This invention relates to a polymeric material and
particularly, although not exclusively, relates to a
5 polyaryletherketone, especially to polyetheretherketone.
The thermoplastic polyaryletherketone polyetheretherketone
has been known for over twenty years. EP0001879B
(Imperial Chemical Industries) describes its preparation
10 and use and states that, to be use£ u1,
polyaryletherketones must have an inherent viscosity (IV)
of at least 0.7 dlg-' (which corresponds to a reduced
viscosity (RV) of at least 0.8 dlg-') measured according
to the method described in EP 0001879B. It is stated
15 that, if the IV is less than 0.7 dlg-', polymers prepared
are not tough but are brittle.
Consequently, whilst polymers of IV less than 0.7 dlg-'
have been prepared none is commercially available and none
20 has been used to manufacture components by, for example,
injection moulding or extrusion.
For many years, Imperial Chemical Industries and its
successor in title, Victrex Plc, were the sole
25 manufacturers of polyetheretherketone. In view of the
aforementioned companies1 accepted understanding as
regards the necessity for any useful polymer to have an IV
of at least 0.7 dlg-', the companies1 lowest viscosity
polyetheretherketone made commercially available had an MV
30 of 0.15 k ~ s m -(~Vi ctrex PEEK (Trade mark) 150) which
corresponds to an IV of 0..755 dlg-'). The company also
sells two higher viscosity materials, namely a medium
viscosity grade (Victrex PEEK 380 having an MV of 0.38
wsm-') and a standard viscosity grade (Victrex PEEK 450
having an MV of 0 . 4 5 kNsmb2).
Since EP0001879B expired other companies have made
5 polyetheretherketone. For example US6566484 B2 (Gharda
Chemicals) describes the preparation of a melt processible
polyetheretherketone polymer. The document describes
preparation of a range of polymers having different IVs,
but there is no suggestion that polymers having an IV of
10 less than 0 . 7 may have any advantageous properties or
commercial use. Gharda Chemicals manufactures and sells
polyetheretherketones; its lowest viscosity grade is
referred to as grade 5600 which is said to have Melt Flow
Rate (MFR) in the range 30-40 cc/l0 minutes. This grade
15 has an IV/W which is substantially the same as that of
Victrex PEEK 150 referred to above. The company also
sells Grades 5400 and 5300 which have substantially the
same IV/MV as Victrex PEEK grades 380 and 450
respectively.
20
It appears to have been accepted for many years in the
area of polyaryletherketones especially as regards
polyetheretherketone (which is by far the predominant
commercially available polyaryletherketone), that polymers
25 having an IV of less than 0 . 7 dlg-' are of no commercial
use. However, the present invention is based on a
surprising discovery that such polymers have useful
properties and that the long accepted statements in
EP0001879B are inaccurate. In particular, it is believed
30 that the test for toughness described in EP0001879B may
not be an accurate predictor of the properties and/or
usefulness of polyaryletherketone polymers.
It is an object of the present invention to provide
polyaryletherketone polymers which have advantageous and
useful properties.
5 According to a first aspect of the present invention,
there is provided a pack comprising a polymeric material
having a melt viscosity (MV) in the range 0.05 to 0.12
k ~ s mw-h~er ein said polymeric material is of a type which
includes :
10
(a) phenyl moieties;
(b) carbonyl moieties; and
(c) ether moieties.
15 MV is suitably measured using capillary rheometry
operating at 400°C at a shear rate of 1000s-~ using a
tungsten carbide die, 0.5x3.175mm.
Although the invention is described in terms of MV this
20 may be equated approximately to IV (measured as described
in EP0001879B) in accordance with figure 1 hereinafter.
It has surprisingly been found that, whilst the viscosity
of the polymeric material is significantly less than that
25 of the lowest viscosity commercially available
polyaryletherketone, the polymeric material has mechanical
properties which are similar to commercially available
Victrex PEEK 150. Advantageously, the lower viscosity may
enable the polymeric material to be used in applications,
30 for example for highly filled composite materials and/or
in injection moulding or extruding components having
relatively thin walls, where higher viscosity (e.9. PEEK
150) material could not be used.
Said polymeric material suitably has an MV of 0.06 kNsm-',
preferably has an MV of at least 0.07 kNsm-', more
preferably at least 0.08 kNsm-'.
5
Said polymeric material may have an MV of less than 0.11
k~sm-', preferably less than 0.10 kNsmb2.
Said polymeric material may have an MV in the range 0.07
10 to 0.12 k ~ s m - ~p,r eferably in the range 0.08 to
0.11 k~sm-', more preferably in the range 0.08 to 0.10
k~sm-~.
Said polymeric material preferably has an MV in the range
15 0.07 to 0.10 k N ~ m -m~o,re preferably in the range 0.08 to
0 .lo k ~ s m - ~ .
Said polymeric material may have a tensile strength,
measured in accordance with ASTM D790 of at least 80 MPa.
20 The tensile strength is preferably in the range 80-110
MPa, more preferably in the range 80-100 MPa.
Said polymeric material may have a flexural strength,
measured in accordance with ASTM D790 of at least 145 MPa.
25 The flexural strength is preferably in the range 145-180
MPa, more preferably in the range 145-165 MPa.
Said polymeric material may have a flexural modulus,
measured in accordance with ASTM D790, of at least 3.5
30 GPa. The flexural modulus is preferably in the range 3.5-
4.5 GPa, more preferably in the range 3.5-4.1 GPa.
Said pack may include at least lkg, suitably at least 5kg,
preferably at least 10kg, more preferably at least 14kg of
material of which at least a part is made up of a said
polymeric material. Said pack may include lOOOkg or less,
5 preferably 500 kg or less of said material. Preferred
packs include 10 to 500 kg of said material.
Said pack may include a composite material as described
hereinafter which includes a said polymeric material.
10
Said pack may include at least lkg, suitably at least 5kg,
preferably at least lOkg, more preferably at least 14kg of
a said polymeric material as described. Said pack may
include 1000kg or less, preferably 500kg or less of said
15 polymeric material. Preferred packs include 10 to 500 kg
of a said polymeric material.
Material in said pack (e.g. a composite material or a said
polymeric material per se) may be in powder or granular
20 form.
Said pack may comprise packaging material (which is
intended to be discarded or re-used) and a desired
material (e.g. a composite material and/or a said
25 polymeric material). Said packaging material preferably
substantially fully encloses said desired material. Said
packaging material may comprise a first receptacle, for
example a flexible receptacle such as a plastics bag in
which said desired material is arranged. The first
30 receptacle may be contained within a second receptacle for
example in a box such as a cardboard box.
Said desired material in said pack may comprise at least
90wt% of a said polymeric material and preferably consists
essentially of a said polymeric material.
5 Preferably, said polymeric material has a moiety of
formula
and/or a moiety of formula
10
15 wherein m,r,s and w independently represent zero or a
positive integer, E and El independently represent an
oxygen atom or a direct link, G represents an oxygen atom,
a direct link or a -0-Ph-0- moiety where Ph represents a
phenyl group and Ar is selected from one of the following
20 moieties (i) to (vi) which is bonded via one or more of its
phenyl moieties to adjacent moieties
(iii) (-t"eoa \ /
Unless otherwise stated in this specification, a phenyl
moiety has 1 - linkages to moieties to which it is
bonded.
15 In (i), the middle phenyl may be 1,4- or 1,3-substituted.
Said polymeric material may include more than one different
type of repeat unit of formula I; and more than one
different type of repeat unit of formula 11. Preferably,
however, only one type of repeat unit of formula I or I1 is
5 provided.
Said moieties I and I1 are suitably repeat units. In the
polymeric material, units I and I1 are suitably bonded to
one another - that is, with no other atoms or groups being
10 bonded between units I and 11.
Where w is greater than zero, the respective phenylene
moieties may independently have 1,4- or 1,3-linkages to the
other moieties in the repeat units of formulae 11.
15 Preferably, said phenylene moieties have 1,4- linkages.
Suitably, "an represents the mole % of units of formula I
in said polymeric material, suitably wherein each unit I is
the same; and "bN represents the mole % of units of formula
20 I1 in said polymeric material, suitably wherein each unit
I1 is the same. Preferably, a is in the range 45-100, more
preferably in the range 45-55, especially in the range 48-
52. Preferably, b is in the range 0-55, more preferably in
the range 45-55, especially in the range 48-52.
25 Preferably, the ratio of a to b is in the range 0.9 to 1.1
and, more preferably, is about 1. Suitably, the sum of a
and b is at least 90, preferably at least 95, more
preferably at least 99, especially about 100. Preferably,
said polymeric material consists essentially of moieties I
30 and 11.
Said polymeric material may be a homopolymer having a
repeat unit of general formula
or a random or block copolymer of at least two different
units of IV, wherein A and B independently represent 0 or 1
5 and E,E1 ,G,Ar,m,r,s and w are as described in any statement
herein.
As an alternative to a polymeric material comprising
unit (s) IV discussed above, said polymeric material may be
10 a homopolymer having a repeat unit of general formula
or a random or block copolymer of at least two different
units of IV* wherein A and B, independently represent 0 or
15 1 and E, E , GI Ar, m, r, s and w are as described in any
statement herein.
Preferably, m is in the range 0-3, more preferably 0-2,
especially 0-1. Preferably, r is in the range 0-3, more
20 preferably 0-2, especially 0-1. Preferably, s is 0 or 1.
Preferably, w is 0 or 1.
Preferably, said polymeric material is a homopolymer having
a repeat unit of general formula IV.
Preferably Ar is selected from the following moieties (vii)
to (xiii) :
(xii) a
(xiii)
5 In (vii) , the middle phenyl may be 1,4- or 1,3-
substituted.
Preferably, (xi) is selected from a 1,2-, 1 - or a 1,5-
moiety; and (xii) is selected from a 1,6-, 2,3-, 2,6- or a
10 2,7- moiety.
Suitable moieties Ar are moieties (i) , (ii), (iii) and (iv)
and, of these, moieties (i), (ii) and (iv) are preferred.
Other preferred moieties Ar are moieties (vii) , (viii) ,
(ix) and (x) and, of these, moieties (vii), (viii) and (x)
5 are especially preferred.
An especially preferred class of polymeric material are
polymers (or copolymers) which consist essentially of
phenyl moieties in conjunction with ketone and/or ether
10 moieties. That is, in the preferred class, the polymeric
material does not include repeat units which include -S-, -
SOz- or aromatic groups other than phenyl. Preferred
polymeric materials of the type described include:
(a) a polymer consisting essentially of units of
formula IV wherein Ar represents moiety (iv), E
and El represent oxygen atoms, m represents 0, w
represents 1, G represents a direct link, s
represents 0, and A and B represent 1 (i.e.
polyetheretherketone).
(b) a polymer consisting essentially of units of
formula IV wherein E represents an oxygen atom, El
represents a direct link, Ar represents a moiety
of structure (i) , m represents 0, A represents 1,
B represents 0 (i . e . polyetherketone) ;
(c) a polymer consisting essentially of units of
formula IV wherein E represents an oxygen atom, Ar
represents moiety ( ) * m represents 0, El
represents a direct link, A represents 1, B
represents 0, (i.e. polyetherketoneketone).
(d) a polymer consisting essentially of units of
formula IV wherein Ar represents moiety (i), E and
El represent oxygen atoms, G represents a direct
link, m represents 0, w represents 1, r represents
0, s represents 1 and A and B represent 1. (i .e.
polyetherketoneetherketoneketone).
(e) a polymer consisting essentially of units of
formula IV, wherein Ar represents moiety (iv), E
and El represents oxygen atoms, G represents a
direct link, m represents 0, w represents 0, s, r,
A and B represent 1 (i.e.
polyetheretherketoneketone).
(f) a polymer comprising units of formula IVY wherein
Ar represents moiety (iv) , E and Ey represent
oxygen atoms, m represents 1, w represents 1, A
represents 1, B represents 1, r and s represent 0
and G represents a direct link (i.e. polyetherdiphenyl-
ether-phenyl-ketone-phenyl-.)
Said polymeric material is preferably semi-crystalline.
The level and extent of crystallinity in a polymer is
preferably measured by wide angle X-ray diffraction (also
25 referred to as Wide Angle X-ray Scattering or WAXS), for
example as described by Blundell and Osborn (Polymer -24,
953, 1983). Alternatively, crystallinity may be assessed
by Differential Scanning Calerimetry (DSC).
30 The level of crystallinity in said polymeric material may
be at least I%, suitably at least 3%, preferably at least
5% and more preferably at least 10%. In especially
preferred embodiments, the crystallinity may be greater
than 30%, more preferably greater than 40%, especially
greater than 45%.
The glass transition temperature (Tg) of said polymeric
5 material may be at least 1 4 0 s~ui~ta~bl y at least 144'~. In
some cases it may be greater than 1 ~ 1640°c, ~164O~C, ~
170°C, 190°C or greater than 250°C or even 300'~. In a
preferred embodiment, the glass transition temperature is
in the range 140°C to 145OC.
10
The main peak of the melting endotherm (Tm) for said
polymeric material (if crystalline) may be at least 300°C.
Said polymeric material may consist essentially of one of
15 units (a) to (f) defined above. Alternatively, said
polymeric material may comprise a copolymer comprising at
least two units selected from (a) to ( f ) defined above.
Preferred copolymers include units (a). For example, a
copolymer may comprise units (a) and (f) ; or may comprise
20 units (a) and (e) .
In preferred embodiments, said polymeric material is
selected from polyetheretherketone and polyetherketone.
In an especially preferred embodiment, said polymeric
25 material is polyetheretherketone.
In a preferred embodiment said pack comprises
polyetheretherketone having an MV in the range 0.07 to
0.12 kNsm-', preferably in the range 0.08 to 0.11 k ~ s m - ~ ,
30 especially in the range 0.08 to 0.10 msm-'.
According to a second aspect of the invention, there is
provided a receptacle containing at least lkg (preferably
at least 5k9, more preferably at least 50kg) of a said
polymeric material as described according to said first
aspect.
5 The polymeric material described may enable highly filled
composite materials to be prepared in view of its
relatively low viscosity. Thus, according to a third
aspect of the present invention, there is provided a
composite material which comprises a polymeric material
10 having an MV in the range 0.05 to 0.12 kNsm-2 (preferably
in the range 0.07 to 0.10 kNsmb2, more preferably in the
range 0.08 to 0.10 kNsmb2) and a filler means, wherein
said polymeric material is of a type which includes:
15 (a) phenyl moieties;
(b) carbonyl moieties; and
(c) ether moieties.
Said polymeric material may have any feature of said
20 polymeric material described according to said first
aspect. Said polymeric material is preferably
polyetheretherketone.
Said filler means may include a fibrous filler or a non-
25 fibrous filler. Said filler means may include both a
fibrous filler and a non-fibrous filler.
A said fibrous filler may be selected from inorganic
fibrous materials, high-melting organic fibrous materials
30 and carbon fibre.
A said fibrous filler may be selected from glass fiber,
carbon fibre, asbestos fiber, silica fiber, alumina fiber,
zirconia fiber, boron nitride fiber, silicon nitride
fiber, boron fiber, fluorocarbon resin fibre and potassium
titanate fiber. Preferred fibrous fillers are glass fibre
and carbon fibre.
5
A said non-fibrous filler may be selected from mica,
silica, talc, alumina, kaolin, calcium sulfate, calcium
carbonate, titanium oxide, ferrite, clay, glass powder,
zinc oxide, nickel carbonate, iron oxide, quartz powder,
10 magnesium carbonate, fluorocarbon resin and barium
sulfate. The non-fibrous fillers may be introduced in the
form of powder or flaky particles.
Preferably said filler means comprises one or more fillers
15 selected from glass fibre, carbon fibre, carbon black and
a fluorocarbon resin.
Said composite material may comprise one or more polymeric
material (s) of a type described above with MV as
20 described. Preferably, said composite material comprises
only a single type of polymeric material. Said single
type is preferably polyetheretherketone.
Said composite material suitably includes 30 to 80wt% of
25 polymeric material (s) of the type described, (which is
preferably a single type of polymeric material, especially
polyetheretherketone) and 20 to 70wt% of filler means.
Preferably, said composite material comprises 30 to 70wt%
of polymeric material and 30 to 7Owt% of filler means.
30 More preferably, said composite material comprises 40 to
65wt% of polymeric material and 35 to 60wt% of filler
means. In an especially preferred embodiment, said
composite material comprises 40 to 60wt% of polymeric
material and 40 to 60wt% of filler means.
The ratio of the wt% of polymeric material to the wt% of
5 filler means may be in the range 0.6 to 1.6, preferably
0.65 to 1.5.
The ratio of the wt% of filler means to the wt% of
polymeric material is preferably at least 0.65, more
10 preferably at least 0.8, especially at least 1.
Said composite material may be in granular form.
According to a fourth aspect of the invention there is
15 provided a method of making a composite material the
method comprising:
(i) selecting a polymeric material having an MV in the
range 0.05 to 0.12 k ~ s m -(p~r eferably in the range 0.07 to
20 0.10 k~sm-~mo,r e preferably in the range 0.08 to 0.10
k~sm-~)w,h erein said polymeric material is of a type
which includes:
(a) phenyl moieties;
25 (b) carbonyl moieties; and
(c) ether moieties;
AND
30 (ii) contacting said polymeric material with a filler
means to prepare said composite material.
Said polymeric material selected may have any feature of
said polymeric material described herein. Said polymeric
material is preferably polyetheretherketone.
5 Said filler means and the composite material prepared may
independently have any features of the filler means and
composite material described herein.
Said composite material may be prepared as described in
10 P C T / G B ~ O O ~ / OanOd ~t~he~ ~co ntent of the aforementioned
document is incorporated herein by reference.
Said composite material may be prepared by contacting
melted polymeric material with said filler means.
15
As described above, the polymeric material may
advantageously be used in injection moulding or extrusion
to manufacture components. Thus, according to a fifth
aspect of the invention, there is provided a method of
20 making a component, the method comprising extruding or
injection moulding a polymeric material having an MV in
the range 0.05 to 0.12 Msm-2 (preferably in the range
0.07 to 0.10 k~sm-~mo,r e preferably in the range 0.08 to
0.10 Msm-'1, wherein said polymeric material is of a type
25 which includes:
(a) phenyl moieties;
(b) carbonyl moieties; and
(c) ether moieties.
30
Said polymeric material may have any feature of said
polymeric material described according to any of the above
,aspects. Said polymeric material is preferably
polyetheretherketone.
Said method preferably involves selecting a precursor
5 material from which to make the component wherein said
precursor material comprises a said polymeric material and
sub j ecting the precursor material to a temperature above
its melting temperature in an extrusion or injection
moulding apparatus. Suitably, said precursor material is
10 heated to a temperature of greater than 300°C, preferably
greater than 340°C. It is suitably heated to a
temperature not exceeding 450°C.
Said precursor material may consist essentially of a said
15 polymeric material described herein or a said composite
material described herein.
Suitably, in the method, at least 0.5g, preferably at
least lg, more preferably at least 5g, especially at least
20 log is selected in order to make the component.
The method may be used to make components having
relatively thin walls. Thus, the invention, in a sixth
aspect relates to a method of making a component which has
25 a wall which includes a region having a thickness of 3mm
or less, the method comprising:
(A) selecting a precursor material which comprises a
polymeric material having an MV in the range 0.05 to 0.12
30 lc~sm-(~p referably in the range 0.07 to 0.10 k~sm-~mo,r e
preferably in the range 0.08 to 0.10 ic~srn-~)w,h erein said
polymeric material is of a type which includes:
(a) phenyl moieties;
(b) carbonyl moieties; and
(c) ether moieties;
5 AND
(B) treating said precursor material, thereby to form said
component.
10 Preferably, the component includes a region having a
thickness of 2mm or less, more preferably lmm or less.
Said treatment described in (B) preferably involves melt
processing said precursor material. Melt processing is
15 preferably carried out by extrusion or injection moulding.
Suitably, said component includes a region having an area
of at least 0. 5cm2, preferably at least 1 cm2, more
preferably at least 5cmZ having a thickness as described.
20 Thus, in one embodiment, said component may include a
region of at least 0.5cm2 which has a thickness of 3mm,
preferably of 2mm or less.
A said polymeric material as described herein may be made
25 by any suitable method. An electrophilic process may be
used as described in US6566484B2; or a nucleophilic process
may be used as described in EP00001879B or ~C~/G~99/02833.
A nucleophilic process is preferred.
30 MV may be controlled as described in EP 0001879B.
Any features of any aspect of any invention or embodiment
described herein may be combined with any feature of any
aspect of any other invention or embodiment described
herein mutatis mutandis.
Specific embodiments of the invention will now be described
5 by way of example, with reference to the accompanying
figure which is a plot illustrating the relationship
between MV and IV.
VICTREX PEEK 150P (Trade Mark) , Victrex PEEK 150GL30 (Trade
10 Mark) and Victrex PEEK 150CA130 may be obtained from
Victrex Plc, UK.
All chemicals referred to herein were used as received from
Sigma-Aldrich Chemical Company, Dorset, UK, unless
15 otherwise stated.
Example 1 - Preparation of polyetheretherketone
A 250ml flanged flask fitted with a ground glass Quickfit
20 lid, stirrer/stirrer guide, nitrogen inlet and outlet was
charged with 4,4'-difluorobenzophenone (22.489, 0.103
mole), hydroquinone (11. Olg, 0.1 . mole) and
diphenylsulphone (49g) and purged with nitrogen for over 1
hour. The contents were then heated under a nitrogen
25 blanket to between 140 and 150'~ to form an almost
colourless solution. While maintaining a nitrogen
blanket, dried sodium carbonate (10.61g, 0.1 mole) and
potassium carbonate (0.278g1 0.002 mole) was added. The
temperature was raised to 200°C and held for 1 hour;
30 raised to 250'~ and held for 1 hour; raised to 315OC and
maintained for 2 hour.
The reaction mixture was allowed to cool, milled and
washed with acetone and water. The resulting polymer was
dried in an air oven at 120'~ producing a powder. The
polymer had a melt viscosity at 400'~~1 000sec-~o f 0.089
5 IcNsm-'.
The polymer was compression moulded at 400°C in a press
(20tonnes, 5 minutes) into a thin film approximately 0.2mm
thick and cooled from 4 0 0 ~to~ 120°C in 30 minutes to
10 induce complete crystallisation and then allowed to cool
to room temperature.
The film was then hinged through 180° followed by hinging
through 3 6 0 ~ ~ .Th is process was repeated 5 times and the
15 film survived without breaking and was therefore
considered to be tough.
Example 2a-d - Preparation of samples of
polyetheretherketone with different melt viscosities
The procedure described in Example 1 was repeated except
the polymerisation time was varied to produce
polyetheretherketone with different melt viscosities. The
details are given in Table 1 below.
25
Table 1
Toughness
Test
Tough
Tough
Tough
Melt
Viscosity
(msrn-')
0.089
0.150
0.117
Example
1
2a
2b
Reaction
Time
(mins)
12 0
180
160
Example 3 - Large Scale production of polyetheretherketone
5 The procedure described in Example 1 was repeated on a
larger scale to produce sufficient material to carry out
mechanical and melt flow testing. Five batches were
produced, Examples 3a-el with Melt Viscosities measured at
400°C and 1000s-~ of 0.144, 0.110 0.089, 0.076 and
10 0.059k~sm-re~s pectively.
Brittle
Brittle
Example 4a-d - Melt Flow Index of polyetheretherketones
0.075
0.06
2c
2d
The Melt Flow Index of the polyetheretherketone samples
15 from Examples 3c13e, a sample of Victrex PEEK 150P and
blends of Examples 3d and 3a in a weight ratio of 77 : 23
and Examples 3e and 3a in a weight ratio of 64 : 36 were
measured on a CEAST Melt Flow Tester 6941.000. The polymer
was placed in the barrel of the Melt Flow Tester apparatus
20 and heated to 400'~. The polymer was then extruded under a
constant shear stress by inserting a weighted piston
(2.16kg) into the barrel and extruding through a tungsten
carbide die, 2.095mmbore x 8.00Omm. The MFI (Melt Flow
Index) is the average mass of polymer (in g) extruded in
25 10 min. The results are detailed in Table 2 below.
90
60
Table 2
5 Example 5 - Spiral Flow of Low viscosity
Example
4a
4b
4c
4d
4e
polyetheretherketones
Spiral flow measurements were made on a spiral flow mould
at a melt temperature of 370 and 3 9 0 ~an~d 1 and 2mm mould
10 depth at a mould temperature of 185OC with an injection
pressure of 140Bar and the flow length determined. The
results are detailed in Table 3 below.
Melt Flow
Index
(g/l~mins)
87
117
83
78
41
Polyetheretherketone
Sample
Example 3c
Example 3e
Example 3d (77wt%)
+
Example 3a (23wt%)
Example 3e (64wt%)
+
Example 3a (36wt%)
Victrex PEEK 150P
Melt
Viscosity
(kNsm-)2
0.089
0.059
0.09
0.09
0.150
Table 3
Example Polyetheretherketone
Sample
Victrex PEEK 150P
Victrex PEEK 150P
Victrex PEEK 150P
Victrex PEEK 150P
Mould Mould Flow
Length
(mm)
302
Examples 6a-e - Mechanical Properties of Low Viscosity
polyetheretherketones
Samples of polyetheretherketone from Examples 3c, 3d, 3e,
10 Victrex PEEK 150P, the 60:40wt% blend of Example 3d and 3b
the 30:30:30:10wt% blend of Examples 3b, 3c, 3d and 3e,
the 77:23wt% blend of Example 3d and 3a and the 64:36wt%
blend of Example 3e and 3a were injection moulded using a
barrel temperature of 350-360°c, nozzle temperature 365O~,
15 mould temperature 145-155°C, holding pressure 3OBar,
injection pressure of 140Bar and a screw speed of 45rpm to
produce standard test pieces for mechanical property
evaluation. The results are detailed in Table 4 below.
Example
Table 4
Polyetheretherketone Melt
Sample I viscosity
Example 3d (60wt%)
Ex3e (10wt%) +
Example 3d (77wt%) 0.09
+
Example 3a (23wt%)
I
Example 3e (64wt%) 0.09
+
Example 3a (36wt%)
I
Victrex PEEK 150P 1 0 .I50
I
ASTM D638
Strength Strength
(MPa) (a) (90.0 1 1MP5a7l. 9(b )
98.1 149.8
Modulus
3.7
(b) ASTM D790
10 Example 7a - d - Melt Flow Index and Mechanical Properties
of filled, low viscosity polyetheretherketones
The polyetheretherketone from the 64:36wt% blend of
Example 3e and 3a was compounded separately with 3Owt%
glass fibre (Owens Corning OCP CS D165-11C)and 30wt%
carbon fibre (SGL Sigrafil C25 SO06 APS) on a ZSK 25 WLE
Twin Screw Extruder, Examples 7a and 7c respectively. The
Melt Flow Index of the two compounds at 400°C and 2.16kg
5 was determined and compared to Victrex PEEK 150GL30 and
150CA30 which are commercial grades of
polyetheretherketone containing 30wt% glass fibre and
carbon fibre respectively. The results are detailed in
Table 5 below.
10
Compounds Example 7a and 7d were injection moulded using a
barrel temperature of 370-380°C, nozzle temperature 380°C,
mould temperature 180-~OOOC, holding pressure 3OBar,
injection pressure 140Bar and a screw speed of 45rpm into
15 standard test pieces and their mechanical properties
determined and compared to those of to Victrex PEEK
150GL30 and 150CA30. The results are detailed in Table 5
below.
Sample
I Glass Fibre (30wt%)
I
I
7b I Victrex PEEK 150GL30
7a
I
7 c Blend [3e (64wt%)
Blend [3e (64wt0)
I Carbon Fibre (30wt%)
I
7 d Victrex PEEK 150CA30
Table 5
(a) ASTM D638
(b) ASTM D790
Flexural
Modulus
(GPa) (b)
10.2
Flexural
Strength
(MPa) (b)
242.1
Melt Flow
Index
(g/lomin)
3 0
Tensile
Strength
(MPa) (a)
155.8
Example 8a - q - Melt Flow Index and Mechanical Properties
of highly filled, low viscosity polyetheretherketones
The polyetheretherketone from the 64:36wt% blend of
5 Example 3e and 3a was compounded separately with 40wt%,
50wt%, 60wt% and 70wt% glass fibre (Owens Corning OCF
D165A-11C)and 4Owt%, 50wt% and 60wt% carbon fibre (SGL
Sigrafil C25 SO06 APS) on a ZSK 25 WLE Twin Screw
Extruder, Examples 8a - 8g respectively. The Melt Flow
10 Index of the compounds at 4 0 0 ~an~d 2.16kg was determined
and compared to Victrex PEEK^^ 150GL30 and 150CA30 which
are commercial grades of polyetherkeone containing 30wt%
glass fibre and carbon fibre respectively. The results are
detailed in Tables 6a and 6b below.
15
Compounds Example 8a - 8g were injection moulded using a
barrel temperature of 370-380~C,n ozzle temperature 380°C,
mould temperature 180 -2 Oo°C, holding pressure 30Bar and a
screw speed of 45rpm into standard test pieces and their
20 mechanical properties determined and compared to those of
Victrex PEEK 150GL30 and 150CA30. The results are detailed
in Table 6a and 6b below.
Table 6a
Flexural
Modulus
(GP~)")
13.7
17 -4
21.8
Flexural
Strength
(hPa)(c)
3 14
327
342
Notched
Izod
(k.T/m2)")
12.6
13.4
12.5
Tensile
Strength
(h4Pa)")
211
228
227
Example
8a
8b
8c
Glass
Fibre
(wt%)
40
50
60
Polyetheretherketone
Sample
(%wtfa)
6 0
50
40
Melt
Flow
Jndex
(gll Omin)
26.9
17.9
11.9
L I I I I I I
(a) Polyetheretherketone sample Blend
3e (64wt%) +3a (36wt%)
(b) IS0 527
8d
(d) IS0180
320
252.5
(c) IS0 178-1993 (E)
26.0
Victrex PEEK 150GL30 10.0
30
Table 6b
15 Example 9a - b - Melt Flow Index and Mechanical Properties
8.9
8.8
7 0 7.8
of mica filled, low viscosity polyetheretherketones
198
14
The polyetheretherketones from the 64:36wt% blend of
163.5
(a) Polyetheretherketone sample Blend
Flexural
Strength
(MPa)(')
338
3 54
357
312.7
Example
8e
8f
89'
Examples 3e and 3a, and Victrex 150P were compounded with
Carbon
Fibre
(wt%)
40
5 0
6 0
Polyetheretherketone
Sample
60
50
40
30wt% mica (CMMP, micronised mica 325 mesh) on a ZSK 25
Flexural
Modulus
(GP~)(')
25.1
31.3
36.8
1 Victrex PEEK 150CA30 18.7
20 WLE Twin Screw Extruder, Examples 9a - 9b respectively.
Notched
Izod
7.8
6.8
6.3
7.9
Melt
Flow
Index
(g/ 1 Omin)
17
6.5
4.8
The Melt Flow Index of the compounds at 4 0 0 ~an~d 2.16kg
Tensile
Strength
(MFa)@)
229
229
221
12
was determined. The results are detailed in Table 7 below.
208.6
Compounds Example 9a - 9b were injection moulded using a
barrel temperature of 370-380°C, nozzle temperature 380°C,
mould temperature 180-200°c, holding pressure 30Bar and a
screw speed of 45rpm into standard test pieces and their
5 mechanical properties determined The results are detailed
in Table 7.
Table 7
10 (b) Victrex PEEK 150P
(c) IS0 527
Notched
Izod
(kUm2)("
2.9
3.2
(d) IS0 178-1993 (E)
(a) Polyetheretherketone sample Blend
(e) IS0 180
Flexural
Strength
(MPa)")
139
152
Tensile
Strength
@@a)")
84
85
15 Example 10a - lob- Melt Flow Index and Mechanical
Properties of highly filled, low viscosity
polyetheretherketones
Flexural
Modulus
(GP~)")
7.5
7.3
Example
9a
9b
The polyetheretherketones from the 64:36wt% blend of
Polyetheretherketone
Sample
(%wt)
7 0 'a)
7 0 'b'
Mica
(wt%)
30
3 0
Example 3e and 3a, and Victrex 150P were compounded with
20 15wt% carbon fibre (SGL Sigrafil C25 S006), 15wt%
polytetrafluoroethylene (PTFE) (Asahi Glass Fluoropolymers
Fluon FL 1650) and 21wt% polyethersulphone (PES) (BASF
Ultrason E301O) on a ZSK 25 WLE Twin Screw Extruder,
Examples 10a - lob respectively. The Melt Flow Index of
Melt
Flow
Index
(gll Omin)
61.2
25.1
25 the compounds at 4 0 0 ~an~d 10kg was determined. The
results are detailed in Table 8a.
(a) Polyetheretherketone sample Blend
3e (64wt%) +3a (36wt%)
(b) Victrex PEEK 150P
(c) IS0 527
(d) IS0 178-1993 (E)
(e) IS0 180
Table 8a
10 Compounds Example 10a - lob were injection moulded using a
barrel temperature of 370 -380°C, nozzle temperature 380°c,
mould temperature 180-200°C, holding pressure 30Bar and a
screw speed of 45rpm into standard test pieces and their
mechanical properties determined. The results are detailed
15 in Table 8b.
Table 8b
Example
10a
lob
PTFE
(W%)
15
15
(b) Victrex PEEK 150P
Melt Flow
Index
(g/l Omin)
125.3
58.5
(c) IS0 527
Carbon
Fibre
15
15
Polyetheretherketone
Sample
(%wt)
4 9 'a'
4 9 'b'
Notched
Izod
(k.T~m~)(~)
4.4
5.5
(d) IS0 178-1993 (E)
PES
(wt%)
21
21
(a) Polyetheretherketone sample Blend
Flexural
Strength
217
239
Flexural
Modulus
(GP~)(~)
9.8
11.0
PTFE
(wt%)
15
15
Example
10a
lob
Tensile
Strength
(MP~)")
152
158
PES
(wt%)
21
21
Polyetheretherketone
Sample
(%wt)
4 9 'a'
4 9 'b'
Carbon
Fibre
15
15
Example 11 - Preparation of polyetherketone
A 250ml flanged flask fitted with a ground glass Quickfit
lid, stirrerlstirrer guide, nitrogen inlet and outlet was
charged with 4,4'-difluorobenzophenone (33.49g, 0.153
mole) , 4,4' -dihydroxybenzophenone (32.13g, 0.150 mole) and
10 diphenylsulphone (124.5g) and purged with nitrogen for
over 1 hour. The contents were then heated under a
nitrogen blanket to 1 6 0 ~to~ form an almost colourless
solution. While maintaining a nitrogen blanket, dried
sodium carbonate (16. 59g, 0.156 mole) was added. The
15 temperature was raised to 340°C at 1°c/min and held for 2
hour.
The reaction mixture was allowed to cool, milled and
washed with acetone and water. The resulting polymer was
20 dried in an air oven at 120'~ producing a powder. The
polymer had a melt viscosity at 4 0 0 ~10~00~se c-~o f 0.12
kNsmb2.
Example 12a-12d - Large Scale production of
25 polyetherketone
The procedure described in Example 11 was repeated on a
larger scale to produce sufficient material to carry out
mechanical and melt flow testing. Four batches were
30 produced, Examples 12a-dl with Melt Viscosities measured
at 400°C and 1000s-~ of 0.12, 0.10 0.09 and 0.08kNsm-~
respectively.
Example 13a-13b Melt Flow Index of polyetherketone
The Melt Flow Index at 400°C and 2.16kg for the
5 polyetherketone sample from Example 12c and a sample of
Victrex PEK P22 were measured. The results are detailed in
Table 9 below.
Table 9
10 Examples 14a-14e - Mechanical Properties of Low Viscosity
polyetherketones
Melt Flow
Index
(g/l~mins)
140
3 0
Samples of polyetherketones from Examples 12a, 12b, 12c,
12d and Victrex PEK 22P were injection moulded using a
15 barrel temperature of 380-390°c, nozzle temperature 385O~,
mould temperature 155-165°~, holding pressure 3OBar,
injection pressure of 140Bar and a screw speed of 45rpm to
produce standard test pieces for mechanical property
evaluation. The results are detailed in Table 10 below.
Melt
Viscosity
(kN~m-~)
0.09
0.21
Example
13a
13b
Polyetherketone
Sample
Example 12c
Victrex PEK P22
Sample
Example Polyetherketone
I
14a
I
Example 12a
14b
I
I
14e 1 ~ictrex PEK 22P
Example 12b
14c
I
I I
(a) ASTM D638
Example 12c
14d
Table 10
Example 12d
(b) ASTM D790
Example 15a - 15b - Melt Flow Index and Mechanical
Flexural
Modulus
(GPa) 'b'
4.6
4.6
4.6
Properties of filled, low viscosity polyetherketones
Flexural
Strength
(MPa) 'b'
184
18 3
186
Melt
Viscosity
(k~sm-~)
0.12
0.10
0.09
The polyetherketone from Example 12c and Victrex PEK P22
Tensile
Strength
(MPa) 'a'
110
111
114
were compounded with 30wt% glass fibre (Owens Corning OCF
10 CS Dl65A-11C) on a ZSK 25 WLE Twin Screw Extruder,
Examples 15a - 15b respectively. The Melt Flow Index of
the compounds at 4 0 0 ~an~d 2.16kg was determined. The
results are detailed in Table 11 below.
15 Compounds Example 15a - 15b were injection moulded using a
barrel temperature of 375 -410°C, nozzle temperature 3 90°c,
mould temperature 180-200°c, holding pressure 30Bar and a
screw speed of 45rpm into standard test pieces and their
mechanical properties determined. ' he results are detailed
20 in Table 11 below.
Table 11
(a) Polyetherketone Example 12c
Example
8a
8b
(b) Victrex PEK P22
(c) IS0 527
Polyetherketone
Sample
(%wt)
7 0 'a'
7 0 'b'
(d) IS0 178-1993 (E)
(e) IS0 180
Glass
Fibre
(wt%)
30
30
Example 16a -16i - Viscosity and Mechanical Properties of
10 highly filled, low viscosity polyetheretherketones
The polyetheretherketone from the 64:36wt% blend of
Example 3e and 3a was compounded with 0, 3, 6, 9 and 12%
of a liquid crystal polymer (LCP) polymer (Ticona T130,
15 melt point 370°C, glass content 30%) , and with additional
glass fibre (Owens Corning D165-11C) to obtain total glass
content 60%, on a ZSK 25 WLE Twin Screw Extruder, Examples
16a - 16e respectively. The LCP polymer was predried 16
hours at 150°C before compounding.
20 The addition of LCP TI30 was observed to decrease the
extruder torque and to improve fibre wet out.
Melt Flow
Index
(gll Omin)
42
12
Comparative trials were carried out with Victrex 150P
polyketone compounded with 0, 5, 10 and 15% of LCP TI30
25 and with additional glass fibre to make the total glass
content 30%; Examples 16f-16i respectively.
Tensile
Strength
(ma)(")
18 7
175
Flexural
Strength
261
2 7 8
Flexural
Modulus
(GP~)(~)
11.0
10.0
Notched
Izod
(kJIm2)(")
8.9
10.4
The Melt Viscosity of the compounds was determined at
380°C and 1000 s-l, and the Melt Flow Index at 380°C and
2.16kg.
5 Compounds Example 16a-i were injection moulded using a
barrel temperature of 350-360°c, nozzle temperature 365OC,
mould temperature 145-155OC, holding pressure 30Bar and a
screw speed of 45rpm into standard test pieces and their
mechanical properties determined. The results are detailed
10 in Tables 12a and 12b below.
Table 12a
Melt
Viscosity
380°C
(~c~sm-~)
0.51
0.29
0.26
0.23
0.21
0.33
0.30
0.20
0.19
(a) PEEK sample Blend 3e (64wt%) +3a (36wt%)
(b) Victrex PEEK 150P
Melt Flow
Index,
380°C
(g/l~min)
7.8
7.4
5.5
5.3
5.1
8.5
9.5
9.6
9.1
ZSK 25
torque
%
74
57
50
50
50
65
45
39
34
LCP in
recipe,
pphr
0
5.25
10.5
15.75
21
0
5
10
15
Example
16a
16b
16c
16d
16e
16f
16g
16h
16i
LCP
TI30
(wt%)
0
3
6
9
12
0
5
10
15
PEEK
(wt%)
4 0 'a'
37. 9'a'
35. 8'a'
33 .7'a'
31. 6'a'
7 0 'b'
66.5'b'
63 'b'
59. 5'b'
Glass
Fibre
(wt%)
60
59.1
58.2
57.3
56.4
30
28.5
27
25.5
Table 12b
(b) IS0 178-1993 (E)
(c) IS0 180
Unnotched
I zod
k~/rn'(~)
50.1
52.9
48.9
Attention is directed to all papers and documents which
are filed concurrently with or previous to this
specification in connection with this application and
(a) IS0 527
Notched
I zod
k~/rn~(')
10.5
14.0
12.8
Example
16a
16b
16c
a0 which are open to public inspection with this
specification, and the contents of all such papers and
documents are incorporated herein by reference.
All of the features disclosed in this specification
15 (including any accompanying claims, abstract and
drawings), and/or all of the steps of any method or
Flexural
Modulus
(GPa) (b)
20.6
21.2
21.3
Tensile
Strength
(MPa)
230
234
235
process so disclosed, may be combined in any combination,
except combinations where at least some of such features
Flexural
Strength
(MPa) (b)
342
349
340
and/or steps are mutually exclusive.
Each feature disclosed in this specification (including
any accompanying claims, abstract and drawings) may be
replaced by alternative features serving the same,
equivalent or similar purpose, unless expressly stated
5 otherwise. Thus, unless expressly stated otherwise, each
feature disclosed is one example only of a generic series
of equivalent or similar features.
The invention is not restricted to the details of the
10 foregoing embodiment(s). The invention extends to any
novel one, or any novel combination, of the features
disclosed in this specification (including any
accompanying claims, abstract and drawings), or to any
novel one, or any novel combination, of the steps of any
15 method or process so disclosed.

WE CLAIM
1. A composite material which comprises a polymeric
material and a filler means, said polymeric material
having a melt viscosity (MV) in the range 0.05 to 0.12
kNsm-2 wherein said polymeric material is of a type which
includes:
(a) phenyl moieties;
(b) carbonyl moieties; and
(c) ether moieties.
2. A composite material according to claim 1, wherein
said polymeric material has an MV in the range 0.07 to
0.12 kNsm-2, when measured at a shear rate of 1000s-1.
3. A composite material according to claim 1 or claim 2,
wherein said polymeric material has an MV in the range
0.08 to 0.11 kNsm-2, when measured at a shear rate of
1000s-1.
4. A composite material according to any preceding claim,
wherein said polymeric material has an MV in the range
0.08 to 0.10 kNsm-2, when measured at a shear rate of
1000s-1.
5. A composite material according to any preceding claim,
wherein said polymeric material has a tensile strength,
measured in accordance with ASTM D790 of at least 80 MPa.
6. A composite material according to any preceding claim,
wherein said polymeric material has a flexural strength,
measured in accordance with ASTM D790 of at least 145 MPa.
7. A composite material according to any preceding claim,
wherein said polymeric material has a flexural modulus,
measured in accordance with ASTM D790, of at least 3.5
GPa.
8. A composite material according to any preceding claim,
wherein said polymeric material is selected from the group
comprising polyetheretherketone, polyetherketone,
polyetherketoneketone, polyetherketoneetherketoneketone,
polyetheretherketoneketone, polyether-diphenyl-etherphenyl-
ketone-phenyl-.
9. A composite material according to any preceding claim,
wherein said polymeric material is semi-crystalline.
10. A composite material according to any preceding claim,
wherein the glass transition temperature (Tg) of said
polymeric material is at least 140oC.
11. A composite material according to any preceding claim,
wherein said polymeric material is selected from
polyetheretherketone and polyetherketone.
12. A composite material according to any preceding claim,
wherein said polymeric material is polyetheretherketone.
13. A composite material according to any preceding claim,
which comprises polyetheretherketone having an MV in the
range 0.08 to 0.10 kNsm-2.
14. A composite material according to any preceding claim,
wherein said filler means includes a fibrous filler or a
non-fibrous filler.
15. A composite material according to any preceding claim,
wherein said filler means includes a non-fibrous filler.
16. A composite material according to any preceding claim,
wherein said filler means comprises one or more fillers
selected from glass fibre, carbon fibre, carbon black and
a fluorocarbon resin.
17. A composite material according to any preceding claim,
wherein said filler means comprises one or more fillers
selected from glass fibre, carbon black and a fluorocarbon
resin
18. A composite material according to any preceding claim,
wherein said composite material comprises 40 to 65wt% of
polymeric material and 35 to 60wt% of filler means.
19. A composite material according to any preceding claim,
said composite material comprising 40 to 60wt% of
polymeric material and 40 to 60wt% of filler means.
20. A composite material according to any preceding claim,
wherein said material is in granular form.
21. A method of making a composite material the method
comprising:
(i) selecting a polymeric material having an MV in the
range 0.05 to 0.12 kNsm-2, wherein said polymeric material
is of a type which includes:
(a) phenyl moieties;
(b) carbonyl moieties; and
(c) ether moieties;
AND
(ii) contacting said polymeric material with a filler
means to prepare said composite material.
22. A method of making a component, the method comprising
extruding or injection moulding a composite material
according to any preceding claim.
23. A method according to claim 22, which includes
selecting a precursor material from which to make a
component wherein said precursor material comprises a said
composite material and subjecting the precursor material
to a temperature above its melting temperature in an
extrusion or injection moulding apparatus.
24. A pack comprising a polymeric material having a melt
viscosity (MV) in the range 0.05 to 0.12 kNsm-2 wherein
said polymeric material is of a type which includes:
(a) phenyl moieties;
(b) carbonyl moieties; and
(c) ether moieties.
25. A pack according to claim 24 comprising
polyetheretherketone having an MV in the range 0.08 to
0.10 kNsm-2.