Composition

A composition comprises (a) a carboxylic acid compound which contains at least three carbon atoms and (b) an amine such as an ethoxylated amine. The composition may be obtained by conventional powder blending or melt blending techniques. The compositions can be incorporated into an olefin polymer to give a polymer composition which has an increased crystallization temperature and/or improved optical properties.

The present invention relates to compositions, more particularly to 
compositions comprising additive mixtures suitable for incorporation into 
polymer materials, the production of polymer compositions and shaped 
articles formed from such compositions. 
Olefin polymers are readily available and widely used polymeric materials. 
The most excessively available olefin polymers are ethylene and propylene 
polymers, the term "polymer" being used to include copolymers. Propylene 
polymers have a melting point which is generally higher than that of 
ethylene polymers and hence propylene polymers are suitable for use at 
somewhat higher temperatures than ethylene polymers. Ethylene and 
propylene polymers can be used for packaging but moulded articles formed 
from these polymers generally show a high percentage of haze and hence are 
not satisfactory for applications in which good clarity is desirable. 
It is known that the addition of nucleating agents, for example sodium 
benzoate, to olefin polymers provides an increase in the crystallisation 
temperature, and/or an improvement in the optical properties, of the 
polymer. Furthermore, the use of nucleating agents can allow a shorter 
cycle time, and hence better productivity, in an injection moulding 
process. However, the use of such nucleating agents is often limited due 
to their high price, for example dibenzylidene sorbitol, or to dispersin 
problems, for example with sodium benzoate. 
We have now found that mixtures of certain readily available materials are 
effective in increasing the crystallisation temperature, and/or improving 
the optical properties, of olefin polymers. 
According to the present invention there is provided a composition 
comprising (a) a carboxylic acid compound which contains at least three 
carbon atoms; and (b) an amine. 
The carboxylic acid compound is preferably one containing at least two 
carboxylic acid groups attached to an optionally substituted saturated 
aliphatic hydrocarbon group or one containing at least one carboxylic acid 
group attached to an optically substituted ring system. Carboxylic acids 
containing at least two carboxylic acid groups attached to an aliphatic 
hydrocarbon group include glutaric acid, adipic acid, succinic acid, 
suberic acid, pimelic acid, azelaic acid and sebacic acid. Preferred 
carboxylic acids of this type contain two carboxylic acid groups and from 
three to ten carbon atoms. Carboxylic acids containing at least one 
carboxylic acid group attached to a ring system include monocarboxylic 
acids such as benzoic acid, toluic acid, and p-tertiary butyl benzoic 
acid, hydroxycarboxylic acids such as salicylic acid, and dicarboxylic 
acids such as phthalic acid, terephthalic acid, 
cyclohexane-1,2-dicarboxylic acid and cyclohexane-1,4-dicarboxylic acid. 
The amine which is component (b) may be a diamine or a substituted amine, 
for example an ethoxylated amine. Thus component (b) may be a compound of 
general formula I or II: 
##STR1## 
wherein: R is a hydrocarbyl group or a substituted hydrocarbyl group and 
is preferably a hydrocarbyl group containing at least four carbon atoms; 
R.sub.1 is a hydrocarbyl group, a substituted hydrocarbyl group or a group 
(R.sub.3 O).sub.x (C.sub.2 H.sub.4 O).sub.n H; 
R.sub.2 is a hydrocarbyl group, a substituted hydrocarbyl group or a group 
(R.sub.3 O).sub.x (C.sub.2 H.sub.4 O).sub.n H, and may be the same as, or 
different from, R.sub.1 ; 
R.sub.3 is an alkylene group containing 3 to 5 carbon atoms; 
m is an integer and has a value of 1 to 10; 
n is zero or is an integer which has a value of from 1 to 50; and 
x is zero or is an integer which has a value of from 1 to 50. 
Useful mixtures have been obtained in which the amine is a compound of 
formula II wherein at least one of the groups R.sub.1 and R.sub.2 is a 
group (R.sub.3 O).sub.x (C.sub.2 H.sub.4 O).sub.n H in which the value of 
n and/or x is from 1 to 50. A mixture of compounds may be used as 
component (b), for example a mixture of compounds in which the value of at 
least one of m, n and x differs. The mixture may be of compounds in which 
the nature of R varies, for example when R is a mixture of alkyl groups. 
If a mixture of compounds is used, such a mixture may be one of compounds 
of formula II in which there is present at least one group (R.sub.3 
O).sub.x (C.sub.2 H.sub.4 O).sub.n H in which group the value of n and/or 
x varies, and particularly at least one group in which x is zero and the 
value of n varies. 
The group R is preferably an alkyl group and particularly is an alkyl group 
containing at least 8 carbon atoms. Typically R does not contain more than 
20 carbon atoms. 
In the compound of formula I, R.sub.1 is preferably either a hydrogen atom 
[when the values of n and x are zero in the group (R.sub.3 O).sub.x 
(C.sub.2 H.sub.4 O).sub.n H], or is a methyl group or hydroxyethyl group. 
The value of m is preferably from 2 to 6. 
In the compound of formula II, the groups R.sub.1 and R.sub.2 are each, 
independently, either a group R or a group (R.sub.3 O).sub.x (C.sub.2 
H.sub.4 O).sub.n H in which the value of x is zero and n is 0 to 50. 
Preferably the groups R.sub.1 and R.sub.2 are both the same as the group R 
or at least one of R.sub.1 and R.sub.2 is a group (R.sub.3 O).sub.x 
(C.sub.2 H.sub.4 O).sub.n H in which the value of n is 1 to 50. Preferred 
amines are those in which at least one of the groups R, R.sub.1 and 
R.sub.2 is an alkyl group containing at least 8 carbon atoms, especially 
at least 12 carbon atoms. The group R.sub.3 is preferably a propylene 
group. Both n and x can be zero or at least one of n and x has a positive 
value. The value of n and x preferably does not exceed 20 and especially 
does not exceed 15. The group (R.sub.3 O).sub.x (C.sub.2 H.sub.4 O).sub.n 
H may be an OH ended alkylene oxide, for example a propylene oxide, group, 
an OH ended ethylene oxide group or may contain both alkylene oxide and 
ethylene oxide groups. If n and x both have a positive value, it is 
generally preferred that (n+x) has a value of 2 to 50, and preferably does 
not exceed 20 and especially does not exceed 15. 
If the acid or amine contains a substituted group, the substituent may be a 
hydroxy group, one or more halogen atoms, a nitrile group, a 
hydrocarbyloxy group, a hydrocarbonyl group such as an acyl group, a 
hydrocarbyloxycarbonyl or a hydrocarbonyloxy group, whereof the 
hydrocarbyl groups may be further substituted with substituent groups of 
the foregoing types. 
Amines which may be used in the compositions of the present invention 
include 
N,N-bis(hydroxyethyl)alkyl(C.sub.13 to C.sub.15) amine; 
N-methyl-N-hydroxyethyl-alkyl(C.sub.13 to C.sub.15)amine; 
N,N-dimethyl-octadecylamine; 
N,N-bis(hydroxyethyl)-octadecylamine; 
N-methyl-N,N-bis(coco)amine; 
N,N-dimethyl-tallowamine; and 
N-tallow-N,N',N'-tris(hydroxyethyl)-1,3-diaminopropane. 
The molar proportions of (a) and (b) can be varied widely, for example from 
10:1 to 1:10. However, we generally prefer to avoid a large excess of one 
component relative to the other component and hence we generally prefer 
that the molar proportions of (a) and (b) are from 10:1 to 1:3 
particularly 10:1 to 1:1. If component (a) is a dicarboxylic acid or 
component (b) is a diamine, the components may be used in essentially 
stoichiometric proportions, for example one mole of a dicarboxylic acid to 
two moles of a monoamine. 
The composition of the present invention may be incorporated into an olefin 
polymer. 
Thus, as a further aspect of the present invention there is provided a 
polymer composition which comprises an olefin polymer, a carboxylic acid 
compound which contains at least three carbon atoms and an amine. 
The carboxylic acid compound and the amine are components (a) and (b) of 
the composition discussed hereinbefore. 
In the polymer composition the proportion of the carboxylic acid compound 
is typically from 0.05 up to 3%, and preferably from 0.1 up to 1%, by 
weight relative to the polymer, and the proportion of the amine is 
typically from 0.05 up to 3%, and preferably from 0.1 up to 1.5%, by 
weight relative to the polymer. 
The olefin polymer (which term is used herein to include both homopolymers 
and copolymers) may be any ethylene homopolymer or copolymer, particularly 
high density polyethylene or linear low density polyethylene which is a 
copolymer of ethylene with a higher olefin monomer such as butene-1, 
hexene-1, octene-1 or 4-methylpentene-1. Alternatively, the olefin polymer 
may be a propylene homopolymer or copolymer, for example a random 
copolymer of propylene with up to 8% by weight, relative to the polymer, 
of ethylene, or a sequential polymer obtained by polymerising propylene in 
the essential absence of other monomers and thereafter copolymerising a 
mixture of ethylene and propylene to give a polymer containing from 5 up 
to 30% by weight of ethylene. 
The polymer composition may be obtained by adding the carboxylic acid and 
the amine separately to the olefin polymer or the acid and the amine may 
be pre-mixed and then added to the olefin polymer. The acid and the amine 
when incorporated into an olefin polymer, result in an increase in the 
crysallisation temperature and/or an improvement in optical properties of 
the polymer. The acid and amine which are used in the composition of the 
first aspect of the present invention can react together and we have found 
that the reaction product is less effective in giving the desired effects 
when incorporated into an olefin polymer. Accordingly, we prefer to avoid 
maintaining these compositions at an elevated temperature, for example 
above 120.degree. C. and especially above 200.degree. C., for a prolonged 
period of time, for example in excess of 15 minutes. 
Some components of the compositions of ethe first aspect of the present 
invention are either liquids or waxy solids at ambient temperature and are 
difficult to handle in this form, especially if accurate metering of the 
components is required. Hence, it may be preferred that the compositions 
are obtained as a polymer masterbatch containing a higher concentration of 
the composition than is required in the final polymer composition. The 
polymer masterbatch may be a mixture obtained by blending, without 
melting, with a particulate polymer. However, it is generally preferred 
that the masterbatch has been obtained by blending with molten polymer, 
and in this case it is particularly preferred that component (a) and 
component (b) are formed into separate masterbatches to minimise reaction 
between components (a) and (b). The amount of additive in the masterbatch 
is dependent on the nature of the particular additive. Typically the 
masterbatch contains at least 5% by weight of additive but in general the 
level of additive does not exceed 50% by weight. A convenient level of 
additive in the masterbatch is 10 to 15% by weight. If components (a) and 
(b) have been formed into separate masterbatches, these may be pre-mixed 
in any desired proportion and the mixture may be added to a polymer. 
Alternatively, the separate materbatches may be added separately to the 
polymer, without being premixed. We have found that with some amines, the 
use of a materbatch not only results in easier handling of the material 
but can also lead to improved colour in the final polymer composition. 
If a polymer masterbatch is formed, it will be appreciated that it is 
desirable that the polymer used to form the masterbatch should be 
compatible with the polymer used for the polymer composition. Thus, the 
polymer used for the masterbatch is preferably of the same general type as 
the polymer used for the polymer composition, for example both polymers 
are low density polyethylene or are both propylene homopolymers. In 
general the amount of masterbatch to be used is a minor proportion of the 
final polymer composition and compatibility may be more readily achieved 
using such relative proportions of the polymers. Typically the masterbatch 
is used in an amount of 1 to 10% by weight of the final composition when 
using a masterbatch containing 10% by weight of the acid and/or amine. 
Conveniently there is used 1 to 6% by weight of an amine masterbatch 
containing 10% by weight of amine and 3 to 5% by weight of an acid 
masterbatch containing 10% by weight of acid. Masterbatches containing 
other proportions of additive are added in the appropriate amounts in 
dependence on the level of additive in the masterbatch and the level 
required in the final polymer composition. 
The polymer compositions of the present invention possess an increased 
crystallisation temperature and/or improved optical properties compared to 
the original polymer. We have found that if the olefin polymer is a linear 
low density polyethylene, the incorporation of the carboxylic acid and the 
amine, in addition to giving improvements in optical properties and/or 
crystallisation temperature, can also result in improved gloss. 
The polymer composition of the present invention may also include other 
additives which are conventionally added to olefin polymers. Thus, the 
polymer composition may include other nucleating agents and we have 
observed further improvements in crystallisation temperature and/or in 
optical properties in compositions containing finely divided silica in 
proportions of less than 1% by weight relative to the polymer. By finely 
divided silica is meant silica having an average particle size of not more 
than 5 micrometers and especially not more than one micrometer. 
The polymer composition also typically includes additives to at least 
partially inhibit the degradation of the olefin polymer component of the 
composition. These additives include, inter alia, antioxidants, light 
stabilisers, antacids, lubricants and, as necessary, copper or metal 
deactivators. The proportion of each of such additives is typically less 
than 2% by weight based on the olefin polymer and is general does not 
exceed 1% by weight based on the olefin polymer. A wide range of additives 
which provide some inhibition of the degradation of olefin polymers are 
known and the skilled worker will be able to select appropriate additives 
in accordance with the particular olefin polymer and the conditions under 
which it is to be processed and used. Examples of additives which can be 
used include, inter alia, 
1,1,3-tris(2-methyl-4-hydroxy-5-tertiarybutylphenyl)butane in combination 
with dilaurylthiodipropionate; 
polymerised 1,2-dihydro-2,2,4-trimethylquinoline; 
2,6-di-tertiarybutyl-4-methylphenol; 
4,4-thio-bis-(6-tertiarybutyl-4-methylphenol); 
4,4-thio-bis-(6-tertiarybutyl-4-methylphenol); 
oxalic acid bis(benzylidene hydrazide); 
N,N'-bis(beta-3,5-ditertiarybutyl-4-hydroxyphenylpropiono)hydrazide; 
pentaerythritol-tetra-[3-(3,5-di-tertiary-butyl-4-hydroxyphenyl)propionate] 
; 
beta-(3,5-di-tertiary-butyl-4-hydroxyphenyl)-propionic acid-n-octadecyl 
ester; 
2,2-bis[4-(2-(3(3,5-di-tertiary-butyl-4-hydroxyphenyl)propionyl)oxy)ethoxy) 
phenyl]propane; 
2-(2'-hydroxyphenyl)-benzotriazole derivatives; 
2-hydroxybenzophenones such as 4-octoxy-2-hydroxybenzophenone; 
sterically hindered amines such as 4-benzoyl-2,2,6,6-tetramethylpiperidine; 
tris(2,4-di-tertiary-butylphenyl)phosphite; 
calcium stearate; 
zinc stearate; and 
dehydrotalcite. 
The polymeric compositions in accordance with the present invention may be 
formed into film and other shaped articles by any stable technique, 
particularly by extrusion or, especially, by injection moulding. We have 
found that the effectiveness of the composition of a carboxylic acid and 
an amine can be dependent to some extent on the technique used to obtain 
the shaped article. Particularly useful effects have been noted when the 
shaped article has been obtained by injection moulding. 
The composition of the present invention, and the polymer composition, may 
be obtained by blending the components of the composition together using 
any known, suitable technique as discussed previously herein. The polymer, 
carboxylic acid and amine may be mixed under conditions in which the 
polymer is molten, the mixture granulated and the granulated polymer used 
in a subsequent melt processing stage to give a shaped article, 
particularly by injection moulding. However, in order to minimise the time 
during which the acid and amine are mixed at elevated temperature, it is 
preferred that the acid and amine are added separately, or as a mixture 
obtained by a solids blending technique, to the polymer at the final stage 
of producing a shaped polymer article, for example at the injection 
moulding stage. 
The production of compositions and polymer compositions in accordance with 
the present invention are described in the following illustrative 
examples, in which some properties of the compositions produced are also 
given. Unless otherwise stated, percentages in the polymer composition are 
by weight relative to the polymer component.

EXAMPLES 1 TO 4 
Compositions were prepared by blending the components together on a two 
roll mill, the front roll being at 190.degree. C. and the back roll being 
at 150.degree. C. The polymer was added first and worked until melting 
occurred. The additives were then added to the mill and working was 
continued until the additives were completely homogenised (this required 
10 to 15 minutes from the initial addition of the polymer) and there was 
no evidence of particle agglomeration, as indicated by white specks in the 
crepe. The milled composition was granulated using a Pallman granulator. 
The granules were used to obtain a blown film by means of a Brabender 
8266-25D extruder having a 1.9 cm diameter screw having a length:diameter 
ratio of 25:1. The screw was operated at 45 r.p.m. and the temperature 
profile in the extruder to the die was 230.degree. C., 240.degree. C., 
250.degree. C. and 260.degree. C. (at the die). The polymer was extruded 
through an annular die gap of diameter 2.64 cm and width of 1 mm. The 
extruded tube was blown, by air pressure, to a blown film of diameter 
about 15 cm and having an average film thickness of 60 micrometers. 
The crystallisation temperature was determined by cooling a sample of the 
molten polymer composition at a rate of 20.degree. C. per minute using a 
Perkin-Elmer Differential Scanning Calorimeter. Percentage haze was 
determined in accordance with ASTM Test Method D 1003-59T using an "EEL" 
Spherical Haze Meter. 
The results obtained are set out in Table 1, together with the results of 
comparative examples not in accordance with the present invention. 
TABLE 1 
______________________________________ 
Example Additives Crys. temp (d) 
Haze 
or Polymer Type Weight Start Peak (%) 
Comp. E. 
(a) (b) (%) (c) 
(.degree.C.) 
(e) 
______________________________________ 
A I Nil Nil 111.5 107 68 
B I SiO.sub.2 
0.1 119 114 39 
C I A 0.5 117 108.5 
57 
D I AA 0.3 124.5 119.5 
24 
E I AA 0.5 123.5 119.5 
30 
1 I A 2.0 
122 117.5 
22 
AA 0.5 
2 I A 2.0 
AA 0.5 126 122 22 
SiO.sub.2 
0.1 
F I GA 0.3 128 122.5 
20 
G II Nil Nil 112 106.5 
61 
H II A 2.0 107 103.5 
52 
I II AA 0.3 126 121 15 
J II AA 0.5 129 125 18 
3 II A 2.0 
125.5 121.5 
26 
AA 0.5 
4 II A 2.0 
AA 0.5 128.5 125 16 
SiO.sub.2 
0.1 
K II GA 0.3 129 126 12 
______________________________________ 
Notes to TABLE 1 
(a) I is propylene homopolymer `Propathene` (Registered Trade Mark) grade 
GWE 26, available from Imperial Chemical Industries PLC. II is propylene 
homopolymer Novolen grade 1100 LX, available from BASF AG. 
(b) SiO.sub.2 is a finely divided hydrophobic silica, Sipernat 50S, 
available from Degussa AG. A is an ethoxylated amine of the type 
RN[(C.sub.2 H.sub.4 O).sub.n H].sub.2 where n has a value of one and R is 
a mixture of linear and branched aliphatic groups containing from 13 to 1 
carbon atoms. AA is adipic acid. GA is glutaric acid. 
(c) % weight is weight of additive relative to the polymer. 
(d) Crystallisation temperature is as determined by differential scanning 
calorimetry using a cooling rate of 20.degree. C./minute. 
(e) % haze is as determined in accordance with ASTM Test Method D 100359T 
and is measured on a sample of the film formed. 
EXAMPLES 5 AND 6 
The procedure of Examples 1 to 4 was repeated using two different linear 
low density polyethylenes and different additives, the processing 
conditions being the same. 
The results obtained are set out in Table 2, together with the results of 
comparative examples not in accordance with the present invention. 
TABLE 2 
______________________________________ 
Example Additives Haze Gloss 
or Polymer Type Weight (%) (%) 
Comp. Ex. 
(f) (b) (h) (%) (c) (e) (i) 
______________________________________ 
L III Nil Nil 22 41 
M III LD 15 14 66 
5 III LD 1 
A 0.1 10 78 
AA 0.5 
N IV Nil Nil 34 20 
O IV LD 15 22 63 
6 IV LD 15 
A 0.1 13 65 
AA 0.5 
______________________________________ 
Notes to Table 2 
(b), (c) and (e) are all as defined in Notes to Table 1. 
(f) III is a linear low density polyethylene available from Essochem as 
grade LL 1201. IV is a linear low density polyethylene available from 
Essochem as grade LL 1417. 
(h) LD is low density polyethylene and is available from Essochem as LD 
183. 
(i) % gloss is as determined on a sample of the film formed using the 
procedure of British Standard 2782, Method 515B. 
EXAMPLES 7 TO 10 
Further compositions were produced by the procedure of Examples 1 to 4 and 
the results are given in Table 3. 
TABLE 3 
______________________________________ 
Example Additives Crys. temp (d) 
Haze 
or Polymer Type Weight Start Peak (%) 
Comp. Ex. 
(j) (b) (%) (c) 
(.degree.C.) 
(.degree.C.) 
(e) 
______________________________________ 
P V Nil Nil 110.5 106 67 
Q V A 2.0 113 106.5 
46 
7 V A 0.1 
120.5 114 43 
AA 0.5 
8 V A 2.0 
118.5 113.5 
38 
AA 0.5 
R VI Nil Nil 113 106.5 
78 
S VI A 2.0 112.5 106.5 
72 
9 VI A 0.1 
127.5 122 69 
AA 0.5 
10 VI A 2.0 
127 124.5 
69 
AA 0.5 
______________________________________ 
Notes to Table 3 
(b), (c), (d) and (e) are all as defined in Notes to Table 1. 
(j) V is propylene homopolymer, `Propathene` (Registered Trade Mark) grad 
GWM 22, available from Imperial Chemical Industries PLC. VI is propylene 
copolymer, `Propathene` (Registered Trade Mark) grade GWM 101, available 
from Imperial Chemical Industries PLC. 
EXAMPLES 11 TO 18 
Further compositions were prepared and tested as follows. 
The additives were mixed with particulate polymer by tumble blending and 
extruding the power blend using a Betol extruder having a 25 mm diameter 
screw with a cavity transfer mixer. The temperature profile in the 
extruder was 190.degree. C. up to 220.degree. C., dropping to 205.degree. 
C. at the die. The extruded lace was passed through a water bath, dried 
and then granulated. 
The products obtained were then formed into discs of 8.9 cm diameter and 
1.6 mm thickness by injection moulding the granules using a Boy 30M 
injection moulding machine operating at 240.degree. C. and with a mould 
temperature of 50.degree. C. On ejection from the mould, the moulded discs 
were allowed to cool naturally. 
Haze measurements were effected on the injection moulded discs using a 
Gardner Hazemeter. 
The polymer used was a random copolymer of propylene and ethylene 
containing about 2.6% weight of ethylene and available as `Propathene` 
(Registered Trade Mark) grade PXC 22406 from Imperial Chemical Industries 
PLC. 
The results obtained are set out in Table 4, together with the results of 
comparative examples not in accordance with the present invention. 
TABLE 4 
______________________________________ 
Example Additives Cryst. Haze 
or Type Weight temp. peak 
(%) 
Comp. Ex. 
(b) (k) (%) (c) (.degree.C.) (1) 
(m) 
______________________________________ 
T Nil Nil 104.5 71 
U A 0.5 ND 88 
V A 1.0 ND 84 
W TBA 0.35 124 37 
11 TBA 0.35 
126 20.5 
A 0.54 
X BA 0.35 124 67 
12 BA 0.35 
125.5 27 
A 0.78 
Y AA 0.35 123 58 
13 AA 0.35 
123.5 44 
A 0.66 
14 AA 0.35 
123.5 41 
A 1.31 
Z C12 0.35 115 83 
15 C12 0.35 
120.5 45 
A 0.56 
16 C12 0.35 
120.5 45 
A 1.11 
17 C14 0.35 
121 49 
A 0.56 
18 C14 0.35 
121.5 47 
A 1.11 
______________________________________ 
Notes to Table 4 
(b) and (c) are both as defined in Notes to Table 1. 
(k) TBA is ptertiarybutylbenzoic acid. BA is benzoic acid. C12 is 
cyclohexane1,2-dicarboxylic acid. C14 is cyclohexane1,4-dicarboxylic acid 
(1) As determined by differential scanning colorimetry and is the 
temperature of the highest rate of crystallisation on cooling from the 
melt at 20.degree. C./minute. 
(m) % haze is determined in accordance with ASTM Test Method D 100359T 
using a Gardner Hazemeter and is measured on an injection moulded disc. 
ND means Not Determined. 
EXAMPLES 19 TO 25 
The procedure described for Examples 11 to 18 was repeated with the 
exception that the polymer used was a different random copolymer 
containing about 3% weight of ethylene and available as `Propathene` 
(Registered Trade Mark) grade PXC 22265 from Imperial Chemical Industries 
PLC. 
The results obtained are set out in Table 5, together with the results of 
comparative examples not in accordance with the present invention. 
TABLE 5 
______________________________________ 
Additives 
Example Type Cryst. Haze 
or (b) (k) Weight temp. peak 
(%) 
Comp. Ex. 
(n) (%) (c) (.degree.C.) (1) 
(m) 
______________________________________ 
AA Nil Nil 105 58 
AB SA 0.35 121 38 
19 SA 0.35 
123 25 
A 0.89 
AC GA 0.35 122 35 
20 GA 0.35 
123 29 
A 0.8 
AD AA 0.35 121 35 
21 AA 0.35 
122 30 
A 0.72 
AE SUA 0.35 ND 39 
22 SUA 0.35 
ND 34 
A 0.60 
AF BA 0.35 123 56 
23 BA 0.35 
123 46 
A 0.86 
AG TA 0.35 ND 49 
24 TA 0.35 
ND 39 
A 0.77 
AH TBA 0.35 121 34 
25 TBA 0.35 
124 33 
A 0.59 
______________________________________ 
Notes to Table 5 
(b) and (c) are both as defined in Notes to Table 1. 
(k), (l) and (m) are all as defined in Notes to Table 4. 
(n) SA is succinic acid. SUA is suberic acid. TA is toluic acid. 
ND means Not Determined. 
EXAMPLES 26 TO 28 
The procedure described for Examples 11 to 18 was repeated with the 
exception that the polymer used was polymer I as defined in Note (a) in 
Notes to Table 1. 
The results obtained are set out in Table 6. 
TABLE 6 
______________________________________ 
Additives 
Example Type Cryst. Haze 
or (b) (k) Weight temp. peak 
(%) 
Comp. Ex. 
(n) (%) (c) (.degree.C.) (1) 
(m) 
______________________________________ 
AI Nil Nil 116 77 
AJ GA 0.35 132 52 
26 GA 0.35 
133 48 
A 0.8 
AK SA 0.35 132 54 
27 SA 0.35 
135 41 
A 0.89 
AL BA 0.35 133 69 
28 BA 0.35 
135 47 
A 0.86 
______________________________________ 
Notes to Table 6 
(b) and (c) are both as defined in Notes to Table 1. 
(k), (l) and (m) are all as defined in Notes to Table 4. 
(n) is as defined in Notes to Table 5 
EXAMPLES 29 TO 36 
The procedure described for Examples 11 to 18 was repeated using different 
amines and the random copolymer used in Examples 19 to 25. 
The results obtained are set out in Table 7. 
TABLE 7 
______________________________________ 
Additives 
Example Type Haze Relative 
or (b) (k) Weight (%) Clarity 
Comp. Ex. 
(n) (o) (%) (c) (m) (p) 
______________________________________ 
AM Nil Nil 76 37 
AN MHA 0.9 71 35 
29 AA 0.35 
31 150 
MHA 0.9 
AO AA 0.35 43 107 
AP SA 0.35 42 115 
30 SA 0.35 
28 165 
MHA 0.9 
AQ GA 0.35 44 107 
31 GA 0.35 
29 160 
MHA 0.9 
AR DOA 0.35 66 35 
32 GA 0.35 
28 165 
DOA 0.5 
AS MCA 0.5 65 32 
33 GA 0.35 
30 175 
MCA 0.5 
34 GA 0.35 
27 175 
MTA 0.5 
AT THD 0.5 62 37 
35 GA 0.35 
29 165 
THD 0.5 
36 GA 0.35 
29 165 
A 0.5 
______________________________________ 
Notes to Table 7 
(b) and (c) are both as defined in Notes to Table 1. 
(k) and (m) are both as defined in Notes to Table 4. 
(n) is as defined in Notes to Table 5. 
(o) HMA is an ethoxylated amine of the type RR.sub.1 N(C.sub.2 H.sub.4 
O).sub.n H where R.sub.1 is methyl, n has a value of one and R is a 
mixture of linear and branched aliphatic groups containing from 13 to 15 
carbon atoms. DOA is an amine of the type RR.sub.1 R.sub.2 N where R is a 
octadecyl group and R.sub.1 and R.sub.2 are both methyl. MCA is 
N--methylN,N--bis(coco)amine. MTA is N,N--dimethyltallowamine. THD is 
N--tallowN,N',N'--tris(hydroxyethyl)1,3-diaminopropane. 
(p) Relative clarity is a comparison of the clarity of an injection 
moulded disc of the polymer compared to a standard. The apparatus consist 
of a light cabinet with a grid marked on the surface. 82.55 mm (3.25 
inches) above the top of the light cabinet is a flat support having a sli 
cut in it through which the grid is visible. The stand is surrounded by a 
enclosure with darkened interior surfaces. Two reference discs are stacke 
together and placed over the slit to almost totally obscure the image of 
the grid as viewed through this pile of two discs. The test specimens 
(injection moulded discs obtained as described in Examples 11 to 22) are 
stacked over the slit, adjacent to the reference discs, further discs 
being added to the stack until the image of the grid viewed through the 
test specimens is almost totally obscured and corresponds essentially wit 
the image seen through the reference discs. If exact correspondence is no 
achieved, an estimate of part discs is made. The relative clarity is 
expressed as the number of discs in the stack multiplied by 10, that is a 
relative clarity of 100 corresponds to a stack of 10 discs. 
EXAMPLES 37 TO 43 
Masterbatch compositions were prepared using either an acid or an amine. 
The masterbatches were prepared using the random propylene copolymer of 
Examples 19 to 25 and contained either 5% by weight of additive (adipic 
acid or glutaric acid) or 10% by weight of additive (succinic acid or the 
ethoxylated amine RN(C.sub.2 H.sub.4 OH).sub.2 where R is a mixture of 
linear and branched aliphatic groups containing from 13 to 15 carbon 
atoms). The masterbatches were prepared on a Polymix 150 type two roll 
mill (available from Schwabenthan) with the front roll at 190.degree. C. 
and the rear roll at 150.degree. C. The molten polymer was granulated 
using a Pallman type PS/2 granulator. 
Portions of the masterbatches thus obtained were added to a further 
quantity of the same random propylene copolymer in amounts to give the 
desired final level of acid, or acids, and amine, as set out in Table 8. 
The masterbatches were tumble blended with the polymer and the mixture 
thus obtained was extruded, granulated and finally injection moulded as in 
Examples 11 to 18. Injection moulded samples were also prepared by tumble 
blending masterbatches and polymer and injection moulding the mixture with 
no extrusion and granulating stages. 
The compositions produced and the results obtained are set out in Table 8. 
TABLE 8 
______________________________________ 
Additives 
Example Type Relative 
or (b) (k) Weight Clarity 
Comp. Ex. (n) (q) (%) (c) (p) (r) 
______________________________________ 
37 AA 0.30 
SA 0.085 127 
A 0.15 
38 AA 0.30 
SA 0.085 145* 
A 0.15 
39 AA* 0.30 
SA* 0.085 137 
A 0.15 
40 AA* 0.30 
SA* 0.085 165* 
A 0.15 
AU AA 0.30 
105 
SA 0.085 
41 AA 0.30 
122 
A 0.15 
AV AA 0.30 102 
AW GA 0.35 130 
42 GA 0.35 
145 
A 0.15 
43 GA 0.35 
160 
A 0.50 
______________________________________ 
Notes to Table 8 
(b) and (c) are both as defined in Notes to Table 1. 
(k) is as defined in Notes to Table 4. 
(n) is as defined in Notes to Table 5. 
(p) is as defined in Notes to Table 7. 
(q) *These components were added as powders and had not been preformed 
into a masterbatch. 
(r) *These results were obtained using moulded discs obtained by tumble 
blending polymer and additives (either as masterbatch or powder) and 
injection moulding the blended mixture without prior extrusion and 
granulation stages. 
EXAMPLES 44 TO 49 
The procedure described for Examples 11 to 18 was repeated using various 
mixtures of acids and amines and also various preformed reaction products 
of the acids and amines. 
The materials used, and the results obtained, are set out in Table 9. 
TABLE 9 
______________________________________ 
Additives 
Example Type Haze Relative 
or (b) (o) Weight (%) Clarity 
Comp. Ex. 
(s) (%) (c) (m) (p) 
______________________________________ 
AX Nil Nil 76 20 
44 AA 0.35 
48 90 
HMA 0.70 
45 AA 0.35 
46 97 
HMA 0.90 
AY RP 1 1.00 73 42 
AA RP 2 1.65 78 25 
BA RP 3 1.87 74 25 
BB RP 4 1.12 70 27 
BC RP 5 0.72 64 55 
46 AA 0.35 
ND 120 
A 0.50 
47 AA 0.35 
ND 125 
A 0.70 
48 AA 0.35 
ND 125 
A 0.90 
49 AA 0.35 
ND 130 
A 1.8 
______________________________________ 
Notes tc Table 9 
(b) and (c) are both as defined in Notes to Table 1. 
(m) is as defined in Notes to Table 4. 
(o) and (p) are both as defined in Notes to Table 7. 
(s) Each RP is a reaction product of an adipic acid and an amine obtained 
by stirring the acid and amine together, heating the mixture, under 
nitrogen, to 240.degree. C. and maintaining at 240.degree. C. for two 
hours. Reaction appeared to proceed quickly and to be essentially complet 
in 30 minutes. 
RP 1 is the reaction product of AA and HMA in a molar ratio of 1:1. 
RP 2 is the reaction product of AA and HMA in a molar ratio of 1:2. 
RP 3 is the reaction product of AA and A in a molar ratio of 1:2. 
RP 4 is the reaction product of AA and A in a molar ratio of 1:1. 
RP 5 is the reaction product of AA and A in a molar ratio of 2:1. 
Each RP material was used in an amount corresponding to 0.35% by weight o 
adipic acid. The products obtained were esters and in the case of RP 1 
some amide was also found to be present but amide was not detected in the 
other products.