CN102140118A - Cage-shaped silicon-containing quaternary phosphonium inflaming retarding surfactant and preparation method thereof - Google Patents
Cage-shaped silicon-containing quaternary phosphonium inflaming retarding surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a cage-shaped silicon-containing quaternary phosphonium compound, namely 1-alkyl-4-hydroxymethyl-1-silicon hybrid-4-phosphorous hybrid-2,6,7-trioxa bicyclo[2,2,2]-octane quaternary phosphonium salt and a preparation method thereof. The structure of the compound is shown in the specification, wherein R is C1-C2 alkyl or phenyl, and X- is C1- or SO42-/2. The preparation method comprises the following steps: dissolving tetrahydroxymethyl phosphonium and alkyl trimethoxysilane in a molar ratio of 1:1 in an organic solvent; reacting for a while at a certain temperature, and evaporating out methanol generated by reaction through a fractionation device until the amount of the evaporated methanol approaches a theory amount; and purifying so as to obtain the cage-shaped silicon-containing quaternary phosphonium inflaming retarding surfactant. The compound is a difunctional inflaming retarding surfactant and can be used as an inflaming retarding antistat for polyolefin, polyester, polyurethane, nylon, paint and the like.
Description
Technical field
The present invention relates to the siliceous quaternary phosphine type of a kind of cage shape fire-retardant surfactant, being specifically related to a kind of is 1-alkyl-4-methylol-1-sila-4-phospha-2 that raw material makes with Si methylol phosphonium and alkyl trimethoxysilane, 6,7-trioxa-l-phosphabicyclo [2,2,2]-the octane quaternary phosphonium salt compounds and preparation method thereof.This compound is difunctional fire-retardant surfactant, and this compound can be used as the flame-retardant and anti-static agent of materials such as polyolefine, polyester, urethane, nylon, coating.
Background technology
Progress along with science and technology, synthetic materialss such as plastics, rubber, fiber are used for social every field more and more widely, because the inflammableness and the non-conductive property of macromolecular material are often brought disasters such as fire to people, so the research of the fire-retardant and antistatic technology of macromolecular material is extremely paid close attention in the whole world.Particularly coal-mine fire 80% all is owing to the travelling belt static sparking causes, in addition worktable etc. is all had the requirement of flame-retardant and anti-static, so that the fire-retardant material of general requirement all requires is antistatic, also will add static inhibitor when also promptly adding fire retardant.The inventor in same molecule, makes fire-retardant surfactant to the design of fire-retardant and antistatic functional group, can improve chemical atom utilization, reduces production costs, and brings and uses conveniently.The siliceous quaternary phosphonium type of the present invention fire-retardant surfactant is the rigidity cage structure, and physical and chemical performance is stable, owing to contain silicon, two kinds of cooperative flame retardant elements of phosphorus simultaneously in the molecule, it has good flame; The introducing of C-Si, C-P key brings stability the time to improve consistency with material and friendly machining property again to molecule in the molecule; Because it contains the quaternary phosphine cationic structural and the nonpolar structure of line style will have surfactivity preferably, with regard to the phosphoric in the molecule itself, just can play fire-retardant and anlistatig dual function.
Have with material and merge dispersedly preferably because constitutional features of the present invention is formed it, and can also improve the problem not good such as expansion type flame retardant, the fire-retardant difficult problem of market in urgent needs such as solution polyester, nylon with the material amalgamation.So the collaborative highly effective flame-retardant antistatic products of research and development multi-function and multi-element is of practical significance very much.
Summary of the invention
One of purpose of the present invention is to propose a kind of phosphorous, silicon two element cooperative flame retardants and has the bifunctional compound of antistatic property, being specifically related to a kind of is that raw material makes 1-alkyl-4-methylol-1-sila-4-phospha-2 with Si methylol phosphonium and alkyl trimethoxysilane, 6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary alkylphosphonium salt fire-retardant surfactant.Its physical and chemical performance is stable, and flame-retardant and anti-static usefulness height can overcome deficiency of the prior art, and good application and development prospect is arranged.
For achieving the above object, the present invention has adopted following technical scheme:
The siliceous quaternary phosphonium type of a kind of cage shape fire-retardant surfactant compound is characterized in that this compound structure is shown below:
R is C
1-C
12Alkyl or phenyl; X
-Be Cl
-Or SO
4 2-/ 2
Another object of the present invention is to propose the preparation method of the siliceous quaternary phosphonium type of cage shape fire-retardant surfactant, its raw material is cheap and easy to get, and technology is simple, is easy to large-scale production, and technical scheme is as follows:
The preparation method of the siliceous quaternary phosphonium type of cage shape fire-retardant surfactant is characterized in that as mentioned above, and this method is:
With mole (equivalent) than being that 1: 1 Si methylol phosphonium and alkyl trimethoxysilane are in organic solvent, react for some time at a certain temperature, and constantly steam the methyl alcohol that reaction generates by fractionation plant, until the methyl alcohol that steams near theoretical amount, through purification processes, make the siliceous quaternary alkylphosphonium salt of cage shape.
Described organic solvent is toluene, dimethylbenzene, chlorobenzene, dichlorobenzene, diethylene glycol dimethyl ether; Temperature of reaction is 100 ℃～180 ℃; Purification processing method is: to R≤C
5The product of alkyl trimethoxysilane reaction, with the reaction solution crystallisation by cooling, filter, drying makes the siliceous quaternary alkylphosphonium salt of solid cage shape; Purification processing method also can be: to R 〉=C
6The product of alkyl trimethoxysilane reaction, with the reaction solution distilling off solvent, use washing with acetone again, separatory, underpressure distillation goes out low boilers again, makes the siliceous quaternary alkylphosphonium salt of liquid cage shape.Solvent for use reclaims to be reused.
1-methyl of the present invention-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary phosphine vitriol is white powdery solid, its productive rate is 93-97%, 340 ± 10 ℃ of decomposition temperatures; 1-methyl-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary alkylphosphonium salt hydrochlorate is for being white powdery solid, its productive rate is 95%, 330 ± 10 ℃ of decomposition temperatures; 1-propyl group-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary phosphine vitriol is white powdery solid.Its productive rate is 92-97%, 320 ± 10 ℃ of decomposition temperatures; 1-propyl group-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary alkylphosphonium salt hydrochlorate is white powdery solid.Its productive rate is 96%, 290 ± 10 ℃ of decomposition temperatures; 1-octyl group-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary phosphine vitriol is light yellow viscous liquid, its productive rate is 93-94%, 280 ± 10 ℃ of decomposition temperatures, n
D 20=1.6442; 1-octyl group-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary alkylphosphonium salt hydrochlorate is a light yellow viscous liquid, its productive rate is 94%, 270 ± 10 ℃ of decomposition temperatures, n
D 20=1.6340; 1-dodecyl-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary phosphine vitriol is light yellow viscous liquid, its productive rate is 93-94%, 270 ± 10 ℃ of decomposition temperatures, n
D 20=1.6520; 1-dodecyl-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary alkylphosphonium salt hydrochlorate is a light yellow viscous liquid, its productive rate is 92-93%, 260 ± 10 ℃ of decomposition temperatures, n
D 20=1.6450; Its flame-retardant and anti-static agent that is suitable as materials such as polyolefine, polyester, urethane, nylon, coating obtains the usefulness of fire-retardant carbon forming agent, and the composition principle of the siliceous quaternary phosphine type of this cage shape fire-retardant surfactant is shown below:
R is C
1-C
12Alkyl; X
-Be Cl
-Or SO
4 2-/ 2
Compared with prior art, beneficial effect of the present invention is:
1. because the siliceous quaternary alkylphosphonium salt of cage shape of the present invention is the rigidity cage structure, the introducing of C-Si, C-P key in the molecule brings stability the time to improve consistency with material and friendly machining property again to molecule; Contain silicon, two kinds of cooperative flame retardant elements of phosphorus in the molecule simultaneously, flame retardant resistance is preferably arranged; Surfactivity is arranged preferably, just can play fire-retardant and anlistatig dual function because it contains quaternary phosphine cationic structural and the nonpolar structure of line style with regard to the phosphoric in the molecule itself.
2. because feature structure of the present invention and material will have and merge dispersedly preferably, and the consistency of other auxiliary agent and material can be improved, the property hard to tolerate of expansion type flame retardant etc. and material can be improved, the fire-retardant processing difficult problem of market in urgent needs solutions such as solution polyester, nylon.
3. the invention belongs to the collaborative highly effective flame-retardant surfactant product of multi-function and multi-element, it is convenient to use, the atom utilization height, and cost is low, meets the Green Chemistry idea of development.
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 there-necked flask of agitator, thermometer, fractionation plant, add 0.05mol (20.3g) tetra methylol sulfuric acid phosphonium, 0.1mol (13.6g) methyltrimethoxy silane and 35ml toluene, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 112 ℃ gradually, the about 12h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make 1-methyl-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary phosphine vitriol is white powdery solid, and its productive rate is 93%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 2 is in being equipped with the 100ml there-necked flask of agitator, thermometer, fractionation plant, add 0.05mol (20.3g) tetra methylol sulfuric acid phosphonium, 0.1mol (13.6g) methyltrimethoxy silane and 35ml dimethylbenzene, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 142 ℃ gradually, the about 10h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make 1-methyl-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary phosphine vitriol is white powdery solid, and its productive rate is 94%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 3 is in being equipped with the 100ml there-necked flask of agitator, thermometer, fractionation plant, add 0.05mol (20.3g) tetra methylol sulfuric acid phosphonium, 0.1mol (13.6g) methyltrimethoxy silane and 35ml chlorobenzene, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 134 ℃ gradually, the about 11h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make 1-methyl-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary phosphine vitriol is white powdery solid, and its productive rate is 97%, 340 ± 10 ℃ of decomposition temperatures.
Embodiment 4 is in being equipped with the 100ml there-necked flask of agitator, thermometer, fractionation plant, add 0.1mol (19.1g) tetrakis hydroxymethyl phosphonium chloride, 0.1mol (13.6g) methyltrimethoxy silane and 35ml toluene, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 112 ℃ gradually, the about 12h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make 1-methyl-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary alkylphosphonium salt hydrochlorate is white powdery solid, and its productive rate is 95%, 330 ± 10 ℃ of decomposition temperatures.
Embodiment 5 is in being equipped with the 100ml there-necked flask of agitator, thermometer, fractionation plant, add 0.05mol (20.3g) tetra methylol sulfuric acid phosphonium, 0.1mol (16.4g) propyl trimethoxy silicane and 35ml toluene, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 112 ℃ gradually, the about 12h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make 1-propyl group-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary phosphine vitriol is white powdery solid, and its productive rate is 92%, 320 ± 10 ℃ of decomposition temperatures.
Embodiment 6 is in being equipped with the 100ml there-necked flask of agitator, thermometer, fractionation plant, add 0.05mol (20.3g) tetra methylol sulfuric acid phosphonium, 0.1mol (16.4g) propyl trimethoxy silicane and 35ml dimethylbenzene, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 142 ℃ gradually, the about 9h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make 1-propyl group-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary phosphine vitriol is white powdery solid, and its productive rate is 94%, 320 ± 10 ℃ of decomposition temperatures.
Embodiment 7 is in being equipped with the 100ml there-necked flask of agitator, thermometer, fractionation plant, add 0.05mol (20.3g) tetra methylol sulfuric acid phosphonium, 0.1mol (16.4g) propyl trimethoxy silicane and 35ml dichlorobenzene, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 180 ℃ gradually, the about 6h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make 1-propyl group-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary phosphine vitriol is white powdery solid, and its productive rate is 97%, 320 ± 10 ℃ of decomposition temperatures.
Embodiment 8 is in being equipped with the 100ml there-necked flask of agitator, thermometer, fractionation plant, add 0.1mol (19.1g) Si methylol Lv Phosphonium, 0.1mol (16.4g) propyl trimethoxy silicane and 35ml diethylene glycol dimethyl ether, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 164 ℃ gradually, the about 8h of return time, until the methyl alcohol that steams near theoretical amount.And after crystallisation by cooling, filtration, drying make 1-propyl group-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary alkylphosphonium salt hydrochlorate is white powdery solid, and its productive rate is 96%, 290 ± 10 ℃ of decomposition temperatures.
Embodiment 9 is in being equipped with the 100ml there-necked flask of agitator, thermometer, fractionation plant, add 0.05mol (20.3g) tetra methylol sulfuric acid phosphonium, 0.1mol (23.4g) octyl group Trimethoxy silane and 35ml toluene, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 112 ℃ gradually, the about 13h of return time, until the methyl alcohol that steams near theoretical amount.With the reaction solution distilling off solvent, use washing with acetone again, separatory, underpressure distillation goes out low boilers again, make liquid 1-octyl group-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-and octane quaternary phosphine vitriol, productive rate is 93%, refractive index 1.6442,280 ± 10 ℃ of decomposition temperatures.
Embodiment 10 is in being equipped with the 100ml there-necked flask of agitator, thermometer, fractionation plant, add 0.05mol (20.3g) tetra methylol sulfuric acid phosphonium, 0.1mol (23.4g) octyl group Trimethoxy silane and 35ml dimethylbenzene, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 142 ℃ gradually, the about 10h of return time, until the methyl alcohol that steams near theoretical amount.With the reaction solution distilling off solvent, use washing with acetone again, separatory, underpressure distillation goes out low boilers again, make liquid 1-octyl group-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-and octane quaternary phosphine vitriol, productive rate is 94%, refractive index 1.6442,280 ± 10 ℃ of decomposition temperatures.
Embodiment 11 is in being equipped with the 100ml there-necked flask of agitator, thermometer, fractionation plant, add 0.1mol (19.1g) Si methylol Lv Phosphonium, 0.1mol (23.4g) octyl group Trimethoxy silane and 35ml chlorobenzene, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 134 ℃ gradually, the about 12h of return time, until the methyl alcohol that steams near theoretical amount.With the reaction solution distilling off solvent, use washing with acetone again, separatory, underpressure distillation goes out low boilers again, make liquid 1-octyl group-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-and octane quaternary alkylphosphonium salt hydrochlorate, productive rate is 93%, refractive index 1.6340,270 ± 10 ℃ of decomposition temperatures.
Embodiment 12 is in being equipped with the 100ml there-necked flask of agitator, thermometer, fractionation plant, add 0.05mol (20.3g) tetra methylol sulfuric acid phosphonium, 0.1mol (29g) dodecyl Trimethoxy silane and 35ml dimethylbenzene, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 142 ℃ gradually, the about 12h of return time, until the methyl alcohol that steams near theoretical amount.With the reaction solution distilling off solvent, use washing with acetone again, separatory, underpressure distillation goes out low boilers again, make liquid 1-dodecyl-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary phosphine vitriol, productive rate is 93%, refractive index 1.6520,270 ± 10 ℃ of decomposition temperatures.
Embodiment 13 is in being equipped with the 200ml there-necked flask of agitator, thermometer, fractionation plant, add 0.1mol (19.1g) tetrakis hydroxymethyl phosphonium chloride, 0.1mol (29g) dodecyl Trimethoxy silane and 35ml dimethylbenzene, make it to be warming up to 100 ℃ of backflows, and constantly steam the methyl alcohol that reaction generates by fractionation plant, along with the carrying out of reaction, reflux temperature is brought up to 142 ℃ gradually, the about 10h of return time, until the methyl alcohol that steams near theoretical amount.With the reaction solution distilling off solvent, use washing with acetone again, separatory, underpressure distillation goes out low boilers again, make liquid 1-dodecyl-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary alkylphosphonium salt hydrochlorate, productive rate is 92%, refractive index 1.6450,260 ± 10 ℃ of decomposition temperatures.
Claims (7)
1. cage shape quaternary phosphine type alkyl silicate 1-alkyl-4-methylol-1-sila-4-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary phosphonium salt compounds and preparation method thereof is characterized in that the structure of this compound is shown below:
R is C
1-C
12Alkyl or phenyl; X-is Cl
-Or SO
4 2-/ 2
2. 1-alkyl-4-methylol-1-sila-4-phospha-2 according to claim 1,6,7-trioxa-l-phosphabicyclo [2,2,2]-preparation method of octane quaternary alkylphosphonium salt, it is characterized in that this method is: with mole (equivalent) than be 1: 1 Si methylol phosphonium and alkyl trimethoxysilane in organic solvent, react for some time at a certain temperature, and constantly steam the methyl alcohol that reaction generates by fractionation plant, near theoretical amount,, make the siliceous quaternary alkylphosphonium salt of cage shape until the methyl alcohol that steams through purification processes.
3. as 1-alkyl-4-methylol-1-sila-4-phospha-2,6 as described in the claim 2,7-trioxa-l-phosphabicyclo [2,2,2]-and the preparation method of octane quaternary alkylphosphonium salt, it is characterized in that described organic solvent is toluene, dimethylbenzene, chlorobenzene, dichlorobenzene, diethylene glycol dimethyl ether.
4. as 1-alkyl-4-methylol-1-sila-4-phospha-2,6 as described in the claim 2, the preparation method of 7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary alkylphosphonium salt is characterized in that, described reaction at a certain temperature, and temperature is 100 ℃～180 ℃.
5. as 1-alkyl-4-methylol-1-sila-4-phospha-2,6 as described in the claim 2, the preparation method of 7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary alkylphosphonium salt is characterized in that, described reaction for some time, the reaction times is 6-13h.
6. as 1-alkyl-4-methylol-1-sila-4-phospha-2,6 as described in the claim 2, the preparation method of 7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary alkylphosphonium salt is characterized in that described purification processing method is: to R≤C
5The product of alkyl trimethoxysilane reaction, with the reaction solution crystallisation by cooling, filter, drying makes the siliceous quaternary alkylphosphonium salt of solid cage shape.
7. as 1-alkyl-4-methylol-1-sila-4-phospha-2,6 as described in the claim 2, the preparation method of 7-trioxa-l-phosphabicyclo [2,2,2]-octane quaternary alkylphosphonium salt is characterized in that described purification processing method also can be: to R 〉=C
6The product of alkyl trimethoxysilane reaction, with the reaction solution distilling off solvent, use washing with acetone again, underpressure distillation goes out low boilers again, makes the siliceous quaternary alkylphosphonium salt of liquid cage shape.
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| CN105037439A (en) * | 2015-07-07 | 2015-11-11 | 苏州凯马化学科技有限责任公司 | Hydroxymethyl phosphonyl heterocyclic phenylphosphonothioate compound and preparation method therefor |
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| CN101858034A (en) * | 2010-03-25 | 2010-10-13 | 东华大学 | Silicious organic phosphonium salt antibacterial finishing agent and preparation method and application thereof |
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