International Union of Pure and Applied Chemistry
Hi! H I’m polyethylene . What’s your name?
Naming Polymers: buy one get one free Dick Jones IUPAC - Polymer Division
H poly[1-(methoxycarbonyl)-1-methylethane-1,2-diyl] !!
Naming Polymers: buy one get one free Dick Jones IUPAC - Polymer Division
n
A
monomer
A n
polymer
Source-based nomenclature: the polymer is named after the monomer (A) from which it is sourced.
Structure-based nomenclature: the rules of IUPAC organic nomenclature are adopted for naming the constitutional units (-A-) of the polymer.
SOURCE-BASED NOMENCLATURE •
The name of a polymer is made by prefixing the monomer name with ‘poly’.
•
The monomer names used are the systematic or retained names presently recommended by the IUPAC rules of organic nomenclature as found in the ‘Blue Book’. CH3
CH3 n n
CH2
CH C 2
COOCH3
CH CH2
CH C 2
n n
COOCH3
polyethene – monomer systematic name – monomer poly(methyl polystyrene –methacrylate) monomer name retained, name retained, poly(methyl 2-methylpropenoate) – monomer systematic name poly(ethenylbenzene) – monomer systematic name
What about Traditional Names? Based on obsolete monomer names that are not retained in organic IUPAC nomenclature, some traditional polymer names are allowed. Source-based polymer name
Traditional polymer name
polyethene
polyethylene
polypropene
polypropylene
poly(2-methylpropene)
polyisobutene
polytetrafluoroethene
polytetrafluoroethylene
polyaziridine
polyethyleneimine
poly(10-norborn-2-ene)
polynorbornene
•
A polymer with a structure that appears to result from the polymerization of a particular monomer but which has actually been synthesized by a different route is named as if it had been prepared from the apparent monomer.
Apparent monomer CH
CH2
Synthetic procedure
Source-based name poly(vinyl alcohol)
OH
CH
CH2
OAc
CH
CH2
+ H / H2O
n
CH2
CH
n
OH
OAc (CH2)4 O
C
C
O
NH
HN
poly[N,N'-(hexane-1,6-diyl) hexanediamide]
(CH2)6
HOOC O
O C
C
O
O CH2
(CH2)4
COOH
+
H2N
(CH2)6
- H2O
CO
(CH2)4
CONH
(CH2)6
NH
poly(ethylene terephthalate)
CH2 HOOC
H3C
NH2
COOH
+
HO
CH2
CH2
OH
- H2O
OC
COO
CH2
CH2
O n
poly(2,6-dimethyl-1,4phenylene oxide)
H3C O
H3C
H3C HO
OH
- H2O
O n
H3C
H3C
n
Copolymers and complex structures Italicized connectives or prefixes used alone or in combination. COPOLYMERS
FORMAT
-co-
sequential arrangement unknown
-stat-
statistical
poly[styrene-stat-(α-methylstyrene)]
-ran-
random
poly[ethene-ran-(vinyl acetate)]
-alt-
alternating
poly[styrene-alt-(maleic anhydride)]
-per-
periodic
poly(methanal-per-oxirane-per-oxirane)
-block-
block polymers
polystyrene-block-poly(methyl methacrylate)
-graft-
graft polymers
polyethene-graft-poly(butyl acrylate)
??
poly(ethylene-co-propylene)
Copolymers and complex structures TOPOLOGICAL PREFIXES and CONNECTIVES net-
network polymer
ipn-
interpenetrating network
star-
star-shaped polymer
comb-
comb-shaped polymer
branch-
branched polymer
cyclo-
cyclic polymer
STRUCTURE-BASED NOMENCLATURE •
The name of a polymer is made by prefixing the name of the preferred constitutional repeating unit (CRU) with ‘poly’.
•
The names of CRUs are those recommended by the IUPAC rules of organic nomenclature, so back to the ‘Blue Book’.
•
Determining the preferred CRU is just a matter of process.
(1) Write out a large enough portion of the polymer chain as to show the structural repetition…… Br CH2 CH Br
CH O
O CH2
CH2 CH Br
O
(2) The smallest repeating portion is a CRU so identify all the possibilities….. 6?
CH2
O (I)
CH2
CH Br
CH Br O (IV)
O (II) CH Br
CH
CH2
Br O (V)
CH Br
CH2
O
CH2
O
(III) CH2 (VI)
CH Br
(3) Next, in accordance with the IUPAC rules of organic nomenclature, name the divalent subunits that comprise the polymer chain starting with the largest …… ….. they are the bromo-substituted ethylenic, - CH2 - CH2 - , and the oxy, - O - , subunits found in CRUs II, III, IV and VI
(4) Call up ‘seniority rules’ …..
Rule 1, tells us that the basic order of seniority of subunits is: heterocyclic rings and ring systems > heteroatom chains > carbocyclic rings and ring systems > acyclic carbon chains The heteroatomic oxy, - O - , subunit is senior to the acyclic carbon chain bromo-substituted ethylenic, - CH2 - CH2 - , subunit….. …. so the preferred CRU will be either OCHCH2 Br CRU II
or
OCH2CH Br CRU VI
(5) Back to the Rule Book, No. 10d ….. The chain having substituents with the lowest locants is the preferred chain; the 1-bromoethylene unit of CRU II beats the 2-bromoethylene unit of CRU VI and OCHCH2 Br
is the preferred CRU, which is then named from left to right …..
oxy(1-bromoethylene) oxy(1-bromoethylene) or oxy(1-bromoethane-1,2-diyl) …. so the polymer is
poly[oxy(1-bromoethylene)]
Copolymers and other complex structures in Structure-based Nomenclature • No connectives or prefixes such as -co-, -stat-, -ran-, -block-, net-, star- etc. • Only makes use of commas (,) and oblique strokes (/). CH3 CH
CH2
C m
CH2
COOCH3
n
which was polystyrene-co-poly(methyl methacrylate) in source-based nomenclature is now
poly{(1-phenylethylene) , [1-(methoxycarbonyl)-1-methylethylene]} …. and polystyrene-block-poly(methyl methacrylate) is
poly(1-phenylethylene) / poly[1-(methoxycarbonyl)-1-methylethylene] • Simpler but much longer names with increasing complexity.
Ummh?
phew!
Other limitations or advantages? Source-based Nomenclature O
CH
CH2
O CH
CH
CH2 CH
CH2
n
poly(vinyloxirane)
CH2
n
O
H2C H2C
CH
CH
CH
CH
CH2
n
poly(buta-1,3-diene)
CH2 CH CH
CH2 CH2
n
Other limitations or advantages? Structure-based Nomenclature O
CH
CH2
O CH
CH
CH2 CH
CH2
poly{oxy(1-vinylethylene)}
n
CH2
poly(1-oxiranylethylene)
n
O
HC H2C
CH
CH
CH
CH2
CH2
n
poly(but-1-ene-1,4-diyl)
CH2 CH CH
CH2 CH2
n
poly(1-vinylethylene)
Actually, my friends H call me Perspex!
‘The Blue Book’ Nomenclature of Organic Chemistry IUPAC Recommendations and Preferred IUPAC Names 2013 Edited by H A Favre and W H Powell. RSC Publishing, Cambridge, UK [ISBN 978-0-85404-182-4]
‘The Purple Book’
A Brief Guide to Polymer Nomenclature
Compendium of Polymer Terminology and Nomenclature IUPAC Recommendations 2008 Edited by R G Jones, J Kahovec, R Stepto, E S Wilks, M Hess, T Kitayama and W V Metanomski. RSC Publishing, Cambridge, UK [ISBN 978-0-85404-491-7]
