Encyclopedia of polymer science and technology

9408 Pages·106.297 MB·English

by  Jacqueline I Kroschwitz, H F Mark

ACETYLENIC POLYMERS, SUBSTITUTED
Introduction
PolymerizationofacetylenewasfirstachievedbyNattaandhisco-workersusing
a Ti-based catalyst (1). Because of the lack of processability and stability, early
studies on polyacetylenes were motivated by theoretical and spectroscopic inter-
ests only. Then the discovery of the metallic conductivity of doped polyacetylene
(2–6)stimulatedresearchintothechemistryofpolyacetylene,andnowpolyacety-
leneisrecognizedasoneofthemostimportantconjugatedpolymers.Thefinding
by Natta and co-workers was followed by the modification of their catalytic sys-
tem. An explosive expansion in polyacetylene chemistry has been caused by the
entryoftheShirakawacatalystTi(O-n-C H ) –(C H ) Al.Itsveryuniqueability
4 9 4 2 5 3
to give a thin film of polyacetylene (7,8) has attracted the interest of solid-state
physicists, which has significantly contributed to the fundamental chemistry of
conjugatedmacromolecules.
Unfortunately,theintractabilityandunstabilityofpolyacetylenestrictlyin-
hibit its practical applications. Thus, an introduction of substituents onto poly-
acetylene backbone has been investigated to improve its processability. Early
attempts led to the conclusion that only sterically unhindered monosubstituted
acetylenes can be polymerized with the Ti-based Ziegler–Natta catalysts. Tradi-
tional ionic and radical initiators also lack the ability to provide high molecular
weight polymers from substituted acetylenes. In 1974 the first successful poly-
merizationofsubstitutedacetylenewasachievedwhenitwasfoundthat“Group
6”transitionmetalsarequiteactiveforthepolymerizationofphenylacetyleneto
a polymer with molecular weight over 104 (9). After this finding, there has been
muchefforttodevelophighlyactivecatalysts,totunethepolymerproperties,and
1
EncyclopediaofPolymerScienceandTechnology.CopyrightJohnWiley&Sons,Inc.Allrightsreserved.
2 ACETYLENICPOLYMERS,SUBSTITUTED Vol.1
alsotopreciselycontrolthepolymerstructure.Theseenergeticstudieshavepro-
ducedawidevarietyofpolymersfromacetylenederivativesincludingmono-and
disubstitutedacetylenes,α,ω-diynes,and1,3-diacetylenes.Thecarbon–carbonal-
ternatingdoublebondsinmainchainsofthesepolymersprovideanopportunityto
obtainuniquepropertiessuchasconductivity,nonlinearopticalproperties,mag-
netic properties, permeability, photo- and electroluminescent properties, and so
on,whicharenotaccessiblefromthecorrespondingvinylpolymers.
ManypapersintheliteraturehavefollowedthefindingbyMasudaandco-
workers(9).Thisarticlecoverstheliteraturefromthemid-1980suptomid-2000.
Asaresultoftherapidgrowthinthearea,thechemistryofpolymersfromacety-
lene, 1,3-diacetylenes, and α,ω-diacetylenes are excluded (see POLYACETYLENE;
DIACETYLENE and TRIACETYLENE POLYMERS). The first focus is on the polymeriza-
tion reaction of substituted acetylenes with various transition metal catalysts.
Thesynthesisoffunctionallydesignedpolyacetylenesisalsocovered.Readersare
encouragedtoaccessotherreviewsandmonographsonpolyacetylene(10–14),on
1,3-diacetylenes (15–19), and on α,ω-diynes (20,21). Previous review articles are
alsohelpfultosurveythechemistryofsubstitutedpolyacetylenes(10,13,22–29).
Polymerization Catalysts
Avarietyoftransitionmetalcatalystshavebeenfoundtopolymerizesubstituted
acetylenes.EffectivecatalystsrangefromGroup3toGroup10metals.Activityof
catalystsgreatlydependsonmonomerstructure;therefore,itisquiteimportant
torecognizethecharacteristicsofeachcatalyst.Table1listsrecentrepresentative
examplesforthepolymerizationofsubstitutedacetyleneswithvarioustransition
metal catalysts, which will help readers to understand the general features of
catalysts.
Group 3 Transition Metals. Examples for the polymerization of sub-
stituted acetylenes with “Group 3” transition metals are rather limited (134).
Ziegler–NattacatalystsbasedonGroup3transitionmetalspolymerizeacetylene
and its derivatives (32,33,62). The combination of Sc or lanthanide transition
metals with trialkylaluminum, eg, M(naphthenate)– and M(phosphonate)–i-
(C H ) Al, has been proven to provide high molecular weight polymers from
4 9 3
terminal aliphatic and aromatic alkynes. High molecular weight polymers
(M > 30,000) are available from aliphatic linear alkynes such as 1-hexyne
n
and 1-pentyne, whereas 1-alkynes with branching at α or β-position, eg,
3-methyl-1-pentyne and 4-methyl-1-pentyne, result in polymers in low yields
(32,33).Inasimilarway,phenylacetylenepolymerizesinthepresenceofaternary
Table1. SubstitutedAcetylenesThatFormHighMolecularWeightPolymerswithTransitionMetalCatalysts
Monomer Catalyst M ,103 Reference
n
[A]Monosubstitutedaliphatic
acetylenes[HC CR]
R=n-C H W(dmp) Cl –C H MgBr(a) 170 30,31
4 9 4 2 2 5
Nd(naphthenate) –i-(C H ) Al 35 32,33
3 4 9 3
CH(CH )C H Fe(acac) –(C H ) Alb 27 34
3 2 5 3 2 5 3
MoCl –(C H ) Sn 13 34
5 6 5 4
C(CH ) MoCl 33 35
3 3 5
MoOCl -n-Bu Sn-C H OH 149 36
4 4 2 5
MoCl (CO) (AsC H ) ) 335 37
2 3 6 5 2 2
(nbd)Rh+[(η6-C H )B−(C H ) ]c 28 38
6 5 6 5 3
(S)-(CH ) C(CH )C H Fe(acac) –i-(C H ) Alb [η]=1.22 39
2 2 3 2 5 3 4 9 3
Fe(acac) –(C H ) Alb 610 40
3 2 5 3
3
MoCl –(C H ) Sn 15 40
5 6 5 4
[(nbd)RhCl] –(C H ) Nc 96 41
2 2 5 3
Fe(acac) –(C H ) Alb 121 41
3 2 5 3
WCl –(C H ) Sn 14 42
6 6 5 4
Table1. (Continued)
Monomer Catalyst M ,103 Reference
n
Si(CH ) -n-C H WCl –(C H ) Sn 17 44
3 2 6 13 6 6 5 4
NbCl 39 44
5
CH(n-C H )Si(CH ) Mo(CO) –CCl –hν 105 45
5 11 3 3 6 4
n-C F WCl –(C H ) Sn [η]=0.08 46
6 13 6 6 5 4
CO -n-C H [(nbd)RhCl] 20 47
2 4 9 2
CO CH MoCl –(C H ) Sn [η]=0.063 48
2 3 5 6 5 4
CO H MoCl [η]=0.047 48
2 5
(Cp∗RuCl ) 4 49
2 2
CO -(−)-menthyl [(nbd)RhCl] c 250 50
2 2
MoOCl –n-(C H ) Sn 18 50
4 4 9 4
CH N(CH ) Ni(NCS) (P(C H ) ) 16 51
2 3 2 2 6 5 3 2
Pd(P(C H ) ) [C CCH N(CH ) ] 15 52
6 5 3 2 2 3 2 2
CH OH Pd(P(C H ) ) (C CCH OH) 53 52
2 6 5 3 2 2 2
CH -N-indolyl [(nbd)RhCl] –(C H ) Nc 71 53
4 2 2 2 5 3
CH CH(CO C H )PO(OC H ) WCl –C H AlCl 9 54
2 2 2 5 2 5 2 6 2 5 2
CH +P(C H ) B(C H ) − MoCl -(C H ) Sn 12 55
2 6 5 3 6 5 4 5 6 5 4
[B]Monosubstitutedaromaticacetylenes
Phenylacetylenes[HC CC H R]
6 4
R=H WCl –(C H ) Sn 15 56
6 6 5 4
W(CO) –CCl -hν 77 57
6 4
WCl (CO) (As(C H ) ) 33 37
2 3 6 5 3 2
W(CO) –(C H ) CCl -hν 21 58,59
6 6 5 2 2
Fe(acac) -(C H ) Alb 4.2 60,61
3 2 5 3
Sm(naphthenate) -i-(C H ) Al 184 62
3 4 9 3
(cod)Rh(L)PF –NaOHd 8.7 63
6
[(nbd)RhCl] –(C H ) Nc 160 64
2 2 5 3
p-n-C H Fe(acac) -(C H ) Alb 39 65
4 9 3 2 5 3
[(nbd)RhCl] –(C H ) Nc 240 65
2 2 5 3
MoCl -n-(C H ) Sn 9.2 65
5 4 9 4
p-Adme [(nbd)RhCl] –(C H ) Nc >1000 65
2 2 5 3
p-OCH [(nbd)RhCl] –(C H ) Nc 60(Mw) 66
3 2 2 5 3
p-Cl [(nbd)RhCl] –(C H ) Nc 260(Mw) 66
2 2 5 3
p-NO [(cod)RhCl] d 15.5 67
2 2
m-CH NC H [(nbd)RhCl] –(C H ) Nc 588 68
6 5 2 2 5 3
p-I WOCl 19 69
4
p-CO CH (nbd)Rh+[(η6-C H )B−(C H ) ]c 218 38
2 3 6 5 6 5 3
[(nbd)RhCl] –(C H ) Nc 158 70
2 2 5 3
[(nbd)RhCl] –(C H ) Nc 122 71
2 2 5 3
5
p-CO -(-)-menthyl [(nbd)RhCl] –(C H ) Nc 1260 72
2 2 2 5 3
p-(+)-OCONHC∗H(CH )C H [(nbd)RhCl] –(C H ) Nc 320 73
3 6 5 2 2 5 3
[(nbd)RhCl] –(C H ) Nc 51 74
2 2 5 3
p-(1R,2S)CH NHC∗H(CH )C∗H(OH)C H [(nbd)RhCl] c 48 75
2 3 6 5 2
p-N-n-(C H ) [(nbd)RhCl] –(C H ) Nc >1000 76
4 9 2 2 2 5 3
p-N-i-(C H ) [(nbd)RhCl] –(C H ) Nc – ∼
3 7 2 2 2 5 3
Table1. (Continued)
Monomer Catalyst M ,103 Reference
n
o-CH W(CO) –CCl –hν 170 78
3 6 4
WCl –(C H ) Sn 57 78
6 6 5 4
o-CF W(CO) –CCl -hν 260 79
3 6 4
WCl –(C H ) Sn 190 80
6 6 5 4
MoCl -(C H ) Sn 280 80
5 6 5 4
2,5-(CF ) W(CO) –CCl -hν [η]=0.352 81
3 2 6 4
o-Si(CH ) W(CO) –CCl -hν 1200 82
3 3 6 4
MoCl -n-(C H ) Sn-C H OH 43 83
5 4 9 4 2 5
Mo[OCH(CF ) ] ( N-Adm) CHC(CH ) C H (7g)e 14 84
3 2 2 3 2 6 5
o,o,m,m,p-F WCl –(C H ) Sn [η]=0.61 85
5 6 6 5 4
o,o,m,m,-F -p-n-C H WCl –(C H ) Sn 110 85
4 4 9 6 6 5 4
m-N NC H [(nbd)RhCl] –(C H ) Nc 110 86
6 5 2 2 5 3
o-Fc(14)f 7j 16 87
p-CH CHFc(15) f 7j 19 87
6 p-N NFc(16)f 7j 11 87
p-C CC H -p-C CFc(17)f 7j 18 88
6 4
Otheraromaticacetylenes[HC CAr]
Ar=1-Naphthyl 95 89
(3)
WCl –(C H ) Bi 46 90
6 6 5 3
WCl /dioxane 36 91
6
2-Naphthyl WCl –(C H ) Sn 9 92
6 6 5 4
1-Anthryl WCl –(C H ) Sn 37 93
6 6 5 4
2-Anthryl WCl –(C H ) Sn 9 93
6 6 5 4
9-Anthryl WCl Insoluble 90
6
[(nbd)RhCl] –(C H ) Nc 340 97
2 2 5 3
7
[(nbd)RhCl] –(C H ) Nc 11.7 98
2 2 5 3
Table1. (Continued)
Monomer Catalyst M ,103 Reference
n
[(cod)RhCl] d 95.3 99
2
[(nbd)RhCl] –(C H ) Nc 11 100
2 2 5 3
(cod)Rh(NH )Cld 150 101
3
8
Ferrocenyl[(η6-C H )Fe(η6-C H )](12) 7j 16.4 102
5 4 5 5
Ruthenocenyl[(η6-C H )Ru(η6-C H )](13) 7j 16 102
5 4 5 5
[C]Disubstitutedaliphaticacetylenes[R1C CR2]
R1=CH R2=n-C H MoCl 1100(M ) 103
3 3 7 5 w
C H C H WCl –(C H ) Sn Insoluble 104
2 5 2 5 6 6 5 4
(OAr) Ta[C(CH )C(CH )CH-t-C H ](py)g(3) 17.9 105
3 3 3 4 9
Cln-C H MoCl –n-(C H ) Sn 510 106
6 13 5 4 9 4
Brn-C H WCl 7.1 107
4 9 6
CH S-n-C H MoCl -(C H ) SiH 71 108
3 4 9 5 6 5 3
CH Fcf WCl –(C H ) Sn 16 109
3 6 6 5 4
CH Si(CH ) (18) TaCl 130 110
3 3 3 5
NbCl 210 110
5
TaCl -(C H ) Bi 1800 111
5 6 5 3
CH TaCl -(C H ) Bi 80 112
3 5 6 5 3
CH Si(CH ) C H TaCl -(C H ) Sn 150 113
3 3 2 6 5 5 6 5 4
CH Ge(CH ) TaCl 809 114
3 3 3 5
TaCl Insoluble 115
5
[D]Disubstitutedaromaticacetylenes[RC CAr]
R=CH Ar=C H TaCl [η]=2.70 116
3 6 5 5
9 TaCl -n-(C H ) Sn 600 117
5 4 9 4
ClC H MoCl -n-(C H ) Sn 690(M ) 118
6 5 5 4 9 4 w
ClC H -p-Adme MoCl -n-(C H ) Sn 110 119
6 4 5 4 9 4
C H C H WCl –(C H ) Sn Insoluble 120
6 5 6 5 6 6 5 4
C H C H -p-Si(CH ) TaCl -n-(C H ) Sn 750 121
6 5 6 4 3 3 5 4 9 4
122
C H C H -p-Si(C H ) TaCl -n-(C H ) Sn 1900 123
6 5 6 4 6 5 3 5 4 9 4
C H TaCl -n-(C H ) Sn >100 124
6 5 5 4 9 4
Table1. (Continued)
Monomer Catalyst M ,103 Reference
n
C H C H -p-OC(CF ) C[CF(CF ) ] TaCl -n-(C H ) Sn [η]=0.87 125
6 5 6 4 3 3 2 2 5 4 9 4
C H C H -p-C H TaCl -n-(C H ) Sn Insoluble 126
6 5 6 4 6 5 5 4 9 4
C H C H -p-N-Carbazolyl TaCl -n-(C H ) Sn 190 127
6 5 6 4 5 4 9 4
C H C H -p-Ge(CH ) TaCl -9-BBN 1000 128
6 5 6 4 3 3 5
C H C H -p-t-C H TaCl -n-(C H ) Sn 460 129
6 5 6 4 4 9 5 4 9 4
C H C H -p-CH C H TaCl -n-(C H ) Sn 350 126
6 5 6 4 2 6 5 5 4 9 4
C H C H -p-Adme TaCl -n-(C H ) Sn 2200 119
6 5 6 4 5 4 9 4
[E]Cyclicacetylenes
Cyclooctyne (CO) W=C(C H )OCH (4) Insoluble 130
1 5 6 5 3
0 (t-C H O) Mo C-n-C H g Insoluble 131
4 9 3 3 7
W (O-t-C H ) g Insoluble 132
2 4 9 6
PdCl (C H CN) Insoluble 133
2 6 5 2
admp=OC H -o,o-(CH ) .
6 3 3 2
bacac.=acetyleacetonate.
cnbd=bicyclo[2.2.1]hepta-2,5-diene(2,5-norbornadiene).
dcod=1,5-cyclooctadiene,
eAdm=1-adamantyl.
fpy=pyridine,Ar=o,o-i-(C H ) C H .
3 7 2 6 3
gRing-openingpolymerization.