Patent Application: US-63945884-A

Abstract:
this invention relates to novel polymers of dipropargylamine and derivatives thereof , a process for preparing same and the electrically conductive polymers resulting from doping poly and derivatives thereof .

Description:
dipropargylamine and derivatives thereof of the formula : ## str2 ## wherein r is h , c 2 h 5 , ( ch 3 ) 3 c and ## str3 ## are polymerized in an inert atmosphere either ( 1 ) by heating at a temperature in the range 150 ° to 185 ° c . or ( 2 ) in an organic diluent containing a catalytic amount of pdcl 2 or wcl 6 , said diluent having a refluxing temperature in the range of 50 ° to 120 ° c . the resulting polymers , all hereinafter for the sake of brevity being referred to as dipropargylamine polymers , contain recurring structural units of the formula : ## str4 ## wherein r is as aforestated . the polymerization catalyst is present in an amount ranging from 0 . 25 to 2 % by weight of the monomer being polymerized . organic diluents employed in the polymerization having refluxing temperatures in the range of 50 ° to 120 ° c . include , but are not limited to , pyridine , benzene , toluene and hexane . the polymers have a weight average molecular weight in the range 5 , 000 to 10 , 000 . the dipropargylamine polymers can be made electrically conductive by p - doping using conventional methods . a wide variety of doping materials may suitably be employed in doping the dipropargylamine polymers to effectively modify its room temperature electrical conductivity . since the conductivity of the starting dipropargylamine polymers will be relatively low to begin with , i . e ., on the order of about 10 - 10 to 10 - 14 ohm - 1 cm - 1 , the required modification for most practical applications will be to effect an increase in conductivity . dopants suitable for effecting an increase in the room temperature p - type electrical conductivity of the dipropargylamine polymers starting material are electron acceptor dopants , including , for example , br 2 , i 2 , icl , ibr , asf 5 , cl 2 , hbr , bf 3 , bcl 3 , so 2 , so 3 , so 2 cl 2 , pof 3 , no 2 , hcn , icn , o 2 , sif 4 , no , tetracyanoquinodimethane ( tcnq ) and transition metal carbonyl , phosphine and olefin derivatives . each of these electron acceptor dopants will effect an increase , to varying degrees , in the room temperature p - type electrical conductivity of the dipropargylamine polymers starting material . the extent to which any given electron acceptor dopant will increase the conductivity of the dipropargylamine polymer will depend upon the degree of doping up to a certain point at which the maximum conductivity is obtained for that dopant . such maximum conductivity will generally be obtained at a degree of doping not greater than about 0 . 50 mole of electron acceptor dopant per mole of monomer unit . the highest room temperature p - type electrical conductivity thus far achieved in accordance with the present invention , i . e ., 10 - 3 ohm - 1 cm - 1 , was obtained with iodine doped dipropargylamine polymers containing about 0 . 5 mole of iodine per mole of monomer unit . in carrying out the method of the present invention for producing a p - type doped dipropargylamine polymers , the polymers are contacted with a dopant , which may be either in the vapor phase or in solution , whereby uptake of the dopant into the dipropargylamine polymer molecules occurs to a degree proportional to the dopant concentration and the contacting period . the contacting period is controlled so that the corresponding degree of doping will be such as to provide the resulting period dipropargylamine polymer with p - type electrical conductivity . for example , with the preferred electron acceptor dopants in accordance with the present invention , e . g ., iodine , the starting dipropargylamine polymer may be contacted in vacuum with the vapor of the electron acceptor dopant for a contacting period ranging from a few seconds to about 24 hours to provide a degree of doping within the range of from less than 0 . 10 to 0 . 50 moles of electron acceptor dopant per mole of monomer unit and thereby provide the doped dipropargylamine polymer with room temperature p - type electrical conductivity within the range of from about 10 - 7 to 10 - 3 ohm - 1 cm - 1 . a preferred doping procedure is to fill a vessel with powdered polymer to be doped . the vessel is then evacuated , and the vapor of the dopant is then allowed to enter the vessel . the doping procedure may also be carried out by placing the starting dipropargylamine polymer powder in a solution of the dopant , i . e ., tcnq or iodine , in an appropriate organic solvent inert to the dipropargylamine polymer , such as , for example , benzene , cyclohexane , tetrahydrofuran or the like . by trial and error , it is found what length of time is necessary to leave the dipropargylamine polymer in the solution to obtain the desired degree of doping . at the completion of the doping period , the doped polymers are removed from the doping solution and rinsed in an additional amount of the organic solvent to remove any residual doping solution therefrom , and the excess solvent is then pumped off in a high vacuum . thermogravimetric analysis of polymers were carried out on a dupont thermal analyzer , model 1090 . samples were preheated and cooled at room temperature in a desiccator prior to analysis . electrical conductivity of the polymers was measured on pellets compressed under 50 atm pressure using two nickel electrodes with a keithley electrometer ( 610 a ). the following examples will aid in explaining , but expressly not limit , the instant invention . unless otherwise noted , all parts and percentages are by weight . a mixture of 0 . 15 mole of t - butylamine , 0 . 35 mole of anhydrous , powdered potassium carbonate and 250 moles of ether was stirred mechanically and 0 . 25 mole of propargylbromide was added dropwise . the mixture was refluxed for about 10 hours . water was added to dissolve the salt . the ether layer was separated and the aqueous layer was extracted twice with ether . the combined ether solution was dried over anhydrous mgso 4 . the dipropargyl - t - butylamine produced was distilled at 63 °- 65 ° c ./ 20 mm hg to yield a yellowish liquid in a 45 % yield : ir 3300 , 3100 , 2980 and 2940 cm - 1 ; nmr ( cdcl 3 ) δ1 . 10 , 2 . 20 and 3 . 45 . propargyl bromide ( 0 . 75 mole ) was added dropwise with stirring to 1 mole of 70 % aqueous solution of ethylamine while maintaining the temperature at 35 °- 45 ° c . for 5 - 8 hours . after slow cooling to room temperature , 1 . 1 mole of sodium hydroxide solution was added dropwise with stirring over a 1 hour period . the layers were separated , the aqueous portion was extracted with ether and the extract was combined with the amine layer . the ethereal solution was dried over anhydrous potassium carbonate and fractionally distilled at 84 °- 87 ° c ./ 65 mm hg . to obtain a yellowish liquid , yield 45 %; ir 3300 , 2950 - 2980 ; 2120 cm - 1 ; nmr ( cdcl 3 ) δ , 0 . 88 - 1 . 25 , 2 . 20 - 2 . 70 , 3 . 20 - 3 . 40 . acetyl chloride ( 0 . 1 mole ) was added dropwise into the chloroform solution containing triethylamine ( 0 . 15 mole ) and 0 . 1 mole of purified n , n - dipropargylamine with constant stirring . the precipitate was separated by filtration and the chloroform solution was washed twice with water . the solution was then dried over anhydrous potassium carbonate . the dipropargylacetamide produced was distilled ( b . p . 80 °- 82 ° c ./ 15 mm hg ) and obtained in 80 % yield . ir 3300 , 3100 , 2990 and 1650 cm - 1 : nmr ( neat / tms ) δ2 . 0 , 2 . 45 - 2 . 60 and4 . 0 - 4 . 1 . dipropargylamine ( 5 . 0 g ), commercially available from aldrich chemical co ., and purified by distillation , b . p . 62 °- 65 ° c ./ 11 mm hg . were sealed in a glass tube and heated at b 175 ° c . for 4 days . a black , solid polymer product having a melting point in excess of 360 ° c . with no acetylene bond absorption at 2100 cm - 1 was obtained in quantitative yield . the product was not soluble in methylene chloride , tetrahydrofuran , pyridine or trifluoroacetic acid . dipropargylamine ( 3 . 0 g ), commercially available from aldrich chemical co ., and purified by distillation , b . p . 61 °- 65 ° c ./ 11 mm hg . were admixed with 1 % by weight of the monomer of pdcl 2 catalyst and 40 ml pyridine . the admixture was refluxed for 2 hours . the resultant dipropargylamine polymer product was obtained as a black solid having a melting point in excess of 360 ° c . in a 50 % yield . the product was slightly soluble in pyridine and contained no acetylene bond absorption . example 4 was repeated except that 5 . 0 g of dipropargyl - t - butylamine from example 1 was substituted for the dipropargylamine . a black , solid product in quantitative yield was obtained . the polymer product was soluble in pyridine and methylene chloride and decomposed at 230 ° c . example 5 was repeated except that 5 . 0 g of dipropargyl - t - butylamine was substituted for the dipropargylamine . the resultant dipropargyl - t - butylamine polymer was obtained in a 45 % yield . the polymer was soluble in pyridine , tetrahydrofuran and methylene chloride . the polymer decomposed at 170 ° c . example 4 was repeated except that 5 . 0 g of dipropargylethylamine was substituted for the dipropargylamine . the resultant dipropargylethylamine polymer was obtained as a brown solid in an 80 % yield . the polymer was soluble in pyridine . example 5 was repeated except that 5 . 0 g of dipropargylethylamine was substituted for the dipropragylamine . the resultant dipropargylethylamine polymer product was obtained as a brown solid in a 40 % yield . example 4 was repeated except that 5 . 0 g of dipropargylacetamide from example 3 was substituted for the dipropargylamine . the resultant dipropargylacetamide polymer product was obtained as a black , shiny solid in a quantitative yield having a melting point in excess of 360 ° c . the polymer product was soluble in pyridine and tetrahydrofuran and contained no acetylene bond absorption . example 5 was repeated except that 5 . 0 g of dipropargylacetamide from example 3 was substituted for the dipropargylamine . the resultant dipropargylacetamide polymer product was obtained as a black solid in a 40 - 50 % yield . the polymer product had a melting point in excess of 360 ° c . and was soluble in pyridine and methylene chloride . example 5 was repeated except that 5 . 0 g of dipropargylethylamine was substituted for the dipropargylamine , 1 % by weight of the monomer of wcl 6 was used as the catalyst , and 40 ml of benzene was substituted for the pyridine . the admixture was refluxed for 2 hours . the resultant dipropargylethylamine polymer product was obtained as a brown solid in a 10 % yield . various of the polymers from examples 4 - 12 were p - doped and measured for electrical conductivity . charge transfer complexes of the dipropargylamine polymers with tetracyanoquinodimethane ( tcnq ) were prepared by stirring a mixture of a weight amount of the polymer and tcnq in tetrahydrofuran at room temperature for several hours . the complex obtained was filtered , washed with methanol and dried under reduced pressure . the conductivity of the complex ( 0 . 5 : 1 mole ratio of tcnq to the monomer unit ) is set out in table i . additionally shown in table i is the electrical conductivity when the dipropargylamine polymers were p - doped with i 2 . crystals of i 2 were placed in a desiccator along with a weighed amount of the polymer and left to stand for several days . the results of the i 2 doping are also shown in table i : table i______________________________________electrical conductivities of polymers electricalpolymer / polymerization conductivitycondition dopant ( ohm . sup .- 1 cm . sup .- 1 at 25 ° c .) ______________________________________dipropargyl - t - butylamine -- 10 . sup .- 14 - 10 . sup .- 12 ( thermal ) i . sub . 2 10 . sup .- 6 tcnq 10 . sup .- 7 ( pdcl . sub . 2 catalyst ) -- 10 . sup .- 12 tcnq 10 . sup .- 5 i . sub . 2 10 . sup .- 7dipropargylamine polymer -- 10 . sup .- 12 ( thermal ) i . sub . 2 10 . sup .- 6 tcnq 10 . sup .- 6 ( pdc1 . sub . 2 catalyst ) -- 10 . sup .- 12 tcnq 10 . sup .- 5 i . sub . 2 10 . sup .- 4dipropargylacetamide -- 10 . sup .- 10 ( thermal ) i . sub . 2 10 . sup .- 4 tcnq 10 . sup .- 7 ( pdcl . sub . 2 catalyst ) -- 10 . sup .- 13 tcnq 10 . sup .- 4 i . sub . 2 10 . sup .- 6dipropargylethylamine -- 10 . sup .- 14 ( thermal ) i . sub . 2 10 . sup .- 5 tcnq 10 . sup .- 5 ( pdcl . sub . 2 catalyst ) -- 10 . sup .- 13 tcnq 10 . sup .- 4 i . sub . 2 10 . sup .- 3wcl . sub . 6 catalyst i . sub . 2 10 . sup . - 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