10. Tariq Al-Anie- Ms Format(1)

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SYNTHESIS, CHARACTERIZATION AND STUDY OF NOVEL ALKYNE POLYMERS

TARIQ ABED-JALEEL

Department of Chemistry, College of Science, University of Anbaar, Iraq

ABSTRACT

A Novel acetylenic polymers were prepared through a polymeriation of a new monomers using an ionic radical

process of the transition comple!"

#!idative Coupling process has been used forpolydiacetylene $%DA& synthesis, while a free radical

polymeriation methods under atmospheric N' gas, has been used, for polyacetylene syntheses $%A&" (he synthesied

polymers were characteried by )(*I+, - N.+ spectra, viscosity and .wtaverage" (he new acetylene polymers were

used as composites on polystyrene to improve the /lectrical Conductivity of the semi* conductor materials" During this

wor0, %dCl', CuClwere used as catalyst, () and D.) as solvent"

KEYWORDS: Al0ynic %olymers, %oly Diacetylene, Composites, Conductivity

INTRODUCTION

Al0ynic polymer, has been of great interest due to its con1ugated functionality group, however, this polymer and

its derivatives have not been well studied because of synthetic difficulties" Con1ugated polymers are attracting chemists

attention for more than two because these polymers e!hibit some unique properties such as conductivity, non*linear optical properties and fluorescence.[1-!

(he conductive polyacetyleneoccupied and demonstrated the importance of industrial "and efficiency proved in

the industry solar cells, polymers batteries and devices as parts in electronic" Different methods were used for %reparation

of these polymers including thermal polymeriation, photo and radiation["-#!. Al0ynicpolymers used as part of the

conductive such diodes at the electric form"[$!

(he common way to produce this type of polymers is the ay method which uses transitional catalysis such as

$cuprous chloride&, 2laser Coupling method and /glitonmethod are used palladium, molybdenum, and copper as

comple!es catalysts, of initiations polymeriation"[%- &!

+ecent research able us to produce polyacetylene similitude or li0e to the semiconductor or the connected metal,

where con1ugated polyacetylene is relatively have small energy gap '1 - "()*" Doping methods was increased the

movement of charge carriers which gives ability of the high electrical conductive in the doping case and the common

materials, used with doping are iodine, bromine, and arsenicare made in several methods, including of electrical, chemical

comple!es and the charge transfer the double method has been used in this study" chemical doping and composite are a

method to increase the electrical conductivity properties .[+-113 %olydiacetylenes$%DAs& are con1ugated polymeric materials

with unique optical properties" %oly Diacetylenes was discovered by Carl 2laser in -456" It involves cuprous chloride

$CuCl& promoted o!idative homo*coupling reaction of terminal al0ynes in the presence of o!ygenin organic solvents,

ammonia and ammonium chloride"[1 !

./0(.20 (3456/0(.20

I7(57/47/8 J4257/8 49 A8(3 /73

N/25/8 S;(7;(0 'IJANS*

ISSN'P*: 1+-"<1"= ISSN'E*: 1+-"<

V48. ", I002( ", J27 - J28 <1#, $+-&<

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S>7?(00, C?/5/;(5@/47 /73 S23> 49 N4)(8 A8>7( P48>(50 %<

(he purpose of this paper is synthesis a novel poly*acetylene 'PA* and

%oly*Diacetylene 'PDA*from polymeriation reaction of terminal acetylenic monomers which were prepared in

the laboratory" product was doping with iodine element 'I* to improve electrical conductivity by increasing the o!idative

degree and electrons transfer ability in the polymers chains, (hen the composites was prepared from $ PA& and $PDA& on

the polystyrene, to development of the electrical conductivity properties of the insulating materials to semiconductor"

EPERIMENTAL SECTION

M/(5/80 /73 P54;(325(

C?(;/80: m*ydro!ybenaldhyde, /thanol $absolute&, methanol, D.), Chloroform, Sulfuric acid, %otassium

hydro!ide, %yridine and Ammonium chloride from 7D Co" %* hydr!y phenyl ethanmide* $paracetamol powder& from

China Co" (etrahydrofuran $()&, Iodin, Diethylether, Dichloromethane and %ropargyl bromide from )lu0a Co" (he

reaction monitored by thin layer chromatograph $(8C& carried out on silica plate" All solvents were purified prior to use

according to standard literature methods"

I7052(7/47: (he products were characteried by - N.+ spectra recorded an a 7ru0er "<< .9

spectrometer in CDCl: as the solvent and (.S as internal stander in al 7aath ;Univ* Syria" )(*I+ spectra were recorded

on Nicoletir -<<)(I+ ; spectrometer from =<< to =<<< cm *-and samples in >7rdisc form" /lectrical Conductivity were

measured in Digital pico ammeter +oo0ee India and .elting points were obtained from a )isher*?ohns melting apparatus"

M474(5 S>7?(00: Al0ynicmonomers were synthesied by the reaction of propargyl bromide with unsaturated

al0yneic halide +@, through SN mechanisma*-(?/73(--?(74>54/-1->7( 'A*, - -;/5/83(?>3( G-

?(74> G54/>7( 'B*.

(7(5/8 S>7?(; P54;(325(

In a three*nec0, round bottomed flas0 equipped with a reflu! condenser, a dropping funnel, thermo*meter and

provided with a magnetic stirrer" (he flas0 was charged with al0aline base $'"Bg, <"== mmol, >#& dissolved in an organic

solvent $'Bml alcohol& period stirring of -B minutes, $' * '"Bg, <"<-5 mmol& of substrate such as

$m*ydro!ybenaldhyde&, was added to the mi!ture" A $'ml, <"<-5 mmol& of freshly distilled %ropargyl bromide was then

added drop*wise to the well stirred reaction mi!ture, the reaction mi!ture was heated to 5<*<C <" After '*:h reaction

stopped and mi!ture cooled to room temperature" Ice water was added on reaction mi!ture and the crude product e!tracted

twice with $' -'ml& in dichloroethylen" (he organic layer evaporated and crystallied product obtained" Crystals was dried

in an oven for 'h at B< C<" melting point and )(*I+ Spectral was recorded"

P48>(50 S>7?(00

S>7?(00 49 P48>-D/;(>8(7( 'PDA*: %olymeriation carried out under atmosphere o!ygen$pure and dry&"In

#<8 flas0 $equipped with small side tube contacted with ballonet as the o!ygen stores& <.#1 of monomer $A& and<"=mg

%alladium chloride %dCl' $catalyst& dissolved in ml pyridine, then mi!ed with a solution of <"-g cuprous chloride

CuCl $co * catalyst& in :ml ()" (he reaction mi!ture was stirred at "<C< under #!ygen for # ?50, the polymeriation

stopped by the added a few drops of methanol, when the balloon sie was stability" After the polymeriation time the

resulting polymer solution was precipitated into an e!cess amount of methanol" (he precipitated polymer was filtered and

dried at =< C< for =hrs" (he dried yellow crystal polymer gives a yield %%, melting point, )(*I+ and N+ Spectral was

./0(.20 (3456/0(.20






S>7?(00, C?/5/;(5@/47 /73 S23> 49 N4)(8 A8>7( P48>(50 %1

recorded"

S>7?(00 49 P48>-A;(>8(7( 'PA*:%olymeriation was carried out under pure and dry Nitrogen gas N '"In B< ml

flas0 <"=:g of monomer 'B* was dissolved in : ml D.), 4. %alladium chloride $catalyst& dissolved in <"Bml pyridine,

and then stirred at room temperature under Nitrogen $N'& atmosphere for =hrs" (he polymeriation stopped by adding few

drops of methanol" (he product was filtered under vacuum pressure and recrystallied from methanol" A white crystal of

polymer $%As& was obtained at yield $<" .elting point, )(*I+ spectral was recorded"

D47 49 P48>(50 prepared %olymers have been doped by chemical doping method due to increase the

electrical conductivity, using the pure iodine within the system designed for this purpose, which consists of two flas0

connected through pipe provider for closure and opening is lin0ed to a pipe connected to a vacuum pump" eat of iodine

and allowed vapor to pass through a lin0 of connect to a second flas0 containing specimens of polyacetylene"

P5(/5/47 49 ;440(0 48>(50: In a -<< ml round flas0 equipped with a condensation, -g of pure

polystyrene $%sty& was dissolved in -< ml beneneas a solvent, and <":g of 'PDA* 45 'PA*al0ynic polymers was dissolved

in -< ml benene else, were together added to the reaction flas0" After that heating of the mi!ture to warm and stirred for -

hr, the mi!ture was poured into a glass mold capacity - cm ! -<cm for preparation of the thin film, and leave to dry at

room temperature for -<hrs"film were cut and compression in I+ device specimens of - ton pressure, to ma0e discs at -"B

cm for diameter and thic0ness ranges $<"<6 * <"--& mm due to measuring electrical conductivity" (he composites were

prepared in the different percentages of polymers on the polystyrene T/8( 1.

T/8( 1: C440(0 49 'P0> A8>7;48>(50* 7 D99(5(7 C47;(75/47

N4 C440(0 C47;(75/47 WV

- Composites $%sty %A& <"-<E E <"<4

E E <"<'

' Composites $%sty %DA& <"'<4

E E <"<<:

E E <"<<B

M(/025((7 49 V0;40> /73 A)(5/( M48(;28/5 W(?

Average molecular weight were measured by viscosity method'

−v M

* .Several mathematically equation are used

to calculated the true viscosity of novel polymers" +elative Fiscosity was calculated by use eq"-

<< t

t rel ==

η

η µ

$-&

S(;9; V0;40> > (.:

-

<

<

<

<−=

−

=

−

= rel t

t t spe η

η

η η η

$'&

+educed Fiscosity with eq:

./0(.20 (3456/0(.20






% T/5 A(3-J/8((8

C

red

C

sP red

-−==

η η η

$:&

Inherent Fiscosity eq"=

C

red inh

η η

ln=

" $=&

Intrinsic Fiscosity at eq"B

[ ] oC inhC

sP

c

→=

=

→

&$<

η η

η

G $B&

(hen drawn of the linear relationship between the values of the reduced viscosity on the y*a!is against the

concentration of the solution 'C* on the @*a!is" And the intersection of this straight line with the reduced viscosity a!is

represents the intrinsic viscosity'&"

M(/025((7 49 E8(;5;/8 C4732;)>: /lectrical conductivity has been measured of the composites

specimens of 'PDA* and 'PA* using electrical cell was laboratory designed for this purpose" Folumetric connectivity was

measured of to shed suitable voltage between the electrodes and then measure the current output by using the following

equation σ E I8 H AF, where """ A E cross*sectional area cm ', F E voltage, 8 E length specimens in cm, I E currentamps unit

and also the resistance is represent the invers of electrical conductivity cond" $

& E I H F, $*-cm*- E S cm*-&"

RESULTS AND DISCUSSIONS

P5(/5/47 /73 C?/5/;(5@/47 49 ?( T(57/8 A;(>8(7(474(50

.onomer A was prepared from conversion of hydro!yl group in the $p ; hydro!yl phenyl ethamide& paracetamol,

to pheno!ide ion which is a good nucleophile reagent using of alcoholic potassium hydro!ide, it is rapidly attac0 the

propargylbromid, by SN' mechanism reaction" Scheme -

S;?(( 1: S>7?(; R42( 4 M474(5 A

I/; F/;45 'JCC*: .+"#+ NAAS R/7: .%"



S>7?(00, C?/5/;(5@/47 /73 S23> 49 N4)(8 A8>7( P48>(50 %

T?( R(/;47 F4884(3 49 SN M(;?/70, 4 R/38> 945 'A* /0 T(57/8 A8>7(0 M474(5 /0 F48847 :

M474(5 B was prepared with reaction of hydro!yl group in m* ydro!ybenaldehyde and %ropargy l bromide

with alcoholic potassium hydro!ide to formation of 7 compound in 7arbeer reaction method, [1!shown in S;?(( .

S;?(( : S>7?(; R42( 4 M474(5 B

.echanism is shown in below and also followed SN

./0(.20 (3456/0(.20

A






%" T/5 A(3-J/8((8

S(;540;4> methods were used for characteried monomers such as" FT-IR show the characteristic of JC*

stretching for terminal acetylene in monomers 'A,B& where are clearly observed at $:'<< ; ::<< cm*-&, absorption bands

for C*#*C at $--'-* --'-cm*-& indicate of stretching in ether, *C'* at $-=<= cm*-& stretching in aliphatic, CECat $-B< *

-B4cm*-& for aromatic ring, absorption b and s for C* in aromatic ring $:<-<;:<56 cm *-& and pea0 for CE#at$-5B= ;

-<' cm*-&stretching in aldehyde and amide"[1"! are shown in F25( 1,

P5(/5/47 /73 C?/5/;(5@/47 49 ?( P48>- D/;(>8(7( 'PDA*

%olymeriation reaction of 'PDA& includes a two steps, firstly prepared of acetylene dimer AD by 2laser coupling

process of monomer A, and other polymeriation by o!idative coupling under o!ygen atmospheric, by using cuprous

chloride CuCl as catalysts factors, and () as asolvent, where are doing to remove hydrogen atoms from the terminal

acetylene, #n the other hand the using palladium dichloride %dCl' as catalyst were dissolved in pyridinium $basic& which

wor0s to removing the hydrogen atom from acetylene dimer, by reduction one of the two group of triple bond to formation

double bond as free radical ion" (he palladium be acta stripe factors to hydrogen atom and happening of trans $+& group in

the double bond" (he methanol were used to precipitate the polymer at yield 4'K, Schemes '*, (he 'PDA* are

synthesied by the topochemical polymeriation of diacetylenes, and believed the 'PDA* e!ist in two mesomeric forms"

I/; F/;45 'JCC*: .+"#+ NAAS R/7: .%"



S>7?(00, C?/5/;(5@/47 /73 S23> 49 N4)(8 A8>7( P48>(50 %#

S;?(( : S>7?(; R42( 4 'PDA*

Suggested mechanism of %oly Diacetylene $%DA& Synthesis are followed

PDA were Characteried by )(* *I+ Spectra, showed stretching-CC- for Dimer at $':5:cm*-*, CEC Al0enat

$-5:cm*-&, C* al0en $:<'4 cm*-*, F25( 1" N.+ spectral showed the chemical shift to *CJC* C ' at $'"B<&δ$s&,

phenyl group at$4"<&δ$m&* $"=:&δ$m&, + 'CEC*&in $:"4&δ$s&, C E # at $$6"<:&δ$s&, and *CJC ;CE C at $'"&δ $s&,*,

F25( .

./0(.20 (3456/0(.20






%$ T/5 A(3-J/8((8

P5(/5/47 /73 C?/5/;(5@/47 49 ?( P48>- A;(>8(7( 'PA*

PA were prepared by a free radicals %olymeriation of monomer -carbaldehyde*:*pheno!y ;propayne 'B*,

under nitrogen atmospheric $N'&, the reaction includes withdrawing terminal hydrogen atoms from the monomer, then to

reduce the secondary al0ene group by %dCl' $strong catalysts$which dissolved in D.) and pyridine as a base to assist for

removal of hydrogen atoms and brea0ing the one of the '* bonds to conversion SP hybridiation to SP, )rohner and

Luc0e studied the 0inetics of the reaction and found that the initial polymeriation rate is high and that the polyacetylene

yield is proportional to the concentration of the cobalt $catalysis& species" scheme $'&" FT-IR was used to characterie the

polymer" Spectra showed disappeared the triple bond of terminal al0yne J C * in ::<< cm *-, absorption band for ; C J C

* at ':- cm*-, strong stretching band were appeared at -5-B cm *- for" ; CE C *,pea0 at '64< cm *-appears that

corresponds to ; C stretching[1#! absorption band for CE # at-5:< cm *-,in aldehyde group and stretching band at -='5 cm*

-indicate to C* aliphatic*, F25( 1"

S;?(( : S>7?(; R42( 4 'PA*

Spectra of HNMR showed* C'* for al0anes $-"'& δ$s&, Ar ; C aromatic hydrogen at $-"'& δ $s&, +# ; C

ethers in $:":&δ$s&, *CE C; to $B":& δ$m&, phnyl group CEC* aromatic ring $"B& δ$m&, also hydrogen of aromatic ring at

$4"'& δ$m& and *CE# hydrogen for aldehyde at $6"=& δ$s&, F25( .

I/; F/;45 'JCC*: .+"#+ NAAS R/7: .%"



S>7?(00, C?/5/;(5@/47 /73 S23> 49 N4)(8 A8>7( P48>(50 %%

F25( 1: FT-IR S(;52 49 M474(50 P48>(50

./0(.20 (3456/0(.20






%& T/5 A(3-J/8((8

F25( : H1NMR S(;52 49 P48>(50

M(/025((7 49 A)(5/( M48(;28/5 W(?

Average molecular weight of 'PDA* and 'PA& was calculated with .ar0 ;ouwni0 equation:

[ ] a

v.> M ×=

$5&

)rom the values of viscosity which are calculated by use of several mathematically relationship" shown in the

table. ' G "* and F25( ', "*

T/8( : V/82(0 49 S(;9; V0;40> /73 R(32;(3 V0;40> 49 'PDA*

N4C47;"5(8<SP 5(8-10 5(8-1;

--<"'=<"<<<<5-"<'=<"<'==<<

'-<"':<"<<<<B'-"<':<"<':=='":<56':

:-<"-<"<<<<=-"<-<"<-:5-"<'-'

=-<"-=<"<<<<='-"<-=<"<-=:::":::::::

t<E-<

T/8( : V/82(0 49 S(;9; V0;40> /73 R(32;(3 V0;40> 49 'PA*

N4C47;"5(8<SP 5(8-10 5(8-1;

--<"<"<<<5-"<<"<--5"555555

'-<"B4<"<<<B'-"<B4<"<B4---"B:4=5-B

:-<"B<"<<<=-"<B<"<B-<5":4'64

=-<"<=<"<<<='-"<<=<"<<=6"B':4<6B'=

t<E-<

Falues of intrinsic viscosity'*to'PDA* was calculated from F25( : and to'PA* from F25( "

I/; F/;45 'JCC*: .+"#+ NAAS R/7: .%"



S>7?(00, C?/5/;(5@/47 /73 S23> 49 N4)(8 A8>7( P48>(50 %+

F25( : R(8/470? (((7 S(;9; V0;40>S /73 C47;(75/47 49 'PDA*

F25( ": R(8/470? (((7 S(;9; V0;40> 0 /73 C47;(75/47 49 'PA*

Falues of / and were obtained from another polyacetylene has a 0nown values of /, and viscosity are <.",

M +%<<. And by using electronic program with an computing methods"

T/8( ": V/82(0 49 , /,

−v M

/73 I7570; V0;40> 49 PDA /73 PA

((5/25

(I7570; V0;40>'38*/ P48>(5

:<55---B<"'6<"<B%DA

:<'''6<"'6<"<B%A

E8(;5;/8 C4732;)> 49 P48>(50

/lectrical conductivity were calculated for composites polymers in different concentrations and that from division

of output current on the input voltage" Calculated of the polystyrene conductivity give the value is -"--< *-' SCm*-&

$insulators plastic&" Insulator material has low conductivity $-<*-' ; -<*'' SCm*-&, but a semiconductor has

$-<: ; -<*-' SCm*-&" (he conductivity of the polyacetylene composites are increases with increasing concentration of

polymer $proportional relationship&"[1$!T/8( #" F25( #.

T/8( #: V/82(0 49 E8(;5;/8 C4732;)> 49 C440(0 PDA PA

C473. 'S*V ')48*I 7AC47;K"7"C4"

'":6:/*<4'6"'<"<<<<<<4<"'-%A

"45-/*--'6"''":/*<6<"<:'

-"-'::/*-<'6"'B/*<6<"<'B:

-":5645/*-<'6"'=/*<6<"<'-%DA

5"4=6:'/*--'6"''/*<6<"<<:':"='=55/*--'6"'-/*<6<"<<B:

./0(.20 (3456/0(.20

−

v M






&< T/5 A(3-J/8((8

PDA PA

F25( #: R(8/470? (((7 C4732;)> /73 C47;(75/47 49 P48>(5 C440(0

CONCLUSIONS

Successfully anovel 'PDAPA* has been synthesied by o!idative coupling reaction and free radical, which their

prepared from novel monomers and in less time and cost method" Spectroscopic methods )(I+, N.+ of polymers

showed that the characteristic of CE C stretching frequencies in $-5-B * -5:cm *&, $:"44 * B":<δ&, and in monomer

materials showing *JC* of terminal acetylene at $:'<< ; ::<< cm*-&" All results of this study are found to lie in good

agreement with the hypothetical case emphasiing the accuracy of the reactions"

REFERENCES

-" 7aris>is0an,OusufOagci" /lsevier 8td '<<4, =6, '=BB* '=5<"

'" Ooshihito onsho" Al0inori Sae0i and Shu Se0i", International ?ournal of SpectroscopyP '<-', -', ,

--BB*--5="

:" Alan ?" eeger Alan 2" .acDiarmid ide0i Shira0awa, the +oyalSwedish Academy of Sciences" Nobleprice

in chemistry '<<< to discovery conductive polymer

=" 7oChen, ?ianpingDeng and Lantai Oang, Colloid%olym" Sci, '<--,'46,-::;-:6

B" Abbas Ali /smaili, .ohammad Ali Nasseri, amidFesalipoor, A+>IF#C

5" 7eom ?in >im, Dong >ung #h, and ?i Ooung Chang, .acromolecular +esearch, '<<4, -5, ', -<:*-<"

" /unOoung%ar0, ?unLoo>im, Dong?uneAhn, ?ong*.an>im, .acromol" +apidCommun" '<<, '4,--;-B

4" >evin >" Dunham, 8acie and 7a0than S", --B5 igh St, Santa Cru, '<<5CA 6B<5="

6" 7renhart S", artwig Sch"P .algorsats 7"P 2earge N"P Ardreev CP ?uergen S" in spectrochimicaActaP %art A,

'<<B,5-, -:6B*-=<-"

-<" Conte, 2"P /ly, )"P 2allardo, "P 7ortolui, A" ?"P 8iq" Cryst '<<5, :', :5, -'-:*-'':

--" Lei 9hang, aibo@u, Oun Chen, Si Cheng" ACS Appl" .ater" Interfaces, '<-:, B, --, =5<:;=5<5

-'" 8i" S"8 and Stuup S"8, .acromolecules, -66, :o, B:-:*B:'<"

I/; F/;45 'JCC*: .+"#+ NAAS R/7: .%"

http://pubs.acs.org/action/doSearch?action=search&author=Zhang%2C+W&qsSearchArea=author


http://pubs.acs.org/action/doSearch?action=search&author=Xu%2C+H&qsSearchArea=author


http://pubs.acs.org/action/doSearch?action=search&author=Chen%2C+Y&qsSearchArea=author


http://pubs.acs.org/action/doSearch?action=search&author=Cheng%2C+S&qsSearchArea=author



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S>7?(00, C?/5/;(5@/47 /73 S23> 49 N4)(8 A8>7( P48>(50 &1

-:" Dolhem, )"P Al (ahli, )"P 8ievre, C"P Demailly, 2" /ur" ?" #rg" Chem", '<<B, ':, B<-6*B<':

-=" Oori0oSonoda" .olecules" '<--, -5, --6*-=4P doi -<"::6<"

-B" >eda u, aishen Oang, Lei 9hang and Oang Qin "Chemst" scien"'<-:, =, :5=6*:5B:"

-5" 7ora Ooon, ?ustyn?awors0i and ?ong*.an >im", Supramolecular Chemistry '<-:, 'B, -,B=;B6" '<<4, -=,

:=:*:=6"

./0(.20 (3456/0(.20

http://pubs.rsc.org/en/results?searchtext=Author%3AKeda%20Hu


http://pubs.rsc.org/en/results?searchtext=Author%3AHaishen%20Yang


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10. Tariq Al-Anie- Ms Format(1)

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