CN104650138A - Preparation method of flame retardant, namely dimethyl-1, 3-propdioxyl cyclic silane compound - Google Patents
Preparation method of flame retardant, namely dimethyl-1, 3-propdioxyl cyclic silane compound Download PDFInfo
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- CN104650138A CN104650138A CN201510100701.7A CN201510100701A CN104650138A CN 104650138 A CN104650138 A CN 104650138A CN 201510100701 A CN201510100701 A CN 201510100701A CN 104650138 A CN104650138 A CN 104650138A
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- VDCBSKQQTUPBHE-UHFFFAOYSA-N C[Si]1(C)OCCCO1 Chemical compound C[Si]1(C)OCCCO1 VDCBSKQQTUPBHE-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a preparation method of a flame retardant, namely a dimethyl-1, 3-propdioxyl cyclic silane compound. The structure of the compound is as shown in the specification, and the preparation method comprises the following steps: mixing equal moles of 1, 3-propanediol and dimethyldimethoxysilane with an organic solvent in a reactor provided with an efficient fractional distillation device, heating to 80 DEG C, starting to perform boiling fractional distillation reaction, controlling the temperature at the top of a fractional distillation column to be not higher than 65 DEG C, continuously separating generated methanol, gradually heating a reaction system along with the reaction, performing heat preservation reaction at 100-160 DEG C for 5-9h, and distilling out the organic solvent when distilled methanol reaches a theoretical amount to obtain colorless transparent liquid dimethyl-1, 3-propdioxyl cyclic silane. The compound provided by the invention has the advantages of high flame retardance efficiency and good char-forming property, and is suitable for being used as the flame retardant for polyvinyl chloride, polyurethane, epoxy resin, unsaturated resin and other materials; and furthermore, the production process is simple, the equipment investment is low, the cost is low, and the industrial production is easy to implement.
Description
Technical field
The present invention relates to a kind of preparation method of fire retardant dimethyl-1,3-third dioxy basic ring silane compound.Dimethyl-1,3-third dioxy basic ring silane belongs to Halogen organic silicon fibre retardant, is suitable as the fire retardant of the materials such as polyvinyl chloride, urethane, epoxy resin, unsaturated polyester.
Background technology
Synthetic organic polymer material has resistance to chemical attack, light weight, easily processing and the advantage such as attractive in appearance, is widely used in industry-by-industry.But many macromolecular materials are inflammable, to bring people various simultaneously easily, people are made again often to suffer the threat of fire.In order to improve the flammable deficiency of macromolecular material, facilitate the development of fire retardant.When practice finds that fire occurs, halogenated flame retardant can produce the obnoxious flavoures such as hydrogen halide in combustion, causes secondary to endanger.So Halogen, low cigarette, low-poison and combustion-resisting agent have become the emphasis of research and development.Owing to containing C-Si key in organic silicon flame-retardant agent molecule, decomposition temperature is high, Stability Analysis of Structures, good flame retardation effect, also has good one-tenth charcoal effect, the therefore commercioganic urgency property treated of the research and apply tool of organic silicon fibre retardant.
The invention discloses the preparation method of a kind of Halogen, environmental protection fire retarding agent dimethyl-1,3-third dioxy basic ring silane compound.This compound good flame retardation effect, cost is low, technique is simple, be widely used, and has good application and development prospect.
Summary of the invention
The object of the invention is to the preparation method proposing a kind of dimethyl-1,3-third dioxy basic ring silane, its technique is simple, facility investment is few, be easy to large-scale production, and cheaper starting materials is easy to get, with low cost, can overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme, the preparation method of dimethyl-1,3-third dioxy basic ring silane described above, it is characterized in that, the method is:
In the reactor that efficient fractionation plant is housed, add equimolar 1, ammediol and dimethyldimethoxysil,ne and appropriate organic solvent, be warmed up to 80 DEG C of fractionation reactions that come to life, control fractionation column top temperature not higher than 65 DEG C, separate the methyl alcohol of generation continuously, the dimethyldimethoxysil,ne of dissociating along with the carrying out of reaction reduces, the temperature of reaction system raises gradually, at 100 ~ 160 DEG C of insulation reaction 5 ~ 9h, when the methyl alcohol fractionated out reaches theoretical amount, stopped reaction, distill out organic solvent (reclaim and use) and a small amount of low boilers, obtain colourless transparent liquid dimethyl-1, 3-third dioxy basic ring silane.
Organic solvent as above is toluene, dimethylbenzene, dioxane, tetrachloroethane, ethylene glycol diethyl ether or diethylene glycol dimethyl ether, and the 2-5 of its consumption to be organic solvent volume milliliter number be product Theoretical Mass grams doubly.
Dimethyl-1,3-third dioxy basic ring silane of the present invention is colourless transparent liquid, productive rate 96.5% ~ 98.7%, refractive index n
d 25=1.4418, density (25 DEG C) 1.048 ± 0.005g/cm
3, boiling point 218 DEG C.It is suitable as the use of the fire retardant of the materials such as unsaturated polyester, epoxy resin, urethane, polyvinyl chloride.
Preparation technology's principle of dimethyl-1,3-third dioxy basic ring silane is shown below:
Compared with prior art, innovation of the present invention is:
1. fire retardant dimethyl-1,3-third dioxy basic ring silane of the present invention has stable cyclic organic structure, and physical and chemical performance is stablized, good with macromolecular material consistency, can generate fine and close silicon layer of charcoal, have into the anti-drip effect of charcoal, good processability during burning.
2. fire retardant dimethyl-1,3-third dioxy basic ring silane of the present invention belongs to halogen-free flame retardants, meets the demand for development of fire retardant halogen-free environmental, has good application and development prospect.
3. fire retardant dimethyl-1,3-third dioxy basic ring silane preparation method of the present invention is simple, and cheaper starting materials is easy to get, and cost is low, and non-pollutant discharge in technique, is easy to large-scale production.
Accompanying drawing explanation
In order to the stuctures and properties spy further illustrating product provides following accompanying drawing.
1, the infrared spectrogram of dimethyl-1,3-third dioxy basic ring silane, refers to Figure of description Fig. 1.
Fig. 1 shows, 2969cm
-1place is the stretching vibration peak of c h bond; 2890cm
-1place is the stretching vibration peak of the c h bond be connected with oxygen; 1460cm
-1place is the flexural vibration peak of c h bond; 1246cm
-1place is the stretching vibration peak of C-O key; 1065cm
-1place is the stretching vibration peak of Si-O key; 810cm
-1place is the stretching vibration peak of C-Si key.
2, the nuclear magnetic spectrum figure of dimethyl-1,3-third dioxy basic ring silane, refers to Figure of description Fig. 2.
Fig. 2 shows, deuterochloroform is solvent, and δ 0.1-0.3 is Si-CH
3on methyl H peak; δ 1.4-1.6 is the methylene radical H peak of silicon contraposition in ring; δ 3.4-3.75 is the methylene radical H peak be connected with oxygen.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described further.
Embodiment 1 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 7.6g (0.1mol) 1, ammediol, 12.02g (0.1mol) dimethyldimethoxysil,ne and 60ml dioxane, be warmed up to 80 DEG C of fractionation reactions that come to life, control fractionation column top temperature not higher than 65 DEG C, separate the methyl alcohol of generation continuously, the dimethyldimethoxysil,ne of dissociating along with the carrying out of reaction reduces, the temperature of reaction system can raise gradually, 9h is about 100 DEG C of insulation reaction, when the methyl alcohol fractionated out reaches theoretical amount, stopped reaction, distill out organic solvent (reclaim and use) and a small amount of low boilers, obtain colourless transparent liquid dimethyl-1, 3-third dioxy basic ring silane, product yield 96.5%.
Embodiment 2 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 7.6g (0.1mol) 1, ammediol, 12.02g (0.1mol) dimethyldimethoxysil,ne and 40ml toluene, be warmed up to 80 DEG C of fractionation reactions that come to life, control fractionation column top temperature not higher than 65 DEG C, separate the methyl alcohol of generation continuously, the dimethyldimethoxysil,ne of dissociating along with the carrying out of reaction reduces, the temperature of reaction system can raise gradually, 7h is about 110 DEG C of insulation reaction, when the methyl alcohol fractionated out reaches theoretical amount, stopped reaction, distill out organic solvent (reclaim and use) and a small amount of low boilers, obtain colourless transparent liquid dimethyl-1, 3-third dioxy basic ring silane, product yield 97.5%.
Embodiment 3 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 7.6g (0.1mol) 1, ammediol, 12.02g (0.1mol) dimethyldimethoxysil,ne and 50ml dimethylbenzene, be warmed up to 80 DEG C of fractionation reactions that come to life, control fractionation column top temperature not higher than 65 DEG C, separate the methyl alcohol of generation continuously, the dimethyldimethoxysil,ne of dissociating along with the carrying out of reaction reduces, the temperature of reaction system can raise gradually, 6h is about 140 DEG C of insulation reaction, when the methyl alcohol fractionated out reaches theoretical amount, stopped reaction, distill out organic solvent (reclaim and use) and a small amount of low boilers, obtain colourless transparent liquid dimethyl-1, 3-third dioxy basic ring silane, product yield 98.5%.
Embodiment 4 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 7.6g (0.1mol) 1, ammediol, 12.02g (0.1mol) dimethyldimethoxysil,ne and 50ml tetrachloroethane, be warmed up to 80 DEG C of fractionation reactions that come to life, control fractionation column top temperature not higher than 65 DEG C, separate the methyl alcohol of generation continuously, the dimethyldimethoxysil,ne of dissociating along with the carrying out of reaction reduces, the temperature of reaction system can raise gradually, 7h is about 130 DEG C of insulation reaction, when the methyl alcohol fractionated out reaches theoretical amount, stopped reaction, distill out organic solvent (reclaim and use) and a small amount of low boilers, obtain colourless transparent liquid dimethyl-1, 3-third dioxy basic ring silane, product yield 97.9%.
Embodiment 5 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 7.6g (0.1mol) 1, ammediol, 12.02g (0.1mol) dimethyldimethoxysil,ne and 40ml ethylene glycol diethyl ether, be warmed up to 80 DEG C of fractionation reactions that come to life, control fractionation column top temperature not higher than 65 DEG C, separate the methyl alcohol of generation continuously, the dimethyldimethoxysil,ne of dissociating along with the carrying out of reaction reduces, the temperature of reaction system can raise gradually, 8h is about 120 DEG C of insulation reaction, when the methyl alcohol fractionated out reaches theoretical amount, stopped reaction, distill out organic solvent (reclaim and use) and a small amount of low boilers, obtain colourless transparent liquid dimethyl-1, 3-third dioxy basic ring silane, product yield 96.8%.
Embodiment 6 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 7.6g (0.1mol) 1, ammediol, 12.02g (0.1mol) dimethyldimethoxysil,ne and 30ml diethylene glycol dimethyl ether, be warmed up to 80 DEG C of fractionation reactions that come to life, control fractionation column top temperature not higher than 65 DEG C, separate the methyl alcohol of generation continuously, the dimethyldimethoxysil,ne of dissociating along with the carrying out of reaction reduces, the temperature of reaction system can raise gradually, 5h is about 150 DEG C of insulation reaction, when the methyl alcohol fractionated out reaches theoretical amount, stopped reaction, distill out organic solvent (reclaim and use) and a small amount of low boilers, obtain colourless transparent liquid dimethyl-1, 3-third dioxy basic ring silane, product yield 96.9%.
Embodiment 7 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 7.6g (0.1mol) 1, ammediol, 12.02g (0.1mol) dimethyldimethoxysil,ne and 40ml diethylene glycol dimethyl ether, be warmed up to 80 DEG C of fractionation reactions that come to life, control fractionation column top temperature not higher than 65 DEG C, separate the methyl alcohol of generation continuously, the dimethyldimethoxysil,ne of dissociating along with the carrying out of reaction reduces, the temperature of reaction system can raise gradually, 7h is about 120 DEG C of insulation reaction, when the methyl alcohol fractionated out reaches theoretical amount, stopped reaction, distill out organic solvent (reclaim and use) and a small amount of low boilers, obtain colourless transparent liquid dimethyl-1, 3-third dioxy basic ring silane, product yield 98.7%.
Dimethyl-1, the 3-third dioxy basic ring silane of above-mentioned synthesis is also applied in polyvinyl chloride (PVC) by inventor.The limiting oxygen index(LOI) of reference: GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " test sample product.By dimethyl-1,3-third dioxy basic ring silane, plasticizer phthalic acid dioctyl ester (DOP), synergistic flame retardant antimonous oxide (Sb
2o
3) and after polyvinyl chloride mixes in varing proportions, extrude with forcing machine, make the batten that diameter is 3mm, test with HC900-2 limiting oxygen index(LOI) determinator, experiment shows dimethyl-1,3-third dioxy basic ring silane is to PVC excellent flame retardancy, and also have good carbon-forming performance, part test result is as shown in table 1:
The flame retardant properties test data of table 1 dimethyl-1,3-third dioxy basic ring silane
Claims (2)
1. the preparation method of fire retardant dimethyl-1, a 3-third dioxy basic ring silane compound, it is characterized in that, the method is:
Agitator is being housed, thermometer, in the reactor of efficient fractionation plant, add equimolar 1, ammediol and dimethyldimethoxysil,ne and appropriate organic solvent, be warmed up to 80 DEG C of fractionation reactions that come to life, control fractionation column top temperature not higher than 65 DEG C, separate the methyl alcohol of generation continuously, along with the temperature of carrying out reaction system of reaction raises gradually, at 100 ~ 160 DEG C of insulation reaction 5 ~ 9h, when the methyl alcohol fractionated out reaches theoretical amount, stopped reaction, distill out organic solvent and a small amount of low boilers, obtain colourless transparent liquid dimethyl-1, 3-third dioxy basic ring silane, the structure of this compound is shown below:
2. fire retardant dimethyl-1 as claimed in claim 1, the preparation method of 3-third dioxy basic ring silane compound, it is characterized in that: described organic solvent is toluene, dimethylbenzene, dioxane, tetrachloroethane, ethylene glycol diethyl ether or diethylene glycol dimethyl ether, the 2-5 of its consumption to be organic solvent volume milliliter number be product Theoretical Mass grams doubly.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1240780C (en) * | 2001-01-17 | 2006-02-08 | 气体产品与化学公司 | Organosilicon precursor for interlayer medium film with low dielectric constant |
| CN102140115A (en) * | 2011-02-23 | 2011-08-03 | 苏州科技学院 | Flame-retardant plasticizer of methyl silicate trichloroethyl ester compound and preparation method thereof |
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- 2015-03-06 CN CN201510100701.7A patent/CN104650138A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1240780C (en) * | 2001-01-17 | 2006-02-08 | 气体产品与化学公司 | Organosilicon precursor for interlayer medium film with low dielectric constant |
| CN102140115A (en) * | 2011-02-23 | 2011-08-03 | 苏州科技学院 | Flame-retardant plasticizer of methyl silicate trichloroethyl ester compound and preparation method thereof |
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Application publication date: 20150527 |