CN102167707B - Retardant plasticizer methyl silicate ester compound and preparation method thereof - Google Patents

Retardant plasticizer methyl silicate ester compound and preparation method thereof Download PDF

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CN102167707B
CN102167707B CN 201110042942 CN201110042942A CN102167707B CN 102167707 B CN102167707 B CN 102167707B CN 201110042942 CN201110042942 CN 201110042942 CN 201110042942 A CN201110042942 A CN 201110042942A CN 102167707 B CN102167707 B CN 102167707B
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chloropropyl
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CN102167707A (en
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王彦林
韦春胜
王玉红
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Beijing Gao Hang United Technology Co ltd
Sunboway Plastic Manufacture Co ltd
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Suzhou University of Science and Technology
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Abstract

The invention relates to a retardant plasticizer methyl silicate ester compound and a preparation method thereof, in particular to methyl silicic acid tris(1-chloro-1-methylethyl)ester and a preparation method thereof. The compound has the structure shown as CH3Si(OC3H6Cl)3. The preparation method comprises the following steps of: mixing methyltrimethoxy silane and 1-chloro propanol in a certain molar ratio with an organic solvent, heating for refluxing, steaming out quantitative methanol generated in reaction by using a fractionating device, and performing passivation treatment to obtain colorless to light yellow liquid, namely the methyl silicate ester. The methyl silicate ester has good retardant plasticization; moreover, the production process is simple, equipment investment is low, cost is low, pollution is avoided and the invention is suitable for industrial production.

Description

Flame-retardant plasticizer methyl siliconic acid ester cpds and preparation method thereof
Technical field
The present invention relates to a kind of flame-retardant plasticizer methyl siliconic acid ester cpds and preparation method thereof.Be specifically related to a kind of methyl siliconic acid three (chloropropyl) ester cpds and preparation method thereof.Methyl siliconic acid three (chloropropyl) ester belongs to the organic silicon flame-retardant softening agent, is suitable for the fire-retardant plasticizer additives of polyvinyl chloride, urethane, Resins, epoxy, unsaturated polyester etc.
Background technology
Along with the extensive application of synthetic organic polymer material, plasticizer consumption is huge, and in order to solve the inflammable problem of macromolecular material, fire retardant has obtained fast development.The fire retardant consumption is the second largest auxiliary agent that is only second to plasticizer consumption at present.People always wish that from angle easy to use flame retardant resistance and plasticising performance embody in same compound structure, i.e. synthetic flame-retardant plasticizer; Find that from use some material such as polyvinyl chloride itself have good flame, but because the adding of inflammable softening agent makes the inflammable of material change, also namely because the use of softening agent must add fire retardant simultaneously, also remind people to develop new flame-retardant plasticizer in order to overcome this problem.The phosphorous flame-retardant softening agent is existing at present uses, and silicon is that flame-retardant plasticizer is restricted owing to expensive Application and Development.The methyltrimethoxy silane that the inventor has researched and developed out with cheapness is raw material and propylene chlorohydrin prepared in reaction novel flame-retardant softening agent methyl siliconic acid three (chloropropyl) ester.The present invention has increased cheap good flame-retardant plasticizer new variety, can satisfy the demand in market, have a good economic implications again.
Summary of the invention
One of purpose of the present invention is that simple, the fire-retardant plasticity of its synthesis technique is good, can overcome deficiency of the prior art with synthetic a kind of silicon halogen cooperative flame retardant plasticized compound methyl siliconic acid three (chloropropyl) ester of the most cheap methyltrimethoxy silane.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of methyl siliconic acid three (chloropropyl) ester cpds is characterized in that the structure of this compound is shown below:
CH 3Si(OC 3H 6Cl) 3
Another object of the present invention is to propose the preparation method of a kind of methyl siliconic acid as mentioned above three (chloropropyl) ester, its technology is simple, be easy to large-scale production, and raw material is cheap and easy to get, and facility investment is few, and is with low cost, do not produce pollution, and this method is:
Methyltrimethoxy silane and a propylene chlorohydrin of certain mol proportion are mixed with diethylene glycol dimethyl ether, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, carrying out along with reaction, reflux temperature is brought up to 162 ℃ gradually, the about 6h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and an excessive propylene chlorohydrin (reclaim and use) and micro-low boilers through cooling, make methyl siliconic acid three (chloropropyl) ester.
This method also can be:
Methyltrimethoxy silane and a propylene chlorohydrin of certain mol proportion are mixed with dimethylbenzene, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, carrying out along with reaction, reflux temperature is brought up to 140 ℃ gradually, the about 7h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and an excessive propylene chlorohydrin (reclaim and use) and micro-low boilers through cooling, make methyl siliconic acid three (chloropropyl) ester.
This method also can be:
Methyltrimethoxy silane and a propylene chlorohydrin of certain mol proportion are mixed with chlorobenzene, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, carrying out along with reaction, reflux temperature is brought up to 134 ℃ gradually, the about 8h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and an excessive propylene chlorohydrin (reclaim and use) and micro-low boilers through cooling, make methyl siliconic acid three (chloropropyl) ester.
This method also can be:
Methyltrimethoxy silane and a propylene chlorohydrin of certain mol proportion are mixed with ethylene glycol diethyl ether, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, carrying out along with reaction, reflux temperature is brought up to 121 ℃ gradually, the about 10h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and an excessive propylene chlorohydrin (reclaim and use) and micro-low boilers through cooling, make methyl siliconic acid three (chloropropyl) ester.
This method also can be:
Methyltrimethoxy silane and a propylene chlorohydrin of certain mol proportion are mixed with toluene, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, carrying out along with reaction, reflux temperature is brought up to 112 ℃ gradually, the about 12h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and an excessive propylene chlorohydrin (reclaim and use) and micro-low boilers through cooling, make methyl siliconic acid three (chloropropyl) ester.
This method also can be:
Methyltrimethoxy silane and a propylene chlorohydrin of certain mol proportion are mixed with dioxane, make it to be warming up to 102 ℃ of backflows, the about 14h of return time, and constantly steam the methyl alcohol that reaction generates by fractionation plant, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and an excessive propylene chlorohydrin (reclaim and use) and micro-low boilers through cooling, make methyl siliconic acid three (chloropropyl) ester.
Certain mol proportion refers to that the mol ratio of methyltrimethoxy silane and a propylene chlorohydrin is 1: 3~1: 5 as mentioned above.
A propylene chlorohydrin can be 2-propylene chlorohydrin, 1-chloro-2-propanol, trimethylene chlorohydrin or its mixture of isomers as mentioned above.
Methyl siliconic acid three of the present invention (chloropropyl) ester is colourless or weak yellow liquid, and productive rate is 92%~97%.Its flash-point (open cup): 200 ± 5 ℃, decomposition temperature: 250 ± 5 ℃, density is 1.273g/ml, and refractive index is n D 25=1.4486.It is suitable as the usefulness of the flame-retardant plasticizer of materials such as polyvinyl chloride, polyvinyl alcohol, Resins, epoxy, unsaturated polyester, urethane.The synthesis technique principle of methyl three (a chlorine propoxy-) silane is shown below:
CH 3Si(OCH 3) 3+3HOC 3H 6Cl—→CH 3Si(OC 3H 6Cl) 3+3CH 3OH
Compared with prior art, beneficial effect of the present invention is:
1. because organo-silicon ester flame-retardant plasticizer methyl siliconic acid three of the present invention (chloropropyl) ester has the ester structure of stable C-Si bond structure and symmetry, its physical and chemical performance is stable, plasticity is preferably arranged, and containing the dual ignition-proof element of silicon chlorine in the molecule simultaneously has flame retardant resistance preferably again.
2. the present invention is synthetic silicon halogen cooperative flame retardant softening agent methyl siliconic acid three (chloropropyl) ester of raw material with the methyltrimethoxy silane of cheapness, has developed cheap good flame-retardant plasticizer new variety again.
3. preparation method of the present invention is simple, and raw material is cheap and easy to get, and cost is low, is easy to large-scale production.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further.
Embodiment 1 is in being equipped with the 200ml four-hole boiling flask of agitator, thermometer and fractionation plant, add 0.1mol (13.6g) methyltrimethoxy silane and 0.3mol (28.4g) propylene chlorohydrin and 45ml diethylene glycol dimethyl ether, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant (control column top temperature be not higher than 64 ℃), carrying out along with reaction, reflux temperature is brought up to 162 ℃ gradually, the about 6h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive dichlorohydrine (reclaim and use) and low boilers through cooling, make methyl siliconic acid three (chloropropyl) ester, productive rate 92%.Its flash-point (open cup): 200 ± 5 ℃, decomposition temperature: 250 ± 5 ℃, density is 1.273g/ml, and refractive index is n D 25=1.4486.
Embodiment 2 is in being equipped with the 200ml four-hole boiling flask of agitator, thermometer and fractionation plant, add 0.1mol (13.6g) methyltrimethoxy silane and 0.32mol (30.3g) propylene chlorohydrin and 45ml dimethylbenzene, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant (control column top temperature be not higher than 64 ℃), carrying out along with reaction, reflux temperature is brought up to 140 ℃ gradually, the about 7h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive dichlorohydrine (reclaim and use) and low boilers through cooling, make methyl siliconic acid three (chloropropyl) ester, productive rate 94%.Its flash-point (open cup): 200 ± 5 ℃, decomposition temperature: 250 ± 5 ℃, density is 1.273g/ml, and refractive index is n D 25=1.4486.
Embodiment 3 is in being equipped with the 200ml four-hole boiling flask of agitator, thermometer and fractionation plant, add 0.1mol (13.6g) methyltrimethoxy silane and 0.34mol (32.2g) propylene chlorohydrin and 45ml chlorobenzene, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant (control column top temperature be not higher than 64 ℃), carrying out along with reaction, reflux temperature is brought up to 134 ℃ gradually, the about 6h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive dichlorohydrine (reclaim and use) and low boilers through cooling, make methyl siliconic acid three (chloropropyl) ester, productive rate 96%.Its flash-point (open cup): 200 ± 5 ℃, decomposition temperature: 250 ± 5 ℃, density is 1.273g/ml, and refractive index is n D 25=1.4486.
Embodiment 4 is in being equipped with the 200ml four-hole boiling flask of agitator, thermometer and fractionation plant, add 0.1mol (13.6g) methyltrimethoxy silane and 0.38mol (35.9g) propylene chlorohydrin and 45ml ethylene glycol diethyl ether, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant (control column top temperature be not higher than 64 ℃), carrying out along with reaction, reflux temperature is brought up to 122 ℃ gradually, the about 10h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive dichlorohydrine (reclaim and use) and low boilers through cooling, make methyl siliconic acid three (chloropropyl) ester, productive rate 96%.Its flash-point (open cup): 200 ± 5 ℃, decomposition temperature: 250 ± 5 ℃, density is 1.273g/ml, and refractive index is n D 25=1.4486.
Embodiment 5 is in being equipped with the 200ml four-hole boiling flask of agitator, thermometer and fractionation plant, add 0.1mol (13.6g) methyltrimethoxy silane and 0.4mol (37.8g) propylene chlorohydrin and 45ml toluene, make it to be warming up to 104 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant (control column top temperature be not higher than 64 ℃), carrying out along with reaction, reflux temperature is brought up to 112 ℃ gradually, the about 12h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive dichlorohydrine (reclaim and use) and low boilers through cooling, make methyl siliconic acid three (chloropropyl) ester, productive rate 97%.Its flash-point (open cup): 200 ± 5 ℃, decomposition temperature: 250 ± 5 ℃, density is 1.273g/ml, and refractive index is n D 25=1.4486.
Embodiment 6 is in being equipped with the 200ml four-hole boiling flask of agitator, thermometer and fractionation plant, add 0.1mol (13.6g) methyltrimethoxy silane and 0.5mol (47.3g) propylene chlorohydrin and 45ml dioxane, make it to be warming up to 102 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant (control column top temperature be not higher than 64 ℃), carrying out along with reaction, reflux temperature is brought up to 102 ℃ gradually, the about 14h of return time, until the methyl alcohol that steams near theoretical amount.Then distilling off solvent and excessive dichlorohydrine (reclaim and use) and low boilers through cooling, make methyl siliconic acid three (chloropropyl) ester, productive rate 97%.Its flash-point (open cup): 200 ± 5 ℃, decomposition temperature: 250 ± 5 ℃, density is 1.273g/ml, and refractive index is n D 25=1.4486.
Subordinate list 1 preparation example main technologic parameters
Figure BSA00000438074400061
This case contriver also is applied to above-mentioned synthetic methyl siliconic acid three (chloropropyl) ester in the polyvinyl chloride.The limiting oxygen index(LOI) of reference: GB/T2406-2008 " plastics combustibility test method-oxygen index method " test sample product.After getting product flame-retardant plasticizer methyl siliconic acid ester, plasticizer phthalic acid dioctyl ester, synergistic flame retardant antimonous oxide and polyvinyl chloride and mixing in varing proportions, extrude with forcing machine, make the batten that diameter is 3mm, and its flame retardant properties tested, it is as shown in table 2 below to have listed the part test result:
The flame retardant properties test data of table 2 flame-retardant plasticizer methyl siliconic acid ester
Figure BSA00000438074400071

Claims (6)

1. the preparation method of a flame-retardant plasticizer methyl siliconic acid three (chloropropyl) ester, it is characterized in that, this method is: stir down, methyltrimethoxy silane and a propylene chlorohydrin of certain mol proportion are mixed with organic solvent, make it to be warming up to backflow, and constantly steam the methyl alcohol that reaction generates by fractionation plant, carrying out along with reaction, temperature of reaction is brought up to the suitable reflux temperature of mixture gradually, insulation back flow reaction for some time, until the methyl alcohol that steams near theoretical amount, reaction finishes, purified processing then makes colourless to light yellow liquid methyl siliconic acid three (chloropropyl) ester, and described methyl siliconic acid three (chloropropyl) ester has the structure that is shown below: CH 3Si (OC 3H 6Cl) 3, OC in the formula 3H 6Cl is 2-chloro-1-propoxy-, 1-chloro-2-propoxy-or 3-chloro-1-propoxy-.
2. the preparation method of methyl siliconic acid three (chloropropyl) ester according to claim 1, it is characterized in that: described certain mol proportion refers to that the mol ratio of methyltrimethoxy silane and a propylene chlorohydrin is 1: 3~1: 5.
3. the preparation method of methyl siliconic acid three (chloropropyl) ester according to claim 1, it is characterized in that: a described propylene chlorohydrin is 2-propylene chlorohydrin, 1-chloro-2-propanol or trimethylene chlorohydrin.
4. the preparation method of methyl siliconic acid three (chloropropyl) ester according to claim 1 is characterized in that: the suitable reflux temperature that described temperature of reaction is brought up to mixture gradually is to be 102 ℃~162 ℃ according to different solvents and different mol ratios.
5. the preparation method of methyl siliconic acid three (chloropropyl) ester according to claim 1, it is characterized in that: described insulation back flow reaction for some time is 6~14h.
6. according to the preparation method of the described methyl siliconic acid three of claim 1 (chloropropyl) ester, it is characterized in that: described purification process is after reaction finishes, distilling off solvent and an excessive propylene chlorohydrin and micro-low boilers.
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CN102731554B (en) * 2012-07-17 2015-02-25 苏州科技学院 Flame retardant tri(chloropropyl)tribromophenoxychloropropoxyl silicate compound and preparation method thereof
CN104710462A (en) * 2015-03-06 2015-06-17 苏州阳桥化工科技有限公司 Preparation method of dimethyl ethylenedioxy ring silanization compound serving as fire retardant
CN104710455A (en) * 2015-03-06 2015-06-17 苏州阳桥化工科技有限公司 Preparation method of silicon-halogen synergistic flame retardant plasticizer compound
CN104672268A (en) * 2015-03-06 2015-06-03 苏州阳桥化工科技有限公司 Preparation method of dimethyl bis(banzyloxy) silane compound serving as flame retardant

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Andrianov K.A. et al.Reactions of epichlorohydrin and of glycidol with organochlorosilanes.《Russian Chemical Bulletin》.1955,第4卷(第3期),第469-475页. *

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Inventor after: Pan Xianjun

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