Polymeric Materials
This invention relates to polymeric materials. Preferred embodiments relate to thermoplastic
composites comprising polymeric materials for use, for example, in the composites industry.
There is a wide range of thermoplastic polymeric material available for use in industry, either
alone or as part of composite materials. However, industry is constantly demanding materials
with properties which are improved in at least some respect over existing materials.
Polyphenylene sulphide (PPS) is a known polymeric material with a relatively low melting
temperature (Tm) of 290 °C; however its glass transition temperature (Tg) is 85 °C to 100 °C
which is too low for some applications. On the other hand, polyetheretherketone (PEEK) has a
suitable Tg of 143 but its Tm of 343 is much higher than desirable. Nonetheless, PEEK is
the material of choice for many commercial applications because it is highly crystalline and has
outstanding chemical resistance properties.
US 47 7761 (ICI) describes a polymer containing -ether-phenyl-ether-phenyl-carbonyl-phenyl-
(i.e. PEEK) and -ether-phenyl-phenyl-ether-phenyl-carbonyl-phenyl- (i.e. PEDEK) repeat units.
The copolymer is said to have a low Tm. However, there is no disclosure in the cited reference
relating to the level of crystallinity of the copolymer and/or how chemically (e.g. solvent)
resistant it may be in use.
It is an object of the present invention to provide a polymeric material per se and a method of
making such a polymeric material having a relatively low Tm, a relatively high Tg and a
relatively high crystallinity.
This invention is based on the discovery of a method for making copolymers of PEEK and
PEDEK of increased crystallinity compared to materials described in US471 7761 and novel
PEEK/PEDEK copolymers per se.
According to a first aspect of the invention, there is provided a polymeric material having a
repeat unit of formula
-O-Ph-O-Ph-CO-Phand
a repeat unit of formula
-O-Ph-Ph-O-Ph-CO-Ph- I I
wherein Ph represents a phenylene moiety
wherein the repeat units I and I I are in the relative molar properties 1: 11of from 65:35 to 95:5;
and
wherein log 10 (X%) > 1.50 - 0.26 MV;
wherein X% refers to the % crystallinity measured as described in Example 3 1 and MV refers
to the melt viscosity measured as described in Example 30.
The phenylene moieties (Ph) in each repeat unit may independently have 1,4- para linkages to
atoms to which they are bonded or 1,3- meta linkages. Where a phenylene moiety includes
1,3- linkages, the moiety will be in the amorphous phase of the polymer. Crystalline phases will
include phenylene moieties with 1,4- linkages. In many applications it is preferred for the
polymeric material to be highly crystalline and, accordingly, the polymeric material preferably
includes high levels of phenylene moieties with 1,4- linkages.
In a preferred embodiment, at least 95%, preferably at least 99%, of the number of phenylene
moieties (Ph) in the repeat unit of formula I have 1,4-linkages to moieties to which they are
bonded. It is especially preferred that each phenylene moiety in the repeat unit of formula I
has 1,4- linkages to moieties to which it is bonded.
In a preferred embodiment, at least 95%, preferably at least 99%, of the number of phenylene
moieties (Ph) in the repeat unit of formula II have 1,4-linkages to moieties to which they are
bonded. It is especially preferred that each phenylene moiety in the repeat unit of formula I I
has 1,4- linkages to moieties to which it is bonded.
Preferably, the phenylene moieties in repeat unit of formula I are unsubstituted. Preferably,
the phenylene moieties in repeat unit of formula II are unsubstituted.
Said repeat unit of formula I suitably has the structure
Said repeat unit of formula II suitably has the structure
Preferred polymeric materials in accordance with the invention have a crystallinity which is
greater than expected from the prior art. Preferably, log 0 (X%) > 1.50 - 0.23 MV. More
preferably log 10 (X%) > 1.50 - 0.28 MV + 0.06 MV2. The derivation of the aforementioned
relationships is discussed hereinafter with reference to Figure 1.
Said polymeric material may include at least 68 mol%, preferably at least 7 1 mol% of repeat
units of formula I . Particular advantageous polymeric materials may include at least 72 mol%,
or, especially, at least 74 mol% of repeat units of formula I . Said polymeric material may
include less than 90 mol%, suitably 82 mol% or less of repeat units of formula I . Said
polymeric material may include 68 to 82 mol%, preferably 70 to 80 mol%, more preferably 72
to 77 mol% of units of formula I.
Said polymeric material may include at least 10 mol%, preferably at least 18 mol%, of repeat
units of formula II . Said polymeric material may include less than 32 mol%, preferably less
than 29 mol% of repeat units of formula II . Particularly advantageous polymeric materials may
include 28 mol% or less; or 26 mol% or less of repeat units of formula II . Said polymeric
material may include 18 to 32 mol%, preferably 20 to 30 mol%, more preferably 23 to 28 mol%
of units of formula II .
The sum of the mol% of units of formula I and I I in said polymeric material is suitably at least
95 mol%, is preferably at least 98 mol%, is more preferably at least 99 mol% and , especially, is
about 100mol%.
The ratio defined as the mol% of units of formula I divided by the mol% of units of formula II
may be in the range 1.8 to 5.6, is suitably in the range 2.3 to 4 and is preferably in the range
2.6 to 3.3.
The Tm of said polymeric material (suitably measured as described herein) may be less than
330 °C, is suitably less than 320 °C, is preferably less than 3 10°C. In some embodiments, the
Tm may be less than 306 °C. The Tm may be greater than 280 °C, or greater than 290 ,
295 °C or 300 °C. The Tm is preferably in the range 300°C to 3 10°C.
The Tg of said polymeric material (suitably measured as described herein) may be greater
than 130 , preferably greater than 135 , more preferably 140°C or greater. The Tg may be
less than M ° , less than 165 °C, less than 160 °C or less than 155 °C. The Tg is preferably in
the range 145 € to 155 € .
The difference (Tm-Tg) between the Tm and Tg may be at least 13 C, preferably at least
140°C, more preferably at least 150 . The difference may be less than 170 or less than
165 °C. In a preferred embodiment, the difference is in the range 145-1 65 °C.
In a preferred embodiment, said polymeric material has a Tg in the range 145 - 155 °0, a Tm
in the range 300 °C to 3 10°C and the difference between the Tm and Tg is in the range 145
to 165 °C.
Said polymeric material may have a crystallinity measured as described in Example 3 1 of at
least 25%.
Said polymeric material suitably has a melt viscosity (MV) of at least 0.1 0 kNsm 2 , preferably
has a MV of at least 0 .15 kNsm 2 , more preferably at least 0.20 kNsm 2 , especially at least
0.25 kNsm 2 . MV is suitably measured using capillary rheometry operating at 340 °C at a shear
rate of 1000s 1 using a tungsten carbide die, 0.5mm x 3.1 75mm. Said polymeric material may
have a MV of less than 1.8 kNsm 2 , suitably less than 1.2 kNsm 2 .
Said polymeric material may have a tensile strength, measured in accordance with IS0527 of
at least 40 MPa, preferably at least 60 MPa, more preferably at least 80 MPa. The tensile
strength is preferably in the range 80-1 10 MPa, more preferably in the range 80-1 00 MPa.
Said polymeric material may have a flexural strength, measured in accordance with IS01 78 of
at least 130 MPa. The flexural strength is preferably in the range 135-1 80 MPa, more
preferably in the range 140-1 50 MPa.
Said polymeric material may have a flexural modulus, measured in accordance with IS01 78 of
at least 2 GPa, preferably at least 3GPa. The flexural modulus is preferably in the range
3.0-4.5 GPa, more preferably in the range 3.0-4.0 GPa.
Said polymeric material may be in the form of pellets or granules, wherein the pellets or
granules include at least 95wt%, preferably at least 99wt%, especially about 100wt% of said
polymeric material. Pellets or granules may have a maximum dimension of less than 10mm,
preferably less than 7.5mm, more preferably less than 5.0mm.
Said polymeric material may be part of a composition which may include said polymeric
material and a filler means. Said filler means may include a fibrous filler or a non-fibrous filler.
Said filler means may include both a fibrous filler and a non-fibrous filler. A said fibrous filler
may be continuous or discontinuous.
A said fibrous filler may be selected from inorganic fibrous materials, non-melting and highmelting
organic fibrous materials, such as aramid fibres, and carbon fibre.
A said fibrous filler may be selected from glass fibre, carbon fibre, asbestos fibre, silica fibre,
alumina fibre, zirconia fibre, boron nitride fibre, silicon nitride fibre, boron fibre, fluorocarbon
resin fibre and potassium titanate fibre. Preferred fibrous fillers are glass fibre and carbon
fibre.
A fibrous filler may comprise nanofibres.
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, magnesium carbonate, fluorocarbon resin, graphite, carbon powder,
nanotubes and barium sulfate. The non-fibrous fillers may be introduced in the form of powder
or flaky particles.
Said composition may define a composite material which could be prepared as described in
Impregnation Techniques for Thermoplastic Matrix Composites. A Miller and A G Gibson ,
Polymer & Polymer Composites 4(7), 459 - 481 ( 1 996), EP 02 58 and EP 02 59, the
contents of which are incorporated herein by reference. Preferably, in the method, said
polymeric material and said filler means are mixed at an elevated temperature, suitably at a
temperature at or above the melting temperature of said polymeric material. Thus, suitably,
said polymeric material and filler means are mixed whilst the polymeric material is molten. Said
elevated temperature is suitably below the decomposition temperature of the polymeric
material. Said elevated temperature is preferably at or above the main peak of the melting
endotherm (Tm) for said polymeric material. Said elevated temperature is preferably at least
300 C. Advantageously, the molten polymeric material can readily wet the filler and/or
penetrate consolidated fillers, such as fibrous mats or woven fabrics, so the composite material
prepared comprises the polymeric material and filler means which is substantially uniformly
dispersed throughout the polymeric material.
The composite material may be prepared in a substantially continuous process. In this case
polymeric material and filler means may be constantly fed to a location wherein they are mixed
and heated. An example of such a continuous process is extrusion. Another example (which
may be particularly relevant wherein the filler means comprises a fibrous filler) involves
causing a continuous filamentous mass to move through a melt or aqueous dispersion
comprising said polymeric material. The continuous filamentous mass may comprise a
continuous length of fibrous filler or, more preferably, a plurality of continuous filaments which
have been consolidated at least to some extent. The continuous fibrous mass may comprise a
tow, roving, braid, woven fabric or unwoven fabric. The filaments which make up the fibrous
mass may be arranged substantially uniformly or randomly within the mass. A composite
material could be prepared as described in PCT/GB2003/001 872, US6372294 or EP1 2 15022.
Alternatively, the composite material may be prepared in a discontinuous process. In this case,
a predetermined amount of said polymeric material and a predetermined amount of said filler
means may be selected and contacted and a composite material prepared by causing the
polymeric material to melt and causing the polymeric material and filler means to mix to form a
substantially uniform composite material.
The composite material may be formed into a particulate form for example into pellets or
granules. Pellets or granules may have a maximum dimension of less than 0mm, preferably
less than 7.5mm, more preferably less than 5.0mm.
Preferably, said filler means comprises one or more fillers selected from glass fibre, carbon
fibre, carbon black and a fluorocarbon resin. More preferably, said filler means comprises
glass fibre or carbon fibre.
A composition or composite material as described may include 20 to 99.9wt% (e.g. 20 to
70wt%) of said polymeric material and 0 .1 to 80wt% (e.g. 30 to 80wt%) of filler means.
Preferred embodiments include greater than 10wt%, more preferably greater than 40wt% of
filler means.
The invention extends to a composite material as described per se.
According to a second aspect of the invention, there is provided a process for the production of
a polymeric material having a repeat unit of formula
-O-Ph-O-Ph-CO-Ph- I
and a repeat unit of formula
-O-Ph-Ph-O-Ph-CO-Ph- II
wherein Ph represents a phenylene moiety, said process comprising polycondensing a mixture
of at least one dihydroxybenzene compound and at least one dihydroxybiphenyl compound in
the molar proportions 65:35 to 95:5 with at least one dihalobenzophenone in the presence of
sodium carbonate and potassium carbonate wherein :
(i) the mole% of said potassium carbonate is at least 2.5 and/or
(ii) the following relationship (referred to as the "D50/mole% relationship") applies
the of said sodium carbonate in urn
— — = < 46
mole% of potassium carbonate
The D50 of the sodium carbonate may be measured as described in Example 29.
The mole% of said potassium carbonate is suitably defined as:
t r b r o f s of carbon te
-— -—, ; ; ; 100% &total m er m s of yd x r n s s
Under option (i), the mole% of said potassium carbonate may be at least 3 mole%, is
preferably at least 3.5 mole%, is more preferably at least 3.9 mole%. The mole% of said
potassium carbonate may be less than 10mole%, preferably less than 8 mole%, more
preferably less than 6 mole%, especially less than 5 mole%. Preferably, the mole% of said
potassium carbonate is in the range 3.5 to 6 mole%, more preferably in the range 3.5 to 4.9
mole%.
The total mole% of carbonates used in the method ( i .e. the total number of moles of
carbonates used in method divided by the total number of moles of hydroxy monomer(s) used,
expressed as a percentage) is suitably at least 00%.
The total mole% of carbonates may be greater than 00 mole%. It may be less than 05
mole%.
The mole% of sodium carbonate used in the method may be at least 90 mole%, preferably at
least 92 mole%, more preferably at least 95 mole%.
The sum of the mole% (again related to the moles of hydroxy monomer(s)) of sodium
carbonate and potassium carbonate used in the method is preferably at least 100 mole% and
is more preferably greater than 100 mole%. It may be in the range 100-1 05 mole%.
The mole% of carbonates (which term is intended to encompass carbonate (C0 3
~) and
bicarbonate (HC0 3
~)) other than sodium carbonate and potassium carbonate used in the
method is preferably less than 5 mole%, more preferably less than 1 mole% (again related to
the moles of hydroxy monomer(s)).
Preferably, the only carbonates used in the method are sodium carbonate and potassium
carbonate.
Under option (ii), the D50/mole% relationship is preferably less than 44, more preferably less
than 42, especially less than 40. Said relationship may be less than 30 or 26. D50 is suitably
measured as described in Example 29.
Preferably, both the relationships described in options (i) and (ii) apply.
The potassium carbonate selected for use in the method is preferably able to pass through a
500miti mesh screen.
The D50 of said sodium carbonate is suitably less than 140miti , preferably less than 125miti ,
more preferably less than 0miti . The D50 may be at least 50miti .
In the second aspect, the repeat units of formulas I and I I may be as described above in said
first aspect. Thus, the phenylene moieties may be as described in the first aspect. Preferably,
therefore, said repeat unit of formula I suitably has the structure
Said repeat unit of formula II suitably has the structure
The process of the second aspect may comprise selecting a dihydroxybenzene compound of
formula
and selecting a dihydroxybiphenyl compound of formula
The molar proportions of compounds V and VI are preferably in the range 65:35 to 95:5. The
molar proportions may be in the range 68:32-90:1 0 , preferably in the range 70:30-80:20, more
preferably in the range 72:28-77.23.
The process may comprise polycondensing said compounds of formulas V and VI with a
compound of formula
where X1 and X2 independently represent halogen atoms preferably selected from chlorine and
fluorine atoms. Preferably, X1 and X2 represent fluorine atoms.
Preferably, the number of moles of monomers which include chlorine or fluorine atoms which
are polycondensed in the process are at least equal to the number of moles of monomers
which include two hydroxy groups (e.g . compounds V and VI). It is especially preferred that
the number of moles of monomers which include chlorine or fluorine atoms (e.g. compound
VII) is slightly greater than the number of moles of monomers which include two hydroxy
groups.
Preferably, at least 95wt%, more preferably at least 99wt% of monomers used in the process
are made up of monomers of formulae V, VI and VII . Preferably, substantially the only
monomers used in the process are those of formulae V, VI and VII .
Said process of the second aspect is preferably carried out in the presence of a solvent. The
solvent may be of formula
where W is a direct link, an oxygen atom or two hydrogen atoms (one attached to each
benzene ring) and Z and Z', which may be the same or different, are hydrogen atoms or
phenyl groups. Examples of such aromatic sulphones include diphenylsulphone,
dibenzothiophen dioxide, phenoxanthin dioxide and 4-phenylsulphonyl biphenyl.
Diphenylsulphone is a preferred solvent.
The process is preferably carried out under substantially anhydrous conditions. In the
process, the compounds of formula V, VI and VII are suitably contacted in the presence of said
solvent, especially diphenylsulphone. Polymerisation is suitably effected at a temperature
within the range 150 °-400 . In the process, the reactants are suitably heated up to a
maximum temperature which may be greater than 300 °C, for example in the range 300 °C to
350 °C. Preferably, however, prior to reaching the maximum temperature, the reagents may be
held at one or more temperatures lower than the maximum temperature. For example, the
process may involve holding the reagents at a temperature within the range 160-200 °C for at
least 20 minutes; and/or may involve holding the reagents at a temperature within the range
200 to 240 °C for at least 20 minutes.
The process of the second aspect is preferably for making a polymeric material of the first
aspect.
Any invention described herein may be combined with any feature of any other invention
described herein mutatis mutandis.
Specific embodiments of the invention will now be described, by way of example, with
reference to the figures wherein :
Figure 1 is a graph of logi 0 (X%), wherein X refers to the crystallinity v. melt viscosity (MV) for
various PEEK:PEDEK polymeric materials made using various processes;
Figure 2 is a schematic describing the relationship between D50 of sodium carbonate and
mole% excess of potassium carbonate.
The following are referred to herein :
PEEK 50 - refers to polyetheretherketone supplied by Victrex Manufacturing Limited which
has a melt viscosity, measured using capillary rheometry operating at 400 °C and a shear rate
of 000s 1 using a tungsten carbide die (0.5mm x 3 . 75mm), of 0 . 5 kNsm 2 .
Polymers were prepared as described in Example 1 to 28. Subsequent examples include
details on procedures and tests undertaken.
Example 1 - Preparation of 0.5mol polyetheretherketone (PEEK)-
polvetherdiphenyletherketone (PEDEK) copolymer
A 0.5 litre flanged flask fitted with a ground glass lid , stirrer/stirrer guide, nitrogen inlet and
outlet was charged with 4,4'-diflurobenzophenone ( .29g, 0.51 Omol), 1,4-dihydroxybenzene
(41 .30g, 0.375mol), 4,4'-dihydroxydiphenyl (23.28g, 0.1 25mol) and diphenylsulphone
(241 .07g) and purged with nitrogen for 1 hour. The contents were then heated under a
nitrogen blanket to 160 to form an almost colourless solution . While maintaining a nitrogen
blanket, dried sodium carbonate (53.00g, 0.5mol) and potassium carbonate (2.76g, 0.02mol),
both sieved through a screen with a mesh size of 500 micrometres, were added. The
temperature was raised to 185 °C at 1°C/m\n and held for 100 minutes. The temperature was
raised to 205 °C at 1°C/min and held for 20 minutes. The temperature was raised to 3 15°C at
1°C/m\n and held for approximately 60 minutes or until the desired MV was reached as
indicated by the torque rise on the stirrer. The required torque rise was determined from a
calibration graph of torque rise versus MV. The reaction mixture was then poured into a foil
tray, allowed to cool, milled and washed with 2 litres of acetone and then with warm water at a
temperature of 40 - 50 °C until the conductivity of the waste water was < 2m8 . The resulting
polymer powder was dried in an air oven for 12 hours at 120 .
Examples 2 to 9 - Preparation of polyetheretherketone (PEEK)-polyetherdiphenyletherketone
(PEDEK) copolymer
The procedure described in Example 1 was repeated except that the quantity of potassium
carbonate and the mesh size used to sieve the sodium carbonate were varied to provide
polyetheretherketone (PEEK) - polyetherdiphenyletherketone (PEDEK) copolymers of
different crystallinity as shown in Table 1.
Example 10 - Preparation of polyetheretherketone (PEEK)-polyetherdiphenyletherketone
(PEDEK) copolymer based upon Example 1 of US patent no. US471 7761
A 0.5 litre flanged flask fitted with a ground glass lid , stirrer/stirrer guide, nitrogen inlet and
outlet was charged with 4,4'-diflurobenzophenone ( 1 12.38g, 0.51 5mol), 1,4-dihydroxybenzene
(41 .30g, 0.375mol), 4,4'-dihydroxydiphenyl (23.28g, 0.1 25mol) and diphenylsulphone
(243.1 Og) and purged with nitrogen for 1 hour. The contents were then heated under a
nitrogen blanket to 18 C to form an almost colourless solution . While maintaining a nitrogen
blanket, dried sodium carbonate (53.00g, 0.5mol) and potassium carbonate (0.35g, 0.003mol),
both sieved through a screen with a mesh of 500 micrometres, were added. The temperature
was raised to 200 °C at 1°C/m\n and held for 60 minutes. The temperature was raised to 250 °C
at 1°C/m\n and held for 60 minutes. The temperature was raised to 300 °C at 1°C/m\n and held
for 60 minutes. The reaction mixture was then poured into a foil tray, allowed to cool , milled
and washed with 2 litres of acetone and then with warm water at a temperature of 40 - 50 °C
until the conductivity of the waste water was < 2m8 . The resulting polymer powder was dried in
an air oven for 12 hours at 120°C.
Example 11 - Preparation of polvetheretherketone (PEEK) - polvetherdiphenyletherketone
(PEDEK) copolymer
The procedure of Example 10 was followed except that the reagents of Example 11 were
reacted until a higher torque value was achieved compared to Example 10 , so the copolymer
of Example 11 has a higher MV.
Example 12 - Preparation of polvetheretherketone (PEEK)-polyetherdiphenyletherketone
(PEDEK) copolymer based upon US patent no. US471 7761
The procedure described in Example 10 was repeated except that the particle size distribution
of the sodium carbonate was increased (D50 approximately 140miti ) to establish its effect on
polyetheretherketone (PEEK) - polyetherdiphenyletherketone (PEDEK) copolymer crystallinity
as shown in Table 1. The larger particle size of sodium carbonate resulted in no
polymerisation taking place, so a further 4mol% of sodium carbonate and 1mol% of
hydroquinone had to be added to the reaction .
Examples 13 & 14 - Preparation of polvetheretherketone (PEEK)-
polvetherdiphenyletherketone (PEDEK) copolymer
A 0.5 litre flanged flask fitted with a ground glass lid , stirrer/stirrer guide, nitrogen inlet and
outlet was charged with 4,4'-diflurobenzophenone ( 1 11.29g, 0.51 5mol), 1,4-dihydroxybenzene
(41 .30g, 0.375mole), 4,4'-dihydroxydiphenyl (23.28g, 0.1 25mol) and diphenylsulphone
(24.09g) and purged with nitrogen for 1 hour. The contents were then heated under a nitrogen
blanket to 200 °C to form an almost colourless solution. While maintaining a nitrogen blanket,
dried sodium carbonate (53.00g, 0.5mol) and potassium carbonate (3.46g, 0.025mol), both
sieved through a screen with a mesh of 500 micrometres, were added. The temperature was
raised to 250 °C at 1°C/min and held for 15 minutes. The temperature was raised to 320 °C at
1°C/m\n and held for 60 minutes. The reaction mixture was allowed to cool and stand
overnight under a nitrogen blanket. The following day the temperature of the mixture was
raised to 320 °C and held for 150 minutes. The vessel was then charged with 5g of 4,4'-
dichlorodiphenylsulfone and held at 320 °C for a further 30 minutes. The reaction mixture was
then poured into a foil tray, allowed to cool, milled and washed with 2 litres of acetone and
then with warm water at a temperature of 40 - 50 °C until the conductivity of the waste water
was < 2m8 . The resulting polymer powder was dried in an air oven for 12 hours at 120°C.
Examples 15 to 24 - Preparation of polvetheretherketone (PEEK)-
polvetherdiphenyletherketone (PEDEK) copolymer on a 200mol scale
A 300 litre vessel fitted with a lid, stirrer/stirrer guide, nitrogen inlet and outlet was charged with
diphenylsulphone ( 125.52kg) and heated to 150 . Once fully melted 4,4'-
diflurobenzophenone (44.82kg, 205.4mol), 1,4-dihydroxybenzene ( 1 6.51 8kg, 150mol) and
4,4'-dihydroxydiphenyl (9.31 1kg, 50mol) were charged to the vessel. The contents were then
heated to 160 . While maintaining a nitrogen blanket, dried sodium carbonate (21 .368kg,
201 .6mol) and potassium carbonate ( 1 . 1 06kg, 8mol), both sieved through a screen with a
mesh of 500 micrometres, were added . The temperature was raised to 180 °C at 1°C/min and
held for 100 minutes. The temperature was raised to 200 °C at 1 C/min and held for 20
minutes. The temperature was raised to 305 °C at 1°C/min and held until desired melt viscosity
was reached , as determined by the torque rise of the stirrer. The required torque rise was
determined from a calibration graph of torque rise versus MV. The reaction mixture was
poured via a band caster into a water bath, allowed to cool, milled and washed with acetone
and water. The resulting polymer powder was dried in a tumble dryer until the contents
temperature measured 112 °C.
Examples 25 to 28 - Preparation of polvetheretherketone (PEEK)-
polvetherdiphenyletherketone (PEDEK) copolymer on a 200mol scale
The procedure described in Example 15 to 24 was repeated except that the quantity of DPS
was 96.72kg.
Table 1 below includes a summary of Examples 1 to 28. D50 as described herein was
determined as described in Example 29.
Example 29 - General Procedure for Determining D50
The D50 of sodium carbonate was determined by Malvern Laser Diffractometer, using the
associated Mastersizer 3000 software. A Fraunhofer type process was used to eliminate the
requirement of refractive index figures for the samples. Using the Mastersizer 300 software,
the following instrument parameters were set:
A dried sample (<5g) of carbonate was scooped into the hopper at the top of the machine. A
background measurement was run, and then two sample measurements were taken. The feed
rate was started at 7%, but was manually adjusted as the measurement was taken to ensure
the obscuration measurement sat within the 1-6% limits.
In Table 1, the quantity of potassium carbonate is quoted in mole%. Unless otherwise stated
herein, the mole% of potassium carbonate is defined as:
the number of moles of potassium carbonate
X 100 /
the total moles of hydoxy monomer(s) used
Melt viscosity (MV) referred to in Table 1 may be determined as described in Example 30.
Example 30 - Determination of melt viscosity (MV) of polymer
Unless otherwise stated, this was measured using capillary rheometry operating at 340 °C at a
shear rate of 1000s 1 using a tungsten carbide die, 0.5mm x 3 .175mm. The MV measurement
was taken 5 minutes after the polymer had fully melted, which is taken to be 5 minutes after
the polymer is loaded into the barrel of the rheometer.
Table 1
Sodium
Sodium
Example Carbonate Quantity Potassium V (@
Carbonate D50 No. Sieve Size Carbonate (mole%) 340 °C)
(mhi)
(mhi)
1 500 96.7 4 0.22
2 125 67.7 0.25 0.22
3 125 67.7 2 0.28
4 300 93.1 0.25 0.1 4
5 300 93.1 2 0.34
6 500 96.7 0.25 0.1 2
7 500 96.7 0.25 0.1 3
8 500 96.7 0.25 0.31
9 500 96.7 2 0.34
10 500 96.7 0.5 0.1 8
11 500 96.7 0.5 0.30
12 500 140 0.5 0.1 2
13 500 96.7 5 0.62
14 500 96.7 5 0.52
15 500 98.7 4 0.25
16 500 98.7 4 0.203
17 500 98.7 4 0.258
18 500 98.7 4 0.283
19 500 98.7 4 0.324
20 500 98.7 4 0.222
2 1 500 98.7 4 0.26
22 500 98.7 4 0.269
23 500 98.7 4 0.1 86
24 500 98.7 4 0.295
25 500 98.7 4 0.406
26 500 98.7 4 1.707
27 500 98.7 4 1.305
28 500 98.7 4 0.853
Example 3 1 - Differential Scanning Calorimetrv of Polvaryletherketones of Examples 1 to 28
Crystallinity (as reported in Table 2) may be assessed by several methods for example by
density, by ir spectroscopy, by x ray diffraction or by differential scanning calorimetry (DSC).
The DSC method has been used to evaluate the crystallinity that developed in the polymers
from Examples 1 - 28 using a Mettler Toledo DSC1 Star system with FRS5 sensor.
The Glass Transition Temperature (Tg), the Cold Crystallisation Temperature (Tn), the Melting
Temperature (Tm) and Heat of Fusions of Nucleation (DHh ) and Melting (DHiti) for the
polymers from Examples 1 to 28 were determined using the following DSC method.
A dried sample of each polymer was compression moulded into an amorphous film, by heating
7g of polymer in a mould at 40 C under a pressure of 50bar for 2 minutes, then quenching in
cold water producing a film of dimensions 120 x 120mm, with a thickness in the region of
0.20mm . An 8mg plus or minus 3mg sample of each film was scanned by DSC as follows:
Perform and record a preliminary thermal cycle by heating the sample from 30°C
to 400°C at 20°C /min.
Hold for 5 minutes.
Cool at 20°C/min to 30°C and hold for 5mins.
Re-heat from 30°C to 400°C at 20°C/min, recording the Tg, Tn, Tm, DHh and
From the DSC trace resulting from the scan in step 4 , the onset of the Tg was obtained as the
intersection of the lines drawn along the pre-transition baseline and a line drawn along the
greatest slope obtained during the transition. The Tn was the temperature at which the main
peak of the cold crystallisation exotherm reaches a maximum . The Tm was the temperature at
which the main peak of the melting endotherm reach maximum .
The Heat of Fusion for melting (DHiti) was obtained by connecting the two points at which the
melting endotherm deviates from the relatively straight baseline. The integrated area under
the endotherm as a function of time yields the enthalpy (mJ) of the melting transition : the mass
normalised heat of fusion is calculated by dividing the enthalpy by the mass of the specimen
(J/g). The level of crystallisation (%) is determined by dividing the Heat of Fusion of the
specimen by the Heat of Fusion of a totally crystalline polymer, which for polyetheretherketone
is 130J/g.
Results are provided in Table 2 .
Example 32 - Mechanical Properties
The mechanical properties of a blend of the materials of Examples 15 to 19 to give an MV of
0.25kNsm 2 were assessed in a series of tests and the results are provided in Table 3 .
Table 3 also quotes results of mechanical tests undertaken on commercially available Victrex
PEEK 50 for comparison.
Table 3
Discussion
In general terms, it is found that the process described herein can be used to produce
PEEK:PEDEK copolymers which have advantageously higher crystallinities than expected.
Referring to Figure 1, the results from Tables 1 and 2 are plotted. The graph describes log 10
(X%) (i.e. Iog 10 of the % crystallinity measured by DSC as described) v. the melt viscosity (MV)
determined as described ( i .e. using capillary rheometry operating at 340 at a shear rate of
1000s- 1 using a tungsten carbide die 0.5mm x 3.1 75mm. Figure 1 shows a first series of
points, being the results for Examples 1 and 15 to 28, (represented by squares) which have a
crystallinity for a selected MV which is higher than a second series of points, being the results
for Examples 2 to 14 , (represented by triangles). The first series of points relate to polymeric
materials made in processes which use at least 2.5 mole% based on the total moles of
hydroxy monomer(s), whereas the second series of points use less than 2.5 mole% potassium
carbonate based on the total moles of hydroxy monomer(s). It is clear that the level of
potassium carbonate used affects the crystallinity of the PEEK:PEDEK copolymer, resulting in
crystallinity which is higher than would be expected for example based on the disclosure in
US471 7761 . The equation of the line for the second series of points is found to be
log 10 (X%) = 1.45 - 0.24 MV
Figure 1 also includes a first calculated dividing line above the second series of points. The
calculated dividing line is included to delineate polymeric materials which are in accordance
with preferred embodiments of the invention (i.e. materials found above the dividing line) from
those which are not in accordance with preferred embodiments of the invention (i.e. materials
found below the dividing line). The equation of the dividing line is:
log 10 (X%) = 1.50 - 0.26 MV
Thus, for polymeric materials in accordance with preferred embodiments, the following
relationship applies:
logio (X%) > .50 - 0.26 MV
Figure 1 includes a second calculated dividing line above the first calculated dividing line, the
second dividing line defines more preferred embodiments. Thus, more preferred embodiments
fall above the second calculated dividing line and the following relationship applies:
logio (X%) > 1.50 - 0.23 MV
where X and MV are determined as described.
Figure 3 includes a third calculated dividing line above the second calculated dividing line.
The third line defines especially preferred embodiments. Thus, especially preferred
embodiments fall above the third calculated dividing line and the following relationship applies:
logio (X%) > .51 - 0.28 MV + 0.06 MV2
where X and MV are determined as described.
On the basis of the Examples described and other examples, the relationship graphically
represented in Figure 2 was determined. The reference to "poor crystallinity" means the
crystallinity of the PEEKPEDEK copolymers was less than 25%; and the reference to "good
crystallinity" means the crystallinity of the copolymer was greater than 25%.
Referring to Figure 2 , preferred embodiments of the present invention use a process wherein
the mole% of potassium carbonate based on the total moles of hydroxy monomer(s) is greater
than 2.5 mole% or the following applies:
D50 of sodium carbonate in mih
mole% of potassium carbonate
is less or equal to 46.
In view of the differences between polymeric materials in accordance with preferred
embodiments of the present invention and other materials described, NMR was used to
assess materials as described in Example 28.
Example 33 - NMR Analysis of PEEKPEDEK polymers and comparison with PEEK polymer
Pressed films made from the polymeric materials of Example 2 1 (a material in accordance with
a preferred embodiment of the invention), Example 4 , Example 10 and PEEK 150 were
assessed to determine any structural differences.
For the analysis a portion of each pressed film was dissolved in methane sulphonic
acid/methylene dichloride solvent (the standard solvent used for polyaryletherketone
polymers). In each case, the resulting solutions were clear to the naked eye, suggesting total
solubility.
The solutions were examined using a Lambda 300 instrument at 25 °C to produce 3C NMR
spectra. The carbonyl region of the spectrum was expanded and three carbonyl groups were
identified in slightly different chemical environments as follows:
199.7 ppm PEEK homopolymer (seen in the PEEK 150 material assessed) ;
199.35 ppm PEDEK homopolymer;
199.5 ppm PEEK:PEDEK interchange unit (nb this resonance would not be present if the
sample was a blend of two homopolymers (i.e. PEEK and PEDEK)).
On the basis that the PEEK:PEDEK copolymers have a 75:25 composition, the theoretical
areas that would result from the aforementioned resonances if a sample was 100% random
was determined. Then, the areas measured in the spectra were compared to the theoretical
value yielding a % randomness of each PEEK:PEDEK material as described below.
Thus, it appears the process used in accordance with preferred embodiments of the invention
results in production of a more random copolymer which results in an increase in crystallinity
over and above the level of crystallinity that may be expected.
The invention is not restricted to the details of the 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 method or process so disclosed .

CLAIMS
1. A polymeric material having a repeat unit of formula
-O-Ph-O-Ph-CO-Phand
a repeat unit of formula
-O-Ph-Ph-O-Ph-CO-Ph- I I
wherein Ph represents a phenylene moiety;
wherein the repeat units I and I I are in the relative molar properties l :l l of from 65:35 to 95:5;
wherein log 10 (X%) > 1.50 - 0.26 MV;
wherein X% refers to the % crystallinity measured as described in Example 3 1 and MV refers
to the melt viscosity measured as described in Example 30.
2 . A material according to claim 1, wherein at least 95% of the number of phenylene
moieties (Ph) in the repeat unit of formula I have 1,4-linkages to moieties to which they are
bonded ; and at least 95% of the number of phenylene moieties (Ph) in the repeat unit of
formula II have 1,4-linkages to moieties to which they are bonded.
3 . A material according to claim 1 or claim 2 , wherein log 10 (X%) > 1.50 - 0.23 MV.
4 . A polymeric material according to any preceding claim, wherein log 0 (X%) > 1.50 - 0.28
MV + 0.06 MV2.
5 . A material according to any preceding claim, which includes 68mol% to 82mole% of
units of formula I.
6 . A material according to any preceding claim, which includes 72 to 77mole% of units of
formula I.
7 . A material according to any preceding claim, which includes 18 to 32mole% of units of
formula II .
8 . A material according to any preceding claim, which includes 23 to 28mole% of units of
formula II .
9 . A material according to any preceding claim , wherein the sum of the mole% of units of
formulas I and II in said polymeric material is at least 99mole%.
10 . A material according to any preceding claim , wherein Tm is in the range 300 °C to
3 10°C.
11. A material according to any preceding claim , wherein said polymeric material has a Tg
in the range 145°C-1 55 °C, a Tm in the range 300 °C to 3 10°C and the difference between the
Tm and Tg is in the range 145°C to 165 °C.
12 . A material according to any preceding claim, which has a crystallinity of at least 25%.
13 . A material according to any preceding claim , which is part of a composition which
includes said polymeric material and a filler means.
14 . A material according to claim 13 , wherein said filler means comprises one or more fillers
selected from glass fibre, carbon fibre, carbon black and a fluorocarbon resin .
15 . A process for the production of a polymeric material having a repeat unit of formula
-O-Ph-O-Ph-CO-Ph- I
and a repeat unit of formula
-O-Ph-Ph-O-Ph-CO-Ph- II
wherein Ph represents a phenylene moiety, said process comprising polycondensing a mixture
of at least one dihydroxybenzene compound and at least one dihydroxybiphenyl compound in
the molar proportions 65:35 to 95:5 with at least one dihalobenzophenone in the presence of
sodium carbonate and potassium carbonate wherein :
(i) the mole% of said potassium carbonate is at least 2.5 and/or
(ii) the following relationship (referred to as the "D50/mole% relationship") applies
the D of said sodium carbonate in urn
— — = < 46.
mole% of potassium carbonate
16 . A process according to claim 15 , wherein the mole% of said potassium carbonate is at
least 3 mole% and is less than 10 mole%.
17 . A process according to claim 15 or claim 16 , wherein the mole% of said potassium
carbonate is less than 6 mole%.
18 . A process according to any of claims 15 to 17 , wherein the mole% of sodium carbonate
used in the method is at least 90 mole%.
19 . A process according to any of claims 15 to 18 , wherein the sum of the mole% of sodium
carbonate and potassium carbonate used in the method is at least 100 mole%.
20. A process according to any of claims 15 to 19 , wherein the only carbonates used in the
method are sodium carbonate and potassium carbonate.
2 1. A process according to any of claims 15 to 20, wherein the D50/mole% relationship is
less than 30.
22. A process according to any of claims 15 to 2 1, wherein the D50 of said sodium
carbonate is in the range 50 to 140miti .
23. A process according to any of claims 15 to 22, which comprises selecting a
dihydroxybenzene compound of formula
and selecting a dihydroxybiphenyl compound of formula
wherein molar proportions of compounds V and VI are in the range 65:35 to 95:5,
the process comprising polycondensing said compounds of formulas V and VI with a
compound of formula
where X1 and X2 independently represent halogen atoms.
24. A process according to any of claims 15 to 23, wherein at least 95wt% of monomers
used in the process are made up of monomers of formulae V, VI and VII.