CN104693443B - Aggretion type flame-retardant plasticizer dimethyl silicic acid end terephthalate polymer and preparation method thereof - Google Patents
Aggretion type flame-retardant plasticizer dimethyl silicic acid end terephthalate polymer and preparation method thereof Download PDFInfo
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- CN104693443B CN104693443B CN201510098820.3A CN201510098820A CN104693443B CN 104693443 B CN104693443 B CN 104693443B CN 201510098820 A CN201510098820 A CN 201510098820A CN 104693443 B CN104693443 B CN 104693443B
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Abstract
The present invention relates to a kind of aggretion type flame-retardant plasticizer dimethyl silicic acid end terephthalate polymers and preparation method thereof, and the structure of the polymer is shown below：
Description
Technical field
The present invention relates to a kind of aggretion type flame-retardant plasticizer dimethyl silicic acid end terephthalate polymers and preparation method thereof.Two
Methane-siliconic acid end terephthalate polymer category Halogen organosilicon macromolecule auxiliary agent, is suitable as polyvinyl chloride, polyurethane, asphalt mixtures modified by epoxy resin
The flame-retardant plasticizer of the materials such as fat, unsaturated-resin.
Background technology
With the development of society, organic synthesis high molecular material is widely applied in production and construction etc..But
Many high molecular materials are inflammable, have prodigious security risk, seriously affect the safety of people's life.In macromolecule material
Fire retardant is added in material, is made high molecular material that there is fire retardant or non-ignitable performance, is to solve the problems, such as that high molecular material is inflammable at present
Effective way, thus fire retardant industry has obtained development quickly.Wherein halogenated flame retardant is using most, technology is most ripe
Fire retardant, but put into practice when finding that fire occurs, halogen system fire proofing will produce a large amount of smog and toxic during fire-retardant
Corrosive hydrogen halides gas, cause secondary hazards.So while halogenated flame retardant is restricted, Halogen, low cigarette, low toxicity
The emphasis for having become research and development of fire retardant.Wherein silicon systems hinder right agent due to having effective anti-melt drippage, thermal stability good and
The advantages that fire-retardant inhibition smog function admirable, it has also become the hot product of halogen-free flame retardants exploitation at present.Especially there is plasticising
The Silicone-containing Flame Retardant of property, i.e. organic silicon flame-retardant plasticizer are more favored.
The invention discloses a kind of Halogen, environmentally friendly organic silicon flame-retardant plasticizer dimethyl silicic acid end terephthalate polymer and its
Preparation method.The organic silicon flame-retardant plasticizer has into charcoal and plasticity, and good flame retardation effect is at low cost, simple for process, application
Extensively, there is good application and development foreground.
Invention content
It is an object of the present invention to proposing a kind of aggretion type flame-retardant plasticizer dimethyl silicic acid end terephthalate polymer,
Its flame-retarded efficiency is high, and carbon-forming performance is good, also there is plasticity, physical and chemical performance to stablize, halogen-free environmental can overcome in the prior art
It is insufficient.
For achieving the above object, present invention employs following technical solutions：
Dimethyl silicic acid end terephthalate polymer, which is characterized in that the structure of the polymer is shown below：
M=4~6 in formula, n=20~80.
Another object of the present invention is to propose the preparation method of fire retardant dimethyl silicic acid end terephthalate polymer, work
Skill is simple, and equipment investment is few, is easy to large-scale production, and raw material is cheap and easy to get, of low cost, and this method is：
End glycol is dissolved in organic solvent, equimolar dimethyldichlorosilane is added dropwise at 20 DEG C, was added dropwise program-controlled
Temperature processed is no more than 40 DEG C, after dripping off, and 1-2h is warming up to 70-110 DEG C, insulation reaction 4-8h, is added product quality 1%-3%'s
Acid binding agent is adjusted to pH=5-6, stirs 1h, filters while hot, filtrate distilling off solvent and a small amount of low boilers obtain water white transparency liquid
Body dimethyl silicic acid end terephthalate polymer.
This method can also be：
End glycol is dissolved in organic solvent, two bromo-silicane of equimolar dimethyl is added dropwise at 20 DEG C, was added dropwise program-controlled
Temperature processed is no more than 50 DEG C, after dripping off, and 1-2h is warming up to 80-130 DEG C, insulation reaction 4-8h, is added product quality 1%-3%'s
Acid binding agent is adjusted to pH=5-6, stirs 1h, filters while hot, filtrate distilling off solvent and a small amount of low boilers obtain water white transparency liquid
Body dimethyl silicic acid end terephthalate polymer.
Organic solvent as described above is glycol dimethyl ether, acetonitrile, dichloroethanes, dioxane or diethylene glycol diformazan
Ether, dosage are that organic solvent volume ml is hold glycol quality grams 2-5 times.
End glycol as described above is 1,4-butanediol, 1,5-PD or 1,6- hexylene glycols.
Acid binding agent as described above is triethylamine, n,N-Dimethylaniline, melamine or pyridine.
The physical property of the dimethyl silicic acid end terephthalate polymer of the present invention is as follows：
Dimethyl silicic acid -1,4-butanediol ester polymer is colourless transparent liquid, yield 94.8%~98.6%, index of refraction
nD 25=1.4116, density (25 DEG C) 1.124 ± 0.005g/cm3, 282 ± 5 DEG C of decomposition temperature.
Dimethyl silicic acid -1,5-PD ester polymer is colourless transparent liquid, yield 93.8%~98.2%, index of refraction
nD 25=1.4236, density (25 DEG C) 0.978 ± 0.005g/cm3, 308 ± 5 DEG C of decomposition temperature.
Dimethyl silicic acid -1,6- hexylene glycol ester polymer is colourless transparent liquid, and yield is 94.2%~98.9%, refractive power
Rate nD 25=1.4365, density (25 DEG C) 1.145 ± 0.005g/cm3, 278 ± 5 DEG C of decomposition temperature.
Dimethyl silicic acid end terephthalate polymer is suitable as unsaturated-resin, epoxy resin, polyurethane, polyvinyl chloride etc.
The flame-retardant plasticizer of material.
The preparation process principle of dimethyl silicic acid end terephthalate polymer is shown below：
M=4~6, X=Cl or Br in formula, n=20~80.
Compared with prior art, innovation of the invention is：
1. flame-retardant plasticizer dimethyl silicic acid end of the present invention terephthalate polymer has polymerizable organosilicon chain, physical chemistry
Performance is stablized, and has preferable plasticity, and molecular weight is good with high molecular material compatibility greatly, and when burning can generate fine and close silicon charcoal
Layer, there is into the effect of charcoal anti-drip, and processing performance is good.
2. flame-retardant plasticizer dimethyl silicic acid end of the present invention terephthalate polymer does not contain halogen, meets environmental protection fire retarding agent and want
It asks, there is good application and development foreground.
3. flame-retardant plasticizer dimethyl silicic acid end of the present invention terephthalate polymer preparation method is simple, raw material is cheap and easy to get,
It is at low cost, it is easy to large-scale production.
Description of the drawings
Following attached drawing is provided in order to further illustrate the structure and performance spy of product.
1, the infrared spectrogram of dimethyl silicic acid -1,4-butanediol ester polymer, refers to Figure of description Fig. 1：
Fig. 1 shows 2972cm-1Place is the stretching vibration peak of c h bond；2858cm-1Place is stretching for the c h bond being connected with oxygen
Contracting vibration peak；1462cm-1Place is the flexural vibrations peak of c h bond；1247cm-1Place is the stretching vibration peak of C-O keys；1035cm-1Place
For the stretching vibration peak of Si-O, 803cm-1Place is the stretching vibration peak of C-Si keys.
2, the nuclear magnetic spectrum figure of dimethyl silicic acid -1,4-butanediol ester polymer, refers to Figure of description Fig. 2：
Fig. 2 shows that deuterochloroform is solvent, and δ 0.1-0.4 are the peaks methyl H being connected with silicon；δ 1.35-1.75 are methylene
The peaks H；δ 3.3-3.7 are the peaks methylene H being connected with oxygen.
3, the infrared spectrogram of dimethyl silicic acid -1,5-PD ester polymer, refers to Figure of description Fig. 3：
Fig. 3 shows 2980cm-1Place is the stretching vibration peak of c h bond；2844cm-1Place is stretching for the c h bond being connected with oxygen
Contracting vibration peak；1452cm-1Place is the flexural vibrations peak of c h bond；1251cm-1Place is the stretching vibration peak of C-O keys；1032cm-1Place
For the stretching vibration peak of Si-O, 803cm-1Place is the stretching vibration peak of C-Si keys.
4, the nuclear magnetic spectrum figure of dimethyl silicic acid -1,5-PD ester polymer, refers to Figure of description Fig. 4：
Fig. 4 shows that deuterochloroform is solvent, and δ 0.1-0.4 are Si-CH3On the peaks methyl H；δ 1.3-1.85 are methylene H
Peak；δ 3.5-4.0 are the peaks methylene H being connected with oxygen.
5, the infrared spectrogram of dimethyl silicic acid -1,6- hexylene glycol ester polymer, refers to Figure of description Fig. 5：
Fig. 5 shows 2961cm-1Place is the stretching vibration peak of c h bond；2872cm-1Place is the flexible of the c h bond being connected with O
Vibration peak；1496cm-1Place is the flexural vibrations peak of c h bond；1260cm-1Place is the stretching vibration peak of C-O keys；1026cm-1Place is
The stretching vibration peak of Si-O, 803cm-1Place is the stretching vibration peak of C-Si keys.
6, the nuclear magnetic spectrum figure of dimethyl silicic acid -1,6- hexylene glycol ester polymer, refers to Figure of description Fig. 6：
Fig. 6 shows that deuterochloroform is solvent, and δ 0.1-0.3 are Si-CH3On the peaks methyl H；δ 1.4-1.75 are methylene H
Peak；δ 3.3-3.7 are the peaks methylene H being connected with oxygen.
7, the GPC spectrograms of 14 product dimethyl silicic acid of example -1,5-PD ester polymer, refer to Figure of description Fig. 7：
Fig. 7 shows that the number-average molecular weight of dimethyl silicic acid -1,5-PD ester polymer is 4.5 × 103, Weight-average molecular
Amount is 8.6 × 103, profile exponent 1.91.
Specific implementation mode
Technical scheme of the present invention is described further below in conjunction with specific embodiment.
Embodiment 1 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be equipped with drying tube and chlorine
In the 100ml four-hole boiling flasks for changing hydrogen absorption plant, addition 30ml glycol dimethyl ethers and 9.0g (0.1mol) 1,4-butanediol, 20
At DEG C, 12.9g (0.1mol) dimethyldichlorosilane is added dropwise, process control temp is added dropwise and is no more than 40 DEG C, after dripping off, 1h heatings
To 70 DEG C, insulation reaction 8h, about 0.45g triethylamine acid binding agents are added, are adjusted to pH=5-6, stirs 1h, filters while hot, decompression is steamed
Solvent and a small amount of low boilers are distillated, colourless transparent liquid dimethyl silicic acid -1,4-butanediol ester polymer, product yield are obtained
94.8%.
Embodiment 2 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be equipped with drying tube and chlorine
In the 100ml four-hole boiling flasks for changing hydrogen absorption plant, it is added 40ml acetonitriles and 9.0g (0.1mol) 1,4-butanediol, at 20 DEG C, drop
Add 12.9g (0.1mol) dimethyldichlorosilane, process control temp is added dropwise and is no more than 40 DEG C, after dripping off, 1h is warming up to 80 DEG C,
About 0.4g n,N-Dimethylaniline acid binding agents are added in insulation reaction 6h, are adjusted to pH=5-6, stir 1h, filter while hot, and decompression is steamed
Solvent and a small amount of low boilers are distillated, colourless transparent liquid dimethyl silicic acid -1,4-butanediol ester polymer, product yield are obtained
95.6%.
Embodiment 3 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be equipped with drying tube and chlorine
In the 100ml four-hole boiling flasks for changing hydrogen absorption plant, addition 50ml dichloroethanes and 9.0g (0.1mol) 1,4-butanediol, 20 DEG C
Under, 12.9g (0.1mol) dimethyldichlorosilane is added dropwise, process control temp is added dropwise and is no more than 40 DEG C, after dripping off, 1h is warming up to
82 DEG C, insulation reaction 6h, about 0.35g pyridine acid binding agents are added, are adjusted to pH=5-6, stirs 1h, filters, be evaporated under reduced pressure out while hot
Solvent and a small amount of low boilers obtain colourless transparent liquid dimethyl silicic acid -1,4-butanediol ester polymer, product yield
96.3%.
Embodiment 4 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be equipped with drying tube and chlorine
In the 100ml four-hole boiling flasks for changing hydrogen absorption plant, 30ml Isosorbide-5-Nitraes-dioxane and 9.0g (0.1mol) 1,4-butanediol is added,
At 20 DEG C, 12.9g (0.1mol) dimethyldichlorosilane is added dropwise, process control temp is added dropwise and is no more than 40 DEG C, after dripping off, 2h liters
About 0.4g melamine acid binding agents are added to 100 DEG C, insulation reaction 5h in temperature, are adjusted to pH=5-6, stir 1h, filter, subtract while hot
Distilling off solvent and a small amount of low boilers are pressed, obtain colourless transparent liquid dimethyl silicic acid -1,4-butanediol ester polymer, product obtains
Rate 97.7%, weight average molecular weight are 8.5 × 103, number-average molecular weight is 4.1 × 103, profile exponent 2.07.
Embodiment 5 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be equipped with drying tube and chlorine
In the 100ml four-hole boiling flasks for changing hydrogen absorption plant, 30ml diethylene glycol dimethyl ethers and 9.0g (0.1mol) 1,4-butanediol is added,
At 20 DEG C, 12.9g (0.1mol) dimethyldichlorosilane is added dropwise, process control temp is added dropwise and is no more than 40 DEG C, after dripping off, 2h liters
About 0.3g triethylamine acid binding agents are added to 110 DEG C, insulation reaction 4h in temperature, are adjusted to pH=5-6, stir 1h, filter while hot, depressurize
Distilling off solvent and a small amount of low boilers obtain colourless transparent liquid dimethyl silicic acid -1,4-butanediol ester polymer, product yield
98.1%.
Embodiment 6 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be equipped with drying tube and bromine
In the 100ml four-hole boiling flasks for changing hydrogen absorption plant, addition 30ml glycol dimethyl ethers and 9.0g (0.1mol) 1,4-butanediol, 20
At DEG C, two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise, process control temp is added dropwise and is no more than 50 DEG C, after dripping off, 1h heatings
To 80 DEG C, insulation reaction 8h, about 0.45g triethylamine acid binding agents are added, are adjusted to pH=5-6, stirs 1h, filters while hot, decompression is steamed
Solvent and a small amount of low boilers are distillated, colourless transparent liquid dimethyl silicic acid -1,4-butanediol ester polymer, product yield are obtained
95.0%.
Embodiment 7 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be equipped with drying tube and bromine
In the 100ml four-hole boiling flasks for changing hydrogen absorption plant, it is added 40ml acetonitriles and 9.0g (0.1mol) 1,4-butanediol, at 20 DEG C, drop
Add two bromo-silicane of 21.8g (0.1mol) dimethyl, process control temp is added dropwise and is no more than 50 DEG C, after dripping off, 1h is warming up to 80 DEG C,
About 0.35g n,N-Dimethylaniline acid binding agents are added in insulation reaction 7h, are adjusted to pH=5-6, stir 1h, filter while hot, depressurize
Distilling off solvent and a small amount of low boilers obtain colourless transparent liquid dimethyl silicic acid -1,4-butanediol ester polymer, product yield
95.4%.
Embodiment 8 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be equipped with drying tube and bromine
In the 100ml four-hole boiling flasks for changing hydrogen absorption plant, addition 50ml dichloroethanes and 9.0g (0.1mol) 1,4-butanediol, 20 DEG C
Under, two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise, process control temp is added dropwise and is no more than 50 DEG C, after dripping off, 1h is warming up to
82 DEG C, insulation reaction 7h, about 0.4g pyridine acid binding agents are added, are adjusted to pH=5-6, stirs 1h, filters, be evaporated under reduced pressure out molten while hot
Agent and a small amount of low boilers obtain colourless transparent liquid dimethyl silicic acid -1,4-butanediol ester polymer, product yield 96.5%.
Embodiment 9 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be equipped with drying tube and bromine
In the 100ml four-hole boiling flasks for changing hydrogen absorption plant, 30ml Isosorbide-5-Nitraes-dioxane and 9.0g (0.1mol) 1,4-butanediol is added,
At 20 DEG C, two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise, process control temp is added dropwise and is no more than 50 DEG C, after dripping off, 2h liters
About 0.3g triethylamine acid binding agents are added to 100 DEG C, insulation reaction 5h in temperature, are adjusted to pH=5-6, stir 1h, filter while hot, depressurize
Distilling off solvent and a small amount of low boilers obtain colourless transparent liquid dimethyl silicic acid -1,4-butanediol ester polymer, product yield
97.6%.
Embodiment 10 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen bromide absorption plant, 30ml diethylene glycol dimethyl ethers and 9.0g (0.1mol) Isosorbide-5-Nitrae-fourth two is added
At 20 DEG C, two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise in alcohol, and process control temp is added dropwise and is no more than 50 DEG C, after dripping off,
2h is warming up to 130 DEG C, insulation reaction 4h, and about 0.2g triethylamine acid binding agents are added, and is adjusted to pH=5-6, stirs 1h, filters while hot,
Solvent and a small amount of low boilers are evaporated under reduced pressure out, colourless transparent liquid dimethyl silicic acid -1,4-butanediol ester polymer, product are obtained
Yield 98.6%, weight average molecular weight are 6.8 × 103, number-average molecular weight is 3.6 × 103, profile exponent 1.89.
Embodiment 11 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen chloride absorption device, 30ml glycol dimethyl ethers and 10.4g (0.1mol) 1,5- penta 2 is added
At 20 DEG C, 12.9g (0.1mol) dimethyldichlorosilane is added dropwise in alcohol, and process control temp is added dropwise and is no more than 40 DEG C, after dripping off,
1h is warming up to 70 DEG C, insulation reaction 8h, and about 0.45g triethylamine acid binding agents are added, and is adjusted to pH=5-6, stirs 1h, filters while hot,
Solvent and a small amount of low boilers are evaporated under reduced pressure out, colourless transparent liquid dimethyl silicic acid -1,5-PD ester polymer, product are obtained
Yield 93.8%.
Embodiment 12 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen chloride absorption device, it is added 40ml acetonitriles and 10.4g (0.1mol) 1,5-PD, at 20 DEG C,
12.9g (0.1mol) dimethyldichlorosilane is added dropwise, process control temp is added dropwise and is no more than 40 DEG C, after dripping off, 1h is warming up to 80
DEG C, about 0.4g n,N-Dimethylaniline acid binding agents are added in insulation reaction 6h, are adjusted to pH=5-6, stir 1h, filter, subtract while hot
Distilling off solvent and a small amount of low boilers are pressed, obtain colourless transparent liquid dimethyl silicic acid -1,5-PD ester polymer, product obtains
Rate 94.4%.
Embodiment 13 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen chloride absorption device, addition 50ml dichloroethanes and 10.4g (0.1mol) 1,5-PD, 20
At DEG C, 12.9g (0.1mol) dimethyldichlorosilane is added dropwise, process control temp is added dropwise and is no more than 40 DEG C, after dripping off, 1h heatings
To 82 DEG C, insulation reaction 6h, about 0.35g pyridine acid binding agents are added, are adjusted to pH=5-6, stirs 1h, filters while hot, are evaporated under reduced pressure
Go out solvent and a small amount of low boilers, obtains colourless transparent liquid dimethyl silicic acid -1,5-PD ester polymer, product yield
95.2%.
Embodiment 14 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen chloride absorption device, 30ml Isosorbide-5-Nitraes-dioxane and 10.4g (0.1mol) 1,5- penta 2 is added
At 20 DEG C, 12.9g (0.1mol) dimethyldichlorosilane is added dropwise in alcohol, and process control temp is added dropwise and is no more than 40 DEG C, after dripping off,
2h is warming up to 100 DEG C, insulation reaction 5h, and about 0.4g melamine acid binding agents are added, and is adjusted to pH=5-6, stirs 1h, while hot mistake
Filter, is evaporated under reduced pressure out solvent and a small amount of low boilers, obtains colourless transparent liquid dimethyl silicic acid -1,5-PD ester polymer,
Product yield 97.3%.The number-average molecular weight of dimethyl silicic acid -1,5-PD ester polymer is 4.5 × 103, weight average molecular weight
It is 8.6 × 103, profile exponent 1.91.
Embodiment 15 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen chloride absorption device, 30ml diethylene glycol dimethyl ethers and 10.4g (0.1mol) 1,5- penta 2 is added
At 20 DEG C, 12.9g (0.1mol) dimethyldichlorosilane is added dropwise in alcohol, and process control temp is added dropwise and is no more than 40 DEG C, after dripping off,
2h is warming up to 110 DEG C, insulation reaction 4h, and about 0.3g triethylamine acid binding agents are added, and is adjusted to pH=5-6, stirs 1h, filters while hot,
Solvent and a small amount of low boilers are evaporated under reduced pressure out, colourless transparent liquid dimethyl silicic acid -1,5-PD ester polymer, product are obtained
Yield 97.8%.
Embodiment 16 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen bromide absorption plant, 30ml glycol dimethyl ethers and 10.4g (0.1mol) 1,5- penta 2 is added
At 20 DEG C, two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise in alcohol, and process control temp is added dropwise and is no more than 50 DEG C, after dripping off,
1h is warming up to 80 DEG C, insulation reaction 8h, and about 0.45g triethylamine acid binding agents are added, and is adjusted to pH=5-6, stirs 1h, filters while hot,
Solvent and a small amount of low boilers are evaporated under reduced pressure out, colourless transparent liquid dimethyl silicic acid -1,5-PD ester polymer, product are obtained
Yield 94.0%.
Embodiment 17 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen bromide absorption plant, it is added 40ml acetonitriles and 10.4g (0.1mol) 1,5-PD, at 20 DEG C,
Two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise, process control temp is added dropwise and is no more than 50 DEG C, after dripping off, 1h is warming up to 80
DEG C, about 0.35g n,N-Dimethylaniline acid binding agents are added in insulation reaction 7h, are adjusted to pH=5-6, stir 1h, filter, subtract while hot
Distilling off solvent and a small amount of low boilers are pressed, obtain colourless transparent liquid dimethyl silicic acid -1,5-PD ester polymer, product obtains
Rate 94.6%.
Embodiment 18 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen bromide absorption plant, addition 50ml dichloroethanes and 10.4g (0.1mol) 1,5-PD, 20
At DEG C, two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise, process control temp is added dropwise and is no more than 50 DEG C, after dripping off, 1h heatings
To 82 DEG C, insulation reaction 7h, about 0.4g pyridine acid binding agents are added, are adjusted to pH=5-6, stirs 1h, filters, be evaporated under reduced pressure out while hot
Solvent and a small amount of low boilers obtain colourless transparent liquid dimethyl silicic acid -1,5-PD ester polymer, product yield
95.6%.
Embodiment 19 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen bromide absorption plant, 30ml Isosorbide-5-Nitraes-dioxane and 10.4g (0.1mol) 1,5- penta 2 is added
At 20 DEG C, two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise in alcohol, and process control temp is added dropwise and is no more than 50 DEG C, after dripping off,
2h is warming up to 100 DEG C, insulation reaction 5h, and about 0.3g triethylamine acid binding agents are added, and is adjusted to pH=5-6, stirs 1h, filters while hot,
Solvent and a small amount of low boilers are evaporated under reduced pressure out, colourless transparent liquid dimethyl silicic acid -1,5-PD ester polymer, product are obtained
Yield 97.4%.
Embodiment 20 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen bromide absorption plant, 30ml diethylene glycol dimethyl ethers and 10.4g (0.1mol) 1,5- penta 2 is added
At 20 DEG C, two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise in alcohol, and process control temp is added dropwise and is no more than 50 DEG C, after dripping off,
2h is warming up to 130 DEG C, insulation reaction 4h, and about 0.2g triethylamine acid binding agents are added, and is adjusted to pH=5-6, stirs 1h, filters while hot,
Solvent and a small amount of low boilers are evaporated under reduced pressure out, colourless transparent liquid dimethyl silicic acid -1,5-PD ester polymer, product are obtained
Yield 98.2%.The number-average molecular weight of dimethyl silicic acid -1,5-PD ester polymer is 5.2 × 103, weight average molecular weight is
9.1×103, profile exponent 1.75.
Embodiment 21 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen chloride absorption device, be added 30ml glycol dimethyl ethers and 11.8g (0.1mol) 1,6- oneself two
At 20 DEG C, 12.9g (0.1mol) dimethyldichlorosilane is added dropwise in alcohol, and process control temp is added dropwise and is no more than 40 DEG C, after dripping off,
1h is warming up to 70 DEG C, insulation reaction 8h, and about 0.45g triethylamine acid binding agents are added, and is adjusted to pH=5-6, stirs 1h, filters while hot,
Filtrate decompression distilling off solvent and a small amount of low boilers obtain colourless transparent liquid dimethyl silicic acid -1,6- hexylene glycol ester polymer,
Product yield 94.2%.
Embodiment 22 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen chloride absorption device, it is added 40ml acetonitriles and 11.8g (0.1mol) 1,6- hexylene glycols, at 20 DEG C,
12.9g (0.1mol) dimethyldichlorosilane is added dropwise, process control temp is added dropwise and is no more than 40 DEG C, after dripping off, 1h is warming up to 80
DEG C, about 0.4g n,N-Dimethylaniline acid binding agents are added in insulation reaction 6h, are adjusted to pH=5-6, stir 1h, filter while hot, filter
Liquid is evaporated under reduced pressure out solvent and a small amount of low boilers, obtains colourless transparent liquid dimethyl silicic acid -1,6- hexylene glycol ester polymer, production
Product yield 95.0%.
Embodiment 23 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen chloride absorption device, addition 50ml dichloroethanes and 11.8g (0.1mol) 1,6- hexylene glycols, 20
At DEG C, 12.9g (0.1mol) dimethyldichlorosilane is added dropwise, process control temp is added dropwise and is no more than 40 DEG C, after dripping off, 1h heatings
To 82 DEG C, insulation reaction 6h, about 0.3g pyridine acid binding agents are added, are adjusted to pH=5-6, stirs 1h, filters while hot, filtrate decompression is steamed
Solvent and a small amount of low boilers are distillated, colourless transparent liquid dimethyl silicic acid -1,6- hexylene glycol ester polymer, product yield are obtained
96.8%.
Embodiment 24 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen chloride absorption device, be added 30ml Isosorbide-5-Nitraes-dioxane and 11.8g (0.1mol) 1,6- oneself two
At 20 DEG C, 12.9g (0.1mol) dimethyldichlorosilane is added dropwise in alcohol, and process control temp is added dropwise and is no more than 40 DEG C, after dripping off,
2h is warming up to 100 DEG C, insulation reaction 5h, and about 0.4g melamine acid binding agents are added, and is adjusted to pH=5-6, stirs 1h, takes out while hot
Filter, filtrate decompression distilling off solvent and a small amount of low boilers, obtain colourless transparent liquid dimethyl silicic acid -1,6- hexylene glycol polyisocyanate polyaddition
Object, product yield 97.5%, number-average molecular weight are 4.4 × 103, weight average molecular weight is 7.9 × 103, profile exponent 1.80.
Embodiment 25 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen chloride absorption device, be added 30ml diethylene glycol dimethyl ethers and 11.8g (0.1mol) 1,6- oneself two
At 20 DEG C, 12.9g (0.1mol) dimethyldichlorosilane is added dropwise in alcohol, and process control temp is added dropwise and is no more than 40 DEG C, after dripping off,
2h is warming up to 110 DEG C, insulation reaction 4h, and about 0.25g triethylamine acid binding agents are added, and is adjusted to pH=5-6, stirs 1h, filters while hot,
Filtrate distilling off solvent and a small amount of low boilers obtain colourless transparent liquid dimethyl silicic acid -1,6- hexylene glycol ester polymer, product
Yield 97.9%.
Embodiment 26 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen bromide absorption plant, be added 30ml glycol dimethyl ethers and 11.8g (0.1mol) 1,6- oneself two
At 20 DEG C, two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise in alcohol, and process control temp is added dropwise and is no more than 50 DEG C, after dripping off,
1h is warming up to 80 DEG C, insulation reaction 8h, and about 0.4g triethylamine acid binding agents are added, and is adjusted to pH=5-6, stirs 1h, filters while hot, filters
Liquid is evaporated under reduced pressure out solvent and a small amount of low boilers, obtains colourless transparent liquid dimethyl silicic acid -1,6- hexylene glycol ester polymer, production
Product yield 94.4%.
Embodiment 27 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen bromide absorption plant, it is added 40ml acetonitriles and 11.8g (0.1mol) 1,6- hexylene glycols, at 20 DEG C,
Two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise, process control temp is added dropwise and is no more than 50 DEG C, after dripping off, 1h is warming up to 80
DEG C, about 0.35g n,N-Dimethylaniline acid binding agents are added in insulation reaction 7h, are adjusted to pH=5-6, stir 1h, filter while hot, filter
Liquid is evaporated under reduced pressure out solvent and a small amount of low boilers, obtains colourless transparent liquid dimethyl silicic acid -1,6- hexylene glycol ester polymer, production
Product yield 94.9%.
Embodiment 28 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen bromide absorption plant, addition 50ml dichloroethanes and 11.8 (0.1mol) 1,6- hexylene glycols, 20 DEG C
Under, two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise, process control temp is added dropwise and is no more than 50 DEG C, after dripping off, 1h is warming up to
82 DEG C, insulation reaction 7h, about 0.3g pyridine acid binding agents are added, are adjusted to pH=5-6, stirs 1h, filters while hot, filtrate decompression distillation
Go out solvent and a small amount of low boilers, obtains colourless liquid dimethyl silicic acid -1,6- hexylene glycol ester polymer, product yield 97.2%.
Embodiment 29 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen bromide absorption plant, be added 30ml Isosorbide-5-Nitraes-dioxane and 11.8g (0.1mol) 1,6- oneself two
At 20 DEG C, two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise in alcohol, and process control temp is added dropwise and is no more than 50 DEG C, after dripping off,
2h is warming up to 100 DEG C, insulation reaction 5h, and about 0.3g triethylamine acid binding agents are added, and is adjusted to pH=5-6, stirs 1h, filters while hot,
Filtrate decompression distilling off solvent and a small amount of low boilers obtain colourless transparent liquid dimethyl silicic acid -1,6- hexylene glycol ester polymer,
Product yield 97.8%.
Embodiment 30 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading equipped with drying tube and
In the 100ml four-hole boiling flasks of hydrogen bromide absorption plant, be added 30ml diethylene glycol dimethyl ethers and 11.8g (0.1mol) 1,6- oneself two
At 20 DEG C, two bromo-silicane of 21.8g (0.1mol) dimethyl is added dropwise in alcohol, and process control temp is added dropwise and is no more than 50 DEG C, after dripping off,
2h is warming up to 130 DEG C, insulation reaction 4h, and about 0.2g triethylamine acid binding agents are added, and is adjusted to pH=5-6, stirs 1h, filters while hot,
Filtrate distilling off solvent and a small amount of low boilers obtain colourless transparent liquid dimethyl silicic acid -1,6- hexylene glycol ester polymer, product
Yield 98.9%, number-average molecular weight are 5.8 × 103, weight average molecular weight is 9.7 × 103, profile exponent 1.67.
The dimethyl silicic acid end terephthalate polymer of above-mentioned synthesis is also applied to polyvinyl chloride (PVC) by inventor
In.Reference：GB/T2406-2008《Plastics Combustion method for testing performance-oxygen index method》The limit oxygen index of sample.By diformazan
Base silicic acid end terephthalate polymer, plasticizer phthalic acid dioctyl ester (DOP), synergistic flame retardant antimony oxide (Sb2O3) and
Polyvinyl chloride after mixing, is squeezed out in varing proportions with extruder, and the batten of a diameter of 3mm is made, with HC900-2 limit oxygen
Indexer is tested, and experiment shows dimethyl silicic acid end terephthalate polymer to PVC excellent flame retardancies, it is also good at
Charcoal and plasticising performance, part test result is as shown in table 1, table 2 and table 3：
The flame retardant property test data of 1 dimethyl silicic acid of table -1,4-butanediol ester polymer
The flame retardant property test data of 2 dimethyl silicic acid of table -1,5-PD ester polymer
The flame retardant property test data of 3 dimethyl silicic acid -1,6- hexylene glycol ester polymer of table
Claims (3)
1. a kind of preparation method of flame-retardant plasticizer dimethyl silicic acid end terephthalate polymer, which is characterized in that this method is：
End glycol 1,4-butanediol or 1,5-PD are dissolved in organic solvent, equimolar dimethyl two is added dropwise at 20 DEG C
Chlorosilane is added dropwise process control temp and is no more than 40 DEG C, after dripping off, and 1-2h is warming up to 70-110 DEG C, insulation reaction 4-8h, is added
The melamine of product quality 1%-3%, is adjusted to pH=5-6, stirs 1h, filters while hot, filtrate distilling off solvent and a small amount of low
Boiling point object, obtains colourless transparent liquid dimethyl silicic acid end terephthalate polymer, and the structure of the polymer is shown below：
M=4~5 in formula, n=20~80.
2. a kind of preparation method of flame-retardant plasticizer dimethyl silicic acid end terephthalate polymer, which is characterized in that this method is：
End glycol 1,4-butanediol or 1,5-PD are dissolved in organic solvent, equimolar dimethyl two is added dropwise at 20 DEG C
Bromo-silicane is added dropwise process control temp and is no more than 50 DEG C, after dripping off, and 1-2h is warming up to 80-130 DEG C, insulation reaction 4-8h, is added
The melamine of product quality 1%-3%, is adjusted to pH=5-6, stirs 1h, filters while hot, filtrate distilling off solvent and a small amount of low
Boiling point object, obtains colourless transparent liquid dimethyl silicic acid end terephthalate polymer, and the structure of the polymer is shown below：
M=4~5 in formula, n=20~80.
3. the preparation method of flame-retardant plasticizer dimethyl silicic acid end as claimed in claim 1 or 2 terephthalate polymer, feature exist
In：The organic solvent is glycol dimethyl ether, acetonitrile, dichloroethanes, dioxane or diethylene glycol dimethyl ether, dosage
For organic solvent volume ml is 2-5 times of 1,4-butanediol or 1,5-PD quality grams.
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