CN104710455A - Preparation method of silicon-halogen synergistic flame retardant plasticizer compound - Google Patents
Preparation method of silicon-halogen synergistic flame retardant plasticizer compound Download PDFInfo
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- CN104710455A CN104710455A CN201510100259.8A CN201510100259A CN104710455A CN 104710455 A CN104710455 A CN 104710455A CN 201510100259 A CN201510100259 A CN 201510100259A CN 104710455 A CN104710455 A CN 104710455A
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Abstract
The invention relates to a preparation method of a silicon-halogen synergistic flame retardant plasticizer compound, in particular to a preparation method of a flame retardant plasticizer dimethyl silicate dihalogen propyl ester. The structure of the compound is as shown in the following formula: (the formula is as shown in the specification), in the formula, the X2C3H5O is (CH2X) 2CHO or CH2XCHXCH2O, and X is Cl or Br. The preparation method comprises the following steps: replacing the air in a reactor by nitrogen; adding dimethyl dimethoxy silane, an organic solvent and dihalogen propyl alcohol; heating to 75-110 DEG C; carrying out fractional distillation reaction for 5-11 h and controlling the temperature at the top of a fractional distillation column to be not higher than 65 DEG C; quantifying the methyl alcohol generated through the fractional distillation; and purifying to obtain the dimethyl silicate dihalogen propyl ester. The flame retardant is high in flame retardant efficiency, good in plasticity, suitable for being used as polyvinyl chloride, polyurethane, epoxy resin and unsaturated polyester resin flame retardant plasticizers, simple in production process, low in cost and easy to realize industrial production.
Description
Technical field
The present invention relates to the preparation method of a kind of silicon, halogen cooperative flame retardant plasticizer compounds, be specifically related to the preparation method of a kind of silicon, the two dihalo-propyl ester compound of halogen cooperative flame retardant softening agent dimethyl silicic acid, this compound is suitable as the flame-retardant plasticizer of polyvinyl chloride, urethane, epoxy resin, unsaturated polyester etc.
Background technology
Along with the appearance in succession of the fire-retardant legislation of global increasingly stringent, fire safety standard and industry instruction, the market requirement of fire retardant presents a rapidly rising trend, especially more urgent to demand that is novel, efficient and environment friendly flame retardant.Halogenated flame retardant flame retarding efficiency is high, historical development is long, production technology is ripe, is widely used in a lot of field, is one of maximum organic fire-retardant of current global output.But its burning can produce a large amount of harmful hydrogen halide, is therefore restricted in the application in some fields.Silicon-series five-retardant has excellent thermostability, and effective anti-melt drippage and flame-proof smoke-suppressing are one of emphasis of current low cigarette and low-poison and combustion-resisting developing material.Silicon and the excellent ignition-proof element design of halogen these two kinds in same molecular structure, producing cooperative flame retardant effect, thus reach desirable flame retardant effect, is a problem with DEVELOPMENT PROSPECT.
The invention discloses with dihalo-propyl alcohol and dimethyldimethoxysil,ne as main raw material prepares the preparation method of silicon, the two dihalo-propyl ester compound of halogen dual element cooperative flame retardant softening agent dimethyl silicic acid.Silicon and halogen element cooperative flame retardant, under hot conditions, element silicon can promote that macromolecular material becomes charcoal, generates fine and close silicon layer of charcoal; Halogen element generates hydrogen halide when being heated, and itself and the effect of retardant synergist antimonous oxide generate antimony halides and cover material surface, have anoxybiotic effect, or releases can take away heat with gas, reduces the temperature of material and does not fire.Flame-retardant plasticizer preparation method of the present invention is simple, and applied range is with low cost, has good application and development prospect.
Summary of the invention
The object of the invention is to the preparation method proposing the two dihalo-propyl ester compound of flame-retardant plasticizer dimethyl silicic acid, 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, and the method is:
Agitator is being housed, in the reactor of thermometer and fractionation plant, the air in reactor is fallen with nitrogen replacement, add dimethyldimethoxysil,ne, dihalo-propyl alcohol and organic solvent, the mol ratio controlling dimethyldimethoxysil,ne and dihalo-propyl alcohol is 1: 2 ~ 1: 3, be warming up to 75 DEG C ~ 110 DEG C, fractionation reaction 5 ~ 11h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation is except desolventizing, excessive dihalo-propyl alcohol (reclaim and use) and a small amount of low boilers, obtain the two dihalo-propyl ester of dimethyl silicic acid.
Organic solvent as above is acetonitrile, ethylene dichloride, dioxane, diethylene glycol dimethyl ether or glycol dimethyl ether, and its consumption volume milliliter number is 2 ~ 10 times of dimethyldimethoxysil,ne quality grams.
Dihalo-propyl alcohol as above is 1,3-dichloroisopropanol, 1,3-dibromo Virahol, 2,3-dichlorohydrines or 2,3-dibromo-propanol.
Dimethyl silicic acid two (1,3-dichloro isopropyl) ester of the present invention is colourless transparent liquid, and decomposition temperature is 207 DEG C ± 5 DEG C, and refractive index is n
d 25=1.4628, density (25 DEG C) is 1.32g/cm
3; Dimethyl silicic acid two (1,3-dibromo isopropyl) ester is colourless transparent liquid, and decomposition temperature is 233 DEG C ± 5 DEG C, and refractive index is n
d 25=1.5489, density (25 DEG C) is 1.93g/cm
3; Dimethyl silicic acid two (2,3-dichloro third) ester is colourless transparent liquid, and decomposition temperature is 214 DEG C ± 5 DEG C, and refractive index is n
d 25=1.4609, density (25 DEG C) is 1.33g/cm
3; Dimethyl silicic acid two (2,3-dibromo third) ester is colourless transparent liquid, and decomposition temperature is 242 DEG C ± 5 DEG C, and refractive index is n
d 25=1.5473, density (25 DEG C) is 1.96g/cm
3.It is suitable as the flame-retardant plasticizer of the materials such as polyvinyl chloride, urethane, epoxy resin, unsaturated polyester.Preparation technology's principle of the two dihalo-propyl ester of this dimethyl silicic acid is shown below:
X in formula
2c
3h
5o is (CH
2x)
2cHO or CH
2xCHXCH
2o, X=Cl or Br.
Compared with prior art, beneficial effect of the present invention is:
1. the siliceous and halogen ignition-proof element of the two dihalo-propyl ester of dimethyl silicic acid of the present invention, its cooperative flame retardant usefulness is high, and element silicon has into charcoal effect, can effectively prevent material melted by heating from dripping and the secondary combustion that produces.
2. in the two dihalo-propyl ester structure of dimethyl silicic acid of the present invention, Siliciumatom is connected with two methyl, having C-Si key, is organosilicon structures, and organosilicon structures good stability, water tolerance are strong, and be easier to during burning generate fine and close charcoal-silicon layer, flame retardant effect is more excellent.
3. the two dihalo-propyl ester symmetry of dimethyl silicic acid of the present invention is good, physical and chemical performance stable, and owing to having branched chain propyl structure in molecule, good with macromolecular material consistency, intermolecular electrostatic force is less, and product viscosity is little, has good plasticity.
4. the two dihalo-propyl ester technique of dimethyl silicic acid of the present invention is simple, and preparation process does not introduce impurity without the need to adding catalyzer, and without exhaust emission, equipment is simple, with low cost, is suitable for large-scale production, has good application and development prospect.
Accompanying drawing explanation
In order to the stuctures and properties spy further illustrating product provides following accompanying drawing.
1, the infrared spectrogram of dimethyl silicic acid two (1,3-dichloro isopropyl) ester, refers to Figure of description Fig. 1;
Fig. 1 shows, 2846.9cm
-1-2965.2cm
-1place is the stretching vibration absorption peak of C-H, 1005.7cm
-1place is the charateristic avsorption band of Si-O-C, 1093.2cm
-1place is the stretching vibration absorption peak of C-O, 828.4cm
-1place is the stretching vibration absorption peak of C-Cl, 801.7cm
-1place is the charateristic avsorption band of Si-C.
2, the nuclear magnetic spectrogram of dimethyl silicic acid two (1,3-dichloro isopropyl) ester, refers to Figure of description Fig. 2;
Fig. 2 shows, deuterochloroform makees solvent, and δ 0.26-0.33 is SiCH
3upper methyl hydrogen peak, δ 3.59-3.73 is CH (CH
2cl)
2upper chloromethyl hydrogen peak, δ 4.18-4.26 is CH (CH
2cl)
2methyl hydrogen last time peak, the proton peak that δ 7.28 exchanges for solvent carbon deuterium chloride.
3, the infrared spectrogram of dimethyl silicic acid two (1,3-dibromo isopropyl) ester, refers to Figure of description Fig. 3;
Fig. 3 shows, 2839.4cm
-1-2973.7cm
-1place is the stretching vibration absorption peak of C-H, 1009.3cm
-1place is the charateristic avsorption band of Si-O-C, 1094.5cm
-1place is the stretching vibration absorption peak of C-O, 623.9cm
-1place is the stretching vibration absorption peak of C-Br, 803.1cm
-1place is the charateristic avsorption band of Si-C.
4, the nuclear magnetic spectrogram of dimethyl silicic acid two (1,3-dibromo isopropyl) ester, refers to Figure of description Fig. 4;
Fig. 4 shows, deuterochloroform makees solvent, and δ 0.25-0.31 is SiCH
3upper methyl hydrogen peak, δ 3.37-3.49 is CH (CH
2br)
2upper brooethyl hydrogen peak, δ 4.02-4.11 is CH (CH
2br)
2methyl hydrogen last time peak.
Specific embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further.
Embodiment 1 is in the 250ml four-hole bottle that agitator, thermometer and fractionation plant are housed, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 60ml acetonitrile and 12.9g (0.1mol) 1,3-dichloroisopropanol, be warming up to 75 DEG C, fractionation reaction 11h, controls fractionation column top temperature not higher than 65 DEG C, fractionates out the methyl alcohol of generation; After the methyl alcohol separated reaches theoretical amount, underpressure distillation, except desolventizing and a small amount of low boilers, obtains dimethyl silicic acid two (1,3-dichloro isopropyl) ester, productive rate 87.3%.
Embodiment 2 is in the 100ml four-hole bottle that agitator, thermometer and fractionation plant are housed, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 45ml ethylene dichloride and 13.22g (0.11mol) 1,3-dichloroisopropanol, be warming up to 83 DEG C, fractionation reaction 10h, controls fractionation column top temperature not higher than 65 DEG C, fractionates out the methyl alcohol of generation; After the methyl alcohol separated reaches theoretical amount, underpressure distillation, except desolventizing, 1,3-excessive dichloroisopropanol (reclaim and use) and a small amount of low boilers, obtains dimethyl silicic acid two (1,3-dichloro isopropyl) ester, productive rate 91.6%.
Embodiment 3 is in the 100ml four-hole bottle that agitator, thermometer and fractionation plant are housed, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 40ml dioxane and 15.03g (0.125mol) 1,3-dichloroisopropanol, be warming up to 85 DEG C-90 DEG C (along with the carrying out of reaction, system temperature can be elevated to 90 DEG C gradually from 85 DEG C), fractionation reaction 8h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation; After the methyl alcohol separated reaches theoretical amount, underpressure distillation, except desolventizing, 1,3-excessive dichloroisopropanol (reclaim and use) and a small amount of low boilers, obtains dimethyl silicic acid two (1,3-dichloro isopropyl) ester, productive rate 93.4%.
Embodiment 4 is in the 100ml four-hole bottle that agitator, thermometer and fractionation plant are housed, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 30ml glycol dimethyl ether and 16.83g (0.14mol) 1,3-dichloroisopropanol, be warming up to 80 DEG C, fractionation reaction 10h, controls fractionation column top temperature not higher than 65 DEG C, fractionates out the methyl alcohol of generation; After the methyl alcohol separated reaches theoretical amount, underpressure distillation, except desolventizing, 1,3-excessive dichloroisopropanol (reclaim and use) and a small amount of low boilers, obtains dimethyl silicic acid two (1,3-dichloro isopropyl) ester, productive rate 92.7%.
Embodiment 5 is in the 100ml four-hole bottle that agitator, thermometer and fractionation plant are housed, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 15ml dioxane and 18.03g (0.15mol) 1,3-dichloroisopropanol, be warming up to 85 DEG C-100 DEG C (along with the carrying out of reaction, system temperature can be elevated to 100 DEG C gradually from 85 DEG C), fractionation reaction 6h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation; After the methyl alcohol separated reaches theoretical amount, underpressure distillation, except desolventizing, 1,3-excessive dichloroisopropanol (reclaim and use) and a small amount of low boilers, obtains dimethyl silicic acid two (1,3-dichloro isopropyl) ester, productive rate 95.1%.
Embodiment 6 is in the 100ml there-necked flask that agitator, thermometer and fractionation plant are housed, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 60ml acetonitrile and 21.79g (0.1mol) 1,3-dibromo Virahol, be warming up to 75 DEG C, fractionation reaction 11h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation, except desolventizing and a small amount of low boilers, obtains dimethyl silicic acid two (1,3-dibromo isopropyl) ester, productive rate 86.7%.
Embodiment 7 is being equipped with agitator, in the 100ml there-necked flask of thermometer and fractionation plant, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 45ml ethylene dichloride and 23.97g (0.11mol) 1, 3-dibromo Virahol, be warming up to 83 DEG C, fractionation reaction 8h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation is except desolventizing, excessive 1, 3-dibromo Virahol (reclaim and use) and a small amount of low boilers, obtain dimethyl silicic acid two (1, 3-dibromo isopropyl) ester, productive rate 90.4%.
Embodiment 8 is being equipped with agitator, in the 100ml there-necked flask of thermometer and fractionation plant, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 40ml dioxane and 27.24g (0.125mol) 1, 3-dibromo Virahol, be warming up to 85 DEG C-90 DEG C (along with the carrying out of reaction, system temperature can be elevated to 90 DEG C gradually from 85 DEG C), fractionation reaction 8h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation is except desolventizing, excessive 1, 3-dibromo Virahol (reclaim and use) and a small amount of low boilers, obtain dimethyl silicic acid two (1, 3-dibromo isopropyl) ester, productive rate 93.1%.
Embodiment 9 is being equipped with agitator, in the 100ml there-necked flask of thermometer and fractionation plant, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 30ml diethylene glycol dimethyl ether and 30.5g (0.14mol) 1, 3-dibromo Virahol, be warming up to 85 DEG C-100 DEG C (along with the carrying out of reaction, system temperature can be elevated to 100 DEG C gradually from 85 DEG C), fractionation reaction 6h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation is except desolventizing, excessive 1, 3-dibromo Virahol (reclaim and use) and a small amount of low boilers, obtain dimethyl silicic acid two (1, 3-dibromo isopropyl) ester, productive rate 95.2%.
Embodiment 10 is being equipped with agitator, in the 100ml there-necked flask of thermometer and fractionation plant, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 20ml dioxane and 32.68g (0.15mol) 1, 3-dibromo Virahol, be warming up to 80 DEG C, fractionation reaction 10h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation is except desolventizing, excessive 1, 3-dibromo Virahol (reclaim and use) and a small amount of low boilers, obtain dimethyl silicic acid two (1, 3-dibromo isopropyl) ester, productive rate 92.9%.
Embodiment 11 is in the 250ml four-hole bottle that agitator, thermometer and fractionation plant are housed, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 65ml acetonitrile and 12.9g (0.1mol) 2,3-dichlorohydrine, be warming up to 80 DEG C, fractionation reaction 11h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation, except desolventizing and a small amount of low boilers, obtains dimethyl silicic acid two (2,3-dichloro third) ester, productive rate 85.7%.
Embodiment 12 is being equipped with agitator, in the 250ml four-hole bottle of thermometer and fractionation plant, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 40ml diethylene glycol dimethyl ether and 15.03g (0.125mol) 2, 3-dichlorohydrine, be warming up to 85 DEG C-110 DEG C (along with the carrying out of reaction, system temperature can be elevated to 110 DEG C gradually from 85 DEG C), fractionation reaction 5h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation is except desolventizing, excessive 2, 3-dichlorohydrine (reclaim and use) and a small amount of low boilers, obtain dimethyl silicic acid two (2, 3-dichloro third) ester, productive rate 92.9%.
Embodiment 13 is being equipped with agitator, in the 100ml there-necked flask of thermometer and fractionation plant, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 30ml glycol dimethyl ether and 16.83g (0.14mol) 2, 3-dichlorohydrine, be warming up to 83 DEG C, fractionation reaction 9h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation is except desolventizing, excessive 2, 3-dichlorohydrine (reclaim and use) and a small amount of low boilers, obtain dimethyl silicic acid two (2, 3-dichloro third) ester, productive rate 89.4%.
Embodiment 14 is being equipped with agitator, in the 100ml there-necked flask of thermometer and fractionation plant, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 15ml dioxane and 18.03g (0.15mol) 2, 3-dichlorohydrine, be warming up to 85 DEG C-100 DEG C (along with the carrying out of reaction, system temperature can be elevated to 100 DEG C gradually from 85 DEG C), fractionation reaction 6h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation is except desolventizing, excessive 2, 3-dichlorohydrine (reclaim and use) and a small amount of low boilers, obtain dimethyl silicic acid two (2, 3-dichloro third) ester, productive rate 94.8%.
Embodiment 15 is in the 250ml four-hole bottle that agitator, thermometer and fractionation plant are housed, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 60ml acetonitrile and 21.79g (0.1mol) 2,3-dibromo-propanol, be warming up to 80 DEG C, fractionation reaction 11h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation, except desolventizing and a small amount of low boilers, obtains dimethyl silicic acid two (2,3-dibromo third) ester, productive rate 85.3%.
Embodiment 16 is being equipped with agitator, in the 250ml four-hole bottle of thermometer and fractionation plant, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 50ml glycol dimethyl ether and 23.97g (0.11mol) 2, 3-bis-. bromopropyl alcohol, be warming up to 83 DEG C, fractionation reaction 10h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation is except desolventizing, excessive 2, 3-dibromo-propanol (reclaim and use) and a small amount of low boilers, obtain dimethyl silicic acid two (2, 3-dibromo third) ester, productive rate 89.6%.
Embodiment 17 is being equipped with agitator, in the 100ml there-necked flask of thermometer and fractionation plant, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 36ml dioxane and 27.24g (0.125mol) 2, 3-dibromo-propanol, be warming up to 85 DEG C-90 DEG C (along with the carrying out of reaction, system temperature can be elevated to 90 DEG C gradually from 85 DEG C), fractionation reaction 8h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation is except desolventizing, excessive 2, 3-dibromo-propanol (reclaim and use) and a small amount of low boilers, obtain dimethyl silicic acid two (2, 3-dibromo third) ester, productive rate 93.3%.
Embodiment 18 is being equipped with agitator, in the 100ml there-necked flask of thermometer and fractionation plant, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 30ml diethylene glycol dimethyl ether and 30.5g (0.14mol) 2, 3-dibromo-propanol, be warming up to 85 DEG C-100 DEG C (along with the carrying out of reaction, system temperature can be elevated to 100 DEG C gradually from 85 DEG C), fractionation reaction 6h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation is except desolventizing, excessive 2, 3-dibromo-propanol (reclaim and use) and a small amount of low boilers, obtain dimethyl silicic acid two (2, 3-dibromo third) ester, productive rate 95.1%.
Embodiment 19 is being equipped with agitator, in the 100ml there-necked flask of thermometer and fractionation plant, with the air in nitrogen replacement bottle falling, add 6.01g (0.05mol) dimethyldimethoxysil,ne, 20ml dioxane and 32.68g (0.15mol) 2, 3-dibromo-propanol, be warming up to 85 DEG C-95 DEG C (along with the carrying out of reaction, system temperature can be elevated to 95 DEG C gradually from 85 DEG C), fractionation reaction 8h, control fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation is except desolventizing, excessive 2, 3-dibromo-propanol (reclaim and use) and a small amount of low boilers, obtain dimethyl silicic acid two (2, 3-dibromo third) ester, productive rate 94.7%.
Two for the dimethyl silicic acid of above-mentioned preparation dihalo-propyl ester 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.Get product dimethyl silicic acid two dihalo-propyl ester, 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, and its flame retardant properties is tested, list part test result as shown in table 1, table 2, table 3 and table 4:
The flame retardant properties data of table 1 dimethyl silicic acid two (1,3-dichloro isopropyl) ester
The flame retardant properties data of table 2 dimethyl silicic acid two (1,3-dibromo isopropyl) ester
The flame retardant properties data of table 3 dimethyl silicic acid two (2,3-dichloro third) ester
The flame retardant properties data of table 4 dimethyl silicic acid two (2,3-dibromo third) ester
It is generally acknowledged oxygen index reach 27% its for fire retardant material.From table 1-table 4, the two dihalo-propyl ester of dimethyl silicic acid has excellent flame retardant properties to pvc material.Also find in test that the two dihalo-propyl ester of dimethyl silicic acid has good plasticity to polyvinyl chloride, DOP can be replaced in right amount in application, can softening agent be gone easy.
Claims (3)
1. a preparation method for the two dihalo-propyl ester of flame-retardant plasticizer dimethyl silicic acid, it is characterized in that, the method is:
The air in reactor is fallen with nitrogen replacement, add dimethyldimethoxysil,ne, dihalo-propyl alcohol and organic solvent, the mol ratio controlling dimethyldimethoxysil,ne and dihalo-propyl alcohol is 1: 2 ~ 1: 3, be warming up to 75 DEG C ~ 110 DEG C, fractionation reaction 5 ~ 11h, controls fractionation column top temperature not higher than 65 DEG C, fractionate out the methyl alcohol of generation, after the methyl alcohol separated reaches theoretical amount, underpressure distillation, except desolventizing, excessive dihalo-propyl alcohol and a small amount of low boilers, obtains the two dihalo-propyl ester of dimethyl silicic acid.
2. the preparation method of the two dihalo-propyl ester of dimethyl silicic acid according to claim 1, it is characterized in that, described organic solvent is acetonitrile, ethylene dichloride, dioxane, diethylene glycol dimethyl ether or glycol dimethyl ether, and its consumption volume milliliter number is 2 ~ 10 times of dimethyldimethoxysil,ne quality grams.
3. the preparation method of the two dihalo-propyl ester of dimethyl silicic acid according to claim 1, it is characterized in that, described dihalo-propyl alcohol is 1,3-dichloroisopropanol, 1,3-dibromo Virahol, 2,3-dichlorohydrines or 2,3-dibromo-propanol.
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| CN102140111A (en) * | 2011-02-23 | 2011-08-03 | 苏州科技学院 | Methyl tri(2-chloropropyl)silane compound and preparation method thereof |
| CN102153780A (en) * | 2011-02-23 | 2011-08-17 | 苏州科技学院 | Chlorine-containing methyl silicate flame retardant and preparation method thereof |
| CN102167707A (en) * | 2011-02-23 | 2011-08-31 | 苏州科技学院 | Retardant plasticizer methyl silicate ester compound and preparation method thereof |
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Application publication date: 20150617 |