CN102146092B - Pentaerythritol methylsilicate and preparation method thereof - Google Patents
Pentaerythritol methylsilicate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a silicon-containing cage-shaped flame retardant carbon-forming agent 1-methyl-4-hydroxymethyl-1-sila-2,6,7-trioxabicyclo[2.2.2]octane, namely a pentaerythritol methylsilicate compound and a preparation method thereof. The structure of the compound is shown in the formula described in the specification of the invention. In the preparation method, methyl trichlorosilane or methyl trimethoxysilicone reacts with pentaerythritol in organic solvent to prepare pentaerythritol methylsilicate. The pentaerythritol methylsilicate has better flame resistance, carbon-forming property and drop melting resistance and other effects, belongs to a novel halogen-free non-toxic non-corrosive flame retardant carbon-forming agent and has stable physical and chemical properties, good material compatibility, low cost and simple process; and the industrial production of pentaerythritol methylsilicate is easy to realize.
Description
Technical field
The present invention relates to the fire-retardant carbon forming agent 1-methyl of a kind of siliceous cage shape-4-methylol-1-sila-2,6,7-trioxa-l-phosphabicyclo [2; 2; 2]-and octane, i.e. methyl siliconic acid pentaerythritol ester and preparation method thereof, this compound can be used as the fire-retardant char-forming agent of materials such as polyolefine, polyester, urethane, coating.
Background technology
Along with progress three big synthetic materialss of science and technology etc. have obtained widespread use in people's life, its inflammableness has been brought serious day by day disaster hidden-trouble to people, has promoted the development of fire retardant material with this.The consumption of fire retardant also increases very fast immediately, in recent years fire retardant has been proposed stricter requirement again, promptly develops towards efficient, Halogen, nontoxic, smokeless direction.
Exploitation to the friendly halogen-free flame retardants of novel environmental has become the focus that current fire retardant is studied, and wherein the novel organosilicon fire retardant more receives people's favor.Organic silicon fibre retardant is a kind of new and effective, Halogen, low toxicity, low cigarette, eco-friendly fire retardant, also is that a kind of charcoal becoming presses down fumicants.Organic silicon fibre retardant is being given outside the base material excellent flame-retardant, can also improve processing characteristics, resistance toheat of base material etc., for the up-and-coming youngster of fire retardant is quite paid close attention to.
After macromolecular material adds fire retardant, though can stop the burning of material, and material melted by heating drippage and produce secondary combustion often at high temperature.In the application, people always hope to introduce char-forming agent or fire retardant itself has into charcoal property, to overcome the problem of fusion drippage.But also there are not good char-forming agent of cost performance or fire-retardant char-forming agent at present.
Novel flame-retardant char-forming agent of the present invention has market in urgent need property, meets the developing direction of fire retardant, and comprehensive price ratio is high, has very vast potential for future development.
Summary of the invention
One of the object of the invention is to solve the drippage problem of fire retardant material when burning, proposes the fire-retardant carbon forming agent methyl siliconic acid of a kind of siliceous cage shape pentaerythritol ester.Stable, the fire-retardant one-tenth charcoal usefulness of its physical and chemical performance is high, cost is low, good with the macromolecular material consistency, can overcome deficiency of the prior art.
For realizing the foregoing invention purpose, the present invention has adopted following technical scheme:
The fire-retardant char-forming agent methyl siliconic acid of a kind of siliceous cage shape tetramethylolmethane ester cpds is characterized in that the structure of this compound is shown below:
Another object of the present invention is to propose the preparation method of the fire-retardant char-forming agent methyl siliconic acid of a kind of siliceous cage shape pentaerythritol ester, its low in raw material cost is easy to get, and technology is simple, is easy to large-scale production, and technical scheme is following:
The preparation method of methyl siliconic acid pentaerythritol ester is characterized in that as stated, and this method is:
With mol ratio be 1: 1 METHYL TRICHLORO SILANE and tetramethylolmethane in organic solvent, react for some time at a certain temperature, treat that hydrogenchloride has been put after, through crystallisation by cooling, filtration, drying, make the methyl siliconic acid pentaerythritol ester.
Particularly, this method is:
Under 25 ℃; Begin METHYL TRICHLORO SILANE is dropped in the mixture of tetramethylolmethane and acetonitrile, and make it to be warming up to 65 ℃ of backflow 1h, then be warmed up to 80 ℃ of backflows; And lasting back flow reaction 12h; After treating that hydrogenchloride has been put,, make the methyl siliconic acid pentaerythritol ester through crystallisation by cooling, filtration, drying.
This method also can be:
Under 25 ℃; Begin METHYL TRICHLORO SILANE is dropped in the mixture of tetramethylolmethane and dioxane, and make it to be warming up to 65 ℃ of backflow 1h, then be warmed up to 102 ℃ of backflows; And lasting back flow reaction 10h; After treating that hydrogenchloride has been put,, make the methyl siliconic acid pentaerythritol ester through crystallisation by cooling, filtration, drying.
This method also can be:
Under 25 ℃; Begin METHYL TRICHLORO SILANE is dropped in the mixture of tetramethylolmethane and toluene, and make it to be warming up to 65 ℃ of backflow 1h, then be warmed up to 112 ℃ of backflows; And lasting back flow reaction 10h; After treating that hydrogenchloride has been put,, make the methyl siliconic acid pentaerythritol ester through crystallisation by cooling, filtration, drying.
This method also can be:
Under 25 ℃; Begin METHYL TRICHLORO SILANE is dropped in the mixture of tetramethylolmethane and chlorobenzene, and make it to be warming up to 65 ℃ of backflow 1h, then be warmed up to 134 ℃ of backflows; And lasting back flow reaction 9h; After treating that hydrogenchloride has been put,, make the methyl siliconic acid pentaerythritol ester through crystallisation by cooling, filtration, drying.
This method also can be:
Under 25 ℃; Begin METHYL TRICHLORO SILANE is dropped in the mixture of tetramethylolmethane and YLENE, and make it to be warming up to 65 ℃ of backflow 1h, then be warmed up to 140 ℃ of backflows; And lasting back flow reaction 9h; After treating that hydrogenchloride has been put,, make the methyl siliconic acid pentaerythritol ester through crystallisation by cooling, filtration, drying.
This method also can be:
Under 25 ℃; Begin METHYL TRICHLORO SILANE is dropped in the mixture of tetramethylolmethane and diethylene glycol dimethyl ether, and make it to be warming up to 65 ℃ of backflow 1h, then be warmed up to 165 ℃ of backflows; And lasting back flow reaction 6h; After treating that hydrogenchloride has been put,, make the methyl siliconic acid pentaerythritol ester through crystallisation by cooling, filtration, drying.
This method also can be:
With mol ratio is 1: 1 methyltrimethoxy silane and tetramethylolmethane reacts for some time at a certain temperature in organic solvent after, through crystallisation by cooling, filtration, drying, to make the methyl siliconic acid pentaerythritol ester.
Particularly, aforesaid method is:
Methyltrimethoxy silane is added in the mixture of tetramethylolmethane and dioxane, makes it to be warming up to 102 ℃ of backflows, the about 10h of return time, and constantly steam the methyl alcohol that reaction generates through fractionation plant, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make the methyl siliconic acid pentaerythritol ester.
This method also can be:
Methyltrimethoxy silane is added in the mixture of tetramethylolmethane and toluene; Make it to be warming up to 100 ℃ of backflows; And constantly steam the methyl alcohol that reaction generates through fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 112 ℃ gradually; The about 8h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make the methyl siliconic acid pentaerythritol ester.
This method also can be:
Methyltrimethoxy silane is added in the mixture of tetramethylolmethane and chlorobenzene; Make it to be warming up to 100 ℃ of backflows; And constantly steam the methyl alcohol that reaction generates through fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 134 ℃ gradually; The about 7h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make the methyl siliconic acid pentaerythritol ester.
This method also can be:
Methyltrimethoxy silane is added in the mixture of tetramethylolmethane and YLENE; Make it to be warming up to 100 ℃ of backflows; And constantly steam the methyl alcohol that reaction generates through fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 142 ℃ gradually; The about 7h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make the methyl siliconic acid pentaerythritol ester.
This method also can be:
Methyltrimethoxy silane is added in the mixture of tetramethylolmethane and diethylene glycol dimethyl ether; Make it slowly to be warming up to 100 ℃ of backflows; And constantly steam the methyl alcohol that reaction generates through fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 165 ℃ gradually; The about 6h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make the methyl siliconic acid pentaerythritol ester.
Methyl siliconic acid pentaerythritol ester of the present invention is white powdery solid; Its productive rate is 93%～98%; Decomposition temperature is 340 ± 10 ℃; It is suitable as the usefulness of the fire-retardant carbon forming agent of materials such as polyolefine, polyester, urethane, coating, and the synthesis technique principle of this methyl siliconic acid pentaerythritol ester is shown below:
Compared with prior art, beneficial effect of the present invention is:
1. because organic silicon flame-retardant char-forming agent methyl siliconic acid pentaerythritol ester of the present invention has cage structure, its physical and chemical performance is stable, and decomposition temperature is high, and is good with the macromolecular material consistency, can be adapted to the engineering plastics of high temperature process.
2. the compound of the present invention's proposition is designed to cage structure, has introduced element silicon in the molecule again, and having made it into the charcoal effect has fire retardation again, and it and many phosphorus-nitrogen containing flame retardants have good synergetic property and compatibleness.Material is when burning; Form the siliceous coking charcoal resist of form compact and stable at substrate surface; Compare with conventional charcoal layer; Its charcoal layer compact structure is stable, so this charcoal layer has been strengthened heat insulation, disconnected anoxybiotic supply, stop the effusion of superpolymer thermal destruction volatile matter and prevent the molten drop drippage, brings into play good fire retardation.
3. preparation method of the present invention is simple, and raw material is cheap and easy to get, and cost is low, and the solvent of building-up reactions can directly be recycled, and is easy to large-scale production.Therefore good application, DEVELOPMENT PROSPECT are arranged.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further.
Embodiment 1 is in being equipped with the 100ml four-hole boiling flask of whisking appliance, TM, tap funnel, reflux condensing tube; Add 0.1mol (13.62g) tetramethylolmethane and 50ml acetonitrile; Open and stir; Under 25 ℃, drip 0.1mol (14.95g) METHYL TRICHLORO SILANE in about 30min, be warming up to 65 ℃ of backflow 1h after dripping off.Then be warmed up to 80 ℃ of back flow reaction 12h, treat that hydrogenchloride has been put after, through crystallisation by cooling, filtration, drying, make methyl siliconic acid pentaerythritol ester white solid.Its productive rate is 93%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 2 is in being equipped with the 100ml four-hole boiling flask of whisking appliance, TM, tap funnel, reflux condensing tube; Add 0.1mol (13.62g) tetramethylolmethane and 50ml dioxane; Open and stir; Under 25 ℃, drip 0.1mol (14.95g) METHYL TRICHLORO SILANE in about 30min, be warming up to 65 ℃ of backflow 1h after dripping off.Then be warmed up to 102 ℃ of back flow reaction 10h, treat that hydrogenchloride has been put after, through crystallisation by cooling, filtration, drying, make methyl siliconic acid pentaerythritol ester white solid.Its productive rate is 94%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 3 is in being equipped with the 100ml four-hole boiling flask of whisking appliance, TM, tap funnel, reflux condensing tube; Add 0.1mol (13.62g) tetramethylolmethane and 50ml toluene; Open and stir; Under 25 ℃, drip 0.1mol (14.95g) METHYL TRICHLORO SILANE in about 30min, be warming up to 65 ℃ of backflow 1h after dripping off.Then be warmed up to 112 ℃ of back flow reaction 10h, treat that hydrogenchloride has been put after, through crystallisation by cooling, filtration, drying, make methyl siliconic acid pentaerythritol ester white solid.Its productive rate is 94%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 4 is in being equipped with the 100ml four-hole boiling flask of whisking appliance, TM, tap funnel, reflux condensing tube; Add 0.1mol (13.62g) tetramethylolmethane and 50ml chlorobenzene; Open and stir; Under 25 ℃, drip 0.1mol (14.95g) METHYL TRICHLORO SILANE in about 30min, be warming up to 65 ℃ of backflow 1h after dripping off.Then be warmed up to 134 ℃ of back flow reaction 9h, treat that hydrogenchloride has been put after, through crystallisation by cooling, filtration, drying, make methyl siliconic acid pentaerythritol ester white solid.Its productive rate is 95%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 5 is in being equipped with the 100ml four-hole boiling flask of whisking appliance, TM, tap funnel, reflux condensing tube; Add 0.1mol (13.62g) tetramethylolmethane and 50ml YLENE; Open and stir; Under 25 ℃, drip 0.1mol (14.95g) METHYL TRICHLORO SILANE in about 30min, be warming up to 65 ℃ of backflow 1h after dripping off.Then be warmed up to 142 ℃ of back flow reaction 9h, treat that hydrogenchloride has been put after, through crystallisation by cooling, filtration, drying, make methyl siliconic acid pentaerythritol ester white solid.Its productive rate is 95%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 6 is in being equipped with the 100ml four-hole boiling flask of whisking appliance, TM, tap funnel, reflux condensing tube; Add 0.1mol (13.62g) tetramethylolmethane and 50ml diethylene glycol dimethyl ether; Open and stir; Under 25 ℃, drip 0.1mol (14.95g) METHYL TRICHLORO SILANE in about 30min, be warming up to 65 ℃ of backflow 1h after dripping off.Then be warmed up to 165 ℃ of back flow reaction 6h, treat that hydrogenchloride has been put after, through crystallisation by cooling, filtration, drying, make methyl siliconic acid pentaerythritol ester white solid.Its productive rate is 96%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 7 is in being equipped with the 100ml there-necked flask of whisking appliance, TM, fractionation plant; Add 0.1mol (13.62g) tetramethylolmethane and 50ml dioxane, under agitation, add 0.1mol (13.62g) methyltrimethoxy silane; Make it to be warming up to 102 ℃ of backflows; The about 10h of return time, and constantly steam the methyl alcohol that reaction generates through fractionation plant, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make methyl siliconic acid pentaerythritol ester white solid.Its productive rate is 95%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 8 adds 0.1mol (13.62g) tetramethylolmethane and 50ml toluene, under agitation in the 100ml there-necked flask of whisking appliance, TM, fractionation plant is housed; Add 0.1mol (13.62g) methyltrimethoxy silane, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates through fractionation plant; Carrying out along with reaction; Reflux temperature is brought up to 112 ℃ gradually, the about 8h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make methyl siliconic acid pentaerythritol ester white solid.Its productive rate is 95%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 9 adds 0.1mol (13.62g) tetramethylolmethane and 50ml chlorobenzene, under agitation in the 100ml there-necked flask of whisking appliance, TM, fractionation plant is housed; Add 0.1mol (13.62g) methyltrimethoxy silane, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates through fractionation plant; Carrying out along with reaction; Reflux temperature is brought up to 134 ℃ gradually, the about 7h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make methyl siliconic acid pentaerythritol ester white solid.Its productive rate is 96%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 10 adds 0.1mol (13.62g) tetramethylolmethane and 50ml YLENE, under agitation in the 100ml there-necked flask of whisking appliance, TM, fractionation plant is housed; Add 0.1mol (13.62g) methyltrimethoxy silane, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates through fractionation plant; Carrying out along with reaction; Reflux temperature is brought up to 142 ℃ gradually, the about 7h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make methyl siliconic acid pentaerythritol ester white solid.Its productive rate is 97%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 11 adds 0.1mol (13.62g) tetramethylolmethane and 50ml diethylene glycol dimethyl ether, under agitation in the 100ml there-necked flask of whisking appliance, TM, fractionation plant is housed; Add 0.1mol (13.62g) methyltrimethoxy silane, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates through fractionation plant; Carrying out along with reaction; Reflux temperature is brought up to 165 ℃ gradually, the about 6h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make methyl siliconic acid pentaerythritol ester white solid.Its productive rate is 98%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 12 adds 0.1mol (13.62g) tetramethylolmethane and 50ml dichlorobenzene, under agitation in the 100ml there-necked flask of whisking appliance, TM, fractionation plant is housed; Add 0.1mol (13.62g) methyltrimethoxy silane, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates through fractionation plant; Carrying out along with reaction; Reflux temperature is brought up to 180 ℃ gradually, the about 5h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make methyl siliconic acid pentaerythritol ester white solid.Its productive rate is 98%, 340 ± 10 ℃ of decomposition temperatures.
This case contriver also is applied to above-mentioned synthetic methyl siliconic acid pentaerythritol ester in the Vestolen PP 7052.Reference: GB/T2406-2008 " plastics combustibility test method-oxygen index method " surveys the flame retardant properties of product in Vestolen PP 7052.Get product methyl siliconic acid pentaerythritol ester, ammonium polyphosphate and Vestolen PP 7052 mix the back in varing proportions and extrude with forcing machine, and process long 15cm, and diameter is the batten of 3mm and its flame retardant properties tested that test-results is as shown in the table:
Table 1 methyl siliconic acid pentaerythritol ester is to polypropylene fire retardant carbon-forming performance test data table
Can know that by last table the methyl siliconic acid pentaerythritol ester has good fire-retardant one-tenth charcoal property to Vestolen PP 7052, with ammonium polyphosphate good flame synergistic property is arranged.The methyl siliconic acid pentaerythritol ester is the excellent fire retardant char-forming agent.
Claims (4)
1. the fire-retardant char-forming agent 1-methyl of siliceous cage shape-4-methylol-1-sila-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane, promptly methyl siliconic acid tetramethylolmethane ester cpds is characterized in that, the structure of this compound is shown below:
2. the preparation method of methyl siliconic acid pentaerythritol ester according to claim 1 is characterized in that this method is: under 25 ℃; Beginning mol ratio is that 1: 1 METHYL TRICHLORO SILANE drops in the mixture of tetramethylolmethane and organic solvent, and makes it to be warming up to 65 ℃ of backflow 1h, then is warmed up to 80～165 ℃ of the boiling point reflux temperatures of solvent; And lasting back flow reaction 6～12h; After treating that hydrogenchloride has been put,, make the methyl siliconic acid pentaerythritol ester through crystallisation by cooling, filtration, drying.
3. the preparation method of methyl siliconic acid pentaerythritol ester according to claim 1 is characterized in that this method is: with mol ratio is that 1: 1 methyltrimethoxy silane and tetramethylolmethane reacts in organic solvent; And make it to be warming up to 100 ℃ of backflows; And constantly steam the methyl alcohol that reaction generates through fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 80～180 ℃ of the boiling points of solvent gradually; Return time 5-10h; Near theoretical amount, and after crystallisation by cooling, filtration, drying make the methyl siliconic acid pentaerythritol ester until the methyl alcohol that steams.
4. like each described preparation method of claim 2-3, it is characterized in that said organic solvent is: acetonitrile, dioxane, toluene, chlorobenzene, dichlorobenzene, YLENE or diethylene glycol dimethyl ether.
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| CN108864702A (en) * | 2017-05-12 | 2018-11-23 | 苏州科技大学 | A kind of anti-dissolved drip modified polyphenyl thioether material and preparation method thereof |
| CN108864168B (en) * | 2017-05-12 | 2020-10-20 | 苏州科技大学 | Preparation method and application of thiophenylmethyl pentaerythritol silicate |
| CN107652520B (en) * | 2017-11-09 | 2020-07-03 | 青岛岩康塑料机械有限公司 | Flame-retardant polyethylene product and preparation method thereof |
| CN109517009A (en) * | 2018-10-23 | 2019-03-26 | 苏州科技大学 | Three silicon cage alcohol ester compounds of fire retardant phosphorous acid and preparation method thereof |
| CN109503886B (en) * | 2018-10-23 | 2021-03-05 | 苏州科技大学 | Flame-retardant charring agent silicic acid tetrasilicon caged alcohol ester compound and preparation method thereof |
| CN112011089A (en) * | 2020-08-06 | 2020-12-01 | 苏州科技大学 | Active organic silicon nitrogen flame retardant compound and preparation method thereof |
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