CN104710463A - Preparation method of dimethyl-1,2-o- dioxygen base ring silanization compound serving as flame resistant plastifier - Google Patents
Preparation method of dimethyl-1,2-o- dioxygen base ring silanization compound serving as flame resistant plastifier Download PDFInfo
- Publication number
- CN104710463A CN104710463A CN201510100789.2A CN201510100789A CN104710463A CN 104710463 A CN104710463 A CN 104710463A CN 201510100789 A CN201510100789 A CN 201510100789A CN 104710463 A CN104710463 A CN 104710463A
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- reaction
- temperature
- organic solvent
- basic ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a preparation method of a dimethyl-1,2-o- dioxygen base ring silanization compound serving as a flame resistant plastifier. The structure of the compound is shown in the following forluma, wherein R represents methyl, ethyl, propyl or butyl. The preparation method comprises the following steps: in a reactor provided with a high efficiency fraction collector, mixing a 1,2-o-glycol and dimethyl dimethoxy silicon alkane with an organic solvent with equal mols, performing temperature rise to 80 DEG C to start a boiling fractionation reaction, controlling the temperature of a top of a fractionating column not to be higher than a temperature of 65 DEG C, continuously separating generated methanol, along with the reaction, gradually increasing the temperature of a reacting system, performing a heat preservation reaction at the temperature of 100-160 DEG C for 5-9 hours, and when the fractionated methanol achieves a theory amount, distilling off the organic solvent so as to obtain an achromatic transparent liquid dimethyl -1,2- o-dioxygen base ring silicon alkane. The compound is high in collaborative flame resistant efficacy, is good in carbon forming performance, and is suitable for being used as the fire retardant of polyvinyl chloride, polyurethane, an epoxy resin, an unsaturated resin and the like. The production technology is simple, the investment of equipment is few, the cost is low, and the industrialized production is easy to realize.
Description
Technical field
The present invention relates to the preparation method of a kind of flame-retardant plasticizer dimethyl-1,2-adjacent dioxy basic ring silane compound.Dimethyl-1,2-adjacent dioxy basic ring silane belongs to Halogen organic silicon fibre retardant, is suitable as the flame-retardant plasticizer of the materials such as polyvinyl chloride, urethane, epoxy resin, unsaturated polyester.
Background technology
The application of current synthetic organic polymer material is more and more extensive.Because itself has inflammableness, the fire caused also gets more and more, and brings huge threat to the security of the lives and property of people, thus facilitates the fast development of fire retardant and fire retardant material.In inflammable macromolecular material, adding fire retardant, to carry out flame-retardant modified be solve a kind of effective ways of inflammable problem.Wherein halogenated flame retardant developing history is long, and utilisation technology is ripe, and comprehensive cost performance is high, is widely used.But halogenated flame retardant can release obnoxious flavour when burning, and makes it be applied in some field and is restricted.So the research of halogen-free flame retardants, has become one of important directions of fire retardant research.Because the organic silicon fibre retardant decomposition temperature containing C-Si key in molecule is high, Stability Analysis of Structures, good flame retardation effect, also has into charcoal effect, and therefore the research and apply of organic silicon fibre retardant has been developed to hot subject.
The invention discloses the preparation method of a kind of Halogen, environmental protection flame retardant softening agent dimethyl-1,2-adjacent dioxy basic ring silane compound.This compound flame-retarded efficiency is high, and become charcoal good, have plasticity, cost is low, and technique is simple, is widely used, has good application and development prospect.
Summary of the invention
The object of the invention is to the preparation method proposing a kind of flame-retardant plasticizer dimethyl-1,2-adjacent dioxy basic ring silane, its technique is simple, and facility investment is few, is 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-1,2-described above adjacent dioxy basic ring silane, it is characterized in that, the method is:
Agitator is being housed, thermometer, in the reactor of efficient fractionation plant, add equimolar 1, 2-vicinal diamines and dimethyldimethoxysil,ne and appropriate organic solvent, be warmed up to 80 DEG C and start there is backflow, carry out fractionation reaction, control fractionation column top temperature not higher than 65 DEG C, separate the methyl alcohol of generation continuously, along with the lower dimethyldimethoxysil,ne of boiling point of 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, 2-adjacent 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-1,2-of the present invention adjacent dioxy basic ring silane is colourless transparent liquid, and it is suitable as the flame-retardant plasticizer of the materials such as unsaturated polyester, epoxy resin, urethane and polyvinyl chloride.
Preparation technology's principle of dimethyl-1,2-adjacent dioxy basic ring silane is shown below:
Compared with prior art, innovation of the present invention is:
1. flame-retardant plasticizer dimethyl-1 of the present invention, 2-adjacent dioxy basic ring silane has stable cyclic organic structure, physical and chemical performance is stablized, on ring, the introducing of side chain gives product good plasticity, good with macromolecular material consistency, fine and close silicon layer of charcoal can be generated during burning, have into the anti-drip effect of charcoal, good processability.
2. flame-retardant plasticizer dimethyl-1,2-of the present invention adjacent dioxy basic ring silane is not halogen-containing, meets the demand for development of fire retardant halogen-free environmental, has good application and development prospect.
3. flame-retardant plasticizer dimethyl-1,2-of the present invention adjacent dioxy basic ring silane preparation method is simple, and cheaper starting materials is easy to get, and cost is low, 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-1,2-third dioxy basic ring silane, refers to Figure of description Fig. 1.
Fig. 1 shows, 2967cm
-1place is the stretching vibration peak of c h bond; 2879cm
-1place is the stretching vibration peak of the c h bond be connected with oxygen; 1411cm
-1place is the flexural vibration peak of c h bond; 1261cm
-1place is the stretching vibration peak of C-O key; 1069cm
-1place is the stretching vibration peak of Si-O key; 807cm
-1place is the stretching vibration peak of C-Si key.
2, the infrared spectrogram of dimethyl-1,2-fourth dioxy basic ring silane, refers to Figure of description Fig. 2:
Fig. 2 shows, 2972cm
-1place is the stretching vibration peak of c h bond; 2836cm
-1place is the stretching vibration peak of the c h bond be connected with oxygen; 1442cm
-1place is the flexural vibration peak of c h bond; 1258cm
-1place is the stretching vibration peak of C-O key; 1061cm
-1place is the stretching vibration peak of Si-O key; 803cm
-1place is the stretching vibration peak of C-Si key.
3, the infrared spectrogram of dimethyl-1,2-penta dioxy basic ring silane, refers to Figure of description Fig. 3:
Fig. 3 shows, 2981cm
-1place is the stretching vibration peak of c h bond; 2852cm
-1place is the stretching vibration peak of the c h bond be connected with oxygen; 1465cm
-1place is the flexural vibration peak of c h bond; 1260cm
-1place is the stretching vibration peak of C-O key; 1058cm
-1place is the stretching vibration peak of Si-O key; 802cm
-1place is the stretching vibration peak of C-Si key.
4, the nuclear magnetic spectrum figure of dimethyl-1,2-third dioxy basic ring silane, refers to Figure of description Fig. 4:
Fig. 4 shows, deuterochloroform is solvent, and δ 0.1-0.4 is Si-CH
3on methyl H peak; δ 0.65-0.9 is the methyl H peak on ring; δ 3.4-3.7 is the H peak on the methylene radical and tertiary carbon that are connected with oxygen in ring.
5, the nuclear magnetic spectrum figure of dimethyl-1,2-fourth dioxy basic ring silane, refers to Figure of description Fig. 5:
Fig. 5 shows, deuterochloroform is solvent, and δ 0.1-0.4 is the methyl H peak be connected with silicon; δ 0.7-0.95 is the methyl H peak of ethyl end position on ring; δ 1.1-1.65 is the methylene radical H peak on ring on ethyl; δ 3.2-4.1 is the H peak on the methylene radical and tertiary carbon that are connected with oxygen in ring.
6, the nuclear magnetic spectrum figure of dimethyl-1,2-penta dioxy basic ring silane, refers to Figure of description Fig. 6:
Fig. 6 shows, deuterochloroform is solvent, and δ 0.1-0.4 is the methyl H peak be connected with silicon; δ 0.75-1.0 is the methyl H peak of propyl group end position on ring; δ 1.2-1.55 is the methylene radical H peak on ring on propyl group; δ 3.4-4.15 is the H peak on the methylene radical and tertiary carbon that are connected with oxygen in ring.
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, 2-propylene glycol, 12.02g (0.1mol) dimethyldimethoxysil,ne and 60ml1, 4-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, 2-third dioxy basic ring silane, product yield 95.5%, refractive index n
d 25=1.4344, density (25 DEG C) 1.146g/cm
3, boiling point 198 DEG C.
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, 2-propylene glycol, 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, 2-third dioxy basic ring silane, product yield 96.5%, refractive index n
d 25=1.4344, density (25 DEG C) 1.146g/cm
3, boiling point 198 DEG C.
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, 2-propylene glycol, 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, 2-third dioxy basic ring silane, product yield 98.0%, refractive index n
d 25=1.4344, density (25 DEG C) 1.146g/cm
3, boiling point 198 DEG C.
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, 2-propylene glycol, 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, 2-third dioxy basic ring silane, product yield 97.6%, refractive index n
d 25=1.4344, density (25 DEG C) 1.146g/cm
3, boiling point 198 DEG C.
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, 2-propylene glycol, 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, 2-third dioxy basic ring silane, product yield 96.4, refractive index n
d 25=1.4344, density (25 DEG C) 1.146g/cm
3, boiling point 198 DEG C of %.
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, 2-propylene glycol, 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, 2-third dioxy basic ring silane, product yield 96.6%, refractive index n
d 25=1.4344, density (25 DEG C) 1.146g/cm
3, boiling point 198 DEG C.
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, 2-propylene glycol, 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, 2-third dioxy basic ring silane, product yield 98.8%, refractive index n
d 25=1.4344, density (25 DEG C) 1.146g/cm
3, boiling point 198 DEG C.
Embodiment 8 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 9.0g (0.1mol) 1, 2-butyleneglycol, 12.02g (0.1mol) dimethyldimethoxysil,ne and 60ml1, 4-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, 2-fourth dioxy basic ring silane, product yield 96.0%, refractive index n
d 25=1.4401, density (25 DEG C) 1.094g/cm
3, boiling point 202 DEG C.
Embodiment 9 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 9.0g (0.1mol) 1, 2-butyleneglycol, 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, 2-fourth dioxy basic ring silane, product yield 97.5%, refractive index n
d 25=1.4401, density (25 DEG C) 1.094g/cm
3, boiling point 202 DEG C.
Embodiment 10 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 9.0g (0.1mol) 1, 2-butyleneglycol, 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, 2-fourth dioxy basic ring silane, product yield 98.0%, refractive index n
d 25=1.4401, density (25 DEG C) 1.094g/cm
3, boiling point 202 DEG C.
Embodiment 11 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 9.0g (0.1mol) 1, 2-butyleneglycol, 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, 2-fourth dioxy basic ring silane, product yield 97.9%, refractive index n
d 25=1.4401, density (25 DEG C) 1.094g/cm
3, boiling point 202 DEG C.
Embodiment 12 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 9.0g (0.1mol) 1, 2-butyleneglycol, 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, 2-fourth dioxy basic ring silane, product yield 96.5%, refractive index n
d 25=1.4401, density (25 DEG C) 1.094g/cm
3, boiling point 202 DEG C.
Embodiment 13 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 9.0g (0.1mol) 1, 2-butyleneglycol, 12.02g (0.1mol) dimethyldimethoxysil,ne and 60ml 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, 2-fourth dioxy basic ring silane, product yield 97.8%, refractive index n
d 25=1.4401, density (25 DEG C) 1.094g/cm
3, boiling point 202 DEG C.
Embodiment 14 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 9.0g (0.1mol) 1, 2-butyleneglycol, 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, 2-fourth dioxy basic ring silane, product yield 98.5%, refractive index n
d 25=1.4401, density (25 DEG C) 1.094g/cm
3, boiling point 202 DEG C.
Embodiment 15 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 10.4g (0.1mol) 1, 2-pentanediol, 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, 2-penta dioxy basic ring silane, product yield 96.5%, refractive index n
d 25=1.4221, density (25 DEG C) 1.013g/cm
3, boiling point 210 DEG C.
Embodiment 16 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 10.4g (0.1mol) 1, 2-pentanediol, 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, 2-penta dioxy basic ring silane, product yield 97.5%, refractive index n
d 25=1.4221, density (25 DEG C) 1.013g/cm
3, boiling point 210 DEG C.
Embodiment 17 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 10.4g (0.1mol) 1, 2-pentanediol, 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, 2-penta dioxy basic ring silane, product yield 98.5%, refractive index n
d 25=1.4221, density (25 DEG C) 1.013g/cm
3, boiling point 210 DEG C.
Embodiment 18 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 10.4g (0.1mol) 1, 2-pentanediol, 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, 2-penta dioxy basic ring silane, product yield 97.9%, refractive index n
d 25=1.4221, density (25 DEG C) 1.013g/cm
3, boiling point 210 DEG C.
Embodiment 19 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 10.4g (0.1mol) 1, 2-pentanediol, 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, 2-penta dioxy basic ring silane, product yield 96.8%, refractive index n
d 25=1.4221, density (25 DEG C) 1.013g/cm
3, boiling point 210 DEG C.
Embodiment 20 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 10.4g (0.1mol) 1, 2-pentanediol, 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, 2-penta dioxy basic ring silane, product yield 96.9%, refractive index n
d 25=1.4221, density (25 DEG C) 1.013g/cm
3, boiling point 210 DEG C.
Embodiment 21 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 10.4g (0.1mol) 1, 2-pentanediol, 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, 2-penta dioxy basic ring silane, product yield 98.7%, refractive index n
d 25=1.4221, density (25 DEG C) 1.013g/cm
3, boiling point 210 DEG C.
Embodiment 22 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 11.8g (0.1mol) 1, 2-hexylene glycol, 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, 2-own dioxy basic ring silane, product yield 95.6%, refractive index n
d 25=1.4202, density (25 DEG C) 1.011g/cm
3.
Embodiment 23 is being equipped with agitator, thermometer, in the 100ml four-hole boiling flask of efficient fractionation plant, add 11.8g (0.1mol) 1, 2-hexylene glycol, 12.02g (0.1mol) dimethyldimethoxysil,ne and 40ml 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, 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, 2-own dioxy basic ring silane, product yield 96.1%, refractive index n
d 25=1.4202, density (25 DEG C) 1.011g/cm
3.
The dimethyl-1,2-of above-mentioned synthesis adjacent dioxy basic ring silane 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-1,2-adjacent 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, with the test of HC900-2 limiting oxygen index(LOI) determinator, experiment shows dimethyl-1,2-adjacent dioxy basic ring silane is to PVC excellent flame retardancy, the carbon-forming performance had, also has good plasticity, is a kind of good fire-retardant char-forming agent, or a kind of flame-retardant plasticizer preferably, some experimental data is in shown in Table 1-3:
The flame retardant properties test data of table 1 dimethyl-1,2-third dioxy basic ring silane
The flame retardant properties test data of table 2 dimethyl-1,2-fourth dioxy basic ring silane
The flame retardant properties test data of table 3 dimethyl-1,2-penta dioxy basic ring silane
Claims (3)
1. the preparation method of flame-retardant plasticizer dimethyl-1, a 2-adjacent dioxy basic ring silane compound, it is characterized in that, the method is:
In the reactor that efficient fractionation plant is housed, add equimolar 1, 2-vicinal diamines 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, 2-third dioxy basic ring silane, the structure of this compound is shown below:
R=methyl, ethyl, propyl group or butyl in formula.
2. the preparation method of flame-retardant plasticizer dimethyl-1,2-adjacent dioxy basic ring silane compound as claimed in claim 1, is characterized in that: described 1,2-vicinal diamines is 1,2-PD, 1,2-butyleneglycol, 1,2-pentanediol or 1,2-hexylene glycol.
3. flame-retardant plasticizer dimethyl-1 as claimed in claim 1, the preparation method of 2-adjacent 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510100789.2A CN104710463A (en) | 2015-03-06 | 2015-03-06 | Preparation method of dimethyl-1,2-o- dioxygen base ring silanization compound serving as flame resistant plastifier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510100789.2A CN104710463A (en) | 2015-03-06 | 2015-03-06 | Preparation method of dimethyl-1,2-o- dioxygen base ring silanization compound serving as flame resistant plastifier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104710463A true CN104710463A (en) | 2015-06-17 |
Family
ID=53410241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510100789.2A Pending CN104710463A (en) | 2015-03-06 | 2015-03-06 | Preparation method of dimethyl-1,2-o- dioxygen base ring silanization compound serving as flame resistant plastifier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104710463A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2015
- 2015-03-06 CN CN201510100789.2A patent/CN104710463A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| MORKEN, JAMES P. ET AL.: "1,2-Bis((2S,5S)-2,5-dimethylphospholano)benzene (S,S)-Me-DuPhos, 1,2-Bis((2R,5R)-2,5-dimethylphospholano)benzene (R,R)-Me-DuPhos", 《E-EROS ENCYCLOPEDIA OF REAGENTS FOR ORGANIC SYNTHESIS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103992351A (en) | Preparation method of dimethylsilyl dioxyl bi-cage ring phosphate | |
| CN102140115B (en) | Flame-retardant plasticizer of methyl silicate trichloroethyl ester compound and preparation method thereof | |
| CN102167707B (en) | Retardant plasticizer methyl silicate ester compound and preparation method thereof | |
| CN106632485B (en) | Fire retardant benzene siliconic acid disulfide group phospha trioxa cage ring octyl group -4- methyl compounds and preparation method thereof | |
| CN104710463A (en) | Preparation method of dimethyl-1,2-o- dioxygen base ring silanization compound serving as flame resistant plastifier | |
| CN104650136A (en) | Preparation method of flame retardant, namely tris (dimethylchloropropoxy silicon acyloxy ethyl) triazine compound | |
| CN105218859B (en) | Reactive flame retardant organic phosphonate compounds and preparation method thereof | |
| CN104710456A (en) | Preparation method of pentaerythritol double ring dimethyl silicate compound serving as fire retardant | |
| CN104672268A (en) | Preparation method of dimethyl bis(banzyloxy) silane compound serving as flame retardant | |
| CN104710462A (en) | Preparation method of dimethyl ethylenedioxy ring silanization compound serving as fire retardant | |
| CN104725412A (en) | Preparation method of fire-retardant plasticizer dimethyl-1,3-m-dioxo cyclosilane compound | |
| CN105254674A (en) | Alkyl dimethoxy silicic phosphine heterocyclic methyl ester compound and preparing method thereof | |
| CN104710461A (en) | Preparation method of dimethyl-2,4-glutaryl dioxy cyclosilane compound as fire retardant | |
| CN104650138A (en) | Preparation method of flame retardant, namely dimethyl-1, 3-propdioxyl cyclic silane compound | |
| CN104710457A (en) | Tri[(2-dimethylchloridepropoxysiliconacyloxy)ethyl] isocyanurate compound and preparation method thereof | |
| CN104650137A (en) | Preparation method of flame retardant, namely dimethyl neopentyldioxyl cyclic silane compound | |
| CN104693228A (en) | Flame retardant dibenzyl dimethylsilicate compound and preparation method thereof | |
| CN104693445B (en) | The fire-retardant preparation method at charcoal plasticizer diformazan cardinal extremity dioxy base silane polymer | |
| CN104672267A (en) | Preparation method of sencor dimethyl halogenate ethyoxyl silicate ester compound serving as flame retardant | |
| CN104693227A (en) | Flame retardant 1,2-ortho-diol dimethyl silicate compound and preparation method thereof | |
| CN105713039A (en) | Aromatic phosphonic acid esterification compound and method for preparing same | |
| CN104788680A (en) | Polydimethylsilicate tetrabromobisphenol A ester polymer and preparation method thereof | |
| CN103554159B (en) | Two silicic acid dibromo propyl ester compound of fire retardant second dioxy support and preparation method thereof | |
| CN105175450A (en) | Method for preparing methylphenyl methoxyl (phosphorous heterocyclic methoxyl) silane compound | |
| CN103342714A (en) | Flame retardant tetra(tribromophenyl) silicate esterification compound and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150617 |
|
| RJ01 | Rejection of invention patent application after publication |