CN101704954B - Tetraphenyl phenyl graft polysiloxane, preparation method thereof and application thereof - Google Patents
Tetraphenyl phenyl graft polysiloxane, preparation method thereof and application thereof Download PDFInfo
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- CN101704954B CN101704954B CN2009100149299A CN200910014929A CN101704954B CN 101704954 B CN101704954 B CN 101704954B CN 2009100149299 A CN2009100149299 A CN 2009100149299A CN 200910014929 A CN200910014929 A CN 200910014929A CN 101704954 B CN101704954 B CN 101704954B
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Abstract
The invention discloses a tetraphenyl phenyl graft polysiloxane. The structural formula of the tetraphenyl phenyl graft polysiloxane is as shown by an attached drawing of the abstract, and the molecular weight of the tetraphenyl phenyl graft polysiloxane is between 85,000 and 100,000. The invention also discloses a preparation method of the tetraphenyl phenyl graft polysiloxane, which comprises the following steps of: mixing tetraphenyl cyclopentadiene ketene, anhydrous diphenyl ether, and methyl vinyl silicone rubber; and then grafting the mixture onto the methyl vinyl silicone rubber through Diels-Alder reaction. The invention also discloses application of the tetraphenyl phenyl graft polysiloxane. The tetraphenyl phenyl graft polysiloxane can be used as a stationary phase of gas chromatography, can separate general hydrocarbon substances, and has good separation selectivity to environmental pollutants such as substituted isomeride of benzene, condensed aromatics, azepine, oxa and thia condensed aromatics, polycyclic aromatic hydrocarbon and the like by stronger induction and dispersion fierce.
Description
Technical field
The present invention relates to a kind of tetraphenyl phenyl graft polysiloxane and preparation method thereof and application as the gas-chromatography stationary phase.
Background technology
The outstanding feature of capillary gas chromatography is the resolving power height, is widely used in fields such as petrochemical complex, organic synthesis, Physiology and biochemistry, medical and health.Make capillary chromatographic column have superperformances such as Gao Zhuxiao, low activity, high stability, just must synthesize chromatographic stationary phase with excellent properties.In gas-chromatography, polysiloxane is to use stationary phase the most widely, and this class stationary phase also is the important content of chromatogram worker research in recent years.Bernhard X.Mayer etc. has synthesized 50% n-octyl methyl, 50% phenylbenzene polysiloxane (Analyst, 2003,128,1238-1242) and 75% phenylbenzene, 25% dimethyl polysiloxane (J.Sep.Sci., 2002,25,60-66) and with it as the gas-chromatography stationary phase.Though it is a variety of that present alternative gas-chromatography stationary phase has, still lack the stationary phase of highly selective and low-bleed.
Summary of the invention
With reference to above-mentioned prior art, the invention provides a kind of tetraphenyl phenyl graft polysiloxane, can be used as the gas-chromatography stationary phase, its selectivity height, temperature tolerance is good, can be as the separation of many rings and condensed nucleus aromatic mixture.
The present invention is achieved by the following technical solutions:
A kind of tetraphenyl phenyl graft polysiloxane, its general structure is as follows:
Wherein, m, n, p are positive integer, m: n: p=90: 2: 8, molecular weight was 8.5 ten thousand～100,000.
A kind of preparation method of tetraphenyl phenyl graft polysiloxane: be that tetraphenylcyclopentadienone is passed through the Diels-Alder reactive grafting to the methyl ethylene silicon raw rubber, make tetraphenyl phenyl graft polysiloxane.
Described preparation method is specially: add the anhydrous phenyl ether of 50ml, 7.00g methyl ethylene silicon raw rubber (molecular weight 8～90,000) and 2.87g tetraphenylcyclopentadienone in 250ml four-hole round-bottomed flask; Logical nitrogen protection is stirred down and slowly is heated to 250～260 ℃ after feeding intake, and insulation reaction becomes transparent incarnadine to solution by opaque black; Continue reaction 30～35 minutes, stopped reaction is got upper strata thickness product (using separating funnel that upper strata thickness product is told) after being cooled to 100 ℃; The thickness product of gained is placed beaker, add toluene, heated and stirred is fully dissolved the thickness product, and cold slightly back adds methyl alcohol makes product separate out (toluene: the methyl alcohol volume ratio is about 1: 1); With product classification washing 3～5 times as stated above,, obtain the product of molecular weight homogeneous to remove small molecular weight impurity; Filter with ether dissolution, removal of solvent under reduced pressure promptly gets tetraphenyl phenyl graft polysiloxane again.
Described tetraphenylcyclopentadienone is a synthetic by the following method: add 7.0g benzil and 7.0g dibenzyl ketone in three mouthfuls of round-bottomed flasks of 100ml, add the 50ml hot ethanol again; Logical nitrogen protection, heated and stirred, when the approaching boiling of solution, the ethanolic soln of slow Dropwise 5 .0ml potassium hydroxide in solution, the concentration of potassium hydroxide is 0.2g/ml (being that 1.0g potassium hydroxide solid is dissolved in the 5.0ml ethanolic soln), dropwise continue to reflux 15～20 minutes after stopped reaction, the cooling suction filtration, black powder be tetraphenylcyclopentadienone; With it at ethanol: recrystallization in the mixed solvent of toluene=1: 1 (volume ratio).
Described at ethanol: recrystallization is specially in the mixed solvent of toluene=1: 1: 7.0g tetraphenylcyclopentadienone crude product is in the mixed solvent of 75ml ethanol, 75ml toluene, and heated and stirred to dissolving back heat filtering fully gets product.
Described hot ethanol is that temperature is 70～75 ℃ a ethanol, is placed on before the adding in the water-bath, and is standby.
The contents of ethylene of described methyl ethylene silicon raw rubber is 10%, prepare by the following method: in 250ml four-hole round-bottomed flask, add 31.0g octamethylcyclotetrasiloxane and 4.0g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, make above-mentioned two kinds of reactant ring-opening polymerizations get product.Concrete steps are: at 1.33kPa, 40 ℃ were dewatered 30～40 minutes down with reactant; Recover normal pressure, add 0.2～0.3g Tetramethylammonium hydroxide silicon alkoxide, the drying nitrogen bubbling, 70～75 ℃ were reacted 30～35 minutes down; Add end-capping reagent hexamethyldisiloxane 0.2～0.25g again, be warming up to 90～100 ℃, reacted 2～2.5 hours, promptly get water white transparency heavy-gravity methyl ethylene silicon raw rubber.Methyl ethylene silicon raw rubber n-hexane dissolution with obtaining adds ethanol again, and silicon raw rubber is separated out, to remove small molecules and the catalyzer in the silicon raw rubber.
Described Tetramethylammonium hydroxide silicon alkoxide prepares by the following method: Tetramethylammonium hydroxide and octamethylcyclotetrasiloxane are placed round-bottomed flask by mass ratio at 1: 50, under decompression 1.33kPa and nitrogen bubble, be warming up to 60～70 ℃, dewatered 2～4 hours.
Tetraphenyl phenyl graft polysiloxane of the present invention can produce the big ∏ key of delocalization conjugation of electron rich owing to side chain aryl high concentration, has excellent mechanical property, resistance toheat and chromatographic separation selectivity, can be used as the stationary phase of gas-chromatography.Rely on its stronger inducing action and London force, except that separable general hydrocarbons, to the replacement isomer of benzene, condensed-nuclei aromatics and azepine, oxa-, thia condensed-nuclei aromatics, environmental pollutant such as polycyclic aromatic hydrocarbons have excellent separation selectivity.
Stationary phase novel structure of the present invention.The investigator in past just is grafted to phenyl ring on the polysiloxane long-chain as a unit, and the present invention is grafted to tetraphenyl phenyl on the methyl ethylene silicon raw rubber as a structural unit, small amount of ethylene base residual in the stationary phase can at high temperature cause crosslinked, make the temperature tolerance of capillary column higher, column bleeding is littler.
Description of drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of tetraphenyl phenyl graft polysiloxane of the present invention;
Fig. 2 is the separate colors spectrogram of experimental example 1;
Fig. 3 is the separate colors spectrogram of experimental example 2;
Fig. 4 is the separate colors spectrogram of experimental example 3
Fig. 5 is the separate colors spectrogram of experimental example 4.
Embodiment
The present invention is further illustrated below in conjunction with embodiment and experimental example:
(1) tetraphenylcyclopentadienone is synthetic: add 7.0g benzil and 7.0g dibenzyl ketone in three mouthfuls of round-bottomed flasks of 100ml, add the 50ml hot ethanol again; Logical nitrogen protection, heated and stirred, when the approaching boiling of solution, the ethanolic soln of slow Dropwise 5 .0ml potassium hydroxide in solution, the concentration of potassium hydroxide is 0.2g/ml (1.0g potassium hydroxide is dissolved in the 5.0ml ethanol), dropwise continue to reflux 15 minutes after stopped reaction, the cooling suction filtration, black powder be tetraphenylcyclopentadienone; With it at ethanol: recrystallization in the mixed solvent of toluene=1: 1, dry in the air, standby.
(2) preparation of methyl ethylene silicon raw rubber: in 250ml four-hole round-bottomed flask, add 31.0g octamethylcyclotetrasiloxane and 4.0g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, make above-mentioned two kinds of reactant ring-opening polymerizations get product.Concrete steps are: at 1.33kPa, 40 ℃ were dewatered 30 minutes down with reactant; Recover normal pressure, add 0.3g Tetramethylammonium hydroxide silicon alkoxide and (Tetramethylammonium hydroxide and octamethylcyclotetrasiloxane are placed round-bottomed flask by mass ratio at 1: 50, under decompression 1.33kPa and nitrogen bubble, be warming up to 60～70 ℃, dewater and made in 2～4 hours), the drying nitrogen bubbling, 70 ℃ were reacted 30 minutes down; Add end-capping reagent hexamethyldisiloxane 0.2g again, be warming up to 100 ℃, reacted 2 hours, promptly get water white methyl ethylene silicon raw rubber.Methyl ethylene silicon raw rubber n-hexane dissolution with obtaining adds ethanol again, and silicon raw rubber is separated out, to remove small molecules and the catalyzer in the silicon raw rubber.
(3) preparation of tetraphenyl phenyl graft polysiloxane: in 250ml four-hole round-bottomed flask, add the anhydrous phenyl ether of 50ml, 7.00g methyl ethylene silicon raw rubber and 2.87g tetraphenylcyclopentadienone; Logical nitrogen protection is stirred down and slowly is heated to 259 ℃, and insulation reaction becomes transparent incarnadine to solution by opaque black; Continue reaction 30 minutes, stopped reaction uses separating funnel that upper strata thickness product is told after being cooled to 100 ℃; The thickness product of gained is placed beaker, add toluene, heated and stirred is fully dissolved the thickness product, and cold slightly back adds methyl alcohol makes product separate out (toluene: the methyl alcohol volume ratio is about 1: 1); With product classification washing 3～5 times as stated above,, obtain the product of molecular weight homogeneous to remove small molecular weight impurity; Filter with ether dissolution, removal of solvent under reduced pressure promptly gets tetraphenyl phenyl graft polysiloxane again.
The proton magnetic spectrum resonance figure of tetraphenyl phenyl graft polysiloxane of the present invention as shown in Figure 1.
(1) tetraphenylcyclopentadienone is synthetic: add 7.0g benzil and 7.0g dibenzyl ketone in three mouthfuls of round-bottomed flasks of 100ml, add the 50ml hot ethanol again; Logical nitrogen protection, heated and stirred, when the approaching boiling of solution, the ethanolic soln of slow Dropwise 5 .0ml potassium hydroxide in solution, the concentration of potassium hydroxide is 0.2g/ml (1.0g potassium hydroxide is dissolved in the 5.0ml ethanol), dropwise continue to reflux 20 minutes after stopped reaction, the cooling suction filtration, black powder be tetraphenylcyclopentadienone; With it at ethanol: recrystallization in the mixed solvent of toluene=1: 1, dry in the air, standby.
(2) preparation of methyl ethylene silicon raw rubber: in 250ml four-hole round-bottomed flask, add 31.0g octamethylcyclotetrasiloxane and 4.0g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, make above-mentioned two kinds of reactant ring-opening polymerizations get product.Concrete steps are: at 1.33kPa, 40 ℃ were dewatered 40 minutes down with reactant; Recover normal pressure, add 0.2g Tetramethylammonium hydroxide silicon alkoxide and (Tetramethylammonium hydroxide and octamethylcyclotetrasiloxane are placed round-bottomed flask by mass ratio at 1: 50, under decompression 1.33kPa and nitrogen bubble, be warming up to 60～70 ℃, dewater and made in 2～4 hours), the drying nitrogen bubbling, 75 ℃ were reacted 35 minutes down; Add end-capping reagent hexamethyldisiloxane 0.25g again, be warming up to 90 ℃ of reactions 2.5 hours, promptly get water white methyl ethylene silicon raw rubber.Methyl ethylene silicon raw rubber n-hexane dissolution with obtaining adds ethanol again, and silicon raw rubber is separated out, to remove small molecules and the catalyzer in the silicon raw rubber.
(3) preparation of tetraphenyl phenyl graft polysiloxane: in 250ml four-hole round-bottomed flask, add the anhydrous phenyl ether of 50ml, 7.00g methyl ethylene silicon raw rubber and 2.87g tetraphenylcyclopentadienone; Logical nitrogen protection is stirred down and slowly is heated to 253 ℃, and insulation reaction becomes transparent incarnadine to solution by opaque black; Continue reaction 33 minutes, stopped reaction uses separating funnel that upper strata thickness product is told after being cooled to 100 ℃; The thickness product of gained is placed beaker, add toluene, heated and stirred is fully dissolved the thickness product, and cold slightly back adds methyl alcohol makes product separate out (toluene: the methyl alcohol volume ratio is about 1: 1); With product classification washing 5 times as stated above,, obtain the product of molecular weight homogeneous to remove small molecular weight impurity; Filter with ether dissolution, removal of solvent under reduced pressure promptly gets tetraphenyl phenyl graft polysiloxane again.
(1) tetraphenylcyclopentadienone is synthetic: add 7.0g benzil and 7.0g dibenzyl ketone in three mouthfuls of round-bottomed flasks of 100ml, add the 50ml hot ethanol again; Logical nitrogen protection, heated and stirred, when the approaching boiling of solution, the ethanolic soln of slow Dropwise 5 .0ml potassium hydroxide in solution, the concentration of potassium hydroxide is 0.2g/ml (1.0g potassium hydroxide is dissolved in the 5.0ml ethanol), dropwise continue to reflux 16 minutes after stopped reaction, the cooling suction filtration, black powder be tetraphenylcyclopentadienone; Then with it at ethanol: recrystallization in the mixed solvent of toluene=1: 1, dry in the air, standby.
(2) preparation of methyl ethylene silicon raw rubber: in 250ml four-hole round-bottomed flask, add 31.0g octamethylcyclotetrasiloxane and 4.0g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, make above-mentioned two kinds of reactant ring-opening polymerizations get product.Concrete steps are: at 1.33kPa, 40 ℃ were dewatered 35 minutes down with reactant; Recover normal pressure, add 0.25g Tetramethylammonium hydroxide silicon alkoxide and (Tetramethylammonium hydroxide and octamethylcyclotetrasiloxane are placed round-bottomed flask by mass ratio at 1: 50, under decompression 1.33kPa and nitrogen bubble, be warming up to 60～70 ℃, dewater and made in 2～4 hours), the drying nitrogen bubbling, 70～75 ℃ were reacted 30 minutes down; Add end-capping reagent hexamethyldisiloxane 0.22g again, be warming up to 95 ℃ of reactions 2 hours, promptly get water white methyl ethylene silicon raw rubber.Methyl ethylene silicon raw rubber n-hexane dissolution with obtaining adds ethanol again, and silicon raw rubber is separated out, to remove small molecules and the catalyzer in the silicon raw rubber.
(3) preparation of tetraphenyl phenyl graft polysiloxane: in 250ml four-hole round-bottomed flask, add the anhydrous phenyl ether of 50ml, 7.00g methyl ethylene silicon raw rubber and 2.87g tetraphenylcyclopentadienone; Logical nitrogen protection is stirred down and slowly is heated to 250～260 ℃, and insulation reaction becomes transparent incarnadine to solution by opaque black; Continue reaction 30～35 minutes, stopped reaction uses separating funnel that upper strata thickness product is told after being cooled to 100 ℃; The thickness product of gained is placed beaker, add toluene, heated and stirred is fully dissolved the thickness product, and cold slightly back adds methyl alcohol makes product separate out (toluene: the methyl alcohol volume ratio is about 1: 1); With product classification washing 3 times as stated above,, obtain the product of molecular weight homogeneous to remove small molecular weight impurity; Filter with ether dissolution, removal of solvent under reduced pressure promptly gets tetraphenyl phenyl graft polysiloxane again.
Embodiment 4 preparation tetraphenyl phenyl graft polysiloxanes, the preparation method is as follows:
(1) tetraphenylcyclopentadienone is synthetic: add 7.0g benzil and 7.0g dibenzyl ketone in three mouthfuls of round-bottomed flasks of 100ml, add the 50ml hot ethanol again; Logical nitrogen protection, heated and stirred, when the approaching boiling of solution, the ethanolic soln of slow Dropwise 5 .0ml potassium hydroxide in solution, the concentration of potassium hydroxide is 0.2g/ml (1.0g potassium hydroxide is dissolved in the 5.0ml ethanol), dropwise continue to reflux 17 minutes after stopped reaction, the cooling suction filtration, black powder be tetraphenylcyclopentadienone; Then with it at ethanol: recrystallization in the mixed solvent of toluene=1: 1, dry in the air, standby.
(2) preparation of methyl ethylene silicon raw rubber: in 250ml four-hole round-bottomed flask, add 31.0g octamethylcyclotetrasiloxane and 4.0g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, make above-mentioned two kinds of reactant ring-opening polymerizations get product.Concrete steps are: at 1.33kPa, 40 ℃ were dewatered 33 minutes down with reactant; Recover normal pressure, add 0.28g Tetramethylammonium hydroxide silicon alkoxide and (Tetramethylammonium hydroxide and octamethylcyclotetrasiloxane are placed round-bottomed flask by mass ratio at 1: 50, under decompression 1.33kPa and nitrogen bubble, be warming up to 60～70 ℃, dewater and made in 2～4 hours), the drying nitrogen bubbling, 70～75 ℃ were reacted 32 minutes down; Add end-capping reagent hexamethyldisiloxane 0.24g again, be warming up to 100 ℃ of reactions 2 hours, promptly get water white methyl ethylene silicon raw rubber.Methyl ethylene silicon raw rubber n-hexane dissolution with obtaining adds ethanol again, and silicon raw rubber is separated out, to remove small molecules and the catalyzer in the silicon raw rubber.
(3) preparation of tetraphenyl phenyl graft polysiloxane: in 250ml four-hole round-bottomed flask, add the anhydrous phenyl ether of 50ml, 7.00g methyl ethylene silicon raw rubber and 2.87g tetraphenylcyclopentadienone; Logical nitrogen protection is stirred down and slowly is heated to 255 ℃, and insulation reaction becomes transparent incarnadine to solution by opaque black; Continue reaction 30 minutes, stopped reaction uses separating funnel that upper strata thickness product is told after being cooled to 100 ℃; The thickness product of gained is placed beaker, add toluene, heated and stirred is fully dissolved the thickness product, and cold slightly back adds methyl alcohol makes product separate out (toluene: the methyl alcohol volume ratio is about 1: 1); With product classification washing 5 times as stated above,, obtain the product of molecular weight homogeneous to remove small molecular weight impurity; Filter with ether dissolution, removal of solvent under reduced pressure promptly gets tetraphenyl phenyl graft polysiloxane again.
(1) tetraphenylcyclopentadienone is synthetic: add 7.0g benzil and 7.0g dibenzyl ketone in three mouthfuls of round-bottomed flasks of 100ml, add the 50ml hot ethanol again; Logical nitrogen protection, heated and stirred, when the approaching boiling of solution, the ethanolic soln of slow Dropwise 5 .0ml potassium hydroxide in solution, the concentration of potassium hydroxide is 0.2g/ml (1.0g potassium hydroxide is dissolved in the 5.0ml ethanol), dropwise continue to reflux 18 minutes after stopped reaction, the cooling suction filtration, black powder be tetraphenylcyclopentadienone; With it at ethanol: recrystallization in the mixed solvent of toluene=1: 1, dry in the air, standby.
(2) preparation of methyl ethylene silicon raw rubber: in 250ml four-hole round-bottomed flask, add 31.0g octamethylcyclotetrasiloxane and 4.0g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, make above-mentioned two kinds of reactant ring-opening polymerizations get product.Concrete steps are: at 1.33kPa, 40 ℃ were dewatered 38 minutes down with reactant; Recover normal pressure, add 0.22g Tetramethylammonium hydroxide silicon alkoxide and (Tetramethylammonium hydroxide and octamethylcyclotetrasiloxane are placed round-bottomed flask by mass ratio at 1: 50, under decompression 1.33kPa and nitrogen bubble, be warming up to 60～70 ℃, dewater and made in 2～4 hours), the drying nitrogen bubbling, 73 ℃ were reacted 30 minutes down; Add end-capping reagent hexamethyldisiloxane 0.2g again, be warming up to 100 ℃ of reactions 2 hours, promptly get water white methyl ethylene silicon raw rubber.Methyl ethylene silicon raw rubber n-hexane dissolution with obtaining adds ethanol again, and silicon raw rubber is separated out, to remove small molecules and the catalyzer in the silicon raw rubber.
(3) preparation of tetraphenyl phenyl graft polysiloxane: in 250ml four-hole round-bottomed flask, add the anhydrous phenyl ether of 50ml, 7.00g methyl ethylene silicon raw rubber and 2.87g tetraphenylcyclopentadienone; Logical nitrogen protection is stirred down and slowly is heated to 250 ℃, and insulation reaction becomes transparent incarnadine to solution by opaque black; Continue reaction 35 minutes, stopped reaction uses separating funnel that upper strata thickness product is told after being cooled to 100 ℃; The thickness product of gained is placed beaker, add toluene, heated and stirred is fully dissolved the thickness product, and cold slightly back adds methyl alcohol makes product separate out (toluene: the methyl alcohol volume ratio is about 1: 1); With product classification washing 4 times as stated above,, obtain the product of molecular weight homogeneous to remove small molecular weight impurity; Filter with ether dissolution, removal of solvent under reduced pressure promptly gets tetraphenyl phenyl graft polysiloxane again.
(1) tetraphenylcyclopentadienone is synthetic: add 7.0g benzil and 7.0g dibenzyl ketone in three mouthfuls of round-bottomed flasks of 100ml, add the 50ml hot ethanol again; Logical nitrogen protection, heated and stirred, when the approaching boiling of solution, the ethanolic soln of slow Dropwise 5 .0ml potassium hydroxide in solution, the concentration of potassium hydroxide is 0.2g/ml (1.0g potassium hydroxide is dissolved in the 5.0ml ethanol), dropwise continue to reflux 19 minutes after stopped reaction, the cooling suction filtration, black powder be tetraphenylcyclopentadienone; With it at ethanol: recrystallization in the mixed solvent of toluene=1: 1, dry in the air, standby.
(2) preparation of methyl ethylene silicon raw rubber: in 250ml four-hole round-bottomed flask, add 31.0g octamethylcyclotetrasiloxane and 4.0g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, make above-mentioned two kinds of reactant ring-opening polymerizations get product, concrete steps are: at 1.33kPa, 40 ℃ were dewatered 30 minutes down with reactant; Recover normal pressure, add 0.3g Tetramethylammonium hydroxide silicon alkoxide and (Tetramethylammonium hydroxide and octamethylcyclotetrasiloxane are placed round-bottomed flask by mass ratio at 1: 50, under decompression 1.33kPa and nitrogen bubble, be warming up to 60～70 ℃, dewater and made in 2～4 hours), the drying nitrogen bubbling, 70 ℃ were reacted 30 minutes down; Add end-capping reagent hexamethyldisiloxane 0.25g again, be warming up to 100 ℃ of reactions 2 hours, promptly get water white methyl ethylene silicon raw rubber.Methyl ethylene silicon raw rubber n-hexane dissolution with obtaining adds ethanol again, and silicon raw rubber is separated out, to remove small molecules and the catalyzer in the silicon raw rubber.
(3) preparation of tetraphenyl phenyl graft polysiloxane: in 250ml four-hole round-bottomed flask, add the anhydrous phenyl ether of 50ml, 7.00g methyl ethylene silicon raw rubber and 2.87g tetraphenylcyclopentadienone; Logical nitrogen protection is stirred down and slowly is heated to 260 ℃, and insulation reaction becomes transparent incarnadine to solution by opaque black; Continue reaction 30 minutes, stopped reaction uses separating funnel that upper strata thickness product is told after being cooled to 100 ℃; The thickness product of gained is placed beaker, add toluene, heated and stirred is fully dissolved the thickness product, and cold slightly back adds methyl alcohol makes product separate out (toluene: the methyl alcohol volume ratio is about 1: 1); With product classification washing 3 times as stated above,, obtain the product of molecular weight homogeneous to remove small molecular weight impurity; Filter with ether dissolution, removal of solvent under reduced pressure promptly gets tetraphenyl phenyl graft polysiloxane again.
Experimental example 1 tetraphenyl phenyl graft polysiloxane of the present invention is as the application of stationary phase:
Stationary method is coated with the stain stationary phase, kapillary column length 30m, and internal diameter 0.25mm, thickness of liquid film 0.5 μ m uses dicumyl peroxide as linking agent, causes crosslinked down at 150 ℃.The crosslinking column that makes is analyzed benzene class substituent.Chromatographic condition: carrier gas is a nitrogen, and its linear velocity is 10cm/s, and detector is a flame ionization ditector, and the sampler temperature is 250 ℃, and detector temperature is 250 ℃.Kept 3 minutes at 50 ℃, then with the speed temperature programming to 220 of 10 ℃/min ℃.The separate colors spectrogram as shown in Figure 2, peak preface among the figure: 1. benzene; 2. toluene; 3.1-chlorinated benzene; 4.1-ethylbenzene; 5. m-xylene; 6.1-chloro-4-methylbenzene; 7.1,2, the 4-Three methyl Benzene; 8.1, the 3-dichlorobenzene; 9.1-butylbenzene; 10.1-oil of mirbane; 11.1-methyl-2-oil of mirbane; 12.1, the 4-dibromobenzene; 13.1-methyl-4-oil of mirbane; 14.1-chloro-2-oil of mirbane; 15.1-bromo-4-oil of mirbane; 16. biphenyl; 17. ditane; 18.1-methyl-2, the 4-dinitrobenzene; 19.1-chloro-2, the 4-dinitrobenzene.
Experimental example 2 tetraphenyl phenyl graft polysiloxanes of the present invention are as the application of stationary phase:
Chromatographic column is separated the condensed-nuclei aromatics mixture with experimental example 1.Chromatographic condition: carrier gas is a nitrogen, and its linear velocity is 7.5cm/s, and detector is a flame ionization ditector, and the sampler temperature is 330 ℃, and detector temperature is 330 ℃.Since 50 ℃, with the speed temperature programming to 300 of 5 ℃/min ℃ and 300 ℃ of constant temperature 10 minutes.The separate colors spectrogram as shown in Figure 3, peak preface among the figure: 1. naphthalane; 2. spiral shell [4.5] decane; 3.1,2,3, the 4-naphthane; 4. naphthalene; 5.2-methylnaphthalene; 6.8-hydroxyquinoline; 7. ditane; 8.1, the 2-acenaphthene; 9.2-oxyethyl group naphthalene; 10.1-nitro-naphthalene; 11.2,2 '-dihydroxybiphenyl; 12.1-hydroxyl-1, the 2-acenaphthene; 13.4-phenylphenol; 14. it is luxuriant and rich with fragrance; 15.5 hydrogen-indenes-[1,2-b] pyrimidine; 16.9, the 10-amerantrone; 17. tritane; 18. pyrene.
Experimental example 3 tetraphenyl phenyl graft polysiloxanes of the present invention are as the application of stationary phase:
Chromatographic column is with experimental example 1, the aromatics separation mixture.Chromatographic condition: carrier gas is a nitrogen, and its linear velocity is 7.5cm/s, and detector is a flame ionization ditector, and the sampler temperature is 330 ℃, and detector temperature is 330 ℃.Since 50 ℃, with the speed temperature programming to 300 of 5 ℃/min ℃ and 300 ℃ of constant temperature 20 minutes.The separate colors spectrogram as shown in Figure 4, peak preface among the figure: 1. benzaldehyde; 2.1-chloro-2-methylbenzene; 3.2,3,5,7a-tetrahydrochysene-1 hydrogen-indenes; 4. naphthalane; 5. paradibromobenzene; 6. naphthalene; 7.2-methylnaphthalene; 8.4-bromoacetophenone; 9. biphenyl; 10.1,2-two chloro-4-oil of mirbane; 11.1, the 3-dinitrobenzene; 12.1, the 2-dinitrobenzene; 13.2-bromonaphthalene; 14.1-chloro-2, the 4-dinitrobenzene; 15.1-bromo-4-(3-bromopropyl-1-alkene-2-yl) benzene; 16.1, the 3-dibenzyl ketone; 17. it is luxuriant and rich with fragrance; 18. phenyl phenacyl ketone; 19.1,2-acenaphthylene diketone; 20.1, the 10-anthraquinone; 21. tritane; 22.1,8-naphthalene acid anhydride; 23. meta-terphenyl; 24.1,8-dihydroxy-anthracene-9,10-diketone; 25.9,10-hexichol phenanthrene.
Experimental example 4 tetraphenyl phenyl graft polysiloxanes of the present invention are as the application of stationary phase:
Chromatographic column is analyzed coal tar with experimental example 1.Coal tar is one of product in the raw gas that generates of coking industry pyrolysis of coal, and its output accounts for 3%～4% of shove charge coal, and its product is black viscous fluid shape at normal temperatures and pressures.The coal-tar heavy oil density that coking is produced is higher, is 1.16～1.22g/cm
3, mainly to form by polycyclc aromatic compound, alkylaromatic hydrocarbon content is less, and high boiling component is more, Heat stability is good.
Sample is taken from Jinan Refinery, belongs to coal-tar heavy oil, obtains laboratory sample with chloroform dissolving after-filtration.Chromatographic condition: carrier gas is a nitrogen, and its linear velocity is 7.5cm/s, and detector is a flame ionization ditector, and the sampler temperature is 330 ℃, and detector temperature is 330 ℃.Since 50 ℃, with the speed temperature programming to 300 of 5 ℃/min ℃ and 300 ℃ of constant temperature 20 minutes.The separate colors spectrogram as shown in Figure 5, peak preface among the figure: 1.1-chlorinated benzene; 2.1-ethylbenzene; 3.1-chloro-4-methylbenzene; 4. phenylcarbamate; 5. cyclobutyl phenyl-1 (2H)-ketone; 6.2,3,5,7a-tetrahydrochysene-1 hydrogen-indenes; 7.3-phenylpropyl aldehyde; 8. naphthalene; 9.5 hydrogen-indenes; 10.1-methylnaphthalene; 11. biphenyl; 12.2, the 7-dimethylnaphthalene; 13. acenaphthylene; 14.1,2-dihydro acenaphthylene; 15. diphenylene-oxide; 16.9 hydrogen-fluorenes; 17.4-methyl-diphenylene-oxide; 18. dibenzothiophene; 19. it is luxuriant and rich with fragrance; 20.5 hydrogen-indeno [1,2-b] pyridine; 21.7,12-dihydro-benzo [a]-anthracene; 22. pyrene; 23. benzanthrene; 24. benzo [e] pyrene.
By above experiment as can be seen, tetraphenyl phenyl graft polysiloxane of the present invention has big relatively save power as stationary phase for the material that contains phenyl ring, and this is by the structures shape of stationary phase.The tetraphenyl phenyl group that exists on the polysiloxane long-chain has the intensive effect to aromatic hydrocarbons.With the fused-silica capillary column that is coated with the tetraphenyl phenyl graft polysiloxane stationary phase except that separable general hydrocarbons, replacement isomer to benzene, condensed-nuclei aromatics and azepine, oxa-, thia condensed-nuclei aromatics, environmental pollutant such as polycyclic aromatic hydrocarbons have excellent separation selectivity.
Claims (8)
1. tetraphenyl phenyl graft polysiloxane, its general structure is as follows:
Wherein, m, n, p are positive integer, and m: n: p=90: 2: 8, molecular weight was 8.5 ten thousand～100,000.
2. the preparation method of the described a kind of tetraphenyl phenyl graft polysiloxane of claim 1, it is characterized in that: be that tetraphenylcyclopentadienone is passed through the Diels-Alder reactive grafting to the methyl ethylene silicon raw rubber, make tetraphenyl phenyl graft polysiloxane, concrete steps are as follows: add the anhydrous phenyl ether of 50ml, 7.00g methyl ethylene silicon raw rubber and 2.87g tetraphenylcyclopentadienone in the four-hole round-bottomed flask; Logical nitrogen protection is stirred down and slowly is heated to 250～260 ℃ after feeding intake, and insulation reaction becomes transparent incarnadine to solution by opaque black; Continue reaction 30～35 minutes, stopped reaction is got upper strata thickness product after being cooled to 100 ℃; The thickness product of gained is placed beaker, add toluene, heated and stirred is fully dissolved the thickness product, and cold slightly back adds methyl alcohol separates out product; With product classification washing 3～5 times as stated above,, obtain the product of molecular weight homogeneous to remove small molecular weight impurity; Filter with ether dissolution, removal of solvent under reduced pressure promptly gets tetraphenyl phenyl graft polysiloxane again.
3. the preparation method of a kind of tetraphenyl phenyl graft polysiloxane according to claim 2, it is characterized in that, described tetraphenylcyclopentadienone is a synthetic by the following method: add 7.0g benzil and 7.0g dibenzyl ketone in three mouthfuls of round-bottomed flasks, add the 50ml hot ethanol again; Logical nitrogen protection, heated and stirred is when the approaching boiling of solution, the slow ethanolic soln of Dropwise 5 .0ml potassium hydroxide in solution, the concentration of potassium hydroxide is 0.2g/ml, dropwise continue to reflux 15～20 minutes after stopped reaction, the cooling suction filtration gets black powder and is tetraphenylcyclopentadienone; Then with it at ethanol: recrystallization in the mixed solvent of toluene=1: 1.
4. the preparation method of a kind of tetraphenyl phenyl graft polysiloxane according to claim 3, it is characterized in that: described hot ethanol is that temperature is 70～75 ℃ a ethanol, is placed on before the adding in the water-bath, and is standby.
5. the preparation method of a kind of tetraphenyl phenyl graft polysiloxane according to claim 2, it is characterized in that, the contents of ethylene of described methyl ethylene silicon raw rubber is 10%, prepare by the following method: in the four-hole round-bottomed flask, add 31.0g octamethylcyclotetrasiloxane and 4.0g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, at 1.33kPa, 40 ℃ were dewatered 30～40 minutes down with reactant; Recover normal pressure, add 0.2～0.3g Tetramethylammonium hydroxide silicon alkoxide, the drying nitrogen bubbling, 70～75 ℃ were reacted 30～35 minutes down; Add end-capping reagent hexamethyldisiloxane 0.2～0.25g again, be warming up to 90～100 ℃ of reactions 2～2.5 hours, promptly get water white transparency heavy-gravity methyl ethylene silicon raw rubber; Methyl ethylene silicon raw rubber n-hexane dissolution with obtaining adds ethanol again, and silicon raw rubber is separated out, to remove small molecules and the catalyzer in the silicon raw rubber.
6. the preparation method of a kind of tetraphenyl phenyl graft polysiloxane according to claim 5, it is characterized in that, described Tetramethylammonium hydroxide silicon alkoxide prepares by the following method: Tetramethylammonium hydroxide and octamethylcyclotetrasiloxane are placed round-bottomed flask by mass ratio at 1: 50, under decompression 1.33kPa and nitrogen bubble, be warming up to 60～70 ℃, dewatered 2～4 hours.
7. the described a kind of tetraphenyl phenyl graft polysiloxane of claim 1 is as the application of gas-chromatography stationary phase.
8. application according to claim 7, it is characterized in that, usage is as follows: be coated with the stain stationary phase as capillary gas chromatography stationary phase or stationary method, adopt dicumyl peroxide to make initiator, initiation is crosslinked down at 150 ℃, then the crosslinking column that makes is used to analyze benzene class substituent and condensed ring, polycyclic aromatic hydrocarbons.
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