CN105504186A - Preparing method and application of 3,4-bi(4-cyanophenyl)-2,5-diphenyl phenyl grafted polysiloxane - Google Patents

Preparing method and application of 3,4-bi(4-cyanophenyl)-2,5-diphenyl phenyl grafted polysiloxane Download PDF

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CN105504186A
CN105504186A CN201610004580.0A CN201610004580A CN105504186A CN 105504186 A CN105504186 A CN 105504186A CN 201610004580 A CN201610004580 A CN 201610004580A CN 105504186 A CN105504186 A CN 105504186A
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phenyl
bis
phenylbenzene
cyclopentadienone
cyano
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吴波
贺新新
王欢
韩雪
王冰
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Shandong University
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Shandong University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography

Abstract

The invention provides a preparing method and application of 3,4-bi(4-cyanophenyl)-2,5-diphenyl phenyl grafted polysiloxane. The general structural formula is shown in the abstract figure, wherein m:n:p=85:12:3. N-methyl pyrrolidone serves as the solvent, palladium chloride dehydrate and triphenyl phosphine serve as the catalyst, substitution reaction is conducted in the slightly alkaline environment provided by Na2CO3, and a bromine atom on 3,4-bi(4-bromophenyl)-2,5-diphenyl cyclopentadiene ketone phenyl is substituted by a cyanogroup on potassium ferrocyanide to generate 3,4-bi(4-cyanophenyl)-2,5-diphenyl cyclopentadiene ketone; finally, diphenyl ether serves as the solvent, Diels-Alder addition reaction is conducted between 3,4-bi(4-cyanophenyl)-2,5-diphenyl cyclopentadiene ketone and methyl vinyl silicone rubber at high temperature to generate 3,4-bi(4-cyanophenyl)-2,5-diphenyl phenyl grafted polysiloxane. The invention also discloses the application of 3,4-bi(4-cyanophenyl)-2,5-diphenyl phenyl grafted polysiloxane as a gas chromatography stationary phase.

Description

A kind of preparation method of 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane and application
Technical field
The present invention relates to a kind of preparation method and application of 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane, belong to organic compound synthesis technical field.
Background technology
The appearance of, structural similitude compound close along with new environmental pollutant and various high molecular, boiling point, the separation of people to gas-chromatography is had higher requirement.Stationary phase is the core that gas-chromatography is separated, and develop the post effect made new advances high, temperature tolerance is good, has important theory significance and using value to structure proximate, chromatographic stationary phases that polar material separation selectivity that boiling point is close is strong.Phenyl graft polysiloxane stationary phase depends on the polarizability of phenyl group to a great extent for the separation selectivity of polar material (particularly to the isomer mixture of structure proximate), namely comparatively responsive between polar material and stationary phase side-chain radical induced dipole reactive force.Increase the polarizability of polysiloxane side-chain radical, have very important effect (J.Sep.Sci., 2001,24 (6), 473-476) for the separation selectivity improving stationary phase.
A lot of for the research of polysiloxane stationary phase both at home and abroad, these stationary phase to environmental pollutants in the unsatisfactory (J.Sep.Sci. of analytical results of arene isomer, 2003,26 (15-16), 1436-1442) be necessary to prepare and have more specific New Stationary Phase with analyte Intermolecular Forces, to obtaining a series of gas-chromatography Special fixing phasing being suitable for aromatic series environmental pollutant and Industrial products and analyzing.
3, 4-bis-(4-cyano-phenyl)-2, the side chain of 5-phenylbenzene phenyl graft polysiloxane exists the polarizable tetraphenyl phenyl group containing five phenyl ring, be connected with singly-bound between phenyl ring, the large π key of delocalization conjugation of electron rich can be produced, and on many phenyl conjugate ring, introduce cyano group polar substitution group, while adding polysiloxane side-chain radical polarizability, also it is made to strengthen containing the various polarity of unsaturated double-bond and the inducing action of non-polar compound sample molecule, with conventional phenyl, it is abundanter that methyl polysiloxane (OV-17) compares the mechanism of action, selectivity also can better (JournalofMicrocolumnSeparations, 2005, 1 (3), 142-149).
The basic raw material of synthesis 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane is 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone.Phenyl aldehyde carries out reoxidizing generation benzil after benzoic condensation obtains bitter almond oil camphor by the many employings of synthetic method with the cyclopentadienone of many phenyl substituents, benzil and dibenzyl ketone Reactive Synthesis cyclopentadienone (JournalofChemicalEducation, 2015, 92 (8), 1381-1384), but this method is not suitable for the synthesis of many phenyl substituted-cyclopentadienyl ketone of polar functionalities, this is because the phenyl aldehyde containing strong electron-withdrawing group group not easily carries out benzoic condensation generate corresponding bitter almond oil camphor (high correspondence course journal (natural science edition), 1995, 4, 3-5).
Summary of the invention
For solving the problem, the present invention utilizes 3, 4-bis-(4-bromophenyl)-2, the feature that bromine atoms on 5-phenylbenzene cyclopentadienone is easily substituted under high-temperature catalytic condition, the compound Reactive Synthesis of itself and cyano-containing is made to go out 3, 4-bis-(4-cyano-phenyl)-2, 5-phenylbenzene cyclopentadienone, reacted by Diels-Alder again, to 3 of conjugated dienes be contained, 4-bis-(4-cyano-phenyl)-2, 5-phenylbenzene cyclopentadienone and the methyl polysiloxane (C glue) containing vinyl sidechain, high temperature addition reaction is carried out in phenyl ether solvent, synthesize 3, 4-bis-(4-cyano-phenyl)-2, the polysiloxane of 5-phenylbenzene phenyl graft, can be used as GC stationary phase.This stationary phase temperature tolerance is good, has excellent separation selectivity for environmental pollutant such as benzene class substituent, condensed-nuclei aromaticss.
One is the object of the present invention is to provide to prepare the method for 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane.The feature of the method applied in the present invention is in synthesis cyclopentadienone process, utilize 3,4-bis-(4-bromophenyl)-2, the bromine low-pole group of 5-phenylbenzene cyclopentadienone, easily by the feature that strong polar group replaces under high temperature and catalyzer exist, replaces bromine substituent by cyano group, synthesize 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone, the strong polar group overcome containing electron withdrawing group not easily carries out the shortcoming of benzoic condensation.Again by under high temperature 3,4-bis-(4-cyano-phenyl)-2, the vinyl dienophile of 5-phenylbenzene cyclopentadienone divinyl macromer and methylvinyl-polysiloxane side chain carries out Diels-Alder addition reaction and obtains 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane side chain, present method has raw material and is easy to get, and synthesis technique is simple, and separating-purifying is feature easily.
The present invention with N-Methyl pyrrolidone (NMP) for solvent (this solvent evaporates degree is low, and thermostability, chemical stability are all good), with two water Palladous chloride (PdCl 22H 2o) and triphenyl phosphorus (triphenylphosphine) be that (two kinds of catalyst mix use catalyzer, the mechanism of action is abundanter, react faster, more thorough), bromine atoms on 3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone phenyl is replaced by the cyano group on yellow prussiate of potash and obtains 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone.With phenyl ether (diphenylether) for solvent, under high temperature 3,4-bis-(4-cyano-phenyl)-2, there is Diels-Alder addition reaction and obtain 3 in 5-phenylbenzene cyclopentadienone and methyl ethylene silicon raw rubber, 4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane.The polysiloxane stationary method of synthesis is coated with stain and on capillary tube inner wall, makes capillary gas chromatographic column, for the analysis of actual sample.
Reaction formula of the present invention as shown in Figure 7.
The present invention is achieved by the following technical solutions:
The present invention studies discovery:
3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone can be used for synthesis 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane.
3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone can be used for synthesis 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone.
3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone also can be used for the many phenyl substituted-cyclopentadienyl ketone synthesizing polar functionalities.
Present invention also offers a kind of preparation method of 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone,
With 3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone for raw material, by cyanalation Reactive Synthesis 3,4-bis-(4-cyano-phenyl)-2, the 5-phenylbenzene cyclopentadienone of many phenyl conjugation bromine in ring.
Preferably, described cyanalation reaction conditions is: under high temperature and catalyzer existent condition, 3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone and ferrocyanide nak response.
Preferably, described catalyzer is two water Palladous chloride PdCl 22H 2the mixture of O and triphenyl phosphorus triphenylphosphine.
Preferably, the mol ratio of described 3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone, yellow prussiate of potash, two water Palladous chlorides, triphenyl phosphorus is 1:0.39 ~ 0.42:0.01:0.03;
Preferably, described hot conditions is 140 DEG C ~ 160 DEG C.
Present invention also offers a kind of preparation method of 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane,
With 3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone for raw material, by cyanalation Reactive Synthesis 3,4-bis-(4-cyano-phenyl)-2, the 5-phenylbenzene cyclopentadienone of many phenyl conjugation bromine in ring;
With 3,4-bis-of above-mentioned synthesis (4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone and containing the methyl polysiloxane of vinyl sidechain for raw material, high temperature addition, synthesis 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane.
Preferably, described high temperature addition reaction is Diels-Alder reaction.
Concrete steps are as follows
(1) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone is prepared
3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone, yellow prussiate of potash, two water Palladous chlorides, triphenyl phosphorus, anhydrous sodium carbonate, N-Methyl pyrrolidone is added successively, at N in reactor 2the lower heated and stirred 7h of protection, temperature controls at about 140 DEG C.Leave standstill the rear suction filtration of cooling, crude product recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1) obtains black solid powdery product and is 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone, productive rate: 75% ~ 82%, fusing point: 230 ~ 232 DEG C.
(2) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane is prepared
Methyl ethylene silicon raw rubber is added successively, phenyl ether, at N in reactor 2the lower stirring heating of protection, after silicon raw rubber all dissolves, add 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone, continue to heat up, temperature controls at about 240 DEG C.There is a large amount of bubble to produce in reaction process, treat that solution colour becomes transparent burgundy from opaque black, and when reaction system bubble-free produces, stopped reaction.Leave standstill, be cooled to about 100 DEG C, pour product into separating funnel, after being cooled to room temperature, solution is divided into two-layer.Take out upper strata clear yellow viscous thing, with toluene and methanol (V/V=1:2) classification 3 ~ 5 times, removing low molecular weight substance.Finally add ether dissolution and filter, after solvent flashing, the yellow transparent dope that vacuum-drying obtains is 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane, productive rate 28% ~ 34%.
In above-mentioned preparation method described in step (1) 3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone presses document (Synlett, 2011,2011 (09), 1293-1295) synthesis.
In above-mentioned preparation method described in step (1) 3, the mol ratio of 4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone, yellow prussiate of potash, anhydrous sodium carbonate, two water Palladous chlorides, triphenyl phosphorus is 1:0.39 ~ 0.42:0.39 ~ 0.42:0.01:0.03.
The preparation of the methyl ethylene silicon raw rubber described in step (2) with reference to (organosilicon macromolecule and application [M] thereof. Chemical Industry Press .2004,79-80) synthesis.
Methyl ethylene silicon raw rubber described in step (2), nucleus magnetic resonance 1h composes calculation result and shows that its vinyl chain link molar content is 15%.
Methyl ethylene silicon raw rubber medium vinyl chain link described in step (2), 3,4-bis-(4-cyano-phenyl)-2,5-the mol ratio of phenylbenzene cyclopentadienone be 1:1.1 ~ 1.2.
The present invention studies discovery:
3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane can be used for preparative gas chromatography stationary phase.
Concrete grammar is as follows: take methylene dichloride as solvent, be mixed with the polymers soln of 0.5% (W/V), add account for polymer quality 5% dicumyl peroxide as initiator, stationary method is coated with stain in the elastic quartz capillary tube inwall of long 30m, internal diameter 0.25mm, obtains the capillary chromatographic column that thickness of liquid film is about 0.31 μm.Logical N 2under condition, 40 DEG C keep 30min, keep 2h with the ramp to 160 of 1 DEG C/min DEG C, now initiator initiation stationary phase is cross-linked, again with the ramp to 360 DEG C of 1 DEG C/min, keep the obtained crosslinked capillary chromatographic column of 12h, obtained crosslinking column is used for actual sample analysis.
Of the present invention 3,4-bis-(4-cyano-phenyl)-2, the benzene containing 4 benzene ring substitution groups larger for volume is grafted on linear polysiloxane side chain by 5-phenylbenzene phenyl graft polysiloxane as a whole, space steric effect can increase antioxidant property and the heat resistance (J.Sep.Sci. of polymkeric substance, 2002,25 (1-2), 60 – 66).Due to side-chain benzene ring high concentration, can produce the large π key of delocalization conjugation of electron rich, the electronic cloud deformability of side-chain radical is better than single phenyl, and (polarizability calculating single phenyl by literature method is this this stationary phase 3,4-bis-(4-cyano-phenyl)-2,5-the polarizability of diphenyl benzene base side chain be jACS, 1979,101 (24), 7206-7213), can strengthen with the dispersion interaction power of nonpolar sample molecule and with the induced dipole reactive force of polarity sample molecule and dispersion interaction power.In addition, side-chain radical, also with cyano group polar group, can strengthen the polarizability to sample molecule.Therefore, as compared to the low-pole substituted-phenyl graft polysiloxane GC stationary phase such as conventional phenyl and bromine, new polymers side chain polarizability increases, can be stronger with separated sample molecule reactive force, separation selectivity can be better, and heat resistance also improves simultaneously.According to " similar mix " principle selecting chromatographic stationary phases, New Stationary Phase should have excellent separation selectivity for environmental pollutant such as benzene class substituent, condensed-nuclei aromaticss.
Accompanying drawing explanation
Fig. 1 is 3,4-bis-(4-cyano-phenyl)-2,5-proton nmr spectra of phenylbenzene phenyl graft polysiloxane prepared by the embodiment of the present invention 1.
Fig. 2 is 3,4-bis-(4-cyano-phenyl)-2,5-infrared spectrogram of phenylbenzene phenyl graft polysiloxane prepared by the embodiment of the present invention 1.
Fig. 3 is the Separation of Benzene substituent sample chromatogram figure of Application Example 1.
Fig. 4 is the aromatics separation blend sample color atlas of Application Example 2.
Fig. 5 is the separation condensed-nuclei aromatics sample chromatogram figure of Application Example 3.
Fig. 6 is the separating and cracking ethene sample chromatogram figure of Application Example 4.
Fig. 7 is the building-up reactions equation of the present invention 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane.
Wherein, methyl ethylene silicon raw rubber medium vinyl chain link molar content: (n+p)/(m+n+p+2) × 100%.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1:
(1) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone is prepared
5.0g (9.2mmol) 3 is added successively in reactor, 4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone, 1.6g (3.7mmol) yellow prussiate of potash, 0.021g (0.1mmol) two water Palladous chloride, 0.080g (0.3mmol) triphenyl phosphorus, 0.39g (3.7mmol) anhydrous sodium carbonate, 50mLN-methyl-2-pyrrolidone, at N 2the lower heated and stirred 7h of protection, temperature controls at about 140 DEG C.Leave standstill the rear suction filtration of cooling, crude product recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1) obtains 3.2g (7.0mmol) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone black solid powdery product, productive rate 75.6%, m.p:230.3 ~ 230.9 DEG C.
(2) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane is prepared
1.5g (3.0mmol) methyl ethylene silicon raw rubber, 15mL phenyl ether is added successively, at N in reactor 2the lower stirring heating of protection, after silicon raw rubber all dissolves, add 1.5g (3.5mmol) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone in reaction vessel, continue to heat up, temperature controls at about 240 DEG C.There is a large amount of bubble to produce in reaction process, treat that solution colour becomes transparent burgundy from opaque black, and when reaction system bubble-free produces, stopped reaction.Leave standstill, be cooled to about 100 DEG C, pour product into separating funnel, solution is divided into two-layer.Get upper strata clear yellow viscous thing, with toluene and methanol (V/V=1:2) classification 5 times, removing low molecular weight substance.Finally add ether dissolution and filter, after solvent flashing, the 0.8g3 that vacuum-drying obtains, 4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane yellow transparent dope, productive rate 28.6%.
3,4-bis-(4-cyano-phenyl) of the present invention-2,5-phenylbenzene phenyl graft polysiloxane proton nmr spectra as shown in Figure 1.
1HNMR：δ H(300MHz，CDCl 3，ppm)0.042(m，Si-CH 3)，6.314～6.471(s，3H，CH＝CH 2)，6.909(d，2H，Ar-H)，7.05～7.21(m，14H，Ar-H)，7.25(s，1H，Ar-H)7.29～7.39(t，2H，Ar-H)。
3,4-bis-(4-cyano-phenyl) of the present invention-2,5-phenylbenzene phenyl graft polysiloxane infrared spectra as shown in Figure 2
IR (v/cm -1): 3105,2960,2802 (Ar-H stretching vibrations); 2290 (-C ≡ N stretching vibrations); 1590,1260 (Si-CH 3stretching vibration); 1480,1400 (C=C stretching vibrations); 1100,1002 (stretching vibrations of Si-O); 890,802 (Si-(CH 3) 2stretching vibration); 692 (aromatic ring C-H flexural vibration).
Known to Fig. 1 Fig. 2, this product is expection product.
Embodiment 2:
(1) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone is prepared
10g (18.4mmol) 3 is added successively in reactor, 4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone, 3.2g (7.6mmol) yellow prussiate of potash, 0.042g (0.20mmol) two water Palladous chloride, 0.16g (0.6mmol) triphenyl phosphorus, 0.80g (7.6mmol) anhydrous sodium carbonate, 100mLN-methyl-2-pyrrolidone, at N 2the lower heated and stirred 7h of protection, temperature controls at about 140 DEG C.Leave standstill the rear suction filtration of cooling, crude product recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1) obtains 6.0g (13.8mmol) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone black solid powdery product, productive rate 75.1%, m.p:231.2 ~ 231.6 DEG C.
(2) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane is prepared
3.0g (6.0mmol) methyl ethylene silicon raw rubber, 30mL phenyl ether is added successively, at N in reactor 2stirring heating under environment, after silicon raw rubber all dissolves, adds 3.1g (7.1mmol) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone in reaction vessel, continues to heat up, and temperature controls at about 240 DEG C.There is a large amount of bubble to produce in reaction process, treat that solution colour becomes transparent burgundy from opaque black, and when reaction system bubble-free produces, stopped reaction.Leave standstill, be cooled to about 100 DEG C, pour product into separating funnel, solution is divided into two-layer.Get upper strata clear yellow viscous thing, with toluene and methanol (V/V=1:2) classification 4 times, removing low molecular weight substance.Finally add ether dissolution and filter, after solvent flashing, the 1.9g3 that vacuum-drying obtains, 4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane yellow transparent dope, productive rate 33.9%.
Embodiment 3
(1) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone is prepared
10g (18.4mmol) 3 is added successively in reactor, 4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone, 3.3g (7.8mmol) yellow prussiate of potash, 0.042g (0.2mmol) Palladous chloride, 0.16g (0.6mmol) triphenyl phosphorus, 0.81g (7.7mmol) anhydrous sodium carbonate, 100mLN-methyl-2-pyrrolidone, at N 2the lower heated and stirred 7h of protection, temperature controls at about 140 DEG C.Leave standstill the rear suction filtration of cooling, crude product recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1) obtains 6.4g (14.7mmol) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone black solid powdery product, productive rate 80.1%, m.p:230.7 ~ 231.1 DEG C.
(2) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane is prepared
3.0g (6.0mmol) methyl ethylene silicon raw rubber, 30mL phenyl ether is added successively, at N in reactor 2stirring heating under environment, after silicon raw rubber all dissolves, adds 2.9g (6.7mmol) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone in reaction vessel, continues to heat up, and temperature controls at about 240 DEG C.There is a large amount of bubble to produce in reaction process, treat that solution colour becomes transparent burgundy from opaque black, and when reaction system bubble-free produces, stopped reaction.Leave standstill, be cooled to about 100 DEG C, pour product into separating funnel, solution is divided into two-layer.Get upper strata clear yellow viscous thing, with toluene and methanol (V/V=1:2) classification 5 times, removing low molecular weight substance.Finally add ether dissolution and filter, after solvent flashing, the 1.6g3 that vacuum-drying obtains, 4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane yellow transparent dope, productive rate 28.6%.
Embodiment 4
(1) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone is prepared
20g (36.8mmol) 3 is added successively in reactor, 4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone, 6.4g (15.2mmol) yellow prussiate of potash, 0.084g (0.4mmol) Palladous chloride, 0.32g (1.2mmol) triphenyl phosphorus, 1.6g (15.2mmol) anhydrous sodium carbonate, 100mLN-methyl-2-pyrrolidone, at N 2the lower heated and stirred 7h of protection, temperature controls at about 140 DEG C.Leave standstill the rear suction filtration of cooling, crude product recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1) obtains 13g (29.9mmol) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone black solid powdery product, productive rate 81.2%, m.p:230.5 ~ 230.9 DEG C.
(2) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane is prepared
3.0g (6.0mmol) methyl ethylene silicon raw rubber, 30mL phenyl ether is added successively, at N in reactor 2stirring heating under environment, after silicon raw rubber all dissolves, adds 2.9g (6.6mmol) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone in reaction vessel, continues to heat up, and temperature controls at about 240 DEG C.There is a large amount of bubble to produce in reaction process, treat that solution colour becomes transparent burgundy from opaque black, and when reaction system bubble-free produces, stopped reaction.Leave standstill, be cooled to about 100 DEG C, pour product into separating funnel, solution is divided into two-layer.Get upper strata clear yellow viscous thing, with toluene and methanol (V/V=1:2) classification 3 times, removing low molecular weight substance.Finally add ether dissolution and filter, after solvent flashing, the 1.7g3 that vacuum-drying obtains, 4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane yellow transparent dope, productive rate 30.3%.
Embodiment 5
(1) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone is prepared
30g (55.2mmol) 3 is added successively in reactor, 4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone, 9.1g (21.6mmol) yellow prussiate of potash, 0.13g (0.6mmol) Palladous chloride, 0.54g (1.8mmol) triphenyl phosphorus, 2.5g (23.7mmol) anhydrous sodium carbonate, 200mLN-methyl-2-pyrrolidone, at N 2the lower heated and stirred 7h of protection, temperature controls at about 140 DEG C.Leave standstill the rear suction filtration of cooling, crude product recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1) obtains 19g (36.9mmol) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone black solid powdery product, productive rate 79.2%, m.p:231.0 ~ 231.8 DEG C.
(2) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane is prepared
3.0g (6.0mmol) methyl ethylene silicon raw rubber, 30mL phenyl ether is added successively, at N in reactor 2stirring heating under environment, after silicon raw rubber all dissolves, adds 3.1g (7.1mmol) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone in reaction vessel, continues to heat up, and temperature controls at about 240 DEG C.There is a large amount of bubble to produce in reaction process, treat that solution colour becomes transparent burgundy from opaque black, and when reaction system bubble-free produces, stopped reaction.Leave standstill, be cooled to about 100 DEG C, pour product into separating funnel, solution is divided into two-layer.Get upper strata clear yellow viscous thing, with toluene and methanol (V/V=1:2) classification 4 times, removing low molecular weight substance.Finally add ether dissolution and filter, after solvent flashing, the 1.8g3 that vacuum-drying obtains, 4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane yellow transparent dope, productive rate 32.1%.
Embodiment 6
(1) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone is prepared
10g (18.4mmol) 3 is added successively in reactor, 4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone, 3.2g (7.6mmol) yellow prussiate of potash, 0.042g (0.2mmol) Palladous chloride, 0.16g (0.6mmol) triphenyl phosphorus, 0.80g (7.6mmol) anhydrous sodium carbonate, 100mLN-methyl-2-pyrrolidone, at N 2the lower heated and stirred 7h of protection, temperature controls at about 140 DEG C.Leave standstill the rear suction filtration of cooling, crude product recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1) obtains 6.0g (13.8mmol) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone black solid powdery product, productive rate 75.1%, m.p:230.9 ~ 231.4 DEG C.
(2) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane is prepared
3.0g (6.0mmol) methyl ethylene silicon raw rubber, 30mL phenyl ether is added successively, at N in reactor 2the lower stirring heating of protection, after silicon raw rubber all dissolves, add 3.0g (7.0mmol) 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone in reaction vessel, continue to heat up, temperature controls at about 240 DEG C.There is a large amount of bubble to produce in reaction process, treat that solution colour becomes transparent burgundy from opaque black, and when reaction system bubble-free produces, stopped reaction.Leave standstill, be cooled to about 100 DEG C, pour product into separating funnel, solution is divided into two-layer.Get upper strata clear yellow viscous thing, with toluene and methanol (V/V=1:2) classification 4 times, removing low molecular weight substance.Finally add ether dissolution and filter, after solvent flashing, the 1.6g3 that vacuum-drying obtains, 4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane yellow transparent dope, productive rate 28.6%.
The polymkeric substance synthesized by above-described embodiment is coated with stain as GC stationary phase static state and prepares capillary gas chromatographic column in quartz capillary column inwall, the analysis of chromatographic column to actual sample is described further below.
Application Example 1:
In embodiment 13,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane as GC stationary phase, obtained chromatographic column is for separating of benzene substituent (accompanying drawing 3).
Chromatographic condition: column length 30m, internal diameter 0.25mm, thickness of liquid film 0.31 μm, sampler temperature 300 DEG C, hydrogen flame ionization detector temperature 300 DEG C, carrier gas (N 2) linear velocity 8cm/s, sample size 0.4 μ L, splitting ratio is 30:1.Temperature programming: post case temperature 70 C keeps 5min, then with the ramp to 250 DEG C of 6 DEG C/min.
Sample peak sequence: 1. benzene; 2. toluene; 3. monochloro-benzene; 4. ethylbenzene; 5. m-xylene; 6. PARA NITRO CHLOROBENZENE (PNCB); 7.1,2,4-Three methyl Benzene; 8.1,3-dichlorobenzene; 9. butylbenzene; 10. oil of mirbane; 11. Ortho Nitro Toluenes; 12. p nitro ethylbenzene; 13.1,4-dibromo-benzene; 14. para-nitrotoluene; 15. o-Nitrochlorobenzenes; 16. pairs of Nitrobromobenzene; 17. biphenyl; 18. ditanes; 19.1-methyl-2,4-dinitrobenzene; Chloro-2, the 4-dinitrobenzenes of 20.1-.
Application Example 2:
In embodiment 23,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane as GC stationary phase, obtained chromatographic column is for separating of aromatic hydrocarbons mixture (accompanying drawing 4).
Chromatographic condition: column length 30m, internal diameter 0.25mm, thickness of liquid film 0.31 μm, sampler temperature 350 DEG C, hydrogen flame ionization detector temperature 350 DEG C, carrier gas (N 2) linear velocity 9cm/s, sample size 0.4 μ L, splitting ratio is 30:1.Temperature programming: post case temperature 70 C keeps 5min, then with the ramp to 300 DEG C of 6 DEG C/min.
Sample peak sequence: 1. benzene; 2.1,3,5-Three methyl Benzene; 3. parachlorotoluene; 4. tert.-butylbenzene; 5.1,2,4-trimethylbenzene; 6. cymene; 7. n-butylbenzene; 8. santochlor; 9. orthodichlorobenzene; 10. benzyl cyanide; 11. α, α-toluene dichloride; 12. para-nitrotoluene; 13. ortho-nitrochlorobenzenes; 14. pairs of Nitrobromobenzene; 15. ditans; 16. p-nitrobenzyl chloride; 17.2,4-dinitrotoluene (DNT); Chloro-2, the 4-dinitrobenzenes of 18.1-; Fluoro-2, the 4-dinitrobenzenes of chloro-3, the 4-dinitrobenzene 20.1-of 19.1-; Bromo-2, the 4-dinitrobenzenes of 21.1-; 22. tritanes.
Application Example 3:
In embodiment 33,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane as GC stationary phase, obtained chromatographic column is for separating of condensed-nuclei aromatics mixture (accompanying drawing 5).
Chromatographic condition: column length 30m, internal diameter 0.25mm, thickness of liquid film 0.31 μm, sampler temperature 350 DEG C; Hydrogen flame ionization detector temperature 350 DEG C, carrier gas (N 2) linear velocity 10cm/s, sample size 0.4 μ L, splitting ratio is 30:1.Temperature programming: post case temperature 100 DEG C keeps 5min, then with the ramp to 320 DEG C of 6 DEG C/min.
Sample peak sequence: 1. benzene; 2. naphthane (cis); 3. tetraline; 4. naphthalene; 5. thionaphthene; 6. methylbenzene; 7. biphenyl; 8.8-hydroxyquinoline 9. ditane; 10.1,2-acenaphthene; 11.2-naphthyl ethyl ether; 12.1,4-naphthoquinones; 13. dibenzyl ether; 14.1-nitro-naphthalene; 15. parazon; 16. is luxuriant and rich with fragrance; 17. benzils; 18. tritanes; 19. benzoquinones; 20. fluoranthene; 21. pyrenes; 22.1-hydroxyanthraquinone; 23. Tetrabenzene methanes; 24.1,8-dihydroxyanthraquinone.
Application Example 4
In embodiment 43,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane as GC stationary phase, obtained chromatographic column is for separating of cracking ethylene mixture (accompanying drawing 6).
Chromatographic condition: column length 30m, internal diameter 0.25mm, thickness of liquid film 0.31 μm, sampler temperature 400 DEG C; Hydrogen flame ionization detector temperature 400 DEG C, carrier gas (N 2) linear velocity 10cm/s, sample size 0.4 μ L, splitting ratio is 30:1.Temperature programming: post case temperature 50 C keeps 5min, then with the ramp to 360 of 6 DEG C/min DEG C (retaining 15min).
3,4-bis-(4-cyano-phenyl) of the present invention-2,5-phenylbenzene phenyl graft polysiloxane as GC stationary phase, on capillary tube inner wall easy film forming, to be coated with stain performance good.Can find out that the capillary gas chromatographic column post effect made is high, separation selectivity good by accompanying drawing 3,4,5.According to " similar mix " principle, for environmental pollutant such as benzene class substituent, condensed-nuclei aromaticss, there is excellent separation selectivity.As can be seen from accompanying drawing 6, the chromatographic column temperature programming prepared in the present invention can reach 360 DEG C, and therefore chromatographic column has higher temperature tolerance.
Finally should be noted that, the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in previous embodiment, or to wherein partly carrying out equivalent replacement.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.

Claims (10)

1.3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone is 3,4-bis-(4-cyano-phenyl)-2, application in the synthesis of 5-phenylbenzene phenyl graft polysiloxane, it is characterized in that, described building-up process comprises 3, the cyanalation reaction of bromine on 4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone.
2.3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone is 3,4-bis-(4-cyano-phenyl)-2, application in the synthesis of 5-phenylbenzene cyclopentadienone, it is characterized in that, described building-up process comprises 3, the cyanalation reaction of bromine on 4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone.
3. one kind 3,4-bis-(4-cyano-phenyl)-2, the preparation method of 5-phenylbenzene cyclopentadienone, it is characterized in that, with 3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone is raw material, by cyanalation Reactive Synthesis 3,4-bis-(4-cyano-phenyl)-2, the 5-phenylbenzene cyclopentadienone of many phenyl conjugation bromine in ring.
4. method as claimed in claim 3, it is characterized in that, described cyanalation reaction conditions is: under high temperature and catalyzer existent condition, 3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone and ferrocyanide nak response.
5. method as claimed in claim 4, it is characterized in that, described catalyzer is two water Palladous chloride PdCl 22H 2the mixture of O and triphenyl phosphorus triphenylphosphine.
6. method as claimed in claim 5, is characterized in that, the mol ratio of described 3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone, yellow prussiate of potash, two water Palladous chlorides, triphenyl phosphorus is 1:0.39 ~ 0.42:0.01:0.03;
Or described hot conditions is 140 DEG C ~ 160 DEG C.
7. one kind 3,4-bis-(4-cyano-phenyl)-2,5-preparation method of phenylbenzene phenyl graft polysiloxane, is characterized in that,
With 3,4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone for raw material, by cyanalation Reactive Synthesis 3,4-bis-(4-cyano-phenyl)-2, the 5-phenylbenzene cyclopentadienone of many phenyl conjugation bromine in ring;
With 3,4-bis-of above-mentioned synthesis (4-cyano-phenyl)-2,5-phenylbenzene cyclopentadienone and containing the methyl polysiloxane of vinyl sidechain for raw material, high temperature addition, synthesis 3,4-bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane.
8. method as claimed in claim 7, is characterized in that, described high temperature addition reaction is Diels-Alder reaction.
9.3,4-bis-(4-bromophenyl)-2, the application of 5-phenylbenzene cyclopentadienone in many phenyl substituted-cyclopentadienyl ketone synthesis of polar functionalities, it is characterized in that, described building-up process comprises 3, the cyanalation reaction of bromine on 4-bis-(4-bromophenyl)-2,5-phenylbenzene cyclopentadienone.
10. a preparation method for GC stationary phase, is characterized in that, described preparation method comprises the preparation process of 3,4-described in claim 7 or 8 bis-(4-cyano-phenyl)-2,5-phenylbenzene phenyl graft polysiloxane.
CN201610004580.0A 2016-01-04 2016-01-04 Preparing method and application of 3,4-bi(4-cyanophenyl)-2,5-diphenyl phenyl grafted polysiloxane Pending CN105504186A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006068797A1 (en) * 2004-12-20 2006-06-29 Varian, Inc. Ultraporous sol gel monoliths
CN101717350A (en) * 2009-12-08 2010-06-02 南京工业大学 Synthetic method of aryl cyanide in water solution
CN102167829A (en) * 2011-01-19 2011-08-31 山东大学 2-methyl-3,4-diphenyl phenyl-grafted polysiloxane and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006068797A1 (en) * 2004-12-20 2006-06-29 Varian, Inc. Ultraporous sol gel monoliths
CN101717350A (en) * 2009-12-08 2010-06-02 南京工业大学 Synthetic method of aryl cyanide in water solution
CN102167829A (en) * 2011-01-19 2011-08-31 山东大学 2-methyl-3,4-diphenyl phenyl-grafted polysiloxane and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HUICAI REN, ET AL.: "Synthesis and properties of novel perylenebisimide-cored dendrimers", 《DYES AND PIGMENTS》 *
刘磊: "三种可极化的四苯基苯基接枝聚硅氧烷气相色谱固定相的合成及色谱性能研究", 《中国优秀硕士学位论文全文数据库-工程科技Ⅰ辑》 *

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