CN104672267B - The preparation method of fire retardant match gram dimethyl halo ethyoxyl silicate ester compound - Google Patents
The preparation method of fire retardant match gram dimethyl halo ethyoxyl silicate ester compound Download PDFInfo
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- CN104672267B CN104672267B CN201510100506.4A CN201510100506A CN104672267B CN 104672267 B CN104672267 B CN 104672267B CN 201510100506 A CN201510100506 A CN 201510100506A CN 104672267 B CN104672267 B CN 104672267B
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Abstract
The present invention relates to a kind of preparation method of fire retardant match gram dimethyl halo ethyoxyl silicate ester compound, the structure of the compound is shown below:
Description
Technical field
The present invention relates to a kind of preparation methods of fire retardant match gram dimethyl halo ethyoxyl silicate ester compound, specifically relate to
And three { 2- [dimethyl (2- chloroethoxy) silicon acyloxy] ethyl } isocyanuric acid ester and three { 2- [dimethyl (2- bromine oxethyl)
Silicon acyloxy] ethyl isocyanurate compound preparation method, which is suitable as polyvinyl chloride, polyurethane, epoxy
The flame-retardant plasticizer of resin, unsaturated-resin etc..
Background technique
With the development of national economy and the raising of living standards of the people, the application field of high molecular material is synthesized increasingly
Extensively.These high molecular materials be mostly it is inflammable, often cause fire, serious prestige caused to the security of the lives and property of people
The side of body.In order to solve synthetic material it is inflammable the problems such as, it is ensured that the safety that synthetic material uses, most efficient method be added resistance
Fire agent.Due to halogenated flame retardant additive amount it is few, it is cheap and with synthetic material compatibility it is good, do not change the original machine of substrate
Tool processing performance, thus be one of current production rate and the maximum organic fire-retardant of usage amount.But halogenated flame retardant is in burning
Harm to environment receives the query of society, has also been proposed tightened up requirement to halogenated flame retardant in recent years, i.e., towards height
Effect, environmental protection, cheap and good processing performance direction are developed.Therefore, design multielement collaboration halogenated flame retardant is to realize efficient resistance
The purpose of combustion, it has also become one of the hot spot of efficient halogenated flame retardant research and development.Wherein, organosilicon, nitrogen and halogen synergistic fire retardant
Flame-retarded efficiency is high, processing performance is good, and has into charcoal effect, can effectively prevent the two of material melted by heating drippage and generation
Secondary burning, thus by pro-gaze.
The invention discloses one kind with three (2- ethoxy) isocyanuric acid esters (Sai Ke, THEIC), dimethyldichlorosilane or
Two bromo-silicane of dimethyl and 2- ethylene halohydrin are the side of primary raw material preparation match gram dimethyl halo ethyoxyl silicate ester compound
Method.Fire retardant category silicon of the present invention, nitrogen, three element synergistic fire retardant of halogen, are played a role, wherein element silicon by multiple fire retardant mechanism
Fine and close silicon layer of charcoal can be generated, nitrogen expandable flame retardant, halogen element gas phase is fire-retardant, and three element cooperative flame retardants can generate excellent resistance
Fuel efficiency fruit.Fire retardant efficiency of the present invention is high, good with high molecular material compatibility, has a wide range of application, have exploitation well and
Application prospect.
Summary of the invention
It is an object of the invention to propose the preparation method of fire retardant match gram dimethyl halo ethyoxyl silicate ester compound,
Its simple process, equipment investment is few, is easy to large-scale production, and raw material is cheap and easy to get, and low in cost, its technical solution is as follows:
The preparation method of match gram dimethyl halo ethyoxyl silicate ester compound as described above, which is characterized in that this method
Are as follows:
Under nitrogen protection, first make three (2- ethoxy) isocyanuric acids and two bromo-silicane of dimethyldichlorosilane or dimethyl
It reacts, then is reacted with 2- ethylene halohydrin in organic solvent, then cooling, purification process, get Sai Ke dimethyl halo ethyoxyl
Esters of silicon acis.
Specifically, this method are as follows:
Under nitrogen protection, the dimethyldichlorosilane and three (2- ethoxy) isocyanuric acid esters for making molar ratio 3: 1 exist
React 5~9h in organic solvent at 50 DEG C~70 DEG C, then with relative to 3~4 times moles of isocyanuric acid ester of three (2- ethoxy)
2- ethylene halohydrin 6~14h is reacted at 60 DEG C~100 DEG C；Or make two bromo-silicane of dimethyl and three of molar ratio 3: 1
(2- ethoxy) isocyanuric acid ester in organic solvent at 40 DEG C~70 DEG C react 4~7h, then with relative to three (2- hydroxyl second
Base) 3~4 times moles of isocyanuric acid ester of 2- ethylene halohydrin reacts 6~12h at 40 DEG C~100 DEG C；Purified processing must be matched
Gram dimethyl Chloroethoxy esters of silicon acis.
Further, this method specifically:
Under conditions of nitrogen protection, three (2- ethoxy) isocyanuric acid esters are dissolved in volume ml relative to three (2-
Ethoxy) isocyanuric acid ester 10~15 times of quality grams of organic solvent in, 30 DEG C or less be added relative to three (2- hydroxyl second
Base) 3 times moles of isocyanuric acid ester of dimethyldichlorosilane, 50 DEG C~70 DEG C are warming up to, 5~9h of insulation reaction；It is discharged to HCl
Afterwards, 30 DEG C are cooled to hereinafter, the 2- ethylene halohydrin relative to 3~4 times moles of isocyanuric acid ester of three (2- ethoxy) is added dropwise, with drop
Acceleration Control reaction temperature is not higher than 40 DEG C, 60 DEG C~100 DEG C is warming up to after dripping off, 6~14h of insulation reaction；Purified place
Reason, get Sai Ke dimethyl halo ethyoxyl esters of silicon acis.
This method may be used also are as follows:
Under conditions of nitrogen protection, three (2- ethoxy) isocyanuric acid esters are dissolved in volume ml relative to three (2-
Ethoxy) isocyanuric acid ester 10~15 times of quality grams of organic solvent in, 30 DEG C or less be added relative to three (2- hydroxyl second
Base) 3 times moles of isocyanuric acid ester of two bromo-silicane of dimethyl, 40 DEG C~70 DEG C are warming up to, 4~7h of insulation reaction；It is discharged to HBr
Afterwards, 30 DEG C are cooled to hereinafter, the 2- ethylene halohydrin relative to 3~4 times moles of isocyanuric acid ester of three (2- ethoxy) is added dropwise, with drop
Acceleration Control reaction temperature is not higher than 40 DEG C, 40 DEG C~100 DEG C is warming up to after dripping off, 6~12h of insulation reaction；Purified place
Reason, get Sai Ke dimethyl halo ethyoxyl esters of silicon acis.
The specific method of purification process as described above is the melamine being added relative to product theory quality 1%~5%,
Regulation system pH is 5~6, is filtered, and solvent, excessive 2- ethylene halohydrin and a small amount of low boilers are distilled off in filtrate decompression.
2- ethylene halohydrin as described above is ethylene chlorhydrin or ethylene bromohyrin.
Organic solvent as described above is dioxane, tetrahydrofuran, glycol dimethyl ether, acetonitrile or diethylene glycol diformazan
Ether.
The preparation process principle that the present invention matches gram dimethyl halo ethyoxyl esters of silicon acis is shown below:
X=Cl or Br, Y=Cl or Br in formula.
Match gram dimethyl chloride ethyoxyl esters of silicon acis of the invention is colourless or light yellow liquid, and decomposition temperature is 283 ± 5
DEG C, index of refraction nD 25=1.4826, (25 DEG C) of density are 1.32g/cm3；Match gram dimethyl bromine oxethyl esters of silicon acis be it is colourless or
Light yellow liquid, decomposition temperature are 307 ± 5 DEG C, index of refraction nD 25=1.5382, (25 DEG C) of density are 1.68g/cm3.It is suitable
Share the flame-retardant plasticizer for making the materials such as polyvinyl chloride, polyurethane, epoxy resin, unsaturated-resin.
Compared with prior art, the beneficial effects of the present invention are:
1. present invention match gram dimethyl halo ethyoxyl esters of silicon acis is siliceous, three kinds of nitrogen, halogen ignition-proof elements, cooperative flame retardant effect
Can be high, nitrogen has expansion heat insulation, and element silicon has into charcoal effect, can effectively prevent material melted by heating drippage and produces
Raw second-time burning.
2. connecting on silicon atom there are two methyl in present invention match gram dimethyl halo ethyoxyl silicate structure, there is C-Si
Key is organosilicon structures, and organosilicon structures stability is high, water resistance is strong, and when burning is more easily generated fine and close charcoal-silicon layer, resistance
Fuel efficiency fruit is more excellent.
3. dimethyl halo ethyoxyl esters of silicon acis molecular weight is big, volatility is low, symmetry is good, physical chemistry for present invention match gram
Performance is stablized, and belongs to more silicon, more nitrogen, more halogen, polyester structure, and ignition-proof element content is high, the vector construction each other of the atom in molecule,
It is good with high molecular material compatibility, adapt to the high temperature process in engineering material.
It is transparent 4. a present invention match gram dimethyl halo ethyoxyl esters of silicon acis belongs to heterocycle highly branched chain compound of silicate class
Thick liquid has good plasticity.
5. present invention match gram dimethyl halo ethyoxyl esters of silicon acis simple process, synthesis process are not drawn without adding catalyst
Entering impurity, equipment is simple, and it is low in cost, it is suitable for large-scale production, there is good application and development prospect.
Detailed description of the invention
Following attached drawing is provided in order to further illustrate the structure and performance spy of product.
1, the infrared spectrogram for matching gram dimethyl chloride ethyoxyl esters of silicon acis, is detailed in Figure of description Fig. 1；
Fig. 1 shows 2965.3cm-1And 2911.2cm-1Place is the stretching vibration absworption peak of C-H, 1702.8cm-1Place is carbonyl
The stretching vibration absworption peak of base, 1423.7cm-1Place is the bending vibration absorption peak of C-H, 1082.4cm-1Place is the spy of Si-O-C
Levy absorption peak, 826.3cm-1Place is the stretching vibration absworption peak of C-C1,801.9cm-1Place is the characteristic absorption peak of Si-C.
2, the nuclear magnetic spectrogram for matching gram dimethyl chloride ethyoxyl esters of silicon acis, is detailed in Figure of description Fig. 2；
Fig. 2 shows that deuterated chloroform makees solvent, and δ 0.04-0.25 is SiCH3Upper methyl hydrogen peak, δ 3.55-3.61 are
OCH2CH2The upper methylene hydrogen peak being connected with chlorine Cl, δ 3.93-3.98 are OCH2CH2The upper methylene hydrogen peak being connected with oxygen Cl, δ
3.79-3.93 being NCH2CH2The upper methylene hydrogen peak being connected with nitrogen O, δ 4.03-4.16 are NCH2CH2The upper methylene being connected with oxygen of O
Ji Qingfeng, δ 1.56 is water peak, and δ 7.26 is the proton peak of solvent carbon deuterium chloride exchange.
3, the infrared spectrogram for matching gram three (dimethyl bromine oxethyl esters of silicon acis), is detailed in Figure of description Fig. 3；
Fig. 3 shows 2963.7cm-1And 2901.2cm-1Place is the stretching vibration absworption peak of C-H, 1709.6cm-1Place is carbonyl
The stretching vibration absworption peak of base, 1004.9cm-1Place is the characteristic absorption peak of Si-O-C, 557.3cm-1Place is the flexible vibration of C-Br
Dynamic absorption peak, 1112.8cm-1Place is the stretching vibration absworption peak of C-O, 859.4cm-1Place is the characteristic absorption peak of Si-C.
4, the nuclear magnetic spectrogram for matching gram three (dimethyl bromine oxethyl esters of silicon acis), is detailed in Figure of description Fig. 4；
Fig. 4 shows that deuterated chloroform makees solvent, and δ 0.05-0.24 is SiCH3Upper methyl hydrogen peak, δ 3.58-3.69 are
OCH2CH2The upper methylene hydrogen peak being connected with bromine Br, δ 3.88-3.97 are OCH2CH2The upper methylene hydrogen peak being connected with oxygen Br, δ
3.72-3.88 being NCH2CH2The upper methylene hydrogen peak being connected with nitrogen O, δ 3.98-4.14 are NCH2CH2The upper methylene being connected with oxygen of O
Ji Qingfeng, δ 7.28 is the proton peak of solvent carbon deuterium chloride exchange.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment 1 is being equipped with blender, thermometer and condenser pipe, and is inhaled equipped with drying tube and hydrogen halides condenser pipe is suitable for reading
In the 250ml four-hole bottle of receiving apparatus, with the air in nitrogen displacement bottle falling, it is added 8.74g (0.0333mol) three (2- ethoxy)
Isocyanuric acid ester and 100ml dioxane, 30 DEG C or less addition 12.91g (0.1mol) dimethyldichlorosilanes, are warming up to 70
DEG C, insulation reaction 5h；After HCl gas discharges, 30 DEG C are cooled to hereinafter, 8.05g (0.1mol) ethylene chlorhydrin is added dropwise, to be added dropwise
Speed control reaction temperature is not higher than 40 DEG C, 100 DEG C is warming up to after dripping off, insulation reaction 6h；After HCl gas discharges, it is added
0.25g melamine, regulation system pH to 5~6 are filtered, and solvent and a small amount of low boilers, get Sai Ke is distilled off in filtrate decompression
Dimethyl chloride ethyoxyl esters of silicon acis, yield 89.6%.
Embodiment 2 is being equipped with blender, thermometer and condenser pipe, and is inhaled equipped with drying tube and hydrogen halides condenser pipe is suitable for reading
In the 250ml four-hole bottle of receiving apparatus, with the air in nitrogen displacement bottle falling, it is added 8.74g (0.0333mol) three (2- ethoxy)
Isocyanuric acid ester and 150ml tetrahydrofuran, 30 DEG C or less addition 12.91g (0.1mol) dimethyldichlorosilanes, are warming up to 50
DEG C, insulation reaction 9h；After HCl gas discharges, be cooled to 30 DEG C hereinafter, be added dropwise 8.59g (0.1067mol) ethylene chlorhydrin, with
Rate of addition controls reaction temperature and is not higher than 40 DEG C, 60 DEG C is warming up to after dripping off, insulation reaction 12h；After HCl gas discharges,
Be added 0.5g melamine, regulation system pH to 5~6, filter, filtrate decompression be distilled off solvent, excessive ethylene chlorhydrin and
A small amount of low boilers, get Sai Ke dimethyl chloride ethyoxyl esters of silicon acis, yield 90.5%.
Embodiment 3 is being equipped with blender, thermometer and condenser pipe, and is inhaled equipped with drying tube and hydrogen halides condenser pipe is suitable for reading
In the 250ml four-hole bottle of receiving apparatus, with the air in nitrogen displacement bottle falling, it is added 8.74g (0.0333mol) three (2- ethoxy)
Isocyanuric acid ester and 120ml acetonitrile, 30 DEG C or less addition 12.91g (0.1mol) dimethyldichlorosilanes are warming up to 60 DEG C, protect
Temperature reaction 8h；After HCl gas discharges, 30 DEG C are cooled to hereinafter, 9.39g (0.1167mol) ethylene chlorhydrin is added dropwise, speed is added dropwise
Degree control reaction temperature is not higher than 40 DEG C, 80 DEG C is warming up to after dripping off, insulation reaction 8h；After HCl gas discharges, 0.8g is added
Melamine, regulation system pH to 5~6 are filtered, and solvent, excessive ethylene chlorhydrin and a small amount of low boiling is distilled off in filtrate decompression
Point object, get Sai Ke dimethyl chloride ethyoxyl esters of silicon acis, yield 92.3%.
Embodiment 4 is being equipped with blender, thermometer and condenser pipe, and is inhaled equipped with drying tube and hydrogen halides condenser pipe is suitable for reading
In the 250ml four-hole bottle of receiving apparatus, with the air in nitrogen displacement bottle falling, it is added 8.74g (0.0333mol) three (2- ethoxy)
Isocyanuric acid ester and 90ml glycol dimethyl ether, 30 DEG C or less addition 12.91g (0.1mol) dimethyldichlorosilanes, are warming up to
60 DEG C, insulation reaction 7h；After HCl gas discharges, be cooled to 30 DEG C hereinafter, be added dropwise 10.74g (0.1333mol) ethylene chlorhydrin,
40 DEG C are not higher than with rate of addition control reaction temperature, 75 DEG C are warming up to after dripping off, insulation reaction 9h；After HCl gas discharges,
Be added 1.3g melamine, regulation system pH to 5~6, filter, filtrate decompression be distilled off solvent, excessive ethylene chlorhydrin and
A small amount of low boilers, get Sai Ke dimethyl chloride ethyoxyl esters of silicon acis, yield 94.1%.
Embodiment 5 is being equipped with blender, thermometer and condenser pipe, and is inhaled equipped with drying tube and hydrogen halides condenser pipe is suitable for reading
In the 250ml four-hole bottle of receiving apparatus, with the air in nitrogen displacement bottle falling, it is added 8.74g (0.0333mol) three (2- ethoxy)
Isocyanuric acid ester and 90ml dioxane, 30 DEG C or less two bromo-silicanes of addition 21.8g (0.1mol) dimethyl, are warming up to 55 DEG C,
Insulation reaction 6h；After HBr gas discharges, 30 DEG C are cooled to hereinafter, 8.59g (0.1067mol) ethylene chlorhydrin is added dropwise, to be added dropwise
Speed control reaction temperature is not higher than 40 DEG C, 60 DEG C is warming up to after dripping off, insulation reaction 9h；After HBr gas discharges, it is added
0.5g melamine, regulation system pH to 5~6 are filtered, and solvent, excessive ethylene chlorhydrin and a small amount of is distilled off in filtrate decompression
Low boilers, get Sai Ke dimethyl chloride ethyoxyl esters of silicon acis, yield 91.8%.
Embodiment 6 is being equipped with blender, thermometer and condenser pipe, and is inhaled equipped with drying tube and hydrogen halides condenser pipe is suitable for reading
In the 250ml four-hole bottle of receiving apparatus, with the air in nitrogen displacement bottle falling, it is added 8.74g (0.0333mol) three (2- ethoxy)
Isocyanuric acid ester and 100ml acetonitrile, 30 DEG C or less two bromo-silicanes of addition 21.8g (0.1mol) dimethyl are warming up to 40 DEG C, heat preservation
React 7h；After HBr gas discharges, 30 DEG C are cooled to hereinafter, 9.66g (0.12mol) ethylene chlorhydrin is added dropwise, with rate of addition control
Reaction temperature processed is not higher than 40 DEG C, at 40 DEG C after dripping off, insulation reaction 12h；After HBr gas discharges, 1g melamine is added,
Regulation system pH to 5~6, filters, and filtrate decompression is distilled off solvent, excessive ethylene chlorhydrin and a small amount of low boilers, must match
Gram dimethyl chloride ethyoxyl esters of silicon acis, yield 87.7%.
Embodiment 7 is being equipped with blender, thermometer and condenser pipe, and is inhaled equipped with drying tube and hydrogen halides condenser pipe is suitable for reading
In the 250ml four-hole bottle of receiving apparatus, with the air in nitrogen displacement bottle falling, it is added 8.74g (0.0333mol) three (2- ethoxy)
Isocyanuric acid ester and 90ml diethylene glycol dimethyl ether, 30 DEG C or less two bromo-silicanes of addition 21.8g (0.1mol) dimethyl, are warming up to
70 DEG C, insulation reaction 4h；After HBr gas discharges, be cooled to 30 DEG C hereinafter, be added dropwise 10.74g (0.1333mol) ethylene chlorhydrin,
40 DEG C are not higher than with rate of addition control reaction temperature, 100 DEG C are warming up to after dripping off, insulation reaction 6h；It is discharged to HBr gas
Afterwards, 1.3g melamine is added, regulation system pH to 5~6 is filtered, and solvent, excessive ethylene chlorhydrin is distilled off in filtrate decompression
And a small amount of low boilers, get Sai Ke dimethyl chloride ethyoxyl esters of silicon acis, yield 95.8%.
Embodiment 8 is being equipped with blender, thermometer and condenser pipe, and is inhaled equipped with drying tube and hydrogen halides condenser pipe is suitable for reading
In the 250ml four-hole bottle of receiving apparatus, with the air in nitrogen displacement bottle falling, 8.74g (0.0333mol) trihydroxyethyl isocyanide is added
Urea acid esters and 100ml dioxane are added 12.91g (0.1mol) dimethyldichlorosilane, are warming up to 70 DEG C, insulation reaction 5h；
After HCl gas discharges, 30 DEG C are cooled to hereinafter, 12.50g (0.1mol) ethylene bromohyrin is added dropwise, with rate of addition control reaction
Temperature is not higher than 60 DEG C, 100 DEG C is warming up to after dripping off, insulation reaction 8h；After HCl gas discharges, 0.28g melamine is added
Amine, regulation system pH to 5~6 are filtered, and solvent and a small amount of low boilers, get Sai Ke diformazan bromide second is distilled off in filtrate decompression
Oxygroup esters of silicon acis, yield 87.4%.
Embodiment 9 is being equipped with blender, thermometer and condenser pipe, and is inhaled equipped with drying tube and hydrogen halides condenser pipe is suitable for reading
In the 250ml four-hole bottle of receiving apparatus, with the air in nitrogen displacement bottle falling, 8.74g (0.0333mol) trihydroxyethyl isocyanide is added
Urea acid esters and 120ml tetrahydrofuran are added 12.91g (0.1mol) dimethyldichlorosilane, are warming up to 50 DEG C, insulation reaction 9h；
After HCl gas discharges, 30 DEG C are cooled to hereinafter, 13.33g (0.1067mol) ethylene bromohyrin is added dropwise, instead with rate of addition control
Answer temperature not higher than 60 DEG C, after dripping off at 60 DEG C, insulation reaction 14h；After HCl gas discharges, 0.5g melamine is added,
Regulation system pH to 5~6, filters, and filtrate decompression is distilled off solvent, excessive ethylene bromohyrin and a small amount of low boilers, must match
Gram dimethyl bromine oxethyl esters of silicon acis, yield 89.5%.
Embodiment 10 is being equipped with blender, thermometer and condenser pipe, and suitable for reading equipped with drying tube and hydrogen halides in condenser pipe
In the 250ml four-hole bottle of absorption plant, with the air in nitrogen displacement bottle falling, it is different that 8.74g (0.0333mol) trihydroxyethyl is added
Cyanurate and 150ml acetonitrile are added 12.91g (0.1mol) dimethyldichlorosilane, are warming up to 60 DEG C, insulation reaction 8h；To
After HCl gas discharges, 30 DEG C are cooled to hereinafter, 14.58g (0.1167mol) ethylene bromohyrin is added dropwise, with rate of addition control reaction
Temperature is not higher than 60 DEG C, 80 DEG C is warming up to after dripping off, insulation reaction 10h；After HCl gas discharges, 0.95g melamine is added
Amine, regulation system pH to 5~6 are filtered, and filtrate decompression is distilled off solvent, excessive ethylene bromohyrin and a small amount of low boilers, obtains
Match gram dimethyl bromine oxethyl esters of silicon acis, yield 93.3%.
Embodiment 11 is being equipped with blender, thermometer and condenser pipe, and suitable for reading equipped with drying tube and hydrogen halides in condenser pipe
In the 250ml four-hole bottle of absorption plant, with the air in nitrogen displacement bottle falling, it is different that 8.74g (0.0333mol) trihydroxyethyl is added
12.91g (0.1mol) dimethyldichlorosilane is added in cyanurate and 90ml glycol dimethyl ether, is warming up to 70 DEG C, heat preservation is anti-
Answer 6h；After HCl gas discharges, 30 DEG C are cooled to hereinafter, 16.66g (0.1333mol) ethylene bromohyrin is added dropwise, with rate of addition
It controls reaction temperature and is not higher than 60 DEG C, 70 DEG C are warming up to after dripping off, insulation reaction 12h；After HCl gas discharges, 1.5g is added
Melamine, regulation system pH to 5~6 are filtered, and solvent, excessive ethylene bromohyrin and a small amount of low boiling is distilled off in filtrate decompression
Point object, get Sai Ke dimethyl bromine oxethyl esters of silicon acis, yield 94.5%.
Embodiment 12 is being equipped with blender, thermometer and condenser pipe, and suitable for reading equipped with drying tube and hydrogen halides in condenser pipe
In the 250ml four-hole bottle of absorption plant, with the air in nitrogen displacement bottle falling, it is different that 8.74g (0.0333mol) trihydroxyethyl is added
Cyanurate and 100ml dioxane are added two bromo-silicane of 21.8g (0.1mol) dimethyl, are warming up to 60 DEG C, insulation reaction
6h；After HBr gas discharges, 30 DEG C are cooled to hereinafter, 13.33g (0.1067mol) ethylene bromohyrin is added dropwise, with rate of addition control
Reaction temperature processed is not higher than 40 DEG C, 90 DEG C is warming up to after dripping off, insulation reaction 8h；After HBr gas discharges, 0.53g tri- is added
Poly cyanamid, regulation system pH to 5~6 are filtered, and solvent, excessive ethylene bromohyrin and a small amount of low boiling point is distilled off in filtrate decompression
Object, get Sai Ke dimethyl bromine oxethyl esters of silicon acis, yield 93.8%.
Embodiment 13 is being equipped with blender, thermometer and condenser pipe, and suitable for reading equipped with drying tube and hydrogen halides in condenser pipe
In the 250ml four-hole bottle of absorption plant, with the air in nitrogen displacement bottle falling, it is different that 8.74g (0.0333mol) trihydroxyethyl is added
Cyanurate and 120ml acetonitrile are added two bromo-silicane of 21.8g (0.1mol) dimethyl, are warming up to 40 DEG C, insulation reaction 7h；To
After HBr gas discharges, 30 DEG C are cooled to hereinafter, 15g (0.12mol) ethylene bromohyrin is added dropwise, with rate of addition control reaction temperature
Not higher than 40 DEG C, after dripping off at 40 DEG C, insulation reaction 12h；After HBr gas discharges, 1g melamine, regulation system is added
PH to 5~6, filters, and solvent, excessive ethylene bromohyrin and a small amount of low boilers, get Sai Ke dimethyl is distilled off in filtrate decompression
Bromine oxethyl esters of silicon acis, yield 90.2%.
Embodiment 14 is being equipped with blender, thermometer and condenser pipe, and suitable for reading equipped with drying tube and hydrogen halides in condenser pipe
In the 250ml four-hole bottle of absorption plant, with the air in nitrogen displacement bottle falling, it is different that 8.74g (0.0333mol) trihydroxyethyl is added
Two bromo-silicane of 21.8g (0.1mol) dimethyl is added in cyanurate and 90ml diethylene glycol dimethyl ether, is warming up to 70 DEG C, heat preservation
React 4h；After HBr gas discharges, 30 DEG C are cooled to hereinafter, 16.66g (0.1333mol) ethylene bromohyrin is added dropwise, speed is added dropwise
Degree control reaction temperature is not higher than 40 DEG C, 100 DEG C is warming up to after dripping off, insulation reaction 6h；After HBr gas discharges, it is added
1.48g melamine, regulation system pH to 5~6 are filtered, and solvent, excessive ethylene bromohyrin and a small amount of is distilled off in filtrate decompression
Low boilers, get Sai Ke dimethyl bromine oxethyl esters of silicon acis, yield 94.9%.
The match gram dimethyl halo ethyoxyl esters of silicon acis of preparation is applied in polyvinyl chloride (PVC) by inventor.Ginseng
According to: the limit oxygen index of GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " sample.Take match gram diformazan
Base halo ethyoxyl esters of silicon acis, plasticizer phthalic acid dioctyl ester (DOP), synergist antimony oxide (Sb2O3) and polychlorostyrene second
Alkene after mixing, is squeezed out in varing proportions with extruder, and the batten that diameter is 3mm is made, and tests its flame retardant property, and part is tried
It is as shown in Table 1 and Table 2 to test result:
The flame retardant property data of the match gram dimethyl chloride ethyoxyl esters of silicon acis of table 1
The flame retardant property data of the match gram dimethyl bromine oxethyl esters of silicon acis of table 2
According to table 1 and table 2 as can be seen that the present invention has excellent flame retardant effect to pvc material, and can be completely
The defect for overcoming pvc material burning easily to drip.Therefore, the present invention matches gram dimethyl halo ethyoxyl esters of silicon acis with good
Good flame retardant property and at charcoal anti-drip energy.Meanwhile it has also been found that the compound can be fitted with good plasticity in test
Amount replaces DOP, can go easy DOP.
Claims (5)
1. a kind of silicon, nitrogen, three element synergistic fire retardant of halogen match the preparation method of gram dimethyl halo ethyoxyl silicate ester compound,
It is characterized in that, this method are as follows:
Under nitrogen protection, three (2- ethoxy) isocyanuric acid esters is first made to exist with dimethyldichlorosilane or two bromo-silicane of dimethyl
It reacts in organic solvent, then is reacted with ethylene chlorhydrin or ethylene bromohyrin, then purification process, get Sai Ke dimethyl halo ethyoxyl
The structure of esters of silicon acis, the compound is shown below:
Y=Cl or Br in formula.
2. the preparation method of match gram dimethyl halo ethyoxyl esters of silicon acis as described in claim 1, it is characterised in that:
Under conditions of nitrogen protection, three (2- ethoxy) isocyanuric acid esters are dissolved in volume ml relative to three (2- hydroxyl second
Base) isocyanuric acid ester 10~15 times of quality grams of organic solvent in, 30 DEG C or less additions are different relative to three (2- ethoxys)
3 times moles of cyanurate of dimethyldichlorosilane is warming up to 50 DEG C~70 DEG C, 5~9h of insulation reaction；After HCl is discharged, drop
Temperature to 30 DEG C hereinafter, the ethylene chlorhydrin or ethylene bromohyrin relative to 3~4 times moles of isocyanuric acid ester of three (2- ethoxy) is added dropwise,
40 DEG C are not higher than with rate of addition control reaction temperature, 60 DEG C~100 DEG C are warming up to after dripping off, 6~14h of insulation reaction；Through pure
Change processing, get Sai Ke dimethyl halo ethyoxyl esters of silicon acis.
3. the preparation method of match gram dimethyl halo ethyoxyl esters of silicon acis as described in claim 1, it is characterised in that:
Under conditions of nitrogen protection, three (2- ethoxy) isocyanuric acid esters are dissolved in volume ml relative to three (2- hydroxyl second
Base) isocyanuric acid ester 10~15 times of quality grams of organic solvent in, 30 DEG C or less additions are different relative to three (2- ethoxys)
3 times moles of cyanurate of two bromo-silicane of dimethyl, is warming up to 40 DEG C~70 DEG C, 4~7h of insulation reaction；After HBr is discharged, drop
Temperature to 30 DEG C hereinafter, the ethylene chlorhydrin or ethylene bromohyrin relative to 3~4 times moles of isocyanuric acid ester of three (2- ethoxy) is added dropwise,
40 DEG C are not higher than with rate of addition control reaction temperature, 40 DEG C~100 DEG C are warming up to after dripping off, 6~12h of insulation reaction；Through pure
Change processing, get Sai Ke dimethyl halo ethyoxyl esters of silicon acis.
4. matching the preparation method of gram dimethyl halo ethyoxyl esters of silicon acis as described in claims 1 to 3, which is characterized in that described
Organic solvent be dioxane, tetrahydrofuran, glycol dimethyl ether, acetonitrile or diethylene glycol dimethyl ether.
5. matching the preparation method of gram dimethyl halo ethyoxyl esters of silicon acis as described in claims 1 to 3, which is characterized in that described
Purification process be that melamine relative to product theory quality 1%~5% is added, regulation system pH is 5~6, is filtered, filter
Liquid vacuum distillation removes solvent, excessive 2- ethylene halohydrin and a small amount of low boilers.
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| CN103554148A (en) * | 2013-11-08 | 2014-02-05 | 苏州科技学院相城研究院 | Flame retardant cyclo-bromoethyl trisilicate compound and preparation method thereof |
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| CN103554148A (en) * | 2013-11-08 | 2014-02-05 | 苏州科技学院相城研究院 | Flame retardant cyclo-bromoethyl trisilicate compound and preparation method thereof |
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