Patent Application: US-62820505-A

Abstract:
the use of at least one diazonium salt bearing an initiator function , for forming an undercoat obtained by grafting a graft derived from the diazonium salt and bearing an initiator function at the surface of a conductive or semiconductive material on the undercoat , and for forming on the undercoat a polymeric layer obtained by polymerization , in particular free radical polymerization , in situ of at least one monomer , initiated from the initiator function .

Description:
the starting amines were synthesized by a “ one pot ” procedure from 1 -( 4 - aminophenyl ) ethanol and ( 4 - aminophenyl ) methanol . two original diazonium salts bf 4 + n 2 c 6 h 4 ch ( ch 3 ) br 1 and bf 4 −+ n 2 c 6 h 4 ch 2 br 2 were synthesized by standard diazotation methods . 1 g of 2 - amino - 5 - methylbenzylalcohol ( 7 . 28 . 10 − 3 mol ; 1 eq .) and 1 . 23 g of tetramethylammonium bromide ( 8 . 10 − 3 mol ; 1 . 1 eq ) are placed in 5 ml of an aqueous solution of 48 % hydrobromic acid ( 1 . 82 . 10 − 2 mol ; 2 . 5 eq .) in a 50 ml flask . the solution obtained is left under stirring at 150 ° c ., under an argon atmosphere for 15 hours . a yellow precipitate is formed . the reaction mixture is cooled down to 0 ° c ., 5 ml of an aqueous solution of 48 % tetrafluoroboric acid ( 1 . 68 . 10 − 2 mol ; 5 . 6 eq .) cooled down beforehand to 0 ° c . is added . stirring is maintained for 15 minutes . 0 . 55 g of sodium nitrite ( 8 . 10 − 3 mol ; 1 . 1 eq .) is dissolved in a minimum amount of demineralized water . the solution obtained is cooled down to 0 ° c . then it is added progressively to the reaction medium . a brown precipitate appears . stirring is maintained for 30 minutes at 0 ° c ., then the solution is placed in the refrigerator overnight so that the diazonium salt precipitates . after filtration on sintered glass , the precipitate is washed with an aqueous solution of 5 % sodium tetrafluoroborate , methanol , and diethyl ether , then it is dried under vacuum . a brown powder is obtained . 0 . 5 g of 2 - aminobenzylalcohol ( 4 . 6 . 10 − 3 mol , 1 eq .) and 0 . 78 g of tetramethylammonium bromide ( 5 . 06 . 10 − 3 mol ; 1 . 1 eq ) are placed in 5 ml of an aqueous solution of 48 % hydrobromic acid ( 1 . 82 . 10 − 2 mol ; 3 . 96 eq .) in a 50 ml flask . the solution obtained is left under stirring at 150 ° c ., under an argon atmosphere for 15 hours . a yellow precipitate is formed . the reaction mixture is cooled down to 0 ° c ., 4 . 5 ml of an aqueous solution of 48 % tetrafluoroboric acid ( 1 . 64 . 10 − 2 mol ; 3 . 56 eq .) cooled down beforehand to 0 ° c . is added . stirring is maintained for 15 minutes . 0 . 34 g of sodium nitrite ( 5 . 06 . 10 − 3 mol ; 1 . 1 eq .) is dissolved in a minimum amount of demineralized water . the solution obtained is cooled down to 0 ° c ., then it is added progressively to the reaction medium . a brown precipitate appears . stirring is maintained for 30 minutes at 0 ° c ., then the solution is placed in a refrigerator overnight so that the diazonium salt precipitates . after filtration on sintered glass , the precipitate is washed with an aqueous solution of 5 % sodium tetrafluoroborate , methanol , and diethyl ether , then it is dried under vacuum . a brown powder is obtained . the reactions were carried out on carbon electrodes , then transposed onto iron ( fig1 ). a monoelectronic , broad , irreversible wave is observed at ep c =− 0 . 31 v / sce which corresponds to the concerted reduction of the diazonium salts to aryl radical which reacts with the iron surface according to reaction r1 ( see diagram 1 ). during the successive scannings , the height of this wave becomes very low as is usual with diazonium salts , the surface being progressively blocked by the grafting of aryl groups . on iron , this wave cannot be observed , the iron being too easily oxidized . the iron electrodes are carefully polished with diamond paste ( 1 μm ) then ultrasonically rinsed in deoxygenated acetone for 5 minutes in order to avoid to the maximum extent oxidation of the surface . in order to carry out the grafting the operation proceeds by chronoamperometry by applying voltages more negative ( δe =− 0 . 54 v ) than the peak measured on carbon ( and more cathodic than the voltage for iron oxidation ). fig2 shows a sharp drop in current which corresponds to the blocking of the electrode . after grafting , the electrodes are carefully ultrasonically rinsed in acn in order to eliminate the molecules which would only be physically adsorbed on the surface . it is also possible to carry out the grafting by simple immersion of the iron plate treated as previously in a deoxygenated solution with an argon stream 20 mm of 1 or 2 for one hour . after careful rinsing of the electrode in acetone in an ultrasonic bath , it is transferred into a solution containing only the solvent and the electrolyte ( acn + 0 . 1 m nbu 4 bf 4 ). fig3 shows the voltammogram of a vitreous carbon electrode grafted by reduction of 2 : cv + 2 ; an irreversible wave is observed at ep c =− 1 . 98 v / sce corresponding to the reduction of the c — br bond . on the return scan , a peak is observed at ep a =+ 0 . 83 v / sce which corresponds to the oxidation of the bromide formed at the level of the cathodic peak . by comparison , the reduction of benzyl bromide under the same conditions produces a peak at ep c =− 1 . 95 v / sce and the oxidation of tetraethylammonium bromide leads to a peak at ep a = 0 . 86 v / sce . a similar voltammogram is obtained in the case of 1 : cv + 1 ( fig4 ). the cathodic and anodic peaks therefore correspond respectively to the reactions r6 and r 7 of diagram 2 below . the two voltammograms of fig3 and 4 therefore prove the grafting of the vitreous carbon surface by the aryl groups originating from 1 and 2 . fig5 represents the ir spectrum by reflection ( irras ) of an iron surface grafted by 1 : fe + 1 . the most striking difference between the spectrum of the diazonium and the spectrum of the grafted organic layer is the absence of the band at 2258 cm − 1 indicating that the diazonium has indeed been reduced and is not only adsorbed on the surface . the signature of the aromatic group with the ring vibration at 1579 and 1508 cm − 1 ; the vibrations in the plane of the c — h bonds at 1083 cm − 1 and finally the vibrations of c — h outside the plane at 834 , 793 and 700 cm − 1 are clearly observed on the spectrum of fe + 1 . an interesting difference is observed in the zone of the chs ; whilst the vibrations of the aromatic ring are clearly visible in the spectrum of 1 at 3086 cm − 1 , they disappear to the benefit of the aliphatic ch vibrations at 2964 cm − 1 in the spectrum of fe + 1 . this is due to the selection rules which encourage vibrations the dipolar moment of which is perpendicular to the surface , as may be partly the case with the vibrations of the aliphatic ch of 1 . this is probably the same effect which is responsible for the attenuation of the band at 1083 cm − 1 in the spectrum of fe + 1 . fig6 represents the wide scan spectrum of a surface fe + 1 . the presence of the iron peak is observed thus indicating the presence of a relatively thin organic layer ( less than the xps analysis depth which is approximately 5 nm ). the peak of the bromine at 69 ev and that of the carbon at 285 ev prove the presence of the organic layer ( but also of an external contamination as regards the carbon ). the oxygen at 530 ev corresponds to the residual presence of oxide on the surface whilst the nitrogen ( 400 ev ) also originates from a contamination by the atmosphere , whilst the fluorine ( 685 ev ) very probably corresponds to traces of electrolyte remaining on the surface despite rinsing the samples . fig7 shows the spectrum of the c1s peak of the carbon of a sample of fe + 1 , a shoulder is observed corresponding after deconvolution to a peak situated at 283 . 2 ev which is indicative of carbon bonded to the metal , by comparison the iron carbide appears at 283 ev . the spectroscopic characterizations described above clearly show that the brominated grafts have indeed been fixed onto the surface of the iron . it will now be shown that it is possible starting with these grafts used as iniatiators to make the polymers grow on the surface . the surfaces grafted by simple immersion of the plate have characteristics similar to those described above . the experimental conditions for the grafting have been adjusted by using an initiator in solution and we have verified that the polymerization clearly shows the atom transfer radical polymerization ( atrp ) criteria . two monomers were used : on the one hand methyl methacrylate ( mma ) and on the other hand n - butyl acrylate ( anbu ), which should produce respectively methyl polymethacrylate ( vitreous transition temperature tg = 100 ° c .) and n - butyl polyacrylate ( tg =− 55 ° c .). typical experimental conditions are shown in table 1 below ; the previously grafted pellets as described above are immersed in the polymerization solutions ( see experimental conditions in table 1 ). after this stage , the iron plates are carefully ultrasonically rinsed in dichloromethane . a test was carried out in order to verify that the rinsing cycle was sufficient to eliminate the polymer residues adsorbed on the iron surface . an iron plate placed in contact with a pmma - toluene solution is heated for 4 hours at 90 ° c . in the absence of initiator and copper chloride . then , after 4 ultrasonic washings in dichloromethane lasting 5 minutes , analysis of the plate by irras reveals no polymer signal . at this time , pmma remains in the rinsing solvent ( ir analysis ) but the polymer has completely disappeared from the chloroform after a fifth washing . as this rinsing cycle was applied to the iron plates immersed in the polymerization solutions containing cu / cl and the initiator , the signals characteristic of pmma and panbu using irras and xps can be attributed to the grafted and non - adsorbed polymer ( fig1 , 11 , 12 , 13 , 14 ). ( b ) the solutions which have been degassed beforehand containing the ligand pmdeta : pentamethylediethylenetriamine ( see diagram 1 ), the monomer and the initiator 1 - pebr are added under a nitrogen atmosphere to the pellet iron and copper chloride . reaction time : mma 250 minutes for an approximate monomer conversion rate of approximately 40 %, anbu 400 minutes for a conversion rate of 80 %. the surfaces obtained from the diazonium salt 1 should have the following formulae : fig8 a , 8 b , 8 c and 8 d show the images obtained by afm on plates of fe , fe + 1 , iron + 1 + pmma and iron + 1 + panbu . these two last cases involve the grafted polymer coverings without the use of initiator in solution but only the initiator bonded with the iron substrate , but also an iron + 1 + pmma surface obtained in the presence of an initiator added to the solution . the image shows that the morphology of the iron surface is clearly modified by the grafting of the initiator and the consequent polymer coating . the maximum roughness increases in the direction fe & lt ; iron + 1 & lt ; iron + 1 + panbu & lt ; iron + 1 + pmma . the differences between the maximum heights obtained on iron + 1 and iron + 1 + polymer can reach a hundred nanometers . thus , in fig8 e , representing iron + 1 + pmma with an initiator , the thickness reaches approximately 200 nm , which shows that it is possible to obtain relatively thick coatings . fig9 represents the variation in thickness of the grafted layer , the height of the aggregates which can be observed on the surface and the roughness of the latter as a function of the polymerization time of panbu on a surface fe + 1 . it is thus observed that when the layer grows , the roughness remains constant which confirms the fact that dense brushes are obtained : the polymer chains lengthen but their differences in length do not change with their size . fig6 shows the spectrum of an iron surface grafted by the diazonium salt 1 . fig1 has the same surface after mma grafting , i . e ., covered with pmma ( fe + 1 + pmma ). it shows a clear increase in the relative intensities of the c1s and o1s lines relative to that of iron . table 2 shows the surface compositions for the surfaces grafted by 1 then covered with polymers . an increase in the relative proportion of carbon after grafting of the polymers is observed . the surface percentage of oxygen increases more particularly in the case of pmma , which is richer in oxygen than panbu . the percentage of iron reduces substantially , above all in the case of pmma , clearly indicating the growth of an organic layer on the surface . the slight decline during the polymerization of anbu indicates either a finer layer , or an irregular layer with many faults . it is interesting to note that for iron + 1 the line br 3 d is centred at 70 . 8 ev , a clear indication of the presence of bromine in an organic environment and more particularly in a c — br bond . however , after the growth of polymers chains , the presence of bromine is persistent at the surface of the grafted plates . this suggests that all the diazonium salts , which are analogues of grafted atrp initiators , do not react . moreover , on the surface of iron + 1 + polymer , a low bond energy shoulder indicates the possibility of the existence of bromide ions , probably trapped by the polymer , which have not been able to be eliminated during the ultrasonic washing cycle . in the case of iron + 1 + panbu , the chlorine is detected by its principal cl2p line centred at 199 . 2 ev . this value is close to the lower limit of the bond energy range for cl2p in pvc ( 196 . 5 - 198 ev ). unquestionably this shows that the chlorides originating from the catalyst react with the growing grafted chains of polymers in order to finally constitute the terminations of the latter ( see diagram 2 ) in the form of — ch 2 — ch 2 — cl . in order to verify whether the atrp is effectively initiated at the surface , we compared the chemical composition of the surface of iron plates treated in the presence or in the absence of initiator added in solution ( table 3 ). it appears that the absence of initiator in solution does not prevent polymerization taking place at the surface and that is due to the prior grafting of the brominated diazonium salt by electrochemical reduction at the surface of the iron . the higher value of the atomic percentage of carbon in the absence of initiator in solution appears to indicate the presence of longer macromolecular chains . the high - resolution spectrum of the c1s of iron + 1 + pmma ( fig1 ) shows a component centred at 289 ev , characteristic of the carbon o — c ═ o of pmma , the same is true for the iron + 1 + panbu represented in fig1 . the results of the xps analysis therefore demonstrate the presence of the two polymers on the surface of the iron . fig1 shows the spectra of fe + 1 and of fe + 1 + pmma with and without initiator in solution . the most remarkable difference between the spectrum of fe + 1 and the other two is the appearance , after the polymerisation stage , of a very intense band at 1735 cm − 1 which signifies the presence of the polymer by its carbonyl pendant group . this proof of the existence of the grafted pmma on the surface is reinforced by the appearance of broad and symmetrical bands at 1271 and 1148 cm − 1 which are characteristic of the c — o bond . the same is true for fe + 1 + panbu ( see fig1 ). the irras spectra therefore irrefutably confirm the presence of the polymer on the surface . polymerization using nitroxides is a controlled polymerization method based on the reversible blocking of the carrier radical of the active chain by a nitroxide radical . it has been used to grow , on silicon , polystyrene brushes of more of 100 nm ( huang et al ., 2001 ). as indicated in diagram 5 ( see hereafter ), an initiator comprising an alkoxyamine function is grafted onto the surface . during heating , the alkoxyamine group attached to the surface is cut in order to produce the alkyl radical and the stable nitroxide radical : tempo . recombination of the styrenic radical with the stable nitroxide radical ( tempo ) leads to a new alkoxyamine which is capable of thermal decomposition . the establishment of an equilibrium between dormant species and active species thanks to the reversible blocking of the chain in growth by the tempo radical makes it possible to limit the termination reactions and thus control the propagation stage . the diazonium salt of diagram 5 was synthesized from the corresponding amine in hbf 4 in the presence of nano 2 . this diazonium salt is grafted electrochemically while maintaining the voltage of an iron pellet treated as previously for 300 s at − 0 . 8 v / sce in acn + 0 . 1 m nbu 4 bf 4 . the grafting of the initiator was verified by xps which shows a ratio c / n = 19 and o / n = 1 . 3 which is close to that which is expected for the grafted surface ( c / n = 17 and o / n = 1 )( diagram 4 ). the iron pellet grafted as above is immersed in distilled styrene ( 10 ml ) and the temperature is taken to 130 ° c . for 24 hours . the pellet is then washed with dichloromethane ( cycles of 5 minutes , ultrasonically ) in order to remove the polystyrene which is only deposited on the surface . the presence of polystyrene on the surface is confirmed by irras by comparison with a standard polystyrene film . ring opening polymerization of cyclic esters produces biocompatible , biodegradable and bioresorbable aliphatic polyesters . the polymers synthesized by this method are poly ( ε - caprolactone ), poly ( lactide ), poly ( γ - valerolactone ), poly ( glycolic acid ), poly ( β - propiolactone ). poly ( ε - caprolactone ) is a polymer which is of interest as it is miscible with many other polymers . the polymerization is carried out by a coordination - insertion mechanism starting from an initiator of tin octoate ( sn ( oct ) 2 ) or aluminium triisopropanolate ( al ( oipr ) 3 ) or triethylaluminium ( alet 3 ) type ( cf . diagram 5 ). the aluminium or tin alcoholates can be formed in situ by exchange with available hydroxyl functions . in the present case , the hydroxyl function can be provided by the diazonium salt grafted onto the iron surface ( cf . diagram 6 ). the diazonium salt of 4 - aminophenol + n 2 c 6 h 4 oh , 4 - aminobenzyl alcohol + n 2 c 6 h 4 ch 2 oh and 2 -( 4 - aminophenyl ) ethanol was synthesized according to standard diazotation methods by nano 2 in hbf 4 acid medium . these three compounds show in cyclic voltammetry an irreversible and broad wave situated respectively at ep =− 0 . 28 , − 0 . 39 , − 0 . 12 v / sce . the grafting is carried out by maintaining the voltage 300 mv more negative than the peak for 300 s in acn + 0 . 1 m nbu 4 bf 4 . the grafted surface shows by irras the signal characteristic of the alcohol groups at 3380 cm − 1 . the monomers ( ε - caprolactone ) and the solvent ( toluene ) are purified by distillation on cah 2 . the iron plate containing the hydroxyl functions is purified by azeotropic distillations of toluene on a cold wall ( elimination of traces of water ). the solutions of monomer ( ε - caprolactone c = 10 − 2 mol l − 1 ) and initiator ( aluminium tri - isopropylate c = 10 − 3 mol l − 1 ) are then added to the toluene ( 20 ml ) by cannula transfer under an inert atmosphere of nitrogen and the polymerization is carried out at 100 ° c . for 20 hours . the pellet is then ultrasonically rinsed carefully for 20 minutes in toluene then ether . an irras spectrum of the surface shows a peak characteristic of the ester function at 1730 cm − 1 . a small quantity of formulation to be polymerized is deposited using a pipette onto a stainless steel slide covered with an under - layer which had been electrografted beforehand . the film is then formed by spreading the formulation using a “ wire - coater ” ( allowing a given thickness to be obtained ). the stainless steel slide is arranged on a glass plate before being exposed to uv light . the exposure is carried out using a fusion f300s uv lamp mounted on a model lc6e conveyor . after irradiation , the stainless steel slides are cleaned with acetone in order to eliminate any non - polymerized monomer . thickness of the deposit : 10 or 26 μm depending on the “ wire - coater ” used . dose of radiation received : controlled by the transport speed of the conveyor as well as by the number of passes under the lamp . irradiation range : controlled by the type of lamp used ( h or d ) ( fusion uv systems , inc ., md ., usa ). the bulbs used are quartz bulbs comprising a mixture of inert gases constituted by argon , neon and mercury under mean pressure . when a current is applied , the temperature of the mixture increases and vaporizes the small quantity of mercury present : a mercury vapour arc is therefore generated ; this corresponds to a bulb of type h with emission maxima between 240 - 270 nm and 350 - 380 nm . the bulbs of type d are prepared by adding a dopant in order to modify the emission maxima . the quantity of radiation received by the samples as well as the choice of lamp are dictated by the formulation to be polymerized as well as by the nature of the electrografted photoinitiator ( pi ). synthesis with stainless steel slides starting from the diazonium salt derived from benzophenone the tests are carried out in a 0 . 1n sulphuric acid medium and the diazonium salt derived from benzophenone is used at a concentration of 2 . 10 − 3 m . the work electrode is a 316l stainless steel electrode which is cleaned with a detergent and ultrasonically rinsed with distilled water . the counter electrode is a platinum sheet . the surface area ratio between the counter electrode and the work electrode is at least 3 . a continuous flow of argon into the solution allows the oxygen to be driven off . the electrochemical synthesis technique used is cyclic voltammetry . several attempts are made by modifying the final scanning voltage , and by keeping the other parameters fixed , namely a scanning speed of 200 mv / s and number of cycles carried out of 10 , the initial voltage being the equilibrium voltage . the tests were carried out with three final voltages : − 1 , − 1 . 3 and − 1 . 5 v /( ag / ag + ). and in all three cases the infrared analysis makes it possible to show that the stainless steel surface is clearly modified , by the presence of the carbonyl band characteristic of the graft at 1665 cm − 1 ( c ═ o ), 1600 cm − 1 ( elongation c ═ c ). the tests are carried out in a medium of 0 . 1 n sulphuric acid and the 4 - diazonium n - phenylmaleimide tetrafluoroborate salt derived from benzophenone is used at a concentration of 2 . 10 − 3 m . the electrodes used are the same as in the previous case . argon is bubbled through the solution throughout the experiments . the electrochemical synthesis technique used is cyclic voltammetry . several attempts are made by modifying the scanning speed , and by keeping the other parameters fixed , namely a final voltage of − 1 . 7 v /( ag / ag + ) and number of cycles carried out of 10 , the initial voltage being the equilibrium voltage . the tests were carried out with three scanning speeds : 20 , 50 and 200 mv / s . and in all three cases the infrared analysis makes it possible to show that the stainless steel surface is clearly modified , by the presence of the carbonyl band characteristic of the graft at 1730 cm − 1 ( c ═ o ), 1600 and 1535 cm − 1 ( elongation c ═ c ). the tests are carried out in an organic medium , using dimethylformamide ( dmf ) as solvent , tetraethylammonium perchlorate at a concentration of 5 . 10 − 2 m as salt , 4 - nitro benzene diazonium salt at a concentration of 2 . 10 − 3 m as polymerization initiator and the monomer irgacure ( 1 -[ 4 -( 2 - hydroxyethoxy )- phenyl ]- 2 - hydroxy - 2 - methyl - 1 - propane - 1 - one , ciba ) at a concentration of 2 m . the electrochemical synthesis technique used is cyclic voltammetry . several attempts are made by modifying the scanning speed ( 20 and 50 mv / s ), and the number of cycles ( 10 and 20 ). the final voltage is − 3 v /( ag / ag + ), and the initial voltage is the equilibrium voltage . the infrared analysis makes it possible to show that the surface is clearly modified by the polymer , as the characteristic bands are present , although their intensity is quite low ( less than 1 % of transmittance ): 3350 cm − 1 ( oh ), 1672 cm − 1 ( c ═ o ), ˜ 1600 cm − 1 ( elongation c ═ c ). v — immobilization of human serum albumin ( hsa ) on vitreous carbon surfaces modified by ps and pmma the immobilization of hsa on films of pmma ( methyl polymethacrylate ) and ps ( polystyrene ) grafted by atrp ( atom transfer radical polymerization ) onto vitreous carbon plates treated with 1 ( see example 1 ) was carried out at ambient temperature in an aqueous solution ( 0 . 1 m ch 3 coona — ch 3 cooh ) at ph 5 and with a protein concentration of 6 mg / ml . the vitreous carbon plates covered with polymer brushes ( according to the operating method described above ) were incubated in the protein solution , under stirring , for 24 hours . after incubation , the substrates ( plates on which the hsa proteins have been immobilized ) were washed 3 times for 30 minutes in an aqueous solution 5 % ( v / v ) of tween 20 ( surfactant ) and then 3 times with distilled water for 30 minutes , in order to eliminate the physisorbed protein molecules . after drying , the vitreous carbon plates modified by the polymer brushes and immobilizing the proteins were dried under vacuum for one hour and stored under ultra - 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