Note: Descriptions are shown in the official language in which they were submitted.
20394'78
I
K- 1 8023/A/CGM 363
Soluble Polvarvlene ether ketones
The present invention relates to polyarylene ether ketones which are soluble in
halogenated hydrocarbons and contain 2,2'-bis(benzoyl)biphenyl units, to the preparation
thereof, to the mouldings, coatings or sheets made therefrom, and to the use of said
polyarylene ether ketones for modifying matrix resins.
Polyarylene ether ketones are industrial materials having very good mechanical and
thermal properties which are normally insoluble in halogenated hydrocarbons or form
unstable solutions. For example, polyarylene ether ketones containing
4,4'-bis(benzoyl)biphenyl units are disclosed in EP-A-0 194 062. These keto group
containing polyethers have especially good resistance to solvents, for example to
methylene chloride.
For many utilities, especially for modifying duromer matrix resins, polyether ketones are
required which have enhanced solubility properties without any substantial reduction of
the thermal properties, such as glass transition temperature. Surprisingly, it has now been
found that polyarylene ether ketones containing 2,2'-bis(benzoyl)biphenyl units are
readily soluble in customary organic solvents, preferably in halogenated hydrocarbons,
and form stable solutions.
Accordingly, the invention relates to polyarylene ether ketones which are soluble in
halogenated hydrocarbons and have a reduced viscosity of 0.1 to 2.0 dl/g, measured at
25C using a 1 % solution of the polymer in N-methylpyrrolidone (NMP), which
polyarylene ether ketones contain, based on the total number of structural units present in
the polyarylene ether ketone resin, 1-100 mol % of a recurring structural unit of formula I
or Il
2~39478
(R2)n
(R l)m ~ ~ O--Ar
(R2)n
(R2)n
~3 ~ 1' ~ o--Ar2-}
(R2)n
and 99-0 mol % of a recurring structural unit of formula IlI
~o-Ar2 -o-Arl~ (III)
wherein Rl is Cl-C4alkyl, C1-C4alkoxy, C6-C12aryl, C2-C4alkenyl or halogen, and m is O
or an integer from 1-4, R2 is C1-C4alkyl, C1-C4alkoxy, C6-Cl2aryl or halogen, and n is O
or an integer from 1-4, Ar1 is a divalent radical of a bisphenol compound and Ar2 is a
divalent radical of an activated dihalo compound which is able to enter into a nucleophilic
exchange reaction.
'rhe radical Arl in the structural units of formulae l and lll is preferably a group of
formulae IVa to Vg
~ 3~ (IVa), wherein a is O or 1,
2~39478
~3 (IVb), ~3 (IVc),
Z ~ (JVd), wherein b is 1 or 2,
~3 Z ~ Z ~3} (IVe),
~3\/~3/
A (IVf) or
)3
R4 R3
(IVg)
R3 R3
wherein Z is -CO-, -SO2-, -SO-, -S-, -O-, -C(CH3)2, -C(CF3)2, -CH2-, - IC-CH3 or
C6Hs
-PO, Q is a direct bond, -O-, -CH2- or -CO-, R3 is Cl-C4alkyl and R4 is Cl-C4alkyl or
R4
phenyl, which groups are unsubstituted or substituted by one or more Cl-C4alkyl or
Cl-C4alkoxy groups or by halogen atoms.
Preferably Arl is a group of formulae IVa to IVe
2~39478
- 4 -
-~ (TVa), wherein a is O or 1,
~3 ~3 (IVb), ~3 (IVc),
Z ~ (IVd), wherein b is 1 or 2,
or ~3 Z--~ z ~3} (IVe)
wherein Z is -CO-, -SO2-, -SO-, -S-, -O-, -C(CH3)2, -C(CF3)2, -CH2-, or -Cl -CH3,
C6Hs
which groups are unsubstituted or substituted by one or more Cl-C4alkyl or C~-C4alkoxy
groups or by halogen atoms.
The radical Ar2 in the structural units of formulae II and III is preferably a group of
formulae IVh bis IVI
~ X ~ X ~3 (IVh),
wherein c is O or 1,
~ ~d (IVi),
wherein d is 2 or 3 and X is -CO-, -SO2- or -SO-,
2~39478
- 5 -
CN
~ (lVj),
(IVk) or
N~N
~ (IVl),
which groups are unsubstituted or substituted by one or more C1-C4alkyl or Cl-C4alkoxy
groups or halogen atoms.
Preferably Ar2 is a group of formulae IVh or IVi
~ X ~ X~ (IVh),
wherein c is O or 1,
~ ~d (IVi),
wherein d is 2 or 3 and X is -CO-, -SO2- or -SO-, which groups are unsubstituted or
substituted by one or more Cl-C4alkyl or Cl-C4alkoxy groups or halogen atoms.
Preferably the polyarylene ether ketones of this invention contain 5-100 mol % of a
recurring structural unit of formula I or II and 95-0 mol % of a recurring structural unit
formula III.
Most preferably, the polyarylene ether ketones of this invention contain 10-100 mol % of a
recurring structural unit of formula I or II and 90-0 mol % of a recurring structural unit of
formula III. In the polyarylene ether ketones of this invention, the structural units of
formulae I, II and III are preferably unsubstituted.
203~78
Preferred radicals Arl in the structural units of formulae I and nl are typically
~3' ~, ,~3,
~ CH~ , ~ S2~
oCH3
~C~, ~0~,
CF~ ~or
CF3
H3C CH3
o~?
CH3 CH3
Particularly preferred radicals Arl are those of formulae
20~9~78
~g or ~So243
Preferred radicals Ar2 in the structural units of formulae II and III are typically
CN
~ S2~ ~ \~/ or
The polyarylene ether ketones of this invention can be prepared by
(a) polycondensing a dihalo compound of formula V
2)n
~3 ~ (R1)m (V)~
(R1)m ~ C ~ Hal
(R2)n
wherein Rl, R2, m and n are as defined in formula I and Hal is halogen, preferably fluoro
or chloro, or a mixture of a dihalo compound of formula V and a dihalo compound of
formula VI present therein in an amount of up to 99 mol %
Hal-Ar2-Hal (Vl),
2~39478
- 8 -
wherein Ar2 is as defined for formula II and Hal is halogen, preferably fluoro or chloro, in
equimolar amounts, with a diphenol of formula VII
HO-Arl-OH (VII),
or the alkali metal phenolate or alkaline earth metal phenolate thereof, wherein Arl is as
defined for formula I, in the presence of alkali and in an aprotic solvent, or
(b) polycondensing a compound of formula VIII
( R2)n
Ho;~3c ~ (R1)m
(Rl)m ~C~OH (VIII),
(R2)n
or the alka]i metal phenolate or alkaline earth metal phenolate thereof, wherein Rl, R2, m
and n are as defined in claim 1, or a mixture of a compound of formula VIII and a
diphenol of formula VII present therein in an amount of up to 99 mol %, in equimolar
amounts, with a dihalo compound of formula VI, in the presence of alkali and in an aprotic
solvent, until the polyarylene ether ketone has a reduced viscosity of 0.1 to 2.0 dl/g,
measured at 25C using a 1 % solution of the polymer in NMP (1 g of polymer in 100 ml
of NMP)
The preferred procedure comprises polycondensing (a) a dihalo compound of formula V or
a mixture of a dihalo compound of formula V and a dihalo compound of forrnula VIprescnt therein in an amount of up to 95 mol %, preferably of up to 90 mol %, inequimolar amounts, with a diphenol of formula VII, or (b) polycondensing a compo~lnd of
formula VIII or a mixt~lre of a compound of formula VIII and a diphenol of formula VII
present therein in an amount of up to 95 mol %, preferably of up to 90 mol %, inequimolar amounts, with a dihalo compound of formula VI, in the presence of alkali alld
in an aprotic solvent, until the polyalylene ether ketone has a reduced viscosily of ().15 to
2039478
1.8 dl/g, preferably of 0.2-1.5 dl/g.
By equimolar amounts is meant in the context of this invention a molar ratio of dihalo
compound of formula V, or of dihalo compounds of formulae V and Vl, to the diphenol of
formula VII, or a molar ratio of the compound of forrnula VIII, or of the compounds of
formulae VII and VIII, to the dihalo compound of formula VI, of 0.9 to 1.1. The preferred
molar ratio is from 0.95 to 1.05.
The alkali used in this process is ordinarily an alkali metal carbonate or alkaline e,u th
metal carbonate such as sodium, potassium or calcium carbonate. But other alkaline
reagents such as sodium hydroxide, potassium hydroxide or calcium hydroxide can also be
used.
Polar aprotic solvents which can be used in the process of this invention for the
preparation of the novel polyether resins are typically dimethyl sulfoxide, dimethyl
acetamide, diethyl acetamide, tetramethylurea, N-methylcaprolactam,
N-methylpyrrolidone and, preferably, diphenyl sulfone.
The reaction is conveniently carried out at elevated temperature, preferably at the reflux
temperature of the solvent, i.e. in the temperature range up to ca. 350C.
The concurrent use of an entrainer such as chlorobenzene, xylene or toluene is often
expedient in order to be able to remove the water of reaction from the reaction mixture as
an azeotrope.
The compounds of formulae V and VIII are known. For example, the preparation of
2,2'-bis(4-fluorobenzoyl)biphenyl is described in the Journal of American Chemical
Society 1935,57, page 1095 et seq., and the preparation of 4,4'-dichloro-
2,2'-bis(o-chlorobenzoyl)biphenyl is described in the Journal of Organic Chemistry 1984,
49(2), 296-300. The preparation of, for example, 2,2'-bis(4-hydroxybenzoyl)biphenyl is
described in the JouMal of Chemical Society, C, 1969, 2388 et seq., and in the Journal of
Chemical Society 1938, 1561 et seq. The known processes for the preparation of the
compounds of formulae V and VIII give yields of only ca. 30 % of theory.
It has further been found that the compounds of formulae V and VIII are obtained in
substantially higher yield by starting from a 2-iodobenzophenone in the synthesis of the
2~39478
- 10-
biphenyl compounds and heating this compound, in the presence of copper powder, IO C.l.
200C.
Accordingly, the invention also relates to a process for the preparation of compounds of
formulae V and VIII, which comprises heating a compound of formula IX
(R2)n (Rl)m
~C~Y (IX),
wherein Rl, R2, m and n are as defined for formula V or VIII, and Y is halogen or
C1-C4alkoxy, preferably fluoro, chloro or Cl-C2alkoxy, most preferably fluoro or -OCH3,
in the presence of a 0.5 to 3-fold amount by weight of copper powder, based on the
amount by weight of the compound of formula IX, to a temperature in the ran~,e from
150-250C, to give a compound of formula X
~R2)n
1 m R2) (X)
wherein Rl, R2, m, n and Y are as defined for formula IX, and, if Y is C1-C4alkoxy,
reacting said compound with AlCl3, in an organic solvent, with stirring, in the temperature
range of ca. 60-160C, to a compound of formula VIII, using 3-6 mol of AIC13 per I mol
of compound of formula X.
The organic solvent used in this reaction is preferably benzene, toluene, xylene or
chlorobenzene.
The compound of formula X can be prepared by reacting a compound of formula XI
2039478
ll
(R2)n
_~ o
~ ~ C--Cl (XI),
wherein R2 and n are as defined for formula IX, for example 2-iodobenzoyl chloride, in
the presence of a catalytic amount of FeCI3, with a compound of formula XII
(Rl)m
~ (XII),
wherein Rl, m and Y are as defined for formula IX, for example fluorobenzene or anisole.
The dihalo compounds of formula VI are known. They are disclosed, for example, in
DE-OS 30 14 230 and in EP-A-0 001 879. Suitable dihalo compounds of formula Vl are
typically 4,4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, 1,4-bis(4-chloro-
phenylsulfonyl)benzene, 4,4'-bis(4-chlorophenylsulfonyl)biphenyl and 2,6-bis(4-chloro-
phenylsulfonyl)naphth~lene. 2,6- or 2,7-Bis(p-fluorobenzoyl)naphthalene or 2,6- or
2,7-bis(p-chlorobenzoyl)naphthalene are disclosed in DE-OS 3 804 159 and in
POLYMER, 1988, Volume 29, page 358 et seq. Exemplary of further suitable dihalo
compounds are 2,6-difluorobenzonitrile or 2,6-dichlorobenzonitrile.
The diphenols of formula VII are also known compounds and most are commercially
available Typical examples of suitable divalent phenols of formula VII are hydroquinone,
resorcinol, 4,4'-dihydroxybiphenyl, 2,5-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether,
4,4'-~lihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3',5,5'-tetramethyldiphenylsulfone,
4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl-
thioether, 2,2-bis(4-hydroxyp}lenyl)propane or dihydroxynaphthalene. 2,6-Bis(4-}-ydroxy-
benzoyl)naphthalene and 2,7-bis(4-hydroxybenzoyl)naphtha-lene are disclosed in
DE-OS 38 04 159, and chloro- or methyl-substituted 2,6-bis(4-hydroxyben~oyl)-
naphthalene are disclosed in US patent specifications 4 447 592 and 4 275 226. Exemplary
of further suitable divalent phenols are 9,9-bis(4-hydroxyphenyl)fluorene and
- 12- 2~39~7~
6,6'-dihydroxy-3,3,3',3'-tetramethyl- 1,1 '-spirobiindane.
As mentioned at the outset, the polyarylene ether ketones of this invention are soluble in
customary organic solvents, preferably in halogenated, i,.e. chlorinated or fluorinated,
hydrocarbons, especially in chlorinated hydrocarbons such as methylene chloride,trichloromethane, dichloroethane, trichloroethane or chlorobenzene. The novel poly-
arylene ether sulfones are also soluble in polar aprotic solvents such as N-methyl-
pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide and sulfolane, or usually also in
cyclic ethers such as tetrahydrofuran or dioxane, as well as in cyclohexanone orcyclopentanone. On account of their solubility, the polyarylene ether ketones may with
advantage be processed to films or incorporated in other matrix systems.
The solutions of the polymers of this invention are stable over several weeks, i.e. no
turbidity or precipitation of the polymer occurs. The invention therefore further relates to a
solution containing 1 to 75 % by weight, preferably 5 to 50 %, by weight, based on said
solution, of a polyarylene ether ketone of this invention.
The polyarylene ether ketones can be used in the conventional manner for thermoplastics
and processed to mouldings, films, sheets or coatings. The invention thus also relates to
the objects made from the polyarylene ether resins, such as mouldings, coatings, films or
sheets.
Prior to processing, for example as melt or, more particularly, as solution, the polyarylene
ether ketones may be blended with customary modifiers such as fillers, pigments,stabilisers or reinforcing agents such as carbon, boron, metal or glass fibres.
The polyarylene ether ketones may also be used as matrix resins for the fabrication of
f1brous composite systems, for which utility it is possible to use as reinforcing fibres the
fibres conventionally used for reinforcing industrial materials. These fibres may be
organic or inorganic fibres, natural fibres or synthetic fibres, and may be in the form of
fibre bundles as oriented or non-oriented fibres or continuous filaments.
A further preferred utility of the polyarylene ether ketones of this invention is, by virtue of
their solubility, the modification of other matrix resins. Thus, for example, preferably
concentrated solutions of these polymers in customary organic solvents will ordinarily be
used for modifying duromer matrix resins with thermoplastics. It must be possible to
2~39478
- 13-
remove the solvents rapidly after incorporation and they should therefore have as low
boiling points and high volatility points as possible.
The invention further relatcs to the use of the novel polyarylene ether ketones for
modifying thermoplastic and du}omer matrix resins~
The following Examples illustrate the invention.
Preparation of the monomers
2-Iodo-4'-fluorobenzophenone
A solution of 493 g (1.85 mol) of 2-iodobenzoyl chloride in 420 ml of fluorobenzene is
added dropwise at room temperature to a suspension of 247 g (1.85 mol) of AlCI3 and a
catalytic amount of FeCI3 (1.85 g) in 420 ml of fluorobenzene. The reaction mixture is
stirred for 20 hours at room temperature under nitrogen. Excess fluorobenzene is distilled
from the reaction mixture, and the residue is poured, with stirring, into S litres of water.
The precipitate is isolated by filtration, washed with water, and dried in a vacuum drier at
40C. Recrystallisation from hexane gives 501 g (83 % of theory) of 2-iodo-4'-
fluorobenzophenone which melts at 51-52C.
Elemental analysis calculated for Cl3H8FIO:
cal.: C = 47.88 % found: C = 47.72 %
H= 2.47% H= 2.77%
I = 38.91 % I = 39.00 %.
2,2'-Bis(4-fluorobenzoYl)biphenvl
A mixture of 114.3 g (0.35 mol) of 2-iodo-4'-fluorobenzophenone and 343 g of fine copper
powder is heated for 30 minutes to 200C. After cooling to 100C, 300 ml of toluene are
added and the the solution is filtered hot. The residue is washed thoroughly with hot
toluene, and the combined toluene phase is concentrated by evaporation on a rotary
evaporator. Recrystallisation of the residue from ethanol gives 54 g (77 % of theory) of
2,2'-bis(4-fluorobenzoyl)biphenyl which melts at 141-142C.
Elemental analysis calculated for C26H16F22:
cal: C = 78.38 % found: C = 78.31 %
H= 4.05% H= 4.18%
2-lodo-4'-methoxybenzophenone
2039478
- 14-
A suspension of 493 g (1.85 mol) of 2-iodobenzoyl chloride and a catalytic amount of
FeCl3 (6 g) in 1000 ml of anisole is boiled under reflux for 3 hours. The reaction solution
is cooled to room temperature and then diluted with 1 litre of toluene and extracted with 2
litres of water. The organic phase is dried over Na2SO4 and concentrated by evaporation
on a rotary evaporator. The residue is poured, with stirring, into 2 litres of isopropanol.
The precipitate is isolated by filtration and dried in a vacuum drier at 50C, giving 461 g
(74 % of theory) of 2-iodo-4'-methoxybenzophenone which melts at 84-85C.
Elemental analysis calculated for Cl4HllIO2:
cal.: C = 49.73 % found: C = 49.95 %
H = 3.28 % H= 3.28 %
I = 37.53 % I = 37.58 %.
2,2'-Bis(4-methoxvbenzoYl)biphenvl
A mixture of 181.2 g (0.535 mol) of 2-iodo-4'-methoxybenzophenone and 362 g of fine
copper powder is heated for 1 hour to 200C. After cooling to 100C, 700 ml of toluene
are added and the solution is filtered hot. The residue is washed thoroughly with hot
toluene and the combined toluene phase is concentrated by evaporation on a rotary
evaporator. Recrystallisation of the residue from ethanol gives 90 g (80 % of theory) of
2,2'-bis(4-methoxybenzoyl)biphenyl which melts at 156-158C.
Elemental analysis calculated for C28H224:
cal.: C = 79.60 % found: C = 79.62 %
H= 5.25% H= 5.37%.
2,2'-Bis(4-'hYdroxvbenzoyl)biphenyl
154 g (1.15 mol) of AICI3 are added in small increments at room temperature to a solution
of 89 g (0.21 mol) of 2,2'-bis(4-methoxybenzoyl)biphenyl in 1.4 litres of toluene. The
suspension is stirred for 16 hours at 80C under nitrogen. After cooling to roomtemperature, the suspension is poured, with stirring, into 2 litres of water. The precipitate
is isolated by filtration and washed first with water and then with toluene. The residue is
dried in a vacuum drier at 80C, giving 78 g (94 % of theory) of
2,2'-bis(4-hydroxybenzoyl)b~phenyl which melts at 259-261 C.
Elemental analysis calculated for C26H18O4:
cal.: C = 79.17 % found: C = 79.20 %
H= 4.60% H= 4.99%.
Example 1: Polyarylene ether ketone sulfone from 2,2'-bis(4-fluorobenzoyl)biphenyl and
~39478
,5
4,4'-dihydroxydiphenylsulfone
In a round flask with stirrer and inert gas inlet, a mixture of 25.08 g (0.1002 mol) of
4,4'-dihydroxydiphenylsulfone, 97.60 g of diphenylsulfone, 14.60 g (0.1056 mol) of
potassium carbonate and 51 g of xylene is heated at a bath temperature of 200C and a
xylene/water mixture is distilled from the reaction mixture. Towards the end of the
distillation, a vacuum (2 mbar) is briefly applied. Then 39.84 g (0.1000 mol) of2,2'-bis(4-fluorobenzoyl)biphenyl are added to the reaction mixture, the temperature is
raised over 25 minutes (min) to 250C and kept for 1 hour (h). The temperature is then
raised for 1 h to 275C and thereafter further to 300C. This temperature is kept for 4 h,
whereupon the reaction mixture becomes increasingly viscous.
The cooled reaction mixture is taken from the flask and pulverised. After addition of dilute
acetic acid and extraction first with water and then with acetone, the polymer is dissolved
in methylene chloride. A small amount of insoluble material is isolated by filtration and
precipitated from isopropanol. The purified polymer is subsequently dried in a vacuum
drier at 240C. A polyarylene ether ketone sulfone so obtained has a reduced viscosity
(1 % of the polymer in N-methylpyrrolidone (NMP) at 25C, i.e. 1 g of the polymer in
100 ml of NMP) of 0.67 dl/g. The solubility of the polymer in methylene chloride is 20 %
by weight. The glass transition temperature, measured by differential scanning calorimetry
(DSC), is 208C.
Example 2: Polyarylene ether ketone sulfone copolymer of 2,2'-bis(4-fluorobenzoyl)-
biphenyl, 4,4'-dichlorodiphenylsulfone and 4,4'-dihydroxydiphenylsulfone
In accordance with the general procedure described in Example 1, a polyether ketone
sulfone is prepared from 4,4'-dihydroxydiphenylsulfone (0.1001 mol), 2,2-bis(4-fluoro-
benzoyl)biphenyl (0.0250 mol) and 4,4'-dichlorodiphenylsulfone (0.0750 mol) withpotassium carbonate (0.1061 mol). Reaction conditions: 1 h/250C, 1 h/275C, 3 h/280C.
The resultant polymer (red. viscosity = 0.33 dl/g) has a glass transition temperature of
218C. The solubility of the polymer in methylene chloride is more than 25 % by weight.
Example 3: Polyarylene ether ketone sulfone copolymer of 2,2'-bis(4-fluorobenzoyl)-
biphenyl, 4,4'-dichlorodiphenylsulfone and 4,4'-dihydroxydiphenylsulfone
In accordance with the general procedure of Example 1, a polyether ketone sulfone is
prepared from 4,4'-dihydroxydiphenylsulfone (0.4015 mol),
2,2'-bis(4-fluorobenzoyl)biphenyl (0.040 mol) and 4,4'-dichlorodiphenylsulfone
(0.360 mol) with potassium carbonate (0.420 mol). Reaction conditions: 1 h/250C,
20~9478
- 16-
1 h/275C and 5.5 h/280C. The resultant polymer (red. viscosity = 0.87 dl/g) has a glass
transition temperature of 227C. The solubility of the polymer in methylene chloride is
more than 25 %.
Example 4: Polyarylene ether ketone sulfone from 2,2'-bis(4-hydroxybenzoyl)biphenyl
and 4,4'-dichlorodiphenylsulfone
In accordance with the general procedure of Example 1, a polyether ketone sulfone is
prepared from 2,2'-bis(4-hydroxybenzoyl)biphenyl (0.1003 mol) and 4,4'-dichlorodiphen-
ylsulfone (0.1002 mol) with potassium carbonate (0.1085 mol). Reaction conditions:
I h/250C, 1 h/273C and 4 h/300C. The resultant polymer (red. viscosity = 0.17 dl/g)
has a glass transition temperature of 180C. The solubility of the polymer in methylene
chloride is more than 25 %.
Example 5: Polyarylene ether ketone sulfone copolymer of 2,2'-bis(4-hydroxyben~oyl)-
biphenyl, 4,4'-dihydroxydiphenylsulfone and 4,4'-dichlorodiphenylsulfone
In accordance with the general procedure of Example 1, a polyether ketone sulfone is
prepared from 2,2'-bis(4-hydroxybenzoyl)biphenyl (0.0255 mol),
4,4'-dihydroxydiphenylsulfone (0.0754 mol) and 4,4'-dichlorodiphenylsulfone
(0.1001 mol) with potassium carbonate (0.1051 mol). Reaction conditions: 1 h/252C,
1 h/278C and 4 h/302C. The resultant polymer (red. viscosity = 0.33 dl/g) has a glass
transition temperature of 215C. The solubility of the polymer in methylene chloride is
more than 25 %.
Exarnple 6: Polyarylene ether ketone sulfone copolymer of 2,2'-bis(4-hydroxybenzoyl)-
biphenyl, 4,4'-dihydroxydiphenylsulfone and 4,4'-dichlorodiphenylsulfone
In accordance with the general procedure of Example 1, a polyether ketone sulfone is
prepared from 2,2'-bis(4-hydroxybenzoyl)biphenyl (0.0400 mol),
4,4'-dihydroxydiphenylsulfone (0.3615 mol) and 4,4'-dichlorodiphenylsulfone (0.400 mol)
with potassium carbonate (0.4200 mol). Reaction conditions: 1 h/250C, 1 h/275C and
4 h 20 min/280C. The resultant polymer (red. viscosity = 0.60 dl/g) has a glass transition
temperatwre of 226C. The solubility of the polymer in methylene chloride is more than
25%.
Examples 7-14: The Examples listed in the following Table are carried out in accordance
with the general procedure of Example 1.
- 17- 2~3~478
o
c~ E~ _
~ EV v~ oo
o ~:i ~ ~ ~.
C .Co .~ l- o V ov V
~o ~ ~oo
C~ ~ _
_
:E ~ DO ~o ,~, E ~o E .E E ~ E ~, E E, E
13 ~ ~ o ~ O î~l d~o ~,,o r~
2039~78
- 18 -
~'
,~
C7~
.:i ~ o o
,o . I_ ~ V C~ C' E~3
..~ ~ ~ ~o ~ ~ ~o
8 _~ _ ~ ~ .~
.c ~; E . E ~ E E E ~ E ~ E E E E
'~ O ~ O ~ O c~ O ~ 'D O ~i O 'v~ o
~o ~~ Oo ~ ~1 ~
. ~ O
X
- 19-
~rl ~
::~ c) ~ A A
0~
c 3 ~ cs~
~ E c~
~ _ ~ ~ o
.~-~_ C~ ~ V ov~ ~
C~ ~ ~ `1 ~ ~ ~ ~o
~ ~ ~ .c ~ .-. o
2~39478
- 20 -
~ ~ C~
O ~ A A
.C~
E ~ o ~
~ o o
~ O C~ O
o o ~ o oo o ~
.~ ~ ~ I_ oo ~ U~ oo
~ $ ~ ~ . ~
~ _ _ ~t _ ~ ~
.' ~E E ~ E E E ~ E " E ~ E ~ E E E
o Dg ~ ~ O DO
O ~oO ~~ ~ ~1 d~ ~ ~
_~ ... _._
~ _.
2039478
Example 6: The copolymer prepared according to Example 3 is added in the form of a 2()
and 30 parts by weight solution in methylene chloride to a mixture consisting of 50 parts
by weight of tetraglycidyl diaminodiphenylmethane and 50 parts by weight of
triglycidyl-p-aminophenol and the solvent is removed under vacuum. After addition of 50
parts by weight of p-diaminodiphenylsulfone the mixture is cured for 2 hours at 1 60C and
for 2 hours at 210~C. Test specimens are cut from the sheet so obtained and the fracture
toughness by bend notch according to ASTM E 399 are dete}mined.
The following values are obtained:
Addition of thermoplastic fracture toughness
(parts by weight) Jlm2)
273
402
