is acetonitrile, ethylene dichloride, tetrachloroethane, dioxane or diethylene glycol dimethyl ether.
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| CN103524545B (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 propyl ester compounds and preparation method thereof |
| CN103554150B (en) * | 2013-11-08 | 2015-10-21 | 苏州科技学院相城研究院 | Fire retardant match gram three silicic acid dibromo propyl ester 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 |
| CN103554165B (en) * | 2013-11-08 | 2015-12-09 | 苏州科技学院相城研究院 | Two silicic acid chlorine propyl ester compound of fire retardant second dioxy support 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 |
| 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 |
| CN103554153B (en) * | 2013-11-08 | 2016-04-27 | 苏州科技学院相城研究院 | The preparation method of fire retardant three [2-tri-(chloroethoxy) silicon trimethylammonium] chlorinated isocyanurates |
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| CN103554147B (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 propyl ester compounds and preparation method thereof |
| CN103554158B (en) * | 2013-11-08 | 2015-11-25 | 苏州科技学院相城研究院 | Fire retardant two [three (the bromo-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane compounds and preparation method thereof |
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Effective date of registration: 20191118 Address after: 215600 No.11 Renmin Road, Leyu Town, Zhangjiagang City, Suzhou City, Jiangsu Province Patentee after: Zhangjiagang Leyu science and Technology Innovation Park Investment Development Co., Ltd Address before: 215009, CREE campus, 1 hi tech Zone, Suzhou, Jiangsu Province, Suzhou University of science and technology Patentee before: Suzhou University of Science and Technology |