CN101817840B - Silicic ester flame-retardant compound and preparation method thereof - Google Patents
Silicic ester flame-retardant compound and preparation method thereof Download PDFInfo
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- CN101817840B CN101817840B CN201010184226.3A CN201010184226A CN101817840B CN 101817840 B CN101817840 B CN 101817840B CN 201010184226 A CN201010184226 A CN 201010184226A CN 101817840 B CN101817840 B CN 101817840B
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Abstract
The invention relates to a silicic ester flame-retardant compound and a preparation method thereof. The structure of the polymer is shown as the formula in the specification, wherein R' is oxygen, aryl or straight-chain or branched-chain alkyl having 1 to 9 carbon atoms, and R is aryl or straight-chain or branched-chain alkyl having 1 to 10 carbon atoms. The synthesis method comprises the following steps of: mixing silicon tetrachloride and the epoxy compound or the chlorohydrin corresponding to the epoxy compound in the presence of nitrogen protection and at initial temperature of 20 DEG C, and directly reacting under the heating condition; and then cooling, purifying and drying the reaction product to obtain the target product. The compound has stable physical/chemical performance and high flame retardancy as well as good compatibility with polymer substrate, and is safe and environment-friendly, diverse in process, easy to implement and suitable for manufacturers of various scales.
Description
Technical field
The present invention relates to a kind of silicon halogen cooperative flame retardant and preparation technology thereof, be specifically related to a kind of silicic ester flame-retardant compound compound and preparation method thereof, this compound can be used as fire retardant or the softening agent of the materials such as polyvinyl chloride, polyester, polyurethanes, epoxy resin, fiber glass resin, coating.
Background technology
China's solar-grade polysilicon industry (photovoltaic industry) has obtained developing rapidly at present, but the relevant auxiliary facility of this industry does not obtain synchronized development, cause the waste material silicon tetrachloride certainly leading in solar-grade polysilicon industry production process to be utilized effectively or to process.To polysilicon, industry development has formed impassable obstacle in the environmental pollution causing because of cannot processing of silicon tetrachloride.Add the pay attention to day by day of people to environmental protection, cause the processing problem of silicon tetrachloride to become the bottleneck problem that restricts theCourse of PV Industry.But meanwhile element silicon is also because of its unique thermostability, and good dispersiveness, prevents that molten anti-drippage becomes an important directions of current fire retardant development research.Yet, take aspect the fire retardant exploitation that silicon tetrachloride is raw material, there is not so far report, directly limited related industries development.Therefore, silicon tetrachloride is had to urgent realistic meaning and long-range strategic importance at aspects such as the fire retardant industry of the development research ，Dui of flame retardant area China and photovoltaic industries.
Summary of the invention
One of object of the present invention is to propose a kind of silicic ester flame-retardant compound, and its synthesis technique is simple, and physical and chemical performance is stable, and flame-retarded efficiency is high, good with macromolecular material intermiscibility, can overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
, it is characterized in that, the structure of this polymkeric substance is shown below:
Above-mentioned R ' is hydrogen, aryl or the straight or branched alkyl that contains 1～9 C atom, and R is hydrogen, aryl or the straight or branched alkyl that contains 1～10 C atom.
Another object of the present invention is to propose a kind of synthetic method of silicic ester flame-retardant compound, its technique is simple, is convenient to control, and be easy to large-scale production, and raw material is cheap and easy to get, and equipment is simple, with low cost, and its technical scheme is as follows:
The preparation method of silicic ester flame-retardant compound, is characterized in that as mentioned above, and the method is:
Under nitrogen protection, silicon tetrachloride is reacted with the chloro-hydrin(e) that epoxy compounds or epoxy compounds hydrolyzable generate, then reaction product is carried out to cooling, purification, thereby obtain described silicon ester.
Particularly, the method is:
Under nitrogen protection; in the temperature range of 50～100 ℃; making mol ratio is 1: 4～8 silicon tetrachloride and epoxy compounds direct reaction 4～8 hours; or making mol ratio is the chloro-hydrin(e) direct reaction 4～8 hours that 1: 4～8 silicon tetrachloride is corresponding with epoxy compounds; then reaction product is carried out to cooling, purification, thereby obtain described silicon ester.Further, the method is specially:
Under initial temperature is 20 ℃, the condition of nitrogen protection; the mol ratio of controlling silicon tetrachloride and propylene oxide is 1: 4～8; propylene oxide is added drop-wise in silicon tetrachloride; direct addition reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under initial temperature is 20 ℃, the condition of nitrogen protection; the mol ratio of controlling silicon tetrachloride and propylene oxide is 1: 4～8; silicon tetrachloride is added drop-wise in propylene oxide from liquid level; direct addition reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
The method also can be:
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and 2-propylene chlorohydrin is 1: 4～8; at 20 ℃, start silicon tetrachloride to be added drop-wise in 2-propylene chlorohydrin; direct reaction is emitted hydrogenchloride; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and 2-propylene chlorohydrin is 1: 4～8; at 20 ℃, start 2-propylene chlorohydrin to be added drop-wise in silicon tetrachloride; direct reaction is emitted hydrogenchloride; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and 1-chlorine 2-propyl alcohol is 1: 4～8; at 20 ℃, start silicon tetrachloride to be added drop-wise in 1-chlorine 2-propyl alcohol; direct reaction is emitted hydrogenchloride; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and 1-chlorine 2-propyl alcohol is 1: 4～8; at 20 ℃, start 1-chlorine 2-propyl alcohol to be added drop-wise in silicon tetrachloride; direct reaction is emitted hydrogenchloride; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and butylene oxide ring is 1: 4～8; at 20 ℃, start butylene oxide ring to be added drop-wise in silicon tetrachloride; direct reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and butylene oxide ring is 1: 4～8; at 20 ℃, start silicon tetrachloride to be added drop-wise in butylene oxide ring; direct reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and 2-butylene-chlorohydrin is 1: 4～8; at 20 ℃, start 2-butylene-chlorohydrin to be added drop-wise in silicon tetrachloride; direct reaction is emitted hydrogenchloride; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and the chloro-2-butanols of 1-is 1: 4～8; at 20 ℃, start the chloro-2-butanols of 1-to be added drop-wise in silicon tetrachloride; hydrogenchloride is emitted in reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and phenyl ethylene oxide is 1: 4～8; at 20 ℃, start phenyl ethylene oxide to be added in silicon tetrachloride; direct addition reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and 1-phenyl-ethylene chlorhydrin is 1: 4～8; at 20 ℃, start 1-phenyl-ethylene chlorhydrin to be added drop-wise in silicon tetrachloride; hydrogenchloride is emitted in reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and the chloro-2-phenyl-ethanol of 2-is 1: 4～8; at 20 ℃, start the chloro-2-phenyl-ethanol of 2-to be added drop-wise in silicon tetrachloride; hydrogenchloride is emitted in reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Described " slowly heating up " and " with reaction, progressively improving temperature " refer to: because reaction is thermopositive reaction, and silicon tetrachloride boiling point (57.6 ℃) is lower, therefore, when reaction has just started, for preventing silicon tetrachloride boiling, escape, it is lower that temperature of reaction need arrange, and along with constantly carrying out of reaction, the amount of lower boiling raw material silicon tetrachloride reduces gradually and improves lentamente temperature of reaction.
The detailed process that above-mentioned product carries out purification processes is: underpressure distillation steams excessive reactant, reclaims and uses, neutralization washing, separate organic layer, organic layer is carried out to underpressure distillation except anhydrating and low boilers, thereby obtain silicic ester flame-retardant compound, excessive reactant can reclaim use.
Silicic acid four of the present invention (chloropropyl) ester flame-retardant compound is colourless or yellow liquid, and its decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃, productive rate is 95%～99%, degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃), and refractive index is n
d 13=1.4536.
Silicic acid four of the present invention (chlorobutyl) ester flame-retardant compound is colourless or yellow liquid, and its decomposition temperature is 220 ± 5 ℃, and flash-point (open cup) is 205 ± 5 ℃, and productive rate is 95%～99%.
Silicic acid four of the present invention (phenyl-chloride ethyl) ester flame-retardant compound is colourless or yellow liquid, and its decomposition temperature is 292 ± 5 ℃, and flash-point (open cup) is 276 ± 5 ℃, and productive rate is 95%～99%.
It is suitable as fire retardant or the softening agent of the materials such as polyvinyl chloride, polyester, polyurethanes, epoxy resin, fiber glass resin, coating, and the synthesis technique principle of this silicic ester flame-retardant compound is shown below:
Or
Compared with prior art, beneficial effect of the present invention is:
1. the present invention proposes silicate ester compound as fire retardant or softening agent, because silicon and carbon are congenerss, silicate ester compound intermiscibility similar to macromolecular material and plasticity are good; Silicon halogen cooperative flame retardant usefulness is high.
2. silicic ester flame-retardant compound of the present invention synthetic consumed the silicon tetrachloride that polysilicon industry gives off, and is conducive to environmental protection, and contains element silicon better heat stability, therefore there is good application prospect;
3. the synthesis technique of silicic ester flame-retardant compound of the present invention is single step reaction, simple and easy to control, and without special reaction condition, equipment is simple, with low cost, is suitable for large-scale production.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further.
Preparation example 1 is being equipped with agitator, thermometer, efficient backflow prolong and accurate stirring in the 250ml four-hole bottle sealing, pass into nitrogen protection, add 0.1mol silicon tetrachloride, fill a soft seal cover that can extremely stretch and expand prolong is suitable for reading, stir, 20 ℃ of propylene oxide (progressively improving temperature with reaction) that start to drip under liquid level 0.6mol, then be slowly warmed up to 50 ℃, holding temperature reaction is after 8 hours, underpressure distillation goes out excessive reactant recovery and uses, neutralization washing, layering, separated organic layer underpressure distillation is silicic acid four (chloropropyl) ester, its productive rate is 99%, decomposition temperature is 240 ± 5 ℃, flash-point (open cup) is 212 ± 5 ℃, degree Beaume is 13.85 (9 ℃), density is 1.113 (9 ℃), refractive index is n
d 13=1.4536.
Preparation example 2 is being equipped with agitator, thermometer, efficient backflow prolong and accurate stirring in the 250ml four-hole bottle sealing, pass into nitrogen protection, add 0.1mol silicon tetrachloride, fill a soft seal cover that can extremely stretch and expand prolong is suitable for reading, stir, 20 ℃ of propylene oxide (progressively improving temperature with reaction) that start to drip under liquid level 0.5mol, then be slowly warmed up to 60 ℃, holding temperature reaction is after 7 hours, underpressure distillation goes out excessive reactant recovery and uses, neutralization washing, layering, separated organic layer underpressure distillation is silicic acid four (chloropropyl) ester, its productive rate is 97%, decomposition temperature is 240 ± 5 ℃, flash-point (open cup) is 212 ± 5 ℃, degree Beaume is 13.85 (9 ℃), density is 1.113 (9 ℃), refractive index is n
d 13=1.4536.
Preparation example 3 is being equipped with agitator, thermometer, efficient backflow prolong and accurate stirring in the 250ml four-hole bottle sealing, pass into nitrogen protection, add 0.1mol silicon tetrachloride, at the prolong soft seal cover that fills the expansion of can extremely stretching suitable for reading, stir, 20 ℃ of propylene oxide (progressively improving temperature with reaction) that start to drip under liquid level 0.55mol, then be slowly warmed up to 70 ℃, holding temperature reaction is after 6 hours, underpressure distillation goes out excessive reactant recovery and uses, neutralization washing, layering, separated organic layer underpressure distillation is silicic acid four (chloropropyl) ester, its productive rate is 99%, decomposition temperature is 240 ± 5 ℃, flash-point (open cup) is 212 ± 5 ℃, degree Beaume is 13.85 (9 ℃), density is 1.113 (9 ℃), refractive index is n
d 13=1.4536.
Preparation example 4 is being equipped with agitator, thermometer, efficient backflow prolong and accurate stirring in the 250ml four-hole bottle sealing, pass into nitrogen protection, add 0.1mol silicon tetrachloride, fill a soft seal cover that can extremely stretch and expand prolong is suitable for reading, stir, 20 ℃ of propylene oxide (progressively improving temperature with reaction) that start to drip under liquid level 0.48mol, then be slowly warmed up to 80 ℃, holding temperature reaction is after 5 hours, underpressure distillation goes out excessive reactant recovery and uses, neutralization washing, layering, separated organic layer underpressure distillation is silicic acid four (chloropropyl) ester, its productive rate is 98%, decomposition temperature is 240 ± 5 ℃, flash-point (open cup) is 212 ± 5 ℃, degree Beaume is 13.85 (9 ℃), density is 1.113 (9 ℃), refractive index is n
d 13=1.4536.
Preparation example 5 is being equipped with agitator, thermometer, efficient backflow prolong and accurate stirring in the 250ml four-hole bottle sealing, pass into nitrogen protection, add 0.1mol silicon tetrachloride, fill a soft seal cover that can extremely stretch and expand prolong is suitable for reading, stir, 20 ℃ of propylene oxide (progressively improving temperature with reaction) that start to drip under liquid level 0.44mol, then be slowly warmed up to 90 ℃, holding temperature reaction is after 4 hours, underpressure distillation goes out excessive reactant recovery and uses, neutralization washing, layering, separated organic layer underpressure distillation is silicic acid four (chloropropyl) ester, its productive rate is 96%, decomposition temperature is 240 ± 5 ℃, flash-point (open cup) is 212 ± 5 ℃, degree Beaume is 13.85 (9 ℃), density is 1.113 (9 ℃), refractive index is n
d 13=1.4536.
Preparation example 6 is being equipped with agitator, thermometer, efficient backflow prolong and accurate stirring in the 250ml four-hole bottle sealing, pass into nitrogen protection, add 0.1mol silicon tetrachloride, fill a soft seal cover that can extremely stretch and expand prolong is suitable for reading, stir, 20 ℃ of propylene oxide (progressively improving temperature with reaction) that start to drip under liquid level 0.40mol, then be slowly warmed up to 100 ℃, holding temperature reaction is after 4 hours, underpressure distillation goes out excessive reactant recovery and uses, neutralization washing, layering, separated organic layer underpressure distillation is silicic acid four (chloropropyl) ester, its productive rate is 95%, decomposition temperature is 240 ± 5 ℃, flash-point (open cup) is 212 ± 5 ℃, degree Beaume is 13.85 (9 ℃), density is 1.113 (9 ℃), refractive index is n
d 13=1.4536.
Preparation example 7 is in being equipped with the 250ml there-necked flask of agitator and drying tube; pass into nitrogen protection; the 2-propylene chlorohydrin that adds 0.80mol; stir; 20 ℃ drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction); then be slowly warmed up to 60 ℃; holding temperature reaction is after 7 hours; underpressure distillation goes out excessive reactant to be reused, neutralization washing, separated organic layer; underpressure distillation steams water and low boilers is silicic acid four (chloropropyl) ester; its productive rate is 97%, and decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃.Degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃).
Preparation example 8 is in being equipped with the 250ml there-necked flask of agitator and drying tube; pass into nitrogen protection; the 2-propylene chlorohydrin that adds 0.46mol; stir; 20 ℃ drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction); then be slowly warmed up to 80 ℃; holding temperature reaction is after 6 hours; underpressure distillation goes out excessive reactant to be reused, neutralization washing, separated organic layer; underpressure distillation steams water and low boilers is silicic acid four (chloropropyl) ester; its productive rate is 97%, and decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃.Degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃).
Preparation example 9 is in being equipped with the 250ml there-necked flask of agitator and drying tube; pass into nitrogen protection; the 2-propylene chlorohydrin that adds 0.42mol; stir; 20 ℃ drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction); then be slowly warmed up to 100 ℃; holding temperature reaction is after 4 hours; underpressure distillation goes out excessive reactant to be reused, neutralization washing, separated organic layer; underpressure distillation steams water and low boilers is silicic acid four (chloropropyl) ester; its productive rate is 96%, and decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃.Degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃).
Preparation example 10 is equipped with in the 250ml there-necked flask of agitator and drying tube; pass into nitrogen protection; the 1-chlorine 2-propyl alcohol that adds 0.48mol; stir; 20 ℃ drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction); then be slowly warmed up to 60 ℃; holding temperature reaction is after 8 hours; underpressure distillation goes out excessive reactant to be reused, neutralization washing, separated organic layer; underpressure distillation steams water and low boilers is silicic acid four (chloropropyl) ester; its productive rate is 95%, and decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃.Degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃).
Preparation example 11 is in being equipped with the 250ml there-necked flask of agitator and drying tube; pass into nitrogen protection; the 1-chlorine 2-propyl alcohol that adds 0.44mol; stir; 20 ℃ drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction); then be slowly warmed up to 80 ℃; holding temperature reaction is after 6 hours; underpressure distillation goes out excessive reactant to be reused, neutralization washing, separated organic layer; underpressure distillation steams water and low boilers is silicic acid four (chloropropyl) ester; its productive rate is 97%, and decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃.Degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃).
Preparation example 12 is in being equipped with the 250ml there-necked flask of agitator and drying tube; pass into nitrogen protection; the 1-chlorine 2-propyl alcohol that adds 0.4mol; stir; 20 ℃ drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction); then be slowly warmed up to 100 ℃; holding temperature reaction is after 4 hours; underpressure distillation goes out excessive reactant to be reused, neutralization washing, separated organic layer; underpressure distillation steams water and low boilers is silicic acid four (chloropropyl) ester; its productive rate is 95%, and decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃.Degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃).
Preparation example 13 is being equipped with agitator, thermometer, efficient backflow prolong and accurate stirring in the 250ml four-hole bottle sealing, pass into nitrogen protection, add 0.1mol silicon tetrachloride, fill a soft seal cover that can extremely stretch and expand prolong is suitable for reading, stir, 20 ℃ of butylene oxide rings (progressively improving temperature with reaction) that start to drip 0.6mol, then be slowly warmed up to 80 ℃, holding temperature reaction is after 7 hours, underpressure distillation goes out excessive reactant and reuses, neutralization washing, layering, separated organic layer underpressure distillation is silicic acid four (chlorobutyl) ester, its productive rate is 97%, decomposition temperature is 220 ± 5 ℃, flash-point (open cup) is 205 ± 5 ℃.
Preparation example 14 is being equipped with agitator, thermometer, efficient backflow prolong and accurate stirring in the 250ml four-hole bottle sealing, pass into nitrogen protection, the butylene oxide ring that adds 0.5mol, fill a soft seal cover that can extremely stretch and expand prolong is suitable for reading, stir, 20 ℃ start to drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction), then be slowly warmed up to 80 ℃, holding temperature reaction is after 7 hours, underpressure distillation goes out excessive reactant and reuses, neutralization washing, layering, separated organic layer underpressure distillation is silicic acid four (chlorobutyl) ester, its productive rate is 96%, decomposition temperature is 220 ± 5 ℃, flash-point (opening cup) is 205 ± 5 ℃.
Preparation example 15 is being equipped with agitator, thermometer, efficient backflow prolong and accurate stirring in the 250ml four-hole bottle sealing, pass into nitrogen protection, add 0.1mol silicon tetrachloride, fill a soft seal cover that can extremely stretch and expand prolong is suitable for reading, stir, 20 ℃ of phenyl ethylene oxides (progressively improving temperature with reaction) that start to drip 0.5mol, then be slowly warmed up to 80 ℃, holding temperature reaction is after 7 hours, underpressure distillation goes out excessive reactant and reuses, neutralization washing, layering, separated organic layer underpressure distillation is silicic acid four (phenyl-chloride ethyl) ester, its productive rate is 98%, decomposition temperature is 292 ± 5 ℃, flash-point (open cup) is 276 ± 5 ℃.
Preparation example 16 is being equipped with agitator, thermometer, efficient backflow prolong and accurate stirring in the 250ml four-hole bottle sealing, pass into nitrogen protection, add 0.1mol silicon tetrachloride, fill a soft seal cover that can extremely stretch and expand prolong is suitable for reading, stir, 20 ℃ of 1-phenyl-ethylene chlorhydrins (progressively improving temperature with reaction) that start to drip 0.48mol, then be slowly warmed up to 90 ℃, holding temperature reaction is after 8 hours, underpressure distillation goes out excessive reactant and reuses, neutralization washing, layering, separated organic layer underpressure distillation is silicic acid four (phenyl-chloride ethyl) ester, its productive rate is 97%, decomposition temperature is 292 ± 5 ℃, flash-point (open cup) is 276 ± 5 ℃.
Preparation example 17 is being equipped with agitator, thermometer, efficient backflow prolong and accurate stirring in the 250ml four-hole bottle sealing, pass into nitrogen protection, add 0.1mol silicon tetrachloride, fill a soft seal cover that can extremely stretch and expand prolong is suitable for reading, stir, 20 ℃ of chloro-2-phenyl-ethanol of 2-(progressively improving temperature with reaction) that start to drip 0.44mol, then be slowly warmed up to 90 ℃, holding temperature reaction is after 7 hours, underpressure distillation goes out excessive reactant and reuses, neutralization washing, layering, separated organic layer underpressure distillation is silicic acid four (phenyl-chloride ethyl) ester, its productive rate is 96%, decomposition temperature is 292 ± 5 ℃, flash-point (open cup) is 276 ± 5 ℃, .
Table 1
| Silicon tetrachloride | Active epoxy based compound or chloro-hydrin(e) | Temperature | Reaction times | Productive rate | |
| Preparation example 1 | 0.1mol | Propylene oxide 0.6mol | 50℃ | 8 hours | 99％ |
| Preparation example 2 | 0.1mol | Propylene oxide 0.5mol | 60℃ | 7 hours | 97％ |
| Preparation example 3 | 0.1mol | Propylene oxide 0.55mol | 70℃ | 6 hours | 99％ |
| Preparation example 4 | 0.1mol | Propylene oxide 0.48mol | 80℃ | 5 hours | 98％ |
| Preparation example 5 | 0.1mol | Propylene oxide 0.44mol | 90℃ | 4 hours | 96％ |
| Preparation example 6 | 0.1mol | Propylene oxide 0.40mol | 100℃ | 4 hours | 95％ |
| Preparation example 7 | 0.1mol | 2-propylene chlorohydrin 0.80mol | 60℃ | 7 hours | 97％ |
| Preparation example 8 | 0.1mol | 2-propylene chlorohydrin 0.46mol | 80℃ | 6 hours | 97％ |
| Preparation example 9 | 0.1mol | 2-propylene chlorohydrin 0.42mol | 100℃ | 4 hours | 96％ |
| Preparation example 10 | 0.1mol | 1-chlorine 2-propyl alcohol 0.48mol | 60℃ | 8 hours | 95％ |
| Preparation example 11 | 0.1mol | 1-chlorine 2-propyl alcohol 0.44mol | 80℃ | 6 hours | 97％ |
| Preparation example 12 | 0.1mol | 1-chlorine 2-propyl alcohol 0.4mol | 100℃ | 4 hours | 95％ |
| Preparation example 13 | 0.1mol | Butylene oxide ring 0.60mol | 80℃ | 7 hours | 97％ |
| Preparation example 14 | 0.1mol | Butylene oxide ring 0.50mol | 80℃ | 7 hours | 96％ |
| Preparation example 15 | 0.1mol | Phenyl ethylene oxide 0.5mol | 80℃ | 7 hours | 98％ |
| Preparation example 16 | 0.1mol | 1-phenyl-ethylene chlorhydrin 0.48mol | 90℃ | 8 hours | 97％ |
| Preparation example 17 | 0.1mol | The chloro-2-phenyl-ethanol of 2-0.44mol | 90℃ | 7 hours | 96％ |
This case contriver is also applied to above-mentioned synthetic silicic ester flame-retardant compound in polyvinyl chloride.Reference: GB/T2406-2008 < < Plastics Combustion method for testing performance-oxygen index method > > surveys the flame retardant properties of product in polyvinyl chloride.Get product silicic ester flame-retardant compound, plasticizer phthalic acid succinate, synergistic flame retardant antimonous oxide and polyvinyl chloride grind in varing proportions, mix and with forcing machine, extrude afterwards, and make long 15cm, diameter is the batten of 3mm and its flame retardant properties tested, and test-results is as shown in the table:
Table 2
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 9 | 10 | 11 |
| PVC | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Phthalic acid succinate | 40 | 40 | 40 | 40 | 100 | |||||
| Silicic ester flame-retardant compound | 10 | 15 | 20 | 40 | 100 | 40 | 100 | |||
| Trichlorine propyl phosphate | 100 | |||||||||
| Antimonous oxide | 5 | 7.5 | 10 | 20 | 50 | 5 | 5 | |||
| Oxygen index | 31 | 32 | 31 | 36 | 30 | 34 | 29 | 28 | 25 | 22 |
General, oxygen index reaches 27 just can think that its flame retardant properties is better.As seen from the above table, used the polyvinyl chloride of silicic acid four (two chloropropyls) ester to there is excellent flame retardant properties.Compare with conventional fire retardant trichlorine propyl phosphate, silicic acid four (two chloropropyls) ester is better fire retardant.
Claims (7)
1. a silicic ester flame-retardant compound, is characterized in that, the structure of this compound is shown below:
Above-mentioned R ' is that hydrogen, R are phenyl, or R ' is that phenyl, R are hydrogen.
2. the preparation method of silicic ester flame-retardant compound as claimed in claim 1, is characterized in that:
Under nitrogen protection, make the chloro-2-phenyl-ethanol synthesis of silicon tetrachloride and phenyl ethylene oxide, 1-phenyl-ethylene chlorhydrin or 2-, then reaction product is carried out to cooling, purification, thereby obtain described silicic ester flame-retardant compound.
3. preparation method as claimed in claim 2, is characterized in that:
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and phenyl ethylene oxide is 1: 4～8; at 20 ℃, start phenyl ethylene oxide to be added in silicon tetrachloride;. direct addition reaction; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
4. preparation method as claimed in claim 2, is characterized in that:
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and 1-phenyl-ethylene chlorhydrin is 1: 4～8; at 20 ℃, start 1-phenyl-ethylene chlorhydrin to be added drop-wise in silicon tetrachloride; hydrogenchloride is emitted in reaction; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
5. preparation method as claimed in claim 2, is characterized in that:
Under nitrogen protection; the mol ratio of controlling silicon tetrachloride and the chloro-2-phenyl-ethanol of 2-is 1: 4～8; at 20 ℃, start the chloro-2-phenyl-ethanol of 2-to be added drop-wise in silicon tetrachloride; hydrogenchloride is emitted in reaction; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
6. the preparation method as described in any one in claim 2～5, is characterized in that, reaction is without solvent.
7. the preparation method as described in any one in claim 2～5, it is characterized in that, described purification is that underpressure distillation steams excessive reactant, neutralization washing again, separate organic layer, organic layer is carried out to underpressure distillation except anhydrating and low boilers, thereby obtain silicic ester flame-retardant compound, excessive reactant can reclaim use.
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| CN102010521B (en) * | 2010-11-01 | 2013-04-03 | 苏州科技学院 | Silicate ester flame-retardant plasticizer and preparation method thereof |
| CN102050961B (en) * | 2010-11-01 | 2012-10-10 | 苏州科技学院 | Aryl silicate ester flame retardant plasticizer and preparation method thereof |
| CN102731546B (en) * | 2012-07-17 | 2015-03-04 | 苏州科技学院 | Flame retardant trichloroethyltribromophenoxychloropropylsilicate ester compound and preparation method thereof |
| CN102731553B (en) * | 2012-07-17 | 2015-03-04 | 苏州科技学院 | Tris(dichloropropyl) tribromophenoxy chloropropyl silicate compound and preparation method thereof |
| CN102731547B (en) * | 2012-07-17 | 2015-03-04 | 苏州科技学院 | Tetra-(tribromophenoxy chloropropyl) silicate fire retardant compound and preparation method thereof |
| CN102731552B (en) * | 2012-07-17 | 2015-03-04 | 苏州科技学院 | Flame retardant tribromophenoxychloropropoxytri(chloropropyl) silicate compound and preparation method thereof |
| CN109111595B (en) * | 2018-07-21 | 2021-04-23 | 扬州工业职业技术学院 | Novel silicon-based flame retardant and preparation method and application thereof |
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