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Commercial Plasticisers
D. L. BUSZARD
6.1 INTRODUCTION
TABLE 6.2
Plasticiser Abbreviations and Synonyms
TABLE 6.2-contd.
Preferred chemical Preferred Other names and
name" abbreviationsO abbreviations
Dioctyl adipate DOA DEHA, di(2-ethylhexyl) adipate
Dioctyl isophthalate DOIP
Dioctyl maleate DOM
Dioctyl phthalate DOP DEHP, di-(2-ethylhexyl) phthalate
Dioctyl terephthalate DOTP Di-(2-ethylhexyl) terephthalate
Dioctyl azelate DOZ Di-(2-ethylhexyl) azelate
Diphenyl cresyl phosphate DPCP CDP, cresyl diphenyl phosphate;
DPCF tolyl diphenyl phosphate
Dipropylene glycol DPDB
dibenzoate
Diphenyl octyl phosphate DPOP ODP, octyl diphenyl phosphate
DPOF
Diundecyl phthalate DUP
Epoxidised linseed oil ELO
Epoxidised soyabean oil ESO ESBO
Octyl decyl phthalate ODP Di-Alfold 810 phthalate
Poly(propylene adipate) PPA
Poly(propylene sebacate) PPS
Tributyl a-acetyl citrate TBAC
Tri(2-butoxyethyl) phos- TBEP
phate
Tributyl phosphate TBP
Tri(2-chlorethyl) phosphate TCEP
Tricresyl phosphate TCP, TCF, Tritolyl phosphate (particularly
TIP in UK)
Tri(2,3-dibromopropyl) TDBP 'Tris', T23P
phosphate
Tri(2,3-dichloropropyl) TDCP
phosphate
Triethyl a-acetyl citrate TEAC
Triisooctyl trimellitate TIOTM
Trioctyl phosphate TOF Tri(2-ethylhexyl) phosphate
Tetraoctyl pyromellitate TOPM Tetra(2-ethylhexyl) pyromellitate
Trixylyl phosphate TXP, Trixylenyl phosphate
TXF
3,3,5-Trimethylpentane 1,4- TXIB Texanol' isobutyrate
diol diisobutyrate
DBP and DIBP were widely used in PVC in the early 1950s. They
exhibit good efficiency but unfortunately their very high volatility and
poor aqueous extraction resistance lead to poor permanence prop-
erties. They have been replaced in the majority of plasticised PVC
applications by higher molecular weight phthalates, the exception
being certain areas where their rapid gelation properties are required
and their high volatility can be tolerated.
Certain plasticisers can seriously affect the growth of plants. 2 DBP
and DIBP have been shown to be very bad in this respect because of
6 Commercial Plasticisers 153
The Cs phthalates are the largest class of plasticisers in use today. The
most important are DOP, based on 2-ethylhexanol, and DIOP, based
on isooctanol. DA79 P, which was based on a mixed C7 , Cs and ~
branched chain alcohol, has recently ceased manufacture. DOP, DIOP
and DA79 P have very similar properties and are generally regarded as
interchangeable, the choice being dependent on the current supply
position.
More recently, DINP, diisononyl phthalate, based predominantly on
dimethyl-l-heptanols, has become available, giving generally lower
volatilities and lower plastisol viscosities than the Cs phthalates. The
other ~ phthalate, DNP, based on 3,5,5-trimethylheptanol, is
markedly less efficient and finds particular application where low
platisol viscosities are desirable-especially for semi-rigid dip coatings,
slush mouldings and rotational castings.
TABLE 6.3
Properties of Phthalate Plasticisers in PVC Compounds at 54 phr
Name Abbrevi- Liquid properties Extraction resistance
ation at 25°C BS Vola- (% mass loss)
Visco- soft- Cold tile Min-
sity Density ness flex loss eral Olive Deter-
(cSt) (g mr 1) IRHD No. eC) (%) Petrol oil oil Soap gent
Dibutyl ~
phthalate DBP 16 1·035 72 48 -19 17 23 18 19 18 15 r--
Diisobutyl ~
phthalate DIBP 29 1·042 74 45 -5 13 20 12 12 11 14 1;
'"::>~
Dioctyl
phthalate DOP 56 0·980 78 37 -19 1·0 24 19 18 4 3
Diisooctyl
phthalate DIOP 53 0·981 77 39 -16 1·0 24 17 17 4 3
Di-Alphanol
79 phtha-
late DA79P 48 0·983 80 36 -18 1·0 23 18 17 4 4
Dicapryl
phthalate DCP 55 0·968 79 36 -17 1·3 23 16 15 2·5 2·4
Di-n-octyl
phthalate DNOP 31 0·975 77 38 -25 0·7 25 19 23 2·1 2·0
Dinonyl
phthalate DNP 80 0·970 86 26 -8 0·2 24 17 18 2·0 2·0
Diisononyl
phthalate DINP 0·976 80 35 -14 0·3 16 16 15 0·6 0·9
Di-Linevol
79 phtha-
late Dlq9P 33 0·985 76 42 -26 0·8 24 21 21 6 3
Di-Linevol
911 phtha-
late D~l1P 49 0·962 87 27 -27 0·1 26 23 30 1·7 +0·8
Di-Alfol610
phthalate (DROP) 33 0·971 77 38 -27 0·7 21 20 19 3 1·8
Di-Alfol 810 0-
phthalate ODP 37 0·964 81 34 -25 0·2 20 18 18 1·2 0·8 ()
<:>
Diisodecyl 3
phthalate DIDP 85 0·962 84 26 -16 0·1 25 22 3
25 0·3 0·1 '"....
Diundecyl '"
phthalate DUP 54 0·947 91 20 -26 0·2 21 18 22 0 +0·2
a
Diisotri- ~~.
decyl phtha-
00'
late DTDP 243 0·950 95 13 -16 0 26 25 25 +1 +0·2 ;;;
'"
Benzyl butyl
phthalate BBP 45 1·124 79 35 -7 3·8 12 16 18 14 8
Di(2-meth-
oxyethyl)
phthalate DMEP 32 1·167 76 40 -12 10 8 14 15 16 17
Ul
Ul
-
156 D. L. Buszard
TABLE 6.4
Principal Commercial OXO Alcohols
Raw material Feedstock Alcohol
{n-Butanol
Propylene (Propylene) Isobutanol
2-Ethylhexanol
Propylene + butenes 'Heptenes' Isooctanol
Propylene 'Nonenes' Isodecanol
Isobutane 'Diisobutylene' Nonanol
Propylene 'Dodecenes' Tridecanol
Paraffin wax Co C8 olefines {AIPhanol79
Linevol79
TABLE 6.5
Major Producers of Linear Plasticiser Alcohols
7
1,o.sl.' 2 ,ali- mill I
Appa,.nl milling lim.: 15 min
plaslicis., loss
(%wIJ
6
OOP
OL 79P
OIOP
OL 911P
O+--_._---~----r_---_._---___r_
110 130 150 170 190
I.mp. S.tlin9 1° C)
DOP/DOA
to 50:50
If DOP/DOA
60:40
If
f
-10
DOP/DOA
70:30
l3'
f ,.,//
e...
r,,//
~
:s;c
..
;;: DOP
!
a
. -20
(//
l!
Cl.
E
!
it 610P
...
0
t -30
.. '
~--.~---.
_._810P
1 2 3 4 5 6
- Time [days]
Benzyl butyl phthalate is one of the most rapidly fusing plasticisers for
PVC, and in compounding allows regular production rates at lower
temperatures or higher rates at similar temperatures. In addition, it
imparts good stain resistance to vinyl films and hence is frequently used
for clear wear layers in vinyl flooring.
More recently, dioctyl terephthalate (DOTP) has been introduced
commercially in the United States by Eastman Chemicals. This product
is claimed to have lower volatility, and improved permanence and
lacquer mar resistance, compared with DOP.
Modified phthalates, such as Hexaplas OPN (ICI) are also available
from some companies. These have similar low-temperature properties
6 Commercial Plasticisers 159
TABLE 6.6
Comparative Performance of Triaryl Phosphates
Reofos TXP Reofos TTP Reofos
95 65 50
Formulation: PVC 100, plasticiser 54, white lead paste 4, calcium stearate 1.
36
~~
::1
28
26
24
TABLE 6.7
Performance of Different Phosphate Plasticiser Types in PVC Compounds at S4 phr
Reofos 50 TOF Santicizer Santicizer Phosphate DOP
(isopropyl- (trioctyl 141 148 blend (dioctyl
ated phosphate) (octyl- (isodecyl (60% Reofos phthalate)
phenyl diphenyl diphenyl 50140% DOA)
phosphate) phosphate) phosphate)
~
IRHD 83 78 76 78 76 78
BS softness No. 30 38 41 37 41 37 t""
tl:l
Cold flex temperature E;
N
(BS 2782 method .,I:>
104B) (0C) 3 -50 -19 -17 -18 -19 "'-
Volatile loss at 82°C (%) 1·0 1·7 1·7 0·7 2·0 1·1
Extraction resistance
weight loss (%)
Petrol 15 17 22 20 20 24
Mineral oil 13 16 21 17 17 19
Olive oil 13 18 21 16 18 18
Soap 12 12 19 17 12 4
Oxygen index (%) 34 27 29 29 29 24
6 Commercial Plasticisers 163
~
C-o-R
~
R-o-C~C-o-R
II II
o 0
Esters based on trimellitic anhydride have become very popular
primary plasticisers for PVC compounds, for use at high temperatures
or for applications requiring excellent resistance to aqueous extrac-
tants, e.g. washing machine parts. Table 6.8 gives a comparison of the
properties of various trimellitate plasticisers available commercially.
Since trimellitates are normally incorporated into PVC formulations
for high-temperature performance, most plasticiser manufacturers
supply them containing an antioxidant. Whether any additional
antioxidant is required will depend on the particular grade selected and
the ageing conditions to be encountered.
Branched chain trimellitates, such as Reomol ATM (Ciba-Geigy)
generally give better electrical properties, which are required for some
Cl.ble applications, whilst straight chain trimellitates, as with phtha-
lates, give better low-temperature properties.
TABLE 6.8
Properties of Trimellitate Plasticisers in PVC Compounds at 54 phr
Plasticisers Viscosity Density lRHD BS Clash Volatile
25°C 25°C soft- and loss Extraction resistance % mass loss
(cSt) (gml- I ) ness Berg (%) Mineral Olive Deter-
No. ("C) Petrol oil oil Soap gent
~
Tri-Alphanol 79 ~
trimellitate 181 0·995 84 30 -10 0·1 21 14 14 +0·1 +0·3 I:l:l
1:;
Tri-Linevol 79 N
l:l
trimellitate 107 0·993 83 30 -15 0·1 21 14 15 +0·2 +0·3 ~
Triisooctyl
trimellitate 250 0·988 91 20 -7 0·2 22 19 14 +0·4 +0·7
Tri(2-ethylhexyl)
trimellitate 205 0·985 88 24 -10 0·2 22 12 14 +0·4 +0·8
Tri-Alfol810
trimellitate 92·5 0·971 93 17 -20 0·1 26 26 22 +1 +0·8
6 Commercial Plasticisers 165
non-terminated
acid-terminated
RIf-O-C-RI-C4R-O-C-RI-e-1RIf alcohol-terminated
II II II II
o 0 0 0 n
TABLE 6.9 .....
~
Properties of Linear Diester Plasticisers in PVC Compounds at 54 phr
Plasticisers Viscosity Density IRHD BS Clash Volatile
at 25°C at 25°C soft- and loss Extractions (%)
(cSt) (g ml- 1 ) ness Berg (%) Mineral Olive Deter-
No. (0e) Petrol oil oil Soap gent
Diisodecyl
succinate 22·4 0·919 85 26 -38 1·8 25 24 24 4·5 1·9
Isooctyl ester
of AGS acids 13·5 0·928 79 37 -47 7·5 26 23 24 15 8
Isodecyl ester
of AGS acids 23·3 0·917 86 25 -38 1·0 23 23 24 3·5 1
~
Dioctyl t'"'
adipate 12·3 0·924 74 46 -45 2·4 26 22 26 7·5 4·5
t:x:l
Diisooctyl !;;
N
adipate 13·5 0·926 81 33 -48 1·7 25 21 21 8 4 s::.
Diisodecyl ~
adipate 22 0·912 85 27 -39 0·4 27 26 25 1·3 O·g
Benzyl octyl
adipate 14·2 0·916 74 45 -36 3·2 23 23 23 17 7·5
Diisooctyl
azelate 18 0·913 78 37 -47 0·6 24 22 25 1·4 1·0
Dibutyl
sebacate 8·7 0·933 72 48 -52 9 26 26 27 18 6
Dioctyl
sebacate 19·5 0·911 80 35 -51 0·5 24 24 25 0·4 0
Diisooctyl
sebacate 22·4 0·911 80 34 -46 0·4 26 27 26 1
6 Commercial Plasticisers 167
TABLE 6.10
The Effect of Molecular Weight on the Properties of Polypropylene Adipate
Molecular weight 2000 3000 4000 9000
Viscosity at 25°C (P) 150 250 350 850
Hydroxyl value (mg KOH g-l) 55 45 30 25
Compound properties
BS softness No. 27 24 23 20
Cold flex temperature eC) -1·7 -1·5 +2 +5·8
Volatile loss (%) 3·2 2·7 2·4 2·3
Tensile strength (MN m- 2) 17·8 19·8 19·9 20·8
Extraction loss (%)
Hexane 0·4 0·3 0·1 0·1
Mineral oil 1·0 0·4 0·1 0
Soap solution (1 %) 9·0 6·8 4·7 3·8
168 D. L. Buszard
Acid Adipic Adipic Adipic Adipic Adipic Adipic! Adipic! Phthalic Phthalic ~OP
phthalic phthalic anhydride anhydride
anhydride anhydride
Diol 1,2-Pro- 1,3-Bu- Neo- 1,3-Bu- 1,2-Pro- 1,2-Pro- 1,2-Pro- Dieth- 1,2-Pro- 0-
pylene tylene pentyl tylene pylene pylene pylene ylene pylene
glycol glycol glycol glycol glycol glycol glycol glycol glycol ~
Chain stopper Alcohol Alcohol Alcohol None None Alcohol Alcohol Alcohol Alcohol 3
Viscosity at 25°C (cP) 2300 3400 5500 22000 24000 800 32000 700 900 72 3
BS softness No. 32 34 30 25 24 36 29 33 34 45 '"
Cold flex eq -6 -7·5 0 -0·5 -1·5 -5 2 -2 1·5 -20 ~
Tensile strength "tl
(kgfcm- 2 ) 205 211 198 210 202 210 223 191 210 147 f
:::.
Volatile loss (%) 4·1 3·7 3·9 2·9 3·2 4·0 2·9 6·7 12·0 22·4 '"0;'
Volume resistance '"
;;:
(0 em-I) 1 x 1012 8 X lO" 6 X 10 13 1 X 10 12 5 X 10 12 2 X 1013 5 X 1013 3 X 10 12 6 X 1013 2 X 1013
Extraction loss (%)
Hexane 4·2 3·9 2·7 0·7 0·7 5·7 2·8 10·1 15·1 35·0
Mineral oil 3·9 H 1·8 0·1 0·7 5·5 3·4 6·0 4·3 16·0
Water 0·2 0·3 0·1 z.l 2·3 0·6 0·6 1·2 0·3 0
Soap solution (1%) 6·1 5·4 4·7 3·7 4·8 9·3 6·9 11·6 11·4 13·0
Humidity (com- Moderate Moderate Moderate Poor Poor Very Moderate Excellent Very Excellent
patibility) good good
....
0-
\0
170 D. L. Buszard
TABLE 6.13
Properties of Compounds" containing 'Cereclor'
Plasticiser
OlOP 54 38 35
OlDP 62 51 48
Re%s 95 66 30
Ceredor 845 25 15 35
Ceredor 852 30 20
BS softness No. 40 40 40 40 40 40 40 40
Shore A 75 75 75 75 75 75 75 75
Tensile strength
(MNm- Z) 17·3 17-8 17·2 15·6 17-6 16·2 20·1 19·3
% elongation at
break 300 315 320 315 325 330 245 290
Cold flex (0C) -16 -20 -16 -16 -18 -16 -6 -10
% ageing loss (24 h
at 100°C) 0·75 0·95 0·85 0·36 0·74 0·52 0·15 0·6
Volume resistivity
(0 cm x 1013) 2 2 2 0·6 0·5 0·6 6 3
° Formulated for constant BS softness by varying the plasticisers (amounts given in phr)
in otherwise the same formulation.
in the United States; and Toya Soda, Asahi Denka, and Ajinomoto in
Japan.
6.10.3 Monoesters
This group comprises a wide number of different plasticisers, the
majority of which are only of interest in certain specialist formulations.
Examples of these are butyl oleate, phenoxyethyl oleate and
tetrahydrofurfuryl oleate. They are claimed to be good low-
temperature secondary plasticisers with advantages in some plastisol
applications.
An exception which may be included in this class is Mesamoll, an
alkyl sulphonic acid ester, manufactured by Bayer and popular in
Germany. It is a good primary plasticiser with properties similar to the
general-purpose phthalates.
TABLE 6.14
Suitability of Polymeric Materials for Use as Flexible
Seals, etc., in Contact with Plasticisers
Material Ratinlf
Butyl rubber 1
Ethylene propylene rubber 2
Chlorosulphonated polyethylene 4
Natural rubber 4
Nitrile rubber 3
Polyamide 1
Polychloroprene 4
Polyethylene 2
Polypropylene 2
Polytetrafluoroethylene 1
Polyurethane 3
Silicone 2
Viton 2
-10 0 10 20 30 40 50 60 70 80 90 100110120130140
Ttlmptlraturtl, ·C
TABLE 6.15
European and US Plasticiser Manufacturers
Company Classes Trade names
manufactured
Q
United Kingdom
Albright & Wilson 1,2,4 Pliabrac
B.P. Chemicals 1,3,4,6E Bisoflex, Enerflex
Briggs & Townsend 5 Diolpate
Ciba-Geigy 1,2,3,4,5,6A,6F Reofos, Reomol,
Reoplast. Reoplex
Courtaulds 2
Diamond Shamrock
(Europe) 1,3,4,6A Lankroflex
ICI 1,4,6B Ceredor, Hexaplas
Robinson Bros 5 Arbeflex
Scott Bader 1,3,5 Crestapol
Shell Chemicals 1,6E Linevol, Dobane,
Dutrex
Tenneco 2
Victor Wolf 5,6C Wolflex
Austria
Chemie Linz Mollan
Belgium
Argus Chemicals 6A Drapex
Essochem Europe 1 Jayflex
Monsanto Europe 1,2,4,5,6F Santicizer
UCB-FTAL 1,3,4,6F
Denmark
Scandiflex 1,3,4 Scandinol
France
CdF Chemie 1 Gedeflex
D'Electrofine-Chemie 6E
ICI Europa 1,3,4 Hexaplas
Nyco S.A. 6D,6F Nycoflex
Products Chemie Ugine
Kuhlman 1 Plastifiant K
Rhone Poulenic Polymeres 1,2,4,5,6B Garbeflex, Garbefos,
Alaiflex
Germany
BASF 1,4,5,6F Palatinol, Plastomoll,
Palamoll
178 D. L. Buszard
TABLE 6.15-<:ontd.
Classes
Company manufactureda Trade names
TABLE 6. 15-contd.
Classes
Company manufacturedO Trade names
REFERENCES