CN103755733A - Functional organosiloxane containing asymmetrical substituted urea and preparation method thereof - Google Patents
Functional organosiloxane containing asymmetrical substituted urea and preparation method thereof Download PDFInfo
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Abstract
The invention discloses functional organosiloxane containing asymmetrical substituted urea and a preparation method thereof. The preparation method comprises the following steps: carrying out reaction between 4, 4'-dibromodiphenylamine and triphosgene to obtain (i) N, N(/i)-di(4-bromo phenyl) carbamyl chloride; and then, carrying out reaction with 3-aminopropyl triethoxysilane to obtain functional organosiloxane, wherein the organosiloxane is the functional organosiloxane containing asymmetrical substituted urea through the verification of infrared spectrum, ultraviolet spectrum, 1H-NMR (1Hydrogen-Nuclear Magnetic Resonance) and 13C-NMR. The structure of the compound contains a plurality of functional groups such as siloxane, amide, urea groups and bromoaryl. The functional organosiloxane has a potential application value on the respects of molecular imprinting recognition materials, structural flame retardant materials, rare earth light emitting materials, white carbon black and the like. The functional organosiloxane disclosed by the invention is reasonable in synthetic line, mild in condition, easy to operate, low in cost of raw materials and high in product yield.
Description
Technical field
The present invention relates to a kind of Functional silicones oxygen alkane containing asymmetric replacement urea and preparation method thereof.Be specifically related to 1,1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea and its preparation method.
Background technology
Functional silicones oxygen alkane is the important silicoorganic compound of a class, it is the compounds growing up for some special purpose, the reactive group that has energy and the chemically combined reactive group of inorganics in its molecule simultaneously and be combined with organic-matter chemical, its general structure can be expressed as
(OR) 3 si (CH 2 ) n y, n=0～3:Rfor alkyl, normally methyl, ethyl etc.;
yfor organo-functional group, normally vinyl, amino, epoxy group(ing), sulfydryl or urea groups etc.Functional silicones oxygen alkane is mainly used in the aspects such as surfacecti proteon of inorganic material surface processing, polymer modification and metallic substance, common function organic silicon oxygen alkane has the series product such as KH-550, KH-560, KH-570, KH-590, and these products can suitability for industrialized production also be widely applied association area greatly.If KH-550 is 3-aminopropyl triethoxysilane, because existing special siloxanes and alkalescence amino in structure, at present, in a large number as the mineral-filled surface-modifying agent of phenolic aldehyde, polyester, polymeric amide, carbonic ether and urethane, epoxy bonds promotor, KH-550 is widely used in the function nano material of preparing special appearance, structure in field of inorganic nano material in addition.
Although Functional silicones oxygen alkane is used widely in daily life, the shortcoming such as it exists, and structure is single, kind is rare, specific function specific aim is weak, these problems all enjoy investigator to pay close attention to.Current, the exploitation of novel material is to multi-functional proposition requirement, under the background of particularly day by day rising at intelligent material, multi-functional compounds or material become common interest and the target of everybody research, as molecular engram material, fire retardant material, luminescent material and polymer/inorganic thing hybrid material etc.Design and synthetic have specific function or multifuncitonal organosilicon oxygen alkane is significant, if the organo-siloxane containing urea groups is for specific recognition performance molecular engram material; Siloxanes containing bromophenyl is used for structure-type fire retardant, and bromobenzene flame resistant is effective, little on material property impact; The organo-siloxane of amide containing is for rare earth luminescent material and white carbon black modification [Anal. Chem., 2002,74 (2): 458 – 467; Environ. Sci. Technol., 2012,46 (16): 8653-8660; Materials Research Bulletin 2009,44:1334 – 1338].The present invention is based on above function, design a kind of Functional silicones oxygen alkane containing asymmetric trisubstituted ureas, for the preparation of multifuncitonal organosilicon oxygen alkane provides feasible method, up to now, not yet find that there is the compound that patent or bibliographical information the invention discloses.
Summary of the invention
For overcoming the shortcoming that specific function is single, kind is rare of functional siloxanes, the object of this invention is to provide a kind of Functional silicones oxygen alkane containing asymmetric replacement urea and preparation method thereof.
The technical solution adopted in the present invention is: the Functional silicones oxygen alkane containing asymmetric replacement urea of the present invention, and its structural formula is as follows:
R in said structure formula of the present invention is alkoxyl group, is preferably methoxyl group, oxyethyl group; X in formula can be H, F, Cl, Br, I, preferably Br.
The preparation method of the Functional silicones oxygen alkane containing asymmetric replacement urea of the present invention, concrete synthetic route is as follows: 1) in reaction vessel, by 4,4
,-di-substituted-phenyl amine solvent, in methylene dichloride, adds acid-binding agent, then adds high reactivity carbonylation agent, refluxes, stirs, and thin layer is followed the tracks of detection reaction; After reaction finishes, methylene dichloride is removed in underpressure distillation, and crude product column chromatography separating-purifying, obtains light yellow solid intermediate; 2) at reaction vessel, add the synthetic light yellow solid midbody product of step 1), 3-aminopropyl trialkoxy silane, acid-binding agent and ether, pass into N
2protection, under room temperature, thin layer is followed the tracks of detection reaction; After reaction finishes, precipitation is filtered, ether is removed in filtrate decompression distillation, and crude product column chromatography separating-purifying, obtains faint yellow solid.
Described 4,4
,4,4 substituted radicals of the pentanoic in-di-substituted-phenyl amine are preferably H, F, Cl, Br or I.
Alkoxyl group in described 3-aminopropyl trialkoxy silane is preferably methoxy or ethoxy.
Described high reactivity carbonylation agent be preferably phosgene, trichloromethylchloroformate, triphosgene, two (4-oil of mirbane) carbonic ether, carbonyl benzotriazole,
n, N'-carbonyl dimidazoles, tert-Butyl dicarbonate or methylcarbonate.
Described acid-binding agent be preferably triethylamine, tripropyl amine, Tributylamine, tri-isobutylamine,
n, N-diisopropylethylamine or pyridine.
Described 4,4
,-di-substituted-phenyl amine and carbonylation agent mol ratio are 1:1-1:6,4,4
,-di-substituted-phenyl amine and acid-binding agent mol ratio are 1:1-1:8; 4,4
,-di-substituted-phenyl amine and carbonylation agent mol ratio best proportion are 1:3,4,4
,-di-substituted-phenyl amine and acid-binding agent mol ratio best proportion are 1:3.
Described intermediate and 3-aminopropyl trialkoxy silane mol ratio are 1:1-1:3, and intermediate and acid-binding agent mol ratio are 1:1-1:4; Intermediate and 3-aminopropyl trialkoxy silane mol ratio best proportion are 1:1.5, and intermediate and acid-binding agent mol ratio best proportion are 1:2.
Functional silicones oxygen alkane containing asymmetric replacement urea of the present invention is used for 4,4
,-dibromodiphenyl ether has the synthetic and molecularly imprinted polymer of the molecularly imprinted polymer of excellent identity.
Functional silicones oxygen alkane containing asymmetric replacement urea of the present invention is for coupling agent and the dispersion agent of white carbon black modification.
Specifically, provided by the invention 1, the preparation method of 1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea, comprises the steps: with 4,4
,-dibromo pentanoic is raw material, in methylene dichloride, adds triethylamine, triphosgene, backflow, stirring reaction.After reaction finishes, be spin-dried for solvent and add again ether to make solvent, add reactant 3-aminopropyl triethoxysilane, acid binding agent triethylamine, pass into N
2protection, reacts under room temperature.Reaction filters white precipitate after finishing, and ether is removed in filtrate decompression distillation, and crude product column chromatography separating-purifying, obtains faint yellow solid, through UV, FT-IR,
1h-NMR,
13c-NMR test is target product.
Specific function and multifuncitonal organosilicon oxygen alkane receive much concern because it is widely used, and the silicone compounds of synthetic all kinds of novel structures and function is current research emphasis.Brominated flame-retardant is one of main chemical fire retardant, and application is quite extensive; Structure-type fire retardant can increase the consistency with matrix, obviously improves flame-proof composite material flame retardant properties.Molecular imprinting is that Materials science newly plays field, because enjoying investigator, its specific recognition, precordainment and practicality pay close attention to, sacrifice space molecular imprinting method and can improve molecular engram material recognition performance, the conventional group of sacrificing has carbamate, urea groups, carbonic ether etc.Coupling agent is the properties-correcting agent that current chemical industry is most widely used, particularly silane coupling agent and titanate coupling agent, in the processing of all kinds of mineral fillers, macromolecular material and modification, has extensive application.The present invention designs a class specific function compound, both can bring into play specific function, keeps again multi-functional characteristic.Concrete this functional compounds is 1,1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea, and constructional feature is: 4,4
,-dibromo pentanoic is fire-retardant part; Organoalkoxysilane performance coupling agent effect; Urea groups is mainly realized function of molecular engram; One-piece construction embodies structure flame retardant properties, coupling agent performance, function of molecular engram, can also be for rare earth luminescent material and organic synthesis intermediate.
The multi-functional organo-siloxane 1 that the present invention is concrete, the preparation of 1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea is carried out in two steps.The first step, for pentanoic and halo derivatives thereof, because conjugative effect and inductive effect exist simultaneously, reduces amino nucleophilicity greatly, is difficult to and nucleophilic substitution reaction occurs low activity reagent (as isocyanic ester, aldehyde radical etc.).For the nucleophilic substitution reaction of this type of material, generally adopt the activity of highly basic processing or raising reaction reagent to promote reaction to occur, conventional is raising reaction reagent activity.Phosgene is active higher chemical reagent, but phosgene can not be stablized preservation and toxicity is large, but phosgene substitute safe handling, as trichloromethylchloroformate, triphosgene, two (4-oil of mirbane) carbonic ether, carbonyl benzotriazole, N, N'-carbonyl dimidazoles, tert-Butyl dicarbonate, methylcarbonate etc., it is active similar to phosgene, can stablize preservation, in reaction process, do not need special processing, this greatly reduces the condition restriction of reaction.Before reaction starts, reaction solvent methylene dichloride need be as in ice-water bath, to prevent reacting too fast.Triethylamine and so on organic bases for acid binding agent, pyridine is difficult to remove, and the salt color generating is darker, easily affects the color of reaction product.Second step intermediate reacts with excessive 3-aminopropyl trialkoxy silane, generates 1,1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea.This step reaction should add 3-aminopropyl tri-alkoxy in the situation that acid binding agent exists, and prevents that unnecessary side reaction from carrying out.In addition, there is solvent effect in this reaction, and polarity is unfavorable for more greatly reaction, preferably adopts ether to make solvent, as adopted methylene dichloride not react.
In this compounds synthetic, reactant activity is very important on reaction impact, if first carry out 3-aminopropyl trialkoxy silane, reacts with carbonylation agent, and its product can not be with 4,4
,-dibromo diphenylamine reaction, major cause is that halogenated diphenyl amine activity is low, is difficult to react with chloroformyl amine substance.So the general scheme that low activity aromatic amine compounds is prepared urea adopts phosgene and surrogate thereof.
Specifically, the present invention is preferred 1, the purposes of 1-bis-(4 – bromophenyl)-3-(3-ethyl-silicone) propyl group urea: modification, processing as silane coupling agent for inorganic materials such as white carbon blacks; As structure-type fire retardant, be used for fire retardant material; As function of molecular engram monomer, be used for molecular engram material and sensor design thereof; As rare earth luminescent material, be used for electron device; Synthetic for photoelectric material and medicine thereof as organic synthesis intermediate.
Of the present invention 1, the advantage of 1-bis-(4 – bromobenzene)-3-(3-ethyl-silicone) propyl group urea has following aspect:
1, select 4,4
,-dibromo pentanoic is as starting raw material, the arylamine of low nucleophilicity is difficult to and isocyanate reaction, initiative reactive behavior and the molecular structure relation of exploring this compounds of the present invention, employing is stablized highly active triphosgene and is substituted hypertoxic phosgene, and then synthetic bromobenzene replaces urea, realize the high conversion of this type of low activity material, for Design of Organic Synthesis provides a kind of effective, feasible method;
2, this compounds thermostability is higher, through TG test, reaches more than 300 ℃;
3, this type of functional organic compound facile hydrolysis of silicone-containing, with inorganic, macromolecular material interface compatibility is good, is easy to modification, processing;
4, multi-functional group is present among molecular structure simultaneously, for exploitation multifunctional novel material, provides extensive mentality of designing.
Accompanying drawing explanation
Fig. 1, be of the present invention 1, the thermogravimetric curve figure of 1-bis-(4 – bromobenzene)-3-(3-triethoxy is silica-based) propyl group urea.
Fig. 2, be of the present invention 1, the infrared spectrogram of 1-bis-(4 – bromobenzene)-3-(3-triethoxy is silica-based) propyl group urea.
Fig. 3, be of the present invention 1,1-bis-(4 – bromobenzene)-3-(3-triethoxy is silica-based) propyl group urea
1h-NMR figure spectrogram.
Fig. 4, be of the present invention 1,1-bis-(4 – bromobenzene)-3-(3-triethoxy is silica-based) propyl group urea
13c-NMR figure spectrogram.
Fig. 5, be of the present invention 1,1-bis-(4 – bromobenzene)-3-(3-triethoxy is silica-based) propyl group urea UV-Vis abosrption spectrogram in ethanol.
Embodiment
Synthesize as follows 1,1-bis-(4 – bromobenzene)-3-(3-triethoxy is silica-based) propyl group urea, synthetic route is as follows:
Concrete synthesis step is as follows:
(1)
n,Nsynthesizing of-bis-(4-bromophenyl) urea chloride
In being equipped with the 100ml there-necked flask of induction stirring, temperature control unit, by 4,4
,-dibromo pentanoic (0.8175g, 2.5mmol) is dissolved in 50ml methylene dichloride, continues to add triethylamine (1.515g, 15mmol), then add solid triphosgene (2.673g, 9mmol), under room temperature, reflux, stir, thin layer is followed the tracks of detection reaction, stopped reaction after 24h.After reaction finishes, methylene dichloride is removed in underpressure distillation, (the sherwood oil: methylene dichloride=2:1) separating-purifying, obtains micro-yellow solid intermediate 0.84g, warp of column chromatography for crude product
1h-NMR test is intermediate N, N-bis-(4-bromophenyl) urea chloride, productive rate 86.3%;
Synthesizing of (2) 1,1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea
In the 100ml there-necked flask that is equipped with induction stirring, add successively above-mentioned the intermediate N that embodiment is synthetic, N-bis-(4-bromophenyl) urea chloride (0.934g, 2.4mmol), ether 50ml, triethylamine (0.606g, 6mmol), 3-aminopropyl triethoxysilane (0.884g, 4mmol), pass into N
2protection, thin layer is followed the tracks of detection reaction, stops after reacting 12h under room temperature.After reaction finishes, white precipitate is filtered, the ether, (sherwood oil: ethyl acetate=3:1) separating-purifying, obtains faint yellow solid 1.14g, warp of column chromatography for crude product are removed in filtrate decompression distillation
1h-NMR tests as target product is 1,1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea, productive rate 82.7%.
Above-mentioned employing high reactivity carbonylation agent and low activity bromo virtue ammonia react are prepared Functional silicones oxygen alkane, obtain light yellow crystal, and high resolution mass spectrum determining molecular weight is 574.3864.UV spectrum shows that maximum absorption band wavelength (etoh solvent) is positioned at 255 nm, and FT-IR spectrum shows 3224cm
-1, 3037cm
-1, 2975.4 cm
-1, 1654cm
-1, 1533 cm
-1, 1484 cm
-1, 1382 cm
-1, 1304 cm
-1, 1271 cm
-1, 1159 cm
-1, 1074 cm
-1there is absorption.
1h-NMR,
13c-NMR spectroscopic data is in Table 1.In conjunction with spectrum, finally determine that this Functional silicones siloxane compound chemical structural formula is formula I, molecular formula is C
22h
30br
2n
2o
4si;
（I）。
Table 1. structural formula (I) compound
1h-NMR (400MHz) and
13c-NMR (105.5MHz) chemical shift data
Embodiment 2
Synthesizing of 1,1-bis-(4 – bromophenyl)-3-(3-trimethoxy is silica-based) propyl group urea
The intermediate N that adds successively embodiment 1 preparation in the 100ml there-necked flask that is equipped with induction stirring, N-bis-(4-bromophenyl) urea chloride (0.934g, 2.4mmol), ether 50ml, triethylamine (0.606g, 6mmol), 3-aminopropyl trimethoxysilane (0.72g, 4mmol), pass into N
2protection, thin layer is followed the tracks of detection reaction, stops after reacting 12h under room temperature.Reaction filters white precipitate after finishing, and ether is removed in filtrate decompression distillation, column chromatography for crude product (sherwood oil: ethyl acetate=3:1) separating-purifying, obtain faint yellow solid product 1.08g, productive rate 84.4%, with the infrared spectra of embodiment 1, UV spectrum,
1h-NMR and
13c-NMR is determined as 1,1-bis-(4 – bromophenyl)-3-(3-trimethoxy is silica-based) propyl group urea.
Embodiment 3
Synthesizing of 1,1-phenylbenzene-3-(3-triethoxy is silica-based) propyl group urea
In being equipped with the 100ml there-necked flask of induction stirring, temperature control unit, by pentanoic (1.69g, 10mmol) be dissolved in 50ml methylene dichloride, continue to add triethylamine (3.03g, 30mmol), then add solid triphosgene (5.346g, 18mmol), under room temperature, reflux, stir, thin layer is followed the tracks of detection reaction, stopped reaction after 24h.After reaction finishes, methylene dichloride is removed in underpressure distillation, obtains intermediate
n,N-diphenyl amino formyl chloride; In the 100ml there-necked flask that is equipped with induction stirring, add successively this
n,N-diphenyl amino formyl chloride (1.15g, 5mmol), ether 50mL, pyridine (0.48g, 6mmol), 3-aminopropyl triethoxysilane (1.1g, 5mmol), pass into N
2protection, thin layer is followed the tracks of detection reaction, stops after reacting 12h under room temperature.Reaction filters yellow mercury oxide after finishing, and ether is removed in filtrate decompression distillation, column chromatography for crude product (sherwood oil: ethyl acetate=2:1) separating-purifying, obtain yellow liquid 1.83g, productive rate 87.8%, with the infrared spectra of embodiment 1, UV spectrum,
1h-NMR and
13c-NMR is determined as 1,1-phenylbenzene-3-(3-triethoxy is silica-based) propyl group urea.
Embodiment 4
n,Nsynthesizing of-bis-(4-bromophenyl) urea chloride
In being equipped with the 100ml there-necked flask of induction stirring, temperature control unit, by 4,4
,-dibromo pentanoic (0.8175g, 2.5mmol) is dissolved in 50ml methylene dichloride, continues to add triethylamine (1.52g, 15mmol), then adds tert-Butyl dicarbonate (1.605g, 7.5mmol) (or phosgene 0.7425g, 7.5mmol; Or trichloromethylchloroformate 1.478g, 7.5mmol; Or methylcarbonate 0.676g, 7.5mmol), under room temperature, reflux, stir, thin layer is followed the tracks of detection reaction, stopped reaction after 24h.After reaction finishes, methylene dichloride is removed in underpressure distillation, (the sherwood oil: methylene dichloride=2:1) separating-purifying, obtains micro-yellow solid intermediate of column chromatography for crude product
n,N-bis-(4-bromophenyl) urea chloride 0.79g, productive rate 81.1%.
n,Nsynthesizing of-bis-(4-bromophenyl) urea chloride
In being equipped with the 100ml there-necked flask of induction stirring, temperature control unit, by 4,4
,-dibromo pentanoic (0.8175g, 2.5mmol) be dissolved in 50ml methylene dichloride, continue to add DIPEA (1.94g, 15mmol) (or pyridine 1.19g, 15mmol), add again solid triphosgene (2.673g, 9mmol), under room temperature, reflux, stir, thin layer is followed the tracks of detection reaction, stopped reaction after 24h.After reaction finishes, methylene dichloride is removed in underpressure distillation, (the sherwood oil: methylene dichloride=2:1) separating-purifying, obtains micro-yellow solid intermediate of column chromatography for crude product
n,N-bis-(4-bromophenyl) urea chloride 0.83g, productive rate 85.3%.
n,Nsynthesizing of-bis-(4-bromophenyl) urea chloride
In being equipped with the 100ml there-necked flask of induction stirring, temperature control unit, by 4,4
,-dibromo pentanoic (0.8175g, 2.5mmol) is dissolved in 50ml methylene dichloride, continues to add triethylamine (0.76g, 7.5mmol), then add solid triphosgene (2.228g, 7.5mmol), under room temperature, reflux, stir, thin layer is followed the tracks of detection reaction, stopped reaction after 24h.After reaction finishes, methylene dichloride is removed in underpressure distillation, (the sherwood oil: methylene dichloride=2:1) separating-purifying, obtains micro-yellow solid intermediate 0.87g, warp of column chromatography for crude product
1h-NMR test is intermediate
n,N-bis-(4-bromophenyl) urea chloride, productive rate 89.4%.
Embodiment 7
Synthesizing of 1,1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea
The intermediate that adds successively embodiment 6 preparations in the 100ml there-necked flask that is equipped with induction stirring
n,N-bis-(4-bromophenyl) urea chloride (0.934g, 2.4mmol), ether 50ml, triethylamine (0.485g, 4.8mmol), 3-aminopropyl triethoxysilane (0.796g, 3.6mmol), pass into N
2protection, thin layer is followed the tracks of detection reaction, stops after reacting 12h under room temperature.Reaction filters white precipitate after finishing, and ether is removed in filtrate decompression distillation, column chromatography for crude product (sherwood oil: ethyl acetate=3:1) separating-purifying, obtain yellow solid 1.22g, productive rate 88.6%, with the infrared spectra of embodiment 1, UV spectrum,
1h-NMR and
13c-NMR method is determined as 1,1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea.
Embodiment 8
Synthesizing of 1,1-bis-(4-fluorophenyl)-3-(3-triethoxy is silica-based) propyl group urea
In being equipped with the 100ml there-necked flask of induction stirring, temperature control unit, by 4,4 '-difluorodiphenyl amine (2.05g, 10mmol) is dissolved in 50ml methylene dichloride, continues to add triethylamine (3.03g, 30mmol), add again solid triphosgene (5.346g, 18mmol), under room temperature, reflux, stir, thin layer is followed the tracks of detection reaction, stopped reaction after 24h.After reaction finishes, methylene dichloride is removed in underpressure distillation, obtains intermediate
n,N-bis-(4-fluorophenyl) urea chloride; In the 100ml there-necked flask that is equipped with induction stirring, add successively this
n,N-bis-(4-fluorophenyl) urea chloride (1.34g, 5mmol), ether 50mL, pyridine (0.48g, 6mmol), 3-aminopropyl triethoxysilane (1.1g, 5mmol), pass into N
2protection, thin layer is followed the tracks of detection reaction, stops after reacting 12h under room temperature.Reaction filters yellow mercury oxide after finishing, and ether is removed in filtrate decompression distillation, column chromatography for crude product (sherwood oil: ethyl acetate=1:1) separating-purifying, obtain colourless liquid 1.87g, productive rate 82.7%, with the infrared spectra of embodiment 1, UV spectrum,
1h-NMR and
13c-NMR is determined as 1,1-bis-(4-fluorophenyl)-3-(3-triethoxy is silica-based) propyl group urea.
Embodiment 9
Synthesizing of 1,1-bis-(4-chloro-phenyl-)-3-(3-triethoxy is silica-based) propyl group urea
In being equipped with the 100ml there-necked flask of induction stirring, temperature control unit, by 4,4 '-dichloro diphenylamine (2.38g, 10mmol) is dissolved in 50ml methylene dichloride, continues to add triethylamine (3.03g, 30mmol), add again solid triphosgene (5.346g, 18mmol), under room temperature, reflux, stir, thin layer is followed the tracks of detection reaction, stopped reaction after 24h.After reaction finishes, methylene dichloride is removed in underpressure distillation, obtains intermediate
n,N-bis-(4-chloro-phenyl-) urea chloride; In the 100ml there-necked flask that is equipped with induction stirring, add successively this
n,N-bis-(4-chloro-phenyl-) urea chloride (1.51g, 5mmol), ether 50mL, pyridine (0.48g, 6mmol), 3-aminopropyl triethoxysilane (1.1g, 5mmol), pass into N
2protection, thin layer is followed the tracks of detection reaction, stops after reacting 12h under room temperature.Reaction filters yellow mercury oxide after finishing, and ether is removed in filtrate decompression distillation, column chromatography for crude product (sherwood oil: ethyl acetate=2:1) separating-purifying, obtain colourless liquid 2.13g, productive rate 87.5%, with the infrared spectra of embodiment 1, UV spectrum,
1h-NMR and
13c-NMR is determined as 1,1-bis-(4-chloro-phenyl-)-3-(3-triethoxy is silica-based) propyl group urea.
Synthesizing of 1,1-bis-(4-iodophenyl)-3-(3-triethoxy is silica-based) propyl group urea
In being equipped with the 100ml there-necked flask of induction stirring, temperature control unit, by 4,4 '-diiodo-pentanoic (4.21g, 10mmol) is dissolved in 50ml methylene dichloride, continues to add triethylamine (3.03g, 30mmol), add again solid triphosgene (5.346g, 18mmol), under room temperature, reflux, stir, thin layer is followed the tracks of detection reaction, stopped reaction after 24h.After reaction finishes, methylene dichloride is removed in underpressure distillation, obtains intermediate
n,N-bis-(4-iodophenyl) urea chloride; In the 100ml there-necked flask that is equipped with induction stirring, add successively this
n,N-bis-(4-iodophenyl) urea chloride (2.415g, 5mmol), ether 50mL, pyridine (0.48g, 6mmol), 3-aminopropyl triethoxysilane (1.1g, 5mmol), pass into N
2protection, thin layer is followed the tracks of detection reaction, stops after reacting 12h under room temperature.Reaction filters yellow mercury oxide after finishing, and ether is removed in filtrate decompression distillation, column chromatography for crude product (sherwood oil: ethyl acetate=4:1) separating-purifying, obtain colourless liquid 2.95g, productive rate 88.3%, with the infrared spectra of embodiment 1, UV spectrum,
1h-NMR and
13c-NMR is determined as 1,1-bis-(4-iodophenyl)-3-(3-triethoxy is silica-based) propyl group urea.
Embodiment 11
1,1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea is for the synthetic and molecularly imprinted polymer recognition effect of molecularly imprinted polymer
In 100mL beaker, add ethanol 50mL, tetraethyl orthosilicate 5mL, 1,1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea 0.574g (1mmol), hydrochloric acid 2ml (2mol L
-1), under room temperature, stir half an hour.Then add 5mL ammoniacal liquor (25%), occur gel, continue reaction 12h, to increase degree of crosslinking.Dry, grind, screening obtains pressed powder, gets a certain amount of powder, is heated to 300 ℃ and makes it that thermolysis occur, and after 12h, takes out, the reaction of isocyanic ester water becomes amino, then solid particulate is placed in to ethanol, wash-out 6h, obtains molecularly imprinted polymer material.Imprinted polymer material absorption property adopts high performance liquid chromatography test: get a certain amount of molecular engram material and join in template molecule solution, after absorption certain hour, measurement module molecule residual concentration, calculates the two difference and draws molecularly imprinted polymer loading capacity.The loading capacity maximum value of this molecularly imprinted polymer is 19.25 μ mol/g after measured, and its loading capacity is 2.3 times of non-imprinted polymer, has better recognition performance; Selectivity test shows that molecularly imprinted polymer is to 4,4
,-dibromodiphenyl ether has excellent identity, reclaims test and shows that this molecularly imprinted polymer can be used for 4,4 in separated actual sample
,-dibromodiphenyl ether.
Embodiment 12
Precipitated silica surface modification and performance thereof
By 7 g 1,1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea is dissolved in appropriate industrial spirit, then add a small amount of water and ammoniacal liquor to regulate the pH=10 of mixing solutions, 1 h is reacted in 1,1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea generation prehydrolysis.1,1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea is as precipitated silica surface modification coupling agent.Take 200 g precipitated silicas (Jinsha white carbon black company limited provides by Sha County, Fujian Province) through 105 ℃ of dried overnight (removing planar water) in mixing tank, 60 ℃ of preheatings and stir 30 min.Then in mixing tank, add the above-mentioned coupling agent hydrolyzed solution preparing, (stir speed (S.S.) should be greater than 300 rpm/min) takes out after mixing 1 h at a high speed in batches.Then this pretreated compound is moved in baking oven to dry 6 h at 80 ℃, again oven temperature is adjusted to 110 ℃ so that white carbon black shifts out pulverizing after activating 3 h, obtain through the coupling agent modified precipitated silica of 1,1-bis-(4 – bromophenyl)-3-(3-triethoxy is silica-based) propyl group urea.
(1) performance such as the size of the precipitated silica after surface treatment and distribution thereof
Precipitated silica correlation parameter before and after surface treatment relatively list in table 1.By table 1, demonstrated, the median size of surface treated precipitated silica reduces, and causes specific surface area correspondingly to increase; Particularly significantly to reduce be that the particle size homogeneity of white carbon black after surface modification significantly improves to size distribution.
Median size and the size distribution of the precipitated silica before and after table 1. surface treatment
| Sample | Median size (nm) | Size distribution | Specific surface area (m 2/ g, BET method) |
| White carbon black before modification | 349.4 | ?210-6400 | 175 |
| White carbon black after modification | 295.9 | 173-750 | 189.8 |
(2) dispersiveness, result of prevention and the transparency of the precipitated silica before and after surface treatment in lacquer thinner relatively.Under stirring, add respectively a certain amount of surface modification and unmodified precipitated silica in containing the container of lacquer thinner, high-speed stirring 40 min, obtain respectively the dispersion system containing precipitated silica 1.0-4.0%.Standing rear observation surface modification and unmodified precipitated silica dispersiveness, result of prevention and the transparency in lacquer thinner, and compare.Comparative result shows that 1.0-4.0% surface modification precipitated silica Monodispersed in lacquer thinner is even, and surface modification precipitated silica does not disperse inhomogeneously in lacquer thinner, and the white carbon black lacquer thinner suspension of 3-4% content partly deposits.The not sedimentation substantially after standing 24 h of surface modification precipitated silica-lacquer thinner system, is obviously better than the not precipitated silica of surface modification.Surface modification precipitated silica being uniformly distributed with not sedimentation in lacquer thinner causes the transparent printing opacity of surface modification precipitated silica-lacquer thinner system disperseing.The above results is little compared with unmodified precipitated silica because of the particle diameter of surface modification white carbon black in system, and size distribution is more even.
Claims (10)
1. containing a Functional silicones oxygen alkane for asymmetric replacement urea, its structural formula is as follows:
。
2. contain a preparation method for the Functional silicones oxygen alkane of asymmetric replacement urea, it is characterized in that: two steps are synthetic, concrete synthetic route is as follows: 1) in reaction vessel, by 4,4
,-di-substituted-phenyl amine solvent, in methylene dichloride, adds acid-binding agent, then adds high reactivity carbonylation agent, refluxes, stirs, and thin layer is followed the tracks of detection reaction; After reaction finishes, methylene dichloride is removed in underpressure distillation, and crude product column chromatography separating-purifying, obtains light yellow solid intermediate; 2) at reaction vessel, add the synthetic light yellow solid midbody product of step 1), 3-aminopropyl trialkoxy silane, acid-binding agent and ether, pass into N
2protection, under room temperature, thin layer is followed the tracks of detection reaction; After reaction finishes, precipitation is filtered, ether is removed in filtrate decompression distillation, and crude product column chromatography separating-purifying, obtains faint yellow solid.
3. preparation method as claimed in claim 2, is characterized in that: 4,4
,4,4 substituted radicals of the pentanoic in-di-substituted-phenyl amine are selected from H, F, Cl, Br or I.
4. preparation method as claimed in claim 2, is characterized in that: the alkoxyl group in 3-aminopropyl trialkoxy silane is selected from methoxy or ethoxy.
5. preparation method as claimed in claim 2, is characterized in that: high reactivity carbonylation agent be selected from phosgene, trichloromethylchloroformate, triphosgene, two (4-oil of mirbane) carbonic ether, carbonyl benzotriazole,
n, N'-carbonyl dimidazoles, tert-Butyl dicarbonate or methylcarbonate.
6. preparation method as claimed in claim 2, is characterized in that: acid-binding agent be selected from triethylamine, tripropyl amine, Tributylamine, tri-isobutylamine,
n, N-diisopropylethylamine or pyridine.
7. the preparation method as described in claim 2 or 3 or 4 or 5 or 6, is characterized in that: 4,4
,-di-substituted-phenyl amine and carbonylation agent mol ratio are 1:1-1:6,4,4
,-di-substituted-phenyl amine and acid-binding agent mol ratio are 1:1-1:8; 4,4
,-di-substituted-phenyl amine and carbonylation agent mol ratio best proportion are 1:3,4,4
,-di-substituted-phenyl amine and acid-binding agent mol ratio best proportion are 1:3.
8. the preparation method as described in claim 2 or 3 or 4 or 5 or 6, is characterized in that: intermediate and 3-aminopropyl trialkoxy silane mol ratio are 1:1-1:3, and intermediate and acid-binding agent mol ratio are 1:1-1:4; Intermediate and 3-aminopropyl trialkoxy silane mol ratio best proportion are 1:1.5, and intermediate and acid-binding agent mol ratio best proportion are 1:2.
9. the Functional silicones oxygen alkane containing asymmetric replacement urea claimed in claim 1 is used for 4,4
,-dibromodiphenyl ether has the synthetic and molecularly imprinted polymer of the molecularly imprinted polymer of excellent identity.
10. the Functional silicones oxygen alkane of asymmetric replacement urea that contains claimed in claim 1 is for coupling agent and the dispersion agent of white carbon black modification.
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| CN111215041A (en) * | 2020-02-28 | 2020-06-02 | 江苏汉邦科技有限公司 | Method for synthesizing amide reversed-phase liquid chromatography packing |
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| CN106674918A (en) * | 2015-11-05 | 2017-05-17 | 叶晓青 | Polyhydroxybutyrate-containing nano-tube composite wire preparation method |
| CN106674917A (en) * | 2015-11-05 | 2017-05-17 | 叶晓青 | Preparation method of nanotube composite wire containing PBC (Poly Butylene carbonate) |
| CN108368903A (en) * | 2015-12-04 | 2018-08-03 | 舍弗勒技术股份两合公司 | Include the flexible Wet-type friction material of silane |
| CN111215041A (en) * | 2020-02-28 | 2020-06-02 | 江苏汉邦科技有限公司 | Method for synthesizing amide reversed-phase liquid chromatography packing |
| CN114853976A (en) * | 2022-05-19 | 2022-08-05 | 浙江科技学院 | Preparation method of self-repairing carbonyl modified thermoplastic polyurea elastomer |
| CN114853976B (en) * | 2022-05-19 | 2023-07-04 | 浙江科技学院 | Preparation method of self-repairing type carbonyl modified thermoplastic polyurea elastomer |
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