CN101830923A - Silicic acid tetra (dichloropropyl) ester compound and preparation method thereof - Google Patents
Silicic acid tetra (dichloropropyl) ester compound and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a silicic acid tetra (dichloropropyl) ester compound and a preparation method thereof, the structure of the polymer is as shown in the following formula, wherein n is not less than 0 and not more than 4, and the synthetic method is as follows: respectively dripping silicon tetrachloride epoxy with epichlorohydrin, 1,3-dichloro-2-propanol or 2,3-dichloropropanol under the nitrogen protection and at the initial temperature of 25 DEG C, then carrying out direct reaction or reaction in an organic solvent under the heating condition, then purifying reaction products and preparing the silicic acid tetra (dichloropropyl) ester. The silicic acid tetra (dichloropropyl) ester has high thermal stability and good compatibility with polymer material, thereby being an excellent flame retardant plasticizer. Simultaneously, the synthesis process is simple, the equipment investment is low, and the cost is low, thereby being conductive to environmental protection and particularly having great significance for solving the pollution of a large amount of silicon tetrachloride produced by polysilicon.
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 acid four (two chloropropyls) ester cpds and preparation method thereof, this compound can be made the flame-retardant plasticizer of materials such as polyvinyl chloride, polyester, urethane, Resins, epoxy, fiber glass resin, coating.
Background technology
The utilization of sun power is the inevitable approach of energy development, and the large-scale production of polysilicon (photovoltaic industry) is the basic industry that realizes conversion of solar energy.Yet produce one ton of polysilicon and will produce 15-20 ton silicon tetrachloride pollutent.At present, how to handle the bottleneck that the industrial waste silicon tetrachloride has become restriction China's solar energy polycrystalline silicon industry (photovoltaic industry) development.Because of the imperfection of domestic auxiliary facility causes silicon tetrachloride to discharge arbitrarily, and the environmental pollution that causes thus more and more seems more severe.And along with people are more and more higher to the cry of environmental protection, add the adjustment of domestic relevant policies and the variation of world market market, China's polysilicon industry is faced with the test of final and decisive juncture.Therefore the application and development of silicon tetrachloride is to solve the fundamental way that polysilicon pollutes.
People know organic silicon fibre retardant because of its unique thermostability, good dispersiveness, and anti-molten anti-drippage property becomes an important directions of current fire retardant development research.Yet,, still be not reported so far being aspect the feedstock production exploitation fire retardant with the silicon tetrachloride.Therefore silicon tetrachloride is turned waste into wealth the photovoltaic industry of China and fire-retardant industry etc. all are of great immediate significance.
Summary of the invention
One of purpose of the present invention is to propose a kind of silicic acid four (two chloropropyls) ester cpds; For processing of high molecular material already increases a kind of (class) good flame-retardant plasticizer kind.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of silicic acid four (two chloropropyls) ester cpds is characterized in that the structure of this polymkeric substance is shown below:
0≤n≤4 wherein,
Another object of the present invention is to propose the synthetic method of a kind of silicic acid four (two chloropropyls) ester, its technology is simple, is convenient to control, be easy to large-scale production, and raw material is cheap and easy to get, and equipment is simple, and is with low cost, and its technical scheme is as follows:
The preparation method of silicic acid four (two chloropropyls) ester as mentioned above is characterized in that this method is:
Under initial temperature is 25 ℃, the condition of nitrogen protection; make silicon tetrachloride respectively with epoxy chloropropane, 1,3-two chloro-2-propyl alcohol or 2,3-dichlorohydrine direct reaction or in organic solvent, react; reaction product cooled off, purify, thereby obtain silicic acid four (two chloropropyls) ester thereafter.
Particularly, this method is:
Under initial temperature is 25 ℃, the condition of nitrogen protection; with silicon tetrachloride respectively with epoxy chloropropane, 1; 3-two chloro-2-propyl alcohol or 2, the 3-dichlorohydrine is added to together, silicon tetrachloride and epoxy chloropropane, 1; 3-two chloro-2-propyl alcohol or 2; the mol ratio of 3-dichlorohydrine is 1: 4～8, then in 50～100 ℃ temperature range, and direct reaction or in organic solvent, reacted 4～8 hours; reaction product cooled off, purify, thereby obtain silicic acid four (two chloropropyls) ester thereafter.
Further, this method is specially:
Under nitrogen protection; add organic solvent; the mol ratio of control silicon tetrachloride and epoxy chloropropane is 1: 4～8; under 25 ℃, begin silicon tetrachloride is added drop-wise in the epoxy chloropropane; then slowly be warming up to 50 ℃～100 ℃ and reacted 4～8 hours; cool off then, purify, make silicic acid four (two chloropropyls) ester.
Under nitrogen protection; add organic solvent; the mol ratio of control silicon tetrachloride and epoxy chloropropane is 1: 4～8; under 25 ℃, begin epoxy chloropropane is added drop-wise in the silicon tetrachloride; then slowly be warming up to 50 ℃～100 ℃ and reacted 4～8 hours; cool off then, purify, make silicic acid four (two chloropropyls) ester.
In addition, this method can be:
Under nitrogen protection; control silicon tetrachloride and 1; 3-two chloro-2-propyl alcohol mol ratios are 1: 4～8; under 25 ℃, begin silicon tetrachloride is added drop-wise to 1; in the 3-two chloro-2-propyl alcohol, direct reaction is emitted hydrogenchloride, then slowly is warming up to 50 ℃～100 ℃ reactions 4～8 hours; cool off then, purify, make silicic acid four (two chloropropyls) ester.
Under nitrogen protection; add organic solvent; control silicon tetrachloride and 1; 3-dichloro 2-propyl alcohol mol ratio is 1: 4～8, begins 1 under 25 ℃, and 3-two chloro-2-propyl alcohol are added drop-wise in the silicon tetrachloride; emit hydrogenchloride; then slowly be warming up to 50 ℃～100 ℃ reactions 4～8 hours, cool off then, purify, make silicic acid four (two chloropropyls) ester.
This method also can be:
Under nitrogen protection; add organic solvent; control silicon tetrachloride and 2; 3-dichlorohydrine mol ratio is 1: 4～8, begins 2 under 25 ℃, and the 3-dichlorohydrine is added drop-wise in the silicon tetrachloride; emit hydrogenchloride; then slowly be warming up to 50 ℃～100 ℃ reactions 4～8 hours, cool off then, purify, make silicic acid four (two chloropropyls) ester.
Under nitrogen protection; add organic solvent; control silicon tetrachloride and 2; 3-dichlorohydrine mol ratio is 1: 4～8, begins silicon tetrachloride is added drop-wise to 2, in the 3-dichlorohydrine under 25 ℃; emit hydrogenchloride; then slowly be warming up to 50 ℃～100 ℃ reactions 4～8 hours, purify then, make silicic acid four (two chloropropyls) ester.
The detailed process that above-mentioned product carries out purification processes is: remove excessive reactant and/or organic solvent by distillation; Add acid binding agent again, carried out filtering out free acid and a small amount of silicon-dioxide;
Described organic solvent is an ethylene dichloride, tetrachloroethane, chloroform, tetracol phenixin, benzene, toluene, dimethylbenzene etc.; Acid binding agent is trimeric cyanamide, tertiary amine, pyridine, triethylamine, xylidine, Diethyl Aniline etc.
Described " slowly heating up " and " progressively improving temperature with reaction " are meant: because reaction is thermopositive reaction, and silicon tetrachloride boiling point (57.6 ℃) is lower, therefore, when reaction has just begun, escape for preventing the silicon tetrachloride boiling, it is low that temperature of reaction need be provided with, and along with constantly carrying out of reaction, the amount of lower boiling raw material silicon tetrachloride reduces gradually and improves temperature of reaction lentamente.
Silicic acid four of the present invention (two chloropropyls) ester is colourless liquid or weak yellow liquid, and decomposition temperature is 267 ± 5 ℃, and flash-point (open cup) is 260 ± 5 ℃, and productive rate is 93%～98%, and degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃), and refractive index is n
D 20=1.4966.
It is fit to the flame-retardant plasticizer that can make materials such as polyvinyl chloride, polyester, urethane, Resins, epoxy, fiber glass resin, coating, and the synthesis technique principle of this silicic acid four (two chloropropyls) ester is shown below:
0≤n≤4 wherein,
Perhaps
Perhaps
Compared with prior art, beneficial effect of the present invention is
1. because the present invention is to be that basic raw material synthetic silicic acid four (two chloropropyls) ester is the agent of silicon halogen collaborative type flame-retardant with the silicon tetrachloride, after itself and the macromolecular material blend, intermiscibility is good, and can not change the mechanical property of material; Silicon ester and phosphoric acid ester have the similarity of structure, but silicon is compared with phosphorus and shown as more environmental protection.
2. silicic acid four of the present invention (two chloropropyls) ester cpds has consumed the silicon tetrachloride that the polysilicon industry is given off, and helps environmental protection, and contains the element silicon better heat stability, so good prospects for application is arranged;
The diversification of silicic acid four of the present invention (two chloropropyls) ester synthetic method can be direct method, and methods such as organic solvent method are synthetic, and the enterprise that is suitable for various different scales produces;
The synthetic single step reaction that is of silicic acid four 3. of the present invention (two chloropropyls) ester, technology is simple and easy to control, and building-up process need not to add catalyzer, need not the special reaction condition, and equipment is simple, invests for a short time, 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 in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; the epoxy chloropropane that adds 0.80mol; stir; initial temperature is 25 ℃ and begins to splash into 0.10mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 50 ℃ then; the holding temperature reaction is after 8 hours; distill out excessive reactant; cooling is filtered gained liquid and is silicic acid four (two chloropropyls) ester, and its productive rate is 93%; decomposition temperature is 267 ± 5 ℃, and flash-point (open cup) is 260 ± 5 ℃.Degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃), and refractive index is n
D 20=1.4966.
Preparation example 2 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; the epoxy chloropropane that adds 0.6mol; stir; initial temperature is 25 ℃ and begins to splash into 0.10mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 70 ℃ then; the holding temperature reaction is after 6 hours; distill out excessive reactant; cooling is filtered gained liquid and is silicic acid four (two chloropropyls) ester, and its productive rate is 95%; decomposition temperature is 267 ± 5 ℃, and flash-point (open cup) is 260 ± 5 ℃.Degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃), and refractive index is n
D 20=1.4966.
Preparation example 3 is in being equipped with the 250ml there-necked flask of agitator and drying tube; feed nitrogen protection; the epoxy chloropropane that adds 0.50mol; stir; initial temperature is 25 ℃ and begins to splash into 0.10mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 90 ℃ then; the holding temperature reaction is after 4 hours; distill out excessive reactant; cooling is filtered gained liquid and is silicic acid four (two chloropropyls) ester, and its productive rate is 95%; decomposition temperature is 267 ± 5 ℃, and flash-point (open cup) is 260 ± 5 ℃.Degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃), and refractive index is n
D 20=1.4966
Preparation example 4 is in being equipped with the 250ml there-necked flask of agitator and drying tube; feed nitrogen protection; the epoxy chloropropane that adds 0.48mol is dissolved in the trichloromethane of 0.50mol; stir; initial temperature is 25 ℃ and begins to splash into 0.10mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 60 ℃ then, the holding temperature reaction distilled out excessive reactant after 8 hours; cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester, its productive rate is 96%, and decomposition temperature is 267 ± 5 ℃; flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃), and refractive index is n
D 20=1.4966.
Preparation example 5 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; the epoxy chloropropane that adds 0.44mol is dissolved in the ethylene dichloride of 0.50mol; stir; initial temperature is 25 ℃ and begins to splash into 0.10mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 80 ℃ then; the holding temperature reaction is after 6 hours; distill out excessive reactant and solvent; cooling is filtered gained liquid and is silicic acid four (two chloropropyls) ester, and its productive rate is 98%; decomposition temperature is 267 ± 5 ℃, and flash-point (open cup) is 260 ± 5 ℃.Degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃), and refractive index is n
D 20=1.4966.
Preparation example 6 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; the epoxy chloropropane that adds 0.40mol is dissolved in the ethylene dichloride of 0.50mol; stir; initial temperature is 25 ℃ and begins to splash into 0.10mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 100 ℃ then, the holding temperature reaction distilled out excessive reactant and solvent after 4 hours; cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester, its productive rate is 93%, and decomposition temperature is 267 ± 5 ℃; flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃), and refractive index is n
D 20=1.4966.
Preparation example 7 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; add 1 of 0.80mol; 3-dichloro 2-propyl alcohol stirs, and initial temperature is 25 ℃ and drips adding 0.10mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 60 ℃ then; the holding temperature reaction is after 8 hours, and underpressure distillation goes out low boilers, adds trimeric cyanamide 0.002mol; stir cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester, its productive rate is 96%, and decomposition temperature is 268 ± 5 ℃; flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃), and refractive index is n
D 20=1.4966.
Preparation example 8 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; add 1 of 0.60mol; 3-dichloro 2-propyl alcohol is dissolved in the ethylene dichloride of 0.50mol; stir; initial temperature is 25 ℃ and drips 0.10mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 80 ℃ then; the holding temperature reaction distilled out excessive reactant and solvent after 5 hours, added pyridine 0.003mol; stir cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester, its productive rate is 94%, and decomposition temperature is 267 ± 5 ℃; flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃), and refractive index is n
D 20=1.4966.
Preparation example 9 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; with 1 of 0.40mol; 3-dichloro 2-propyl alcohol is dissolved in the dioxane of 0.50mol; stir; initial temperature is 25 ℃ and drips 0.10mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 100 ℃ then; the holding temperature reaction distilled out excessive reactant and solvent after 4 hours, added xylidine 0.003mol; stir cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester, its productive rate is 93%, and decomposition temperature is 267 ± 5 ℃; flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃), and refractive index is n
D 20=1.4966.
Preparation example 10 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; add 1 of 0.80mol; 3-dichloro 2-propyl alcohol stirs, and initial temperature is 25 ℃ and drips 0.10mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 50 ℃ then; the holding temperature reaction is after 7 hours, and underpressure distillation goes out low boilers, adds triethylamine 0.004mol; stir cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester, its productive rate is 97%, and decomposition temperature is 267 ± 5 ℃; flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃), and refractive index is n
D 20=1.4966.
Preparation example 11 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; add 1 of 0.60mol; 3-dichloro 2-propyl alcohol is dissolved in the 0.50mol tetracol phenixin; stir; initial temperature is 25 ℃ and drips 0.10mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 70 ℃ then; the holding temperature reaction distilled out excessive reactant and solvent after 6 hours, added trimeric cyanamide 0.003mol; stir cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester, its productive rate is 97%, and decomposition temperature is 267 ± 5 ℃; flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃), and refractive index is n
D 20=1.4966.
Preparation example 12 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; add 1 of 0.40mol; 3-dichloro 2-propyl alcohol is dissolved in the toluene of 0.50mol; stir; initial temperature is 25 ℃ and drips 0.10mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 90 ℃ then; the holding temperature reaction distilled out excessive reactant and solvent after 4 hours, added Diethyl Aniline 0.003mol; stir cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester, its productive rate is 93%, and decomposition temperature is 267 ± 5 ℃; flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃), and refractive index is n
D 20=1.4966.
Preparation example 13 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; add 2 of 0.80mol; the 3-dichlorohydrine; stir, initial temperature is 25 ℃ and drips 0.10mol silicon tetrachloride (progressively improving temperature with reaction), slowly is warmed up to 60 ℃ then; the holding temperature reaction is after 8 hours; underpressure distillation goes out low boilers, adds triphenylamine 0.002mol, stirs cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester; its productive rate is 97%, and decomposition temperature is 267 ± 5 ℃, and flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃).
Preparation example 14 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; add 2 of 0.60mol; the 3-dichlorohydrine is dissolved in the ethylene dichloride of 0.50mo l; stir, initial temperature is 25 ℃ and drips 0.10mol silicon tetrachloride (progressively improving temperature with reaction), slowly is warmed up to 80 ℃ then; the holding temperature reaction is after 6 hours; distill out excessive reactant and solvent, add pyridine 0.003mol, stir cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester; its productive rate is 96%, and decomposition temperature is 267 ± 5 ℃, and flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃).
Preparation example 15 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; add 2 of 0.40mol; the 3-dichlorohydrine is dissolved in the dimethylbenzene of 0.50mol; stir, initial temperature is 25 ℃ and drips 0.10mol silicon tetrachloride (progressively improving temperature with reaction), slowly is warmed up to 100 ℃ then; the holding temperature reaction is after 4 hours; distill out excessive reactant and solvent, add trimeric cyanamide 0.002mol, stir cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester; its productive rate is 93%, and decomposition temperature is 267 ± 5 ℃, and flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃).
Preparation example 16 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; add 2 of 0.80mol; the 3-dichlorohydrine; stir, initial temperature is 25 ℃ and drips 0.10mol silicon tetrachloride (progressively improving temperature with reaction), slowly is warmed up to 50 ℃ then; the holding temperature reaction is after 8 hours; underpressure distillation goes out low boilers, adds xylidine 0.002mol, stirs cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester; its productive rate is 97%, and decomposition temperature is 267 ± 5 ℃, and flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃).
Preparation example 17 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; add 2 of 0.60mol; the 3-dichlorohydrine is dissolved in the benzene of 0.50mol; stir, initial temperature is 25 ℃ and drips 0.10mol silicon tetrachloride (progressively improving temperature with reaction), slowly is warmed up to 75 ℃ then; the holding temperature reaction is after 6 hours; distill out excessive reactant and solvent, add trimeric cyanamide 0.002mol, stir cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester; its productive rate is 97%, and decomposition temperature is 267 ± 5 ℃, and flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃).
Preparation example 18 is in being equipped with the 250ml four-hole bottle of agitator and drying tube; feed nitrogen protection; add 2 of 0.40mol; the 3-dichlorohydrine is dissolved in the tetrachloroethane of 0.50mol; stir; initial temperature is 25 ℃ and drips 0.10mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 100 ℃ then; the holding temperature reaction is after 4 hours; distill out excessive reactant and solvent, add Diethyl Aniline 0.003mol, stir cooling; filter gained liquid and be silicic acid four (two chloropropyls) ester; its productive rate is 93%, and decomposition temperature is 267 ± 5 ℃, and flash-point (open cup) is 260 ± 5 ℃; degree Beaume is 45.53 (14 ℃), and density is 1.455 (14 ℃).
Table 1
| Tetracol phenixin/mol | Epoxy chloropropane or 1,3-two chloro-2-propyl alcohol or 2,3-dichlorohydrine/mol | Solvent/mol | Acid binding agent/mol | At the beginning temperature/℃ | Temperature/℃ | Reaction times/hour | Productive rate | |
| Preparation example 1 | ??0.10 | Epoxy chloropropane 0.80 | ??25 | ??50 | ??8 | ??93％ | ||
| Preparation example 2 | ??0.10 | Epoxy chloropropane 0.60 | ??25 | ??70 | ??6 | ??95％ | ||
| Preparation example 3 | ??0.10 | Epoxy chloropropane 0.50 | ??25 | ??90 | ??4 | ??95％ | ||
| Preparation example 4 | ??0.10 | Epoxy chloropropane 0.48 | Trichloromethane 0.50 | ??25 | ??60 | ??8 | ??96％ | |
| Preparation example 5 | ??0.10 | Epoxy chloropropane 0.44 | Ethylene dichloride 0.50 | ??25 | ??80 | ??6 | ??98％ | |
| Preparation example 6 | ??0.10 | Epoxy chloropropane 0.40 | Ethylene dichloride 0.50 | ??25 | ??100 | ??4 | ??93％ | |
| Preparation example 7 | ??0.10 | 1,3-two chloro-2-propyl alcohol 0.80 | Trimeric cyanamide 0.002 | ??25 | ??60 | ??8 | ??96％ |
| Tetracol phenixin/mol | Epoxy chloropropane or 1,3-two chloro-2-propyl alcohol or 2,3-dichlorohydrine/mol | Solvent/mol | Acid binding agent/mol | At the beginning temperature/℃ | Temperature/℃ | Reaction times/hour | Productive rate | |
| Preparation example 8 | ??0.10 | 1,3-two chloro-2-propyl alcohol 0.60 | Ethylene dichloride 0.50 | Pyridine 0.003 | ??25 | ??80 | ??5 | ??94％ |
| Preparation example 9 | ??0.10 | 1,3-two chloro-2-propyl alcohol 0.40 | Xylidine 0.003 | ??25 | ??100 | ??4 | ??93％ | |
| Preparation example 0 | ??0.10 | 1,3-two chloro-2-propyl alcohol 0.80 | Triethylamine 0.004 | ??25 | ??50 | ??7 | ??97％ | |
| Preparation example 11 | ??0.10 | 1,3-two chloro-2-propyl alcohol 0.60 | Tetracol phenixin 0.50 | Trimeric cyanamide 0.003 | ??25 | ??70 | ??6 | ??97％ |
| Preparation example 12 | ??0.10 | 1,3-two chloro-2-propyl alcohol 0.40 | Toluene 0.50 | Diethyl Aniline 0.003 | ??25 | ??90 | ??4 | ??99％ |
| Preparation example 13 | ??0.10 | 2,3-dichlorohydrine 0.80 | Triphenylamine 0.002 | ??25 | ??60 | ??8 | ??97％ | |
| Preparation example 14 | ??0.10 | 2,3-dichlorohydrine 0.60 | Ethylene dichloride 0.50 | Pyridine 0.003 | ??25 | ??80 | ??6 | ??96％ |
| Tetracol phenixin/mol | Epoxy chloropropane or 1,3-two chloro-2-propyl alcohol or 2,3-dichlorohydrine/mol | Solvent/mol | Acid binding agent/mol | At the beginning temperature/℃ | Temperature/℃ | Reaction times/hour | Productive rate | |
| Preparation example 15 | ??0.10 | 2,3-dichlorohydrine 0.40 | Toluene 0.50 | Trimeric cyanamide 0.002 | ??25 | ??1100 | ??4 | ??99％ |
| Preparation example 16 | ??0.10 | 2,3-dichlorohydrine 0.80 | Xylidine 0.002 | ??25 | ??50 | ??8 | ??97％ | |
| Preparation example 17 | ??0.10 | 2,3-dichlorohydrine 0.60 | Benzene 0.50 | Trimeric cyanamide 0.002 | ??25 | ??75 | ??6 | ??97％ |
| Preparation example 18 | ??0.10 | 2,3-dichlorohydrine 0.40 | Tetrachloroethane 0.50 | Diethyl Aniline 0.003 | ??25 | ??100 | ??4 | ??93％ |
This case contriver also is applied to above-mentioned synthetic silicic acid four (two chloropropyls) ester in the polyvinyl chloride.Reference: GB/T2406-2008 " (plastics combustibility test method-oxygen index method " flame retardant properties of survey product in polyvinyl chloride.Get product silicic acid four (two chloropropyls) ester, plasticizer phthalic acid succinate, synergistic flame retardant antimonous oxide and polyvinyl chloride mix the back in varing proportions and extrude with forcing machine, and make long 15cm, diameter is the batten of 3mm and its flame retardant properties is tested that test-results is as shown in the table:
Table 2
| Embodiment | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 | ??8 | ??10 | ??11 |
| ??PVC | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
| The phthalic acid succinate | ??40 | ??40 | ??40 | ??40 | ??100 | |||||
| Silicic acid four (two chloropropyls) ester | ??10 | ??15 | ??20 | ??40 | ??100 | ??1100 | ??40 | |||
| The trichlorine propyl phosphate | ??100 | |||||||||
| Antimonous oxide | ??5 | ??7.5 | ??10 | ??20 | ??50 | ??5 | ??5 | |||
| Oxygen index | ??32 | ??32 | ??31 | ??41 | ??36 | ??31 | ??36 | ??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 have excellent flame-retardant.Compare with fire retardant trichlorine propyl phosphate commonly used, silicic acid four (two chloropropyls) ester is better fire retardant.
Claims (14)
1. a silicic acid four (two chloropropyls) ester is characterized in that the structure of this polymkeric substance is shown below:
0≤n≤4 wherein.
2. the preparation method of silicic acid four (two chloropropyls) ester according to claim 1 is characterized in that:
Under initial temperature is 25 ℃, the condition of nitrogen protection; make silicon tetrachloride respectively with epoxy chloropropane, 1,3-two chloro-2-propyl alcohol or 2,3-dichlorohydrine direct reaction or in organic solvent, react; reaction product cooled off, purify, thereby obtain silicic acid four (two chloropropyls) ester thereafter.
3. preparation method as claimed in claim 2 is characterized in that:
Under initial temperature is 25 ℃, the condition of nitrogen protection; with silicon tetrachloride respectively with epoxy chloropropane, 1; 3-two chloro-2-propyl alcohol or 2, the 3-dichlorohydrine is added to together, silicon tetrachloride and epoxy chloropropane, 1; 3-two chloro-2-propyl alcohol or 2; the mol ratio of 3-dichlorohydrine is 1: 4～8, then in 50～100 ℃ temperature range, and direct reaction or in organic solvent, reacted 4～8 hours; reaction product cooled off, purify, thereby obtain silicic acid four (two chloropropyls) ester thereafter.
4. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; add organic solvent; the mol ratio of control silicon tetrachloride and epoxy chloropropane is 1: 4～8; under 25 ℃, begin silicon tetrachloride is added drop-wise in the epoxy chloropropane; then be warming up to 50 ℃～100 ℃ and reacted 4～8 hours; cool off then, purify, make silicic acid four (two chloropropyls) ester.
5. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; add organic solvent; the mol ratio of control silicon tetrachloride and epoxy chloropropane is 1: 4～8; under 25 ℃, begin epoxy chloropropane is added drop-wise in the silicon tetrachloride; then be warming up to 50 ℃～100 ℃ and reacted 4～8 hours; cool off then, purify, make silicic acid four (two chloropropyls) ester.
6. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; control silicon tetrachloride and 1; 3-two chloro-2-propyl alcohol mol ratios are 1: 4～8; under 25 ℃, begin silicon tetrachloride is added drop-wise to 1; in the 3-two chloro-2-propyl alcohol, direct reaction then is warming up to 50 ℃～100 ℃ reactions 4～8 hours; cool off then, purify, make silicic acid four (two chloropropyls) ester.
7. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; add organic solvent; control silicon tetrachloride and 1; 3-dichloro 2-propyl alcohol mol ratio is 1: 4～8, begins 1 under 25 ℃, and 3-two chloro-2-propyl alcohol are added drop-wise in the silicon tetrachloride; emit hydrogenchloride; then be warming up to 50 ℃～100 ℃ reactions 4～8 hours, cool off then, purify, make silicic acid four (two chloropropyls) ester.
8. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; add organic solvent; control silicon tetrachloride and 2; 3-dichlorohydrine mol ratio is 1: 4～8, begins 2 under 25 ℃, and the 3-dichlorohydrine is added drop-wise in the silicon tetrachloride; emit hydrogenchloride; then be warming up to 50 ℃～100 ℃ reactions 4～8 hours, cool off then, purify, make silicic acid four (two chloropropyls) ester.
9. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; add organic solvent; control silicon tetrachloride and 2; 3-dichlorohydrine mol ratio is 1: 4～8, begins silicon tetrachloride is added drop-wise to 2, in the 3-dichlorohydrine under 25 ℃; emit hydrogenchloride; then be warming up to 50 ℃～100 ℃ reactions 4～8 hours, purify then, make silicic acid four (two chloropropyls) ester.
10. as each described preparation method of claim 2～9, wherein, described purification adds acid binding agent then for distilling out excessive reactant or distilling out excessive reactant and solvent, refilters to obtain silicic acid four (two chloropropyls) ester.
11. as claim 2～5,7～9 each described preparation methods, wherein, described organic solvent is selected from ethylene dichloride, tetrachloroethane, chloroform, tetracol phenixin, benzene, toluene, the group that dimethylbenzene is formed.
12. preparation method as claimed in claim 10 is characterized in that, excessive reactant is reclaimed use, and perhaps excessive reactant and solvent recuperation is used.
13. preparation method as claimed in claim 10, wherein, described acid binding agent is selected from the group of trimeric cyanamide, tertiary amine, triethylamine, xylidine, Diethyl Aniline, pyridine composition.
14. silicic acid four as claimed in claim 1 (two chloropropyls) ester is as the application of flame-retardant plasticizer.
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