CN104193970B - A kind of stereospecificity poly-(alcoxyl carbonyl Cabbeen) and its preparation method and application - Google Patents
A kind of stereospecificity poly-(alcoxyl carbonyl Cabbeen) and its preparation method and application Download PDFInfo
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Abstract
The present invention (alcoxyl carbonyl Cabbeen) polymer that a kind of stereospecificity is provided and its preparation method and application.This polymer is prepared by the catalysis α carbonyl diazonium carboxylate polymerization of poly-heterocyclic radical palladium (II), the method uses poly-heterocyclic radical to modify palladium catalyst, utilizes the space steric effect of poly-heterocyclic radical and conjugation stabilizing active intermediate palladium (I) alcoxyl carbonyl Cabbeen carbon radicals to be passed to transfer inserting step progressively and produce the polymer of stereospecificity.The present invention provides new method for the polymer preparing High level of stereoselectivity regularity and highly functionalized, poly-(the alcoxyl carbonyl Cabbeen) of prepared stereospecificity can be applicable to dyestuff, paint, print, the field such as intermingling material.
Description
Technical field
The invention belongs to Polymer Synthesizing field, more particularly to a kind of stereospecificity poly-(alcoxyl carbonyl Cabbeen) and its preparation method and application.
Background technology
Cabbeen polyreaction is to find, at von Pechman in 1898, the type of polymerization that thermal cracking Azimethylene. gradually grows up on the basis of can forming polyethylene; but instability of easily exploding due to diazonium paraffin; the discovery of Zieglar-Natta catalyst simultaneously makes the olefinic polyreaction with crude resources as raw material obtain huge development; being widely used in the fields such as plastics, synthetic fibers and synthetic rubber, this causes the progress to Cabbeen polyreaction slowly.But olefinic polyreaction there is also some limitation, such as cannot obtain in carbochain that each carbon atom is connected with the polymer of polar group, polyolefinic spatial chemistry is difficult to control to.Cabbeen polyreaction can break through these limitation of olefinic polyreaction, provides new way for development highly functionalized carbochain polymer.
Diazonium carbonyl compound is more more stable than diazonium paraffin, be more easy to preparation, and is suitable for commercial synthesis.2002, diazonium carbonyl compound was applied in the Cabbeen polyreaction of metallic copper catalysis (Liu Lijian, 2002).After a while document reports the diazonium carbonyl compound of Metal Palladium and rhodium catalysis Cabbeen polyreaction (Ihara, 2008；De Bruin, 2010).These research work mainly include controlling polymerizate spatial chemistry, improving polymer molecular weight, expansion monomer and Development of Novel catalyst etc., tentatively disclose feature, rule and the potential application foreground of diazonium carbonyl compound Cabbeen polyreaction under metal catalytic, but the explanation for the chain growth mechanism in the Cabbeen polyreaction of metal catalytic and the active specy of polyreaction is confined to the computational reasoning stage, document is had to report this process not radical polymerization process.In actual fabrication process, in addition to expensive rare metal rhodium, iridium catalyst catalysis diazonium carbonyl compound are polymerized the polymer that can obtain stereospecificity, the Cabbeen polyreaction of other metal catalytics can only obtain the atactic polymer of low-molecular-weight.And the configuration of polymer affects character and the applicability of polymer, thus find outstanding metallic catalyst and prepare the poly-Cabbeen of stereoregularity and highly functionalized and become the study hotspot of this area.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, it is provided that a kind of stereospecificity poly-(alcoxyl carbonyl Cabbeen) and its preparation method and application.The present invention uses poly-heterocyclic radical-palladium (II) to be polymerized as catalyst alpha-carbonyl diazonium carboxylate, utilizes the space steric effect of poly-heterocyclic radical and conjugation stabilizing active intermediate palladium (I)-alcoxyl carbonyl Cabbeen carbon radicals to be passed to transfer inserting step progressively and produce poly-(the alcoxyl carbonyl Cabbeen) of stereospecificity.
The technical solution adopted in the present invention is specific as follows:
A kind of stereospecificity poly-(alcoxyl carbonyl Cabbeen), has a structure shown in formula (A):
Wherein n is the positive integer more than 1；R is the linear paraffin base of 1～3 carbon.
One prepares the method for above-mentioned stereospecificity poly-(alcoxyl carbonyl Cabbeen), comprise the following steps: under the conditions of anhydrous and oxygen-free, poly-heterocyclic radical-palladium (II) catalyst is added in organic solvent, it is that 1:20～100 is added dropwise over alpha-carbonyl diazonium carboxylate by the mass ratio of catalyst Yu alpha-carbonyl diazonium carboxylate, constantly it is filled with nitrogen, reacting by heating 16～24 hours under the conditions of 20～200 DEG C, after the cooling of question response liquid, filter out catalyst, add precipitant, drying precipitated, i.e. obtain stereospecificity poly-(alcoxyl carbonyl Cabbeen) solid.
Described alpha-carbonyl diazonium carboxylate is the one in diazonium methyl acetate, ethyl diazoacetate, diazoacetic acid n-pro-pyl ester.
Described poly-heterocyclic radical-palladium (II) is prepared by the following method and obtains: be added dropwise to be dissolved with by the ethanol being dissolved with palladium (II) compound in the chloroform of poly-heterocyclic radical polymer, wherein the mass ratio of palladium compound and poly-heterocyclic radical polymer is 1:1, at 70 DEG C, heated and stirred is reacted 12 hours, filter, be dried to obtain poly-heterocyclic radical-palladium (II) catalyst of black.
Described palladium (II) compound is Palladous chloride. (II), four triphenylphosphine palladium chlorides (II), four chloro palladium (II) acid sodium, perchloric acid two (2,2-bipyridyl) closes palladium (II), two (oxalic acid) closes palladium (II), dichloro four ammino palladium (II), dichloro two (triethyl phosphine) closes palladium (II), dichloro two (triphenylphosphine) closes the one in palladium (II), two chloroformyl conjunction palladiums (II), palladium (II).
Described poly-heterocyclic radical is the one in poly-(N-isopropenyl) pyrrole radicals, poly-(N-isopropenyl) imidazole radicals, poly-(N-isopropenyl) pyrazolyl, poly-(N-isopropenyl) pyridine radicals, poly-(N-isopropenyl) pyrimidine radicals, the most poly-(N-isopropenyl) imidazole radicals.
Described organic solvent is the one in chloroform, toluene, oxolane, pyridine, preferably chloroform.
Described precipitant is the one in ether, petroleum ether, normal hexane, preferably ether.
Above-mentioned stereospecificity poly-(alcoxyl carbonyl Cabbeen) dyestuff, paint, print, application in intermingling material field.
The present invention makes public for the first time the reactive intermediate of poly-heterocyclic radical-palladium (II) catalysis alpha-carbonyl diazonium carboxylate polyreaction simultaneously and is palladium (I)-alcoxyl carbonyl Cabbeen carbon radicals and provides the method detecting such palladium (I)-alcoxyl carbonyl Cabbeen carbon radicals reactive intermediate.
Before making the present invention, the researcher of this area is confined to the computational reasoning stage for the explanation of the chain growth mechanism of the Cabbeen polyreaction based on diazonium carbonyl compound of metal catalytic and the active specy of polyreaction, have document report think metal catalytic Cabbeen polyreaction in there is not free radical activity intermediate, but, inventor finds to add free radical scavenger DMPO (5 in the reaction system to the catalysis alpha-carbonyl diazonium carboxylate polymerization of poly-heterocyclic radical-palladium (II), 5-dimethyl-1-pyrrolin-nitrogen-oxide), the existence of reactive intermediate palladium (I)-alcoxyl carbonyl Cabbeen carbon radicals is detected by electron spin resonance spectrometer.
Therefore, the present invention make public for the first time poly-heterocyclic radical-palladium (II) catalysis alpha-carbonyl diazonium diazonium carboxylate polyreaction to prepare the reactive intermediate of poly-(alcoxyl carbonyl Cabbeen) simultaneously is a kind of new palladium (I)-alcoxyl carbonyl Cabbeen carbon radicals.
Present invention also offers the method detecting this palladium (I)-alcoxyl carbonyl Cabbeen carbon radicals.The method includes that the oxidation state using x-ray photoelectron spectroscopy detection reactive intermediate Metal Palladium is reduced to 1 valency by divalent；Spin traps DMPO is used to combine room temperature electron paramagnetic resonance spectrum (EPR) method detection reactive intermediate palladium (I)-alcoxyl carbonyl Cabbeen carbon radicals.
The present invention uses the step of the oxidation state of x-ray photoelectron spectroscopy detection reactive intermediate Metal Palladium: poly-for different-phase catalyst heterocyclic radical-palladium is filtered out by the polymerization system after reaction terminates, dried employing x-ray photoelectron spectroscopy detection.Wherein testing conditions is beam wavelength λ=0.154nm, and voltage is 40KV, and electric current is 30mA.Detect that the combination of the 3d5/2 track of catalyst metals palladium can be attributed to 1 valency palladium for 336.06eV.In the procatalyst of contrast reaction, the quantivalence of palladium is divalent, illustrates that poly-heterocyclic radical-palladium (II) oxidation state of palladium during interacting with alpha-carbonyl diazonium carboxylate is reduced to 1 valency from divalent.
The condition using spin traps DMPO to combine room temperature electron paramagnetic resonance spectrum (EPR) method detection reactive intermediate palladium (I)-alcoxyl carbonyl Cabbeen carbon radicals in the present invention is room temperature detection, use X-band electronic paramagnetic resonance spectrometer, central field 3360.221G, sweep amplitude 100.00G, microwave power 19.510G, microwave frequency 9.417GHz.The parameter of palladium (the I)-alcoxyl carbonyl Cabbeen carbon radicals captured by DMPO detected: hyperfine splitting constant aN=14.08G, aH=20.76G.
The present invention has the following advantages and beneficial effect:
(1) present invention uses poly-heterocyclic radical-palladium (II) catalyst to replace the rare metal rhodium of costliness, iridium catalyst to prepare poly-(the alcoxyl carbonyl Cabbeen) of stereospecificity, reduce production cost, it is provided that a kind of stereospecificity is good, the new material of highly functionalized.
(2) poly-(the alcoxyl carbonyl Cabbeen) of the stereospecificity prepared by the present invention can be applicable to dyestuff, paint, print, the field such as intermingling material.
Accompanying drawing explanation
Fig. 1 is the route map of poly-(the alcoxyl carbonyl Cabbeen) of polyimidazole base-palladium (II) catalysis alpha-carbonyl diazonium carboxylate polymerization preparation stereospecificity.
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of poly-(the ethoxy carbonyl Cabbeen) of the stereospecificity of polyimidazole base-palladium (II) catalysis ethyl diazoacetate polymerization preparation.
Fig. 3 is the nuclear-magnetism carbon spectrogram of poly-(the ethoxy carbonyl Cabbeen) of the stereospecificity of polyimidazole base-palladium (II) catalysis ethyl diazoacetate polymerization preparation.
Fig. 4 is the Matrix Assisted Laser Desorption time-of-flight mass spectrometry figure of poly-(the ethoxy carbonyl Cabbeen) of the stereospecificity of polyimidazole base-palladium (II) catalysis ethyl diazoacetate polymerization preparation.
Fig. 5 is the x-ray photoelectron energy spectrogram of the front polyimidazole base-palladium of reaction.
Fig. 6 is the x-ray photoelectron energy spectrogram of polyimidazole base-palladium after reaction.
Fig. 7 is the electron paramagnetic resonance spectrum (EPR) figure that spin traps DMPO combines electron paramagnetic resonance spectrum (EPR) method detection reactive intermediate palladium (I)-alcoxyl carbonyl Cabbeen carbon radicals.
Detailed description of the invention
Poly-heterocyclic radical-palladium (II) catalyst employed in following example is prepared by the following method (list of references YoichiM.A.Yamada, Angew.Chem.Int.Ed.2011,50,9437-9441): be added dropwise to the ethanol being dissolved with palladium compound be dissolved with in the chloroform of poly-heterocyclic radical polymer, wherein the mass ratio of palladium compound and poly-heterocyclic radical polymer is 1:1, at 70 DEG C, heated and stirred is reacted 12 hours, filter, be dried to obtain poly-heterocyclic radical-palladium (II) catalyst of black.
Described palladium (II) compound is Palladous chloride. (II), four triphenylphosphine palladium chlorides (II), four chloro palladium (II) acid sodium, perchloric acid two (2,2-bipyridyl) closes palladium (II), two (oxalic acid) closes palladium (II), dichloro four ammino palladium (II), dichloro two (triethyl phosphine) closes palladium (II), dichloro two (triphenylphosphine) closes the one in palladium (II), two chloroformyl conjunction palladiums (II), palladium (II).
Described poly-heterocyclic radical is the one in poly-(N-isopropenyl) pyrrole radicals, poly-(N-isopropenyl) imidazole radicals, poly-(N-isopropenyl) pyrazolyl, poly-(N-isopropenyl) pyridine radicals, poly-(N-isopropenyl) pyrimidine radicals, the most poly-(N-isopropenyl) imidazole radicals.
Embodiment 1
Under the conditions of anhydrous and oxygen-free, with chloroform as solvent, be stirred continuously be passed through nitrogen under conditions of add poly-(N-isopropenyl) imidazole radicals-palladium (II) catalyst, it is added dropwise over ethyl diazoacetate in the ratio that mass ratio is 1:20 of catalyst Yu ethyl diazoacetate, react 17 hours under 65 DEG C of heating conditions, filter out catalyst, ether is used to obtain a large amount of black precipitate as precipitant, dried polymerizate, by nucleus magnetic hydrogen spectrum, polymerization reaction system stock solution is detected, the conversion ratio calculating polymer is 82.99%, time-of-flight mass spectrometry detect the molecular mass of polymer is 11000Da.
Embodiment 2
Under the conditions of anhydrous and oxygen-free, with toluene as solvent, be stirred continuously be passed through nitrogen under conditions of add poly-(N-isopropenyl) pyrrole radicals-palladium (II) catalyst, it is added dropwise over ethyl diazoacetate in the ratio that mass ratio is 1:60 of catalyst Yu ethyl diazoacetate, react 24 hours under 30 DEG C of heating conditions, filter out catalyst, use petroleum ether as precipitant, dried polymerizate, by nucleus magnetic hydrogen spectrum, polymerization reaction system stock solution is detected, the conversion ratio calculating polymer is 67.24%, time-of-flight mass spectrometry detect the molecular mass of polymer is 7300Da.
Embodiment 3
Under the conditions of anhydrous and oxygen-free, with pyridine as solvent, be stirred continuously be passed through nitrogen under conditions of add poly-(N-isopropenyl) pyrimidine radicals-palladium (II) catalyst, it is added dropwise over ethyl diazoacetate in the ratio that mass ratio is 1:80 of catalyst Yu ethyl diazoacetate, react 16 hours under 50 DEG C of heating conditions, filter out catalyst, normal hexane is used to obtain as precipitant, dried polymerizate, by nucleus magnetic hydrogen spectrum, polymerization reaction system stock solution is detected, the conversion ratio calculating polymer is 73.19%, time-of-flight mass spectrometry detect the molecular mass of polymer is 8500Da.
Embodiment 4
Under the conditions of anhydrous and oxygen-free, with oxolane as solvent, be stirred continuously be passed through nitrogen under conditions of add poly-(N-isopropenyl) pyridine radicals-palladium (II) catalyst, it is added dropwise over ethyl diazoacetate in the ratio that mass ratio is 1:100 of catalyst Yu ethyl diazoacetate, react 18 hours under 110 DEG C of heating conditions, filter out catalyst, use ether as precipitant, dried polymerizate, by nucleus magnetic hydrogen spectrum, polymerization reaction system stock solution is detected, the conversion ratio calculating polymer is 88.86%, time-of-flight mass spectrometry detect the molecular mass of polymer is 7200Da.
Embodiment 5
Under the conditions of anhydrous and oxygen-free, with chloroform as solvent, be stirred continuously be passed through nitrogen under conditions of add poly-(N-isopropenyl) pyrrole radicals-palladium (II) catalyst, it is added dropwise over diazoacetic acid methyl ester in the ratio that mass ratio is 1:50 of catalyst Yu diazoacetic acid methyl ester, react 24 hours under 60 DEG C of heating conditions, filter out catalyst, use ether as precipitant, dried polymerizate, by nucleus magnetic hydrogen spectrum, polymerization reaction system stock solution is detected, the conversion ratio calculating polymer is 80.60%, time-of-flight mass spectrometry detect the molecular mass of polymer is 6500Da.
Embodiment 6
Under the conditions of anhydrous and oxygen-free, with toluene as solvent, be stirred continuously be passed through nitrogen under conditions of add poly-(N-isopropenyl) pyrazolyl-palladium (II) catalyst, it is added dropwise over diazoacetic acid n-propyl in the ratio that mass ratio is 1:60 of catalyst Yu diazoacetic acid n-propyl, react 17 hours under 150 DEG C of heating conditions, filter out catalyst, use ether as precipitant, dried polymerizate, by nucleus magnetic hydrogen spectrum, polymerization reaction system stock solution is detected, the conversion ratio calculating polymer is 83.23%, time-of-flight mass spectrometry detect the molecular mass of polymer is 7800Da.
Embodiment 7
Structural confirmation to polyimidazole base-palladium (II) catalysis ethyl diazoacetate polyreaction gained poly-(ethoxy carbonyl Cabbeen), its structural analysis parameter is:
Use Mercury VX-300 nuclear magnetic resonance spectrometer, deuterated reagent chloroform is solvent, tetramethylsilane be internal standard detect polymerizate hydrogen spectrum and carbon compose such as Fig. 2 and Fig. 3.Hydrogen spectrum and the carbon spectrum signal that can be concluded that polymerizate are sharp-pointed and regular unimodal of symmetry, show that obtained polymer is syndiotactic polymer.Wherein chemical shift is 3.15ppm, methine (-CH-) on the unimodal main chain belonging to polymer of 3.16ppm45.89ppm and 45.57ppm, chemical shift is that 171.01ppm and 170.91ppm belongs to carbonyl signals peak, it was demonstrated that resulting polymers is poly-(ethoxy carbonyl Cabbeen).
Use Shimadzu Biotech AximaTOF Matrix Assisted Laser Desorption-time of-flight mass spectrometer, detect to obtain mass spectrum such as Fig. 4 of polymerizate.It is appreciated that repetitive is 86Da from Fig. 4, is attributed to the mass number of ethoxy carbonyl Cabbeen (-CH (COOEt)-) chain link, it was demonstrated that resulting polymers is poly-(ethoxy carbonyl Cabbeen).
Embodiment 8 detects reactive intermediate palladium (the I)-alcoxyl carbonyl Cabbeen carbon radicals of poly-heterocyclic radical-palladium (II) catalysis alpha-carbonyl diazonium carboxylate polymerization reaction system
A () uses x-ray photoelectron spectroscopy (XSAM800) at beam wavelength λ=0.154nm, voltage is 40KV, electric current is to detect poly-heterocyclic radical-palladium catalyst before and after reaction respectively under conditions of 30mA, XPS spectrum figure such as Fig. 5 and Fig. 6 of gained catalyst.Detecting that the combination of the 2d5/2 track of reaction procatalyst Metal Palladium can be attributed to divalent palladium for 336.93eV, the combination with the 2d5/2 track of alpha-carbonyl diazonium carboxylate post catalyst reaction Metal Palladium can be 336.06eV, is attributed to 1 valency palladium.The quantivalence change of palladium catalyst before and after contrast reaction, illustrating that poly-heterocyclic radical-palladium (II) oxidation state of palladium during interacting with alpha-carbonyl diazonium carboxylate is reduced to 1 valency from divalent, the most also explanation has electron transfer to alpha-carbonyl diazonium carboxylate.
B () uses spin traps DMPO to combine electronic paramagnetic resonance spectrometer (Bruker Biospin A200) room temperature 25 DEG C, X-band, central field 3360.221G, sweep amplitude 100.00G, microwave power 19.510G, detects electron paramagnetic resonance spectrum (EPR) figure such as Fig. 7 of reactive intermediate diazonium free radical under conditions of microwave frequency 9.417GHz.The parameter palladium (I) captured by DMPO-alcoxyl carbonyl Cabbeen carbon radicals being detected is: hyperfine splitting constant aN=14.08G, aH=20.76G.
The present invention uses poly-heterocyclic radical-palladium (II) to be polymerized as catalyst alpha-carbonyl diazonium carboxylate, utilizes the space steric effect of poly-heterocyclic radical and conjugation stabilizing active intermediate palladium (I)-alcoxyl carbonyl Cabbeen carbon radicals to be passed to transfer inserting step progressively and produce poly-(the alcoxyl carbonyl Cabbeen) of stereospecificity.Poly-heterocyclic radical-palladium (II) catalyst can instead the rare metal rhodium of costliness, iridium catalyst be applied to prepare in the research of the polymer of stereospecificity and application.Poly-(the alcoxyl carbonyl Cabbeen) of prepared stereospecificity can be applicable to dyestuff, paint, print, the field such as intermingling material.
Claims (4)
1. the method preparing stereospecificity poly-(alcoxyl carbonyl Cabbeen), it is characterised in that include following step
Rapid: under the conditions of anhydrous and oxygen-free, in organic solvent, add poly-heterocyclic radical-palladium (II) catalyst, by catalysis
Agent is that 1:20～100 is added dropwise over alpha-carbonyl diazonium carboxylate, no with the mass ratio of alpha-carbonyl diazonium carboxylate
It is filled with nitrogen disconnectedly, reacting by heating 16～24 hours under the conditions of 20～200 DEG C, after the cooling of question response liquid, filter out
Catalyst, adds precipitant, drying precipitated, i.e. obtains stereospecificity poly-(alcoxyl carbonyl Cabbeen) solid；
Described stereospecificity poly-(alcoxyl carbonyl Cabbeen), has a structure shown in formula (A):
Wherein n is the positive integer more than 1；R is the linear paraffin base of 1～3 carbon；
Described poly-heterocyclic radical-palladium (II) is prepared by the following method and obtains: will be dissolved with palladium (II) chemical combination
The ethanol of thing is added dropwise to be dissolved with in the chloroform of poly-heterocyclic radical polymer, wherein palladium compound and poly-heterocyclic radical
The mass ratio of polymer is 1:1, and at 70 DEG C, heated and stirred is reacted 12 hours, filters, and is dried to obtain black poly-miscellaneous
Ring group-palladium (II) catalyst.
Method the most according to claim 1, it is characterised in that: described palladium (II) compound is chlorination
Palladium (II), four chloro palladium (II) acid sodium, perchloric acid two (2,2-bipyridyl) close palladium (II), two (oxalic acid)
Close palladium (II), dichloro four ammino palladium (II), dichloro two (triethyl phosphine) conjunction palladium (II), dichloro two (three
Phenylphosphine) close the one in palladium (II), two chloroformyl conjunction palladiums (II), palladium (II).
Method the most according to claim 1, it is characterised in that: described poly-heterocyclic radical is poly-(N-isopropyl
Thiazolinyl) pyrrole radicals, poly-(N-isopropenyl) imidazole radicals, poly-(N-isopropenyl) pyrazolyl, poly-(N-
Isopropenyl) pyridine radicals, one in poly-(N-isopropenyl) pyrimidine radicals.
Method the most according to claim 3, it is characterised in that: described poly-heterocyclic radical is poly-(N-isopropyl
Thiazolinyl) imidazoles.
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