Note: Descriptions are shown in the official language in which they were submitted.
-1 20~2~88
K-18272/A/CGM 382
Modified Polvarvlene ether block co~ol~ners
The present invention relates to novel polyarylene ether block copolymers which are
modified with di- or triglycidyl compounds, to a process for their preparation and to
organic solutions which contain said novel polyarylene ether block copolymers.
Polyarylene ethers, such as polyarylene ether sulfones are industrial materials which have
very good mechanical properties, but are only insufficiently soluble in organic solvents.
Typica1 examples of such polyarylene ether sulfones are the commercially available
products Victrex(~) PES sold by ICI and Ultrason~ E sold by BASF.
Solutions of such polyarylene ether sulfones are, in particular, not stable in chlorinated
hydrocarbons. For different utilities, however, a good stable solubility in organic solvents
is desirable. Por example, the modification of thermosetting matrix resins with poly-
arylene ethers is usually carried out with preferably concentrated solutions of these
polymers in customary organic solvents.
A coating solution for polyether sulfones is claimed in US patent specification 3 875 103.
The solution requires selected solvents and a chosen mixture ratio of the components.
Polyarylene ethers which can be obtained by chain lengthening of oligomeric hydroxyl-t-
erminated polyarylene ethers with substantially equimolar amounts of difunctional
coupling components, including also diglycidyl ethers, are disclosed in US patent
specification 4 275 186. Compared with the unmodifed polyether sulfone, the disclosed
diglycidyl ether-modified products have a markedly lower glass transition temperature.
lowering of me glass transition temperature is normally not desirable, as the performance
temperatures of the polymer moulding material are thereby lowered.
Polysiloxane-modified polyarylene ethers are known from French patent 2 547 304. ~he
proportion by weight of siloxane radicals is usually more than 10%, based on the polymer.
Compared with the corresponding unmodified polyarylene ether sulfones, the siloxane
radicals in these copolymers bring about a substantial lowering of the glass transition
20~2~88
tçmperature.
The preparation of polyarylene ether block copolymers is known per se. Thus, forexample, DE-A-3 602 090 discloses the synthesis of block copolymers which contain
sulfone and ketone groups. In Example 8 of this patent specification, an amorphous
polyarylene ether block is prepared in a first step by polycondensing 4,4'-dichloro-
diphenylsulfone and 4,4'-dihydroxydiphenylsulfone in the presence of K2CO3 and, in a
second step, polycondensed onto the chain ends of a polyether ketone block obtained from
4,4'-difluorobenzophenone and hydroquinone. The original block length is not retained in
the known syntheses owing to a randomisation reaction induced by the synthesis.
It has now been found that the reaction of at least two low molecular polyarylene ethers
which differ from each other with di- or triglycidyl compounds in less than equivalent
amounts gives modified polyarylene ether block copolymers which have good solubility in
a number of organic solvents an~ from which solutions with enhanced storage stability can
be prepared, and which, compared with corresponding unmodified polyarylene ethers,
exhibit virtually no diminution of the glass transition temperature. In contrast to the
known syntheses, the original block length is retained in this process.
Accordingly, the invention relates to polyarylene ether block copolymers which are
modified with di- or triglycidyl compounds and which have a reduced viscosity of 0.2 to
1.~ dl/g, measured in a I % solution in dimethyl formamide, which copolymers comprise
(a) 5-95 ~ by weiL~ht of polyarylene ether blocks having number average molecular
weights of 1()0()-6() ()()() and containing identical or different structural repeating units of
formul<l I
-Arl-O-Ar2-0- (1),
(b) 95-5 % by weight of (a) different polyarylene ether blocks having number average
molecular weights of 1000-60 000 and containing identical, different or identical and
different structural units of formula Il
-Ar3-O-Ar4-O- (II) and
(c) 0.2-10 % by weight of identical or different structural units of formula III, IV or V
2~52~88
- 3 -
OH OH OH
I
--CH2--CH--CH2--O --Z~--O CH2--CH--CH2--O --Zl--O--CH2--C~l--CH2-
(III),
OH OH
--CH2--CH--CH2~ CH2--CH--CH2 (IV) or
OH OH
CH2--CH--CH2 Z3 CH2--CH--CH2--
(V),
OH
( 'H2--CH--CH2
wherein Arl, Ar2, Ar3 and Ar4 are each independently of one another a divalent carbo-
cyclic-aromatic radical, Z] is a divalent radical of a cycloaliphatic, aromatic or araliphatic
dihydroxy compound after removal of both hydroxyl groups, m is 0 or an integer from 1 to
about 10, Z2 iS a divalent radical of a cycloaliphatic, aromadc or araliphatic di-secondary
amino compound after removal of both N-hydrogen atoms, and Z3 iS a trivalent radical of
a cycloaliphatic, aromatic or araliphatic compound carrying hydroxyl and/or amino groups
after removal of hydroxy and/or active hydrogen atoms bound to amino nitrogen atoms,
which radicals Arl, Ar2, Ar3, Ar4, Z1, Z2 and Z3 may be unsubstituted or substituted by
one to four Cl-C6alkyl groups, C3-C~Oalkenyl groups, phenyl groups or halogen a~oms,
and in which radicals Zl, Z2 and Z3 one, two, three or four ring carbon atoms may be
replaced by sulfur and/or nitrogen atoms, and the sum of the polyarylene ether blocks (a)
and (b) and of the structural units (c) together is 100 % by weight.
The reduced viscosity of the polymers of this invention extends over a range of c. 0.2 to
1.8 dl/g, corresponding to a number average molecular weight range of c. 15 000 to c.
150 000. Preferred polymers have a number average molecular weight in the range from
10 000 to 80 000.
The expression "polyarylene ether blocks containing different structural repeating units"
shall be understood as comprising those consisting of at least two low molecular
20~2~8
-4-
polyarylene ethers which differ from each other as well as polyarylene ether blocks
containing different structural units within the polymer chain. For example, polyarylene
ether blocks containing different structural repeadng units can be obtained by reacting a
mixture of at 1east two polarylene ethers which differ from each other, typically a mixture
of 4,4'-dihydroxydiphenylsulfone and 4,4'-dichlorodiphenylsulfone (= polyaryleneether A) and of 4,4'-dihydroxybenzophenone and 4,4'-dichlorodiphenylsulfone, with the
corresponding glycidyl compound. On the other hand, polyarylene ether blocks containing
different structura1 repeating units can a1so be obtained by replacing a portion qf the
4,4'-dihydroxydiphenylsulfone used in the preparation of polyarylene ether A with
4,4'~ihydroxybenzophenone. The po1yary1ene ether A' so obtained contains in the
polymer chain different structwal repeating units in random distribution. To prepare the
polyary1ene ether block copolymers of this invention it is a1so possible to use more than
two polyarylene ethers which differ from each other or a polyary1ene ether containing in
the po1ymer chain more than two structura1 repeating units which differ from each other.
If the radica1s Ar~ to Ar4 and Zl to Z3 contain C1-C6a1ky1, said radica1s are branched or,
preferab1y, straight-chain radica1s. Straight-chain alky1 radica1s of 1 to 3 carbon atoms are
preferred. Methyl is especia11y preferred.
ALlcyl radica1s are typically methyl, ethyl, n-propyl, isoprowl, n-butyl, sec-butyl, n-pentyl
and n-hexyl.
Radica1s defined as C3-CIOalkenyl are branched or, preferably, straight-chain radicals.
Alkenyl radicals are typically ptopeny1, a11yl or metha11yl
Halogen subsdtuents are conveniently fluoro, iodo or, preferab1y, chloro or bromo
Radicals defined as divalent carbocyclic-aromatic radica1s or as divalent radica1s of an
aromatic di-secondary amino compound after remova1 of both N-hydrogen atoms or
triva1ent radicals of an aromatic compound containing hydroxyl and/or amino gtoups after
remova1 of the hydroxyl groups and/or acdve hydrogen atoms bound to amino nitrogen
atoms are usua11y aromatic hydtocarbon radica1s carrying six to fourteen ring carbon
atoms which may be substituted by the radica1s cited above. Polynuclear aromatic radicals
may be in the form of condensed systems, or several aromatic systems such as phenylene
radica1s are attached to one another through a direct bond or through linking groups such
2~2~8
as an -O-, -S-, -SO-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -c(c6Hs)2-~ -C(CH3)(C6Hs)- or
-C(CF3)2- group.
Representative of such aromatic hydrocarbon radicals are phenylene, naphthylene,biphenylene and two, three or four phenylene radicals which are attached to one another
through linldng groups.
The aromatic hydrocarbon radicals are usually unsubstituted. They may, however, in turn
also carry one to four substituents, for example Cl-C6aL~cyl groups, halogen atoms or
preferably C3-CIOaLlceny] groups.
Zl as a divalent radical of a cycloaliphatic dihydroxy compound after removal of both
hydroxyl groups, or Z2 as a divalent radical of a cycloaliphatic di-secondary amino
compound after removal of both N-hydrogen atoms, or Z3 as a trivalent cycloaliphatic
radical of a compound containing hydroxyl andlor amino groups after removal of the
hydroxyl groups and/or active hydrogen atoms bound to amino nitrogen atoms, are usually
cycloalkylene groups carrying five or six ring carbon atoms which may be substituted by
the radicals cited above and/or which may form part of an alkylene chain.
Representative exarnples of cycloalkylene radicals are cyclopentylene, cyclohexylene,
methylcyclohexylene, 1,4-bismethylenecyclohexane and 4,4'-methylenebis(cyclo-
hex-l-yl).
An araliphatic radical may be the xylylene radical.
In the cyclic radicals Zl. Z2 and/or Z3, one to four ring carbon atoms may also be replaced
by oxygen, sulfur and/or nitrogen atoms. These may be aromatic or non-aromatic
heterocyclic systems which preferably have five or six members. Preferably one to three
ring carbon atoms are replaced by nitrogen atoms or one or two ring carbon atoms by
oxygen or sulfur atoms. Different hetero atoms may also be present in a ring, for example
a nitrogen atom and an oxygen atom.
Especially in Z2 the hetero atoms may be secondary amino groups contained in the ring
system. Exarnples are cited below.
Arl and Ar3 are preferably each independently of the other a radical of formulae VIa to
2~2~8
- 6-
VIh
~} (VIa), ~ (VIb),
( Rl~p ,~,Rl)p
~3Yl~ (VIc),
(VId),
( Rl~p ~Rl)
~3Y2~ (VIe),
( R~p,~Rl)
~3 Y2~ Y2~ (VIf),
~ (Vlg) or 3~3 (VIh)
wherein Rl is Cl-C6aLkyl, C3-CIOalkenyl, phenyl or halogen, p is an integer from O to 4,
Yl is a direct bond, -SO2-, -CO-, -S-, -SO-, -CH2-, -C(CH3)2-~ -C(c6Hs)2-~
-C(CH3)(C6Hs)- or -C(CF3)2-, Y2 is -CO-, -SO2- or -S- and Q is -CH2-, -O-, -CO- or a
direct bond.
PrefeIably Arl and Ar3 are each independently of the other a radical of formula
20~2~8
-7 -
O O
~}. ~C~ ~B~
CH3
~S~, ~CH2~3 '~C~ or
CH3
CH3
~1~, .
CH3
In the particularly prefelred polyatylene ether block copolymers of this invention, Arl and
Ar3 are each independently of the other a rad~cal of formula
. o
~_11~ ~s~ or
,=, ~ B \d ~ \J
Ar2 and Ar4 are preferably each independently of the other a radical of fonnula VIi-VIn
~Y3-13 (VIi),
205~8
~3Y3~3Y3~} (VL~c),
~3 Y3~3~3 Y3~ (VIl),
~3Y3~Y3~ (VIm) or
CN
O (VIn),
wherein Y3 iS -C-, -S2- or -SO-.
More preferably, Ar2 and Ar4 are each independently of the other a radical of formula
1~
~ so2~ or ~3c
Most preferably, Ar2 and Ar4 are a radical of formula
~SO2~ .
Preferably Z1 is a radical of formulae Vlla to VlIi;
~3 (VIla), ~} (VIIb),
~3Y1~3 (Vllc), ~ c ~ (VlId),
20~2~88
~ (vr~), ~ (vr~,
\~(Vllg), ~ X ~ (Vllh)or
--CH2{~ CH2-- (VIIi),
wherein Yl is a direct bond, -SO2-, -CO-, -S-, -SO-, -CH2-, -C(CH3)2-, -C(C6Hs)2-,
-C(CH3)(C6Hs)- or-C(CF3)2-.
In particular, Zl is a radical of formula
~3 CH~ , ~ C
O CH3 CH3
or ~ cH2~
In the polyarylene ether block copolymers of this invention, Z2 iS preferably a radical of
formulae VIIIa-Vmj
o~o
--N~N-- (VIIIa), --N~fN-- (VIIIb),
o o
20~2~8
10 -
~
--N~r'N-- (VmC), --N~N-- (VIIId),
o o
O~CH3 ~
--N~N--CH2--N~N-- (Vme), --~-- (Vmf)~
O O
--NJJ~N (Vmg),--N J~N-- (VIIIh),
oJ~o CH3 J~J
CH3 CH3 CH3
O O O
--NJ~N--CH2--NJ~N(VIlli) or --NJ~N-- (VIIIj),
~CH3CCH3 C~CH o CH3
and Z3 iS preferably a radical of formula
o-- o
O O N, ----Q --~ \NJJ`N/
7_ o_ I
The polyarylene ether block copolymers of this invention further preferably contain
10-90 % by weight of the polyarylene ether blocks mentioned in (a) and 90-10 % by
weight of the polyarylene ether blocks mentioned in (b). Most preferably the polyarylene
ether block polymers contain 70-30 % by weight of the blocks mentioned in a) and30-70 % by weight of the polyarlyene ether blocks mentioned in b).
2 ~ 8
11
Furthermore, the amount of structura1 units of formula III, IV or V in the polyarylene ether
block copolymers is preferably 0.2-5 % by weight, based on the block copolymer.
The modified polyarylene ether block copolyrners of this invention may be prepared by
(a) reacting 5-95 % by weight of hydroxyl-terminated polyarylene ethers having a number
average molecular weight of c. 1000 60 000 and of formula Ia
HO~ -OtAr2-O~ -O~Ar2-O-Arl-H (Ia),
wherein Arl and Ar2 are as defined above and x is an integer from 4 to 250, and
(b) 95-5 % by weight of (a) different hydroxyl-terminated polyarylene ethers having a
number average molecular weight of 1000 to 60 000 and of formula II
HO-AJ3-OtAr4-0-Ar3-O~Ar4-0-Ar3-OH (IIa),
wherein Ar3 and Ar4 are as defined above and y is an integer from 4 to 250, with (c) 0.2 to
10 % by weight of one or more glycidyl compounds of formula IIIa, IVa or Va
(IIIa),
O OH
CH/2 \CH--C~2-- ~ Zl o--CH2--CH--CH2--O 3--Zl--O CH2 CH 2
O~ O
CHz--CH--CH2--Z2--CH~ CH CH2 (IVa),
o o
CH2--CH--CH2 Z3--CHz--CH--CH2 tva)~
CH2--C~ ~CH2
o
2~2~8
- 12-
whelein Zl. Z2~ Z3 and m are as defined above, to polyarylene ether block copolymers.
The polyarylene ether block copolymers so obtained are disdnguished by tht feature that
the block lengths used therein are virtually retained after the coupling reacdon, i.e. a
randomisatdon caused by at least pardal degradadon of the stalting prepolymers can be
avoided.
Hence the invention also relates to a process for the preparatdon of polyarylene ether block
polymers.
The low molecular hydroxyl-terminated polyarylene ethers of formula Ia or IIa
(prepolymers) used as stardng compounds preferably have a number average molecular
weight of 2000 to 30 000, most preferably of 40ûO to 20 000.
These prepolymers can be obtained in known manner, for example by reacdng a
dihydroxy compound of formula Ib or IIb
HO~ -OH (Ib)
Ho-Ar3-oH (IIb)
with an aromatic dihalo compound of formula Ic or IIc
Hal-Ar2-H?~ (Ic)
Hal-Ar4-Ha~ C)
wherein Arl, Ar2, Ar3 and Ar4 are as defined for formulae I and II and Hal is a halogen
atom, preferably a chlor~ne or fluorine atom.
The dihydroxy compounds of formulae Ib and nb are normally used in excess such that
hydroxyl-terminated prepolymers are obtained. The molar ratios of dichloro/dihydroxy
compounds are so chosen in per se known rnanner that prepolymers having the desired
molecular weight are obtained.
It is, however, also possible to use an excess of the aromadc dihalo component and to
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- 13 -
convert the dihalo-terminated prepolymers by treatment with a base, for example sodium
or potassium hydroxide, into the appropriate hydroxyl-terminated prepolymer.
~t will, of course, be readily understood that monomers each containing one halogen atom
and one hydroxyl group in each molecule can also be used to prepare the prepolymers.
The preparation of the prepolymers is nolrnally carried out in solution. This is usually
done by choosing a solvent in which both starting materials and the prepolymer are at least
partially soluble. Typical examples of such solvents are polar aprotic solvents such as
dirnethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylacetamide, N,N'-dimethylprop-
yleneurea, N-cyclohexylpyrrolidone, N-alkylcaprolactams or, preferably, diphenylsulfone.
The reaction is preferably carried out in the presence of a base to neutralise the hydrogen
halide which evolves. Typical examples of suitable bases are NaOH or KOH and,
preferably, Na2CO3, K2C03 or mixtures of alkali metal or alkaline earth metal carbonates.
The diglycidyl ethers of formula Illa, diglycidyl compounds of formula Vla or triglycidyl
compounds of formula Va used for modifying the prepolymers are known per se and some
are commercially available.
Illustrative examples of particularly preferred compounds of formula Illa are the
diglycidyl ethers of bisphenol F, dihydroxydiphenylsulfone, diallyl bisphenol A and,
preferably, of bisphenol A.
The modification of the prepolymers can be carried out in a solution of a high-boiling inert
solvent. The solvent is so chosen that both starting components and the reaction product
are at least partially dissolved therein. A typical high-boiling solvent which may be used is
diphenyl sulfone. Normally the prepolymer will be charged to the solvent, which may be
in the melt state, followed by the addition of the glycidyl compound or of a solution of the
glycidyl compound in an inert solvent. The modification can be carried out in the presence
or absence of further ingredients or catalysts by reacting phenol or phenolate groups with
epoxy groups. Preferably the reaction mixtures obtained in the synthesis of the
prepolymers are used direct for the modification, without dilution or after dilution with an
organic solvent. Suitable catalysts for the modification reaction may be the bases which
are also used for the preparation of the prepolymers.The reaction temperature is chosen
2~2~8
such that a sufficient reaction rate is ensured. The reaction temperatures are typically in
the range from 100 to 200C.
It is preferred to react the hydroxyl-terminated polyarylene ether of formula Ia and IIa
with 0.5 to 5 % by weight of glycidyl compounds of formula IIIa, IVa or Va.
The thermoplastic polyarylene ether block copolymers may be used in the conventional
manner for thermoplastics and are processed, for example, to mouldings or sheets, or used
as matrix resins, adhesives or coating compositions.
Prior to processing the polymers which may be in the form of moulding powders, melts or,
preferably, solutions, it is possible to add conventional modifiers such as fillers, pigments,
stabilisers, or reinforcing agents such as carbon, boron, metal or glass fibres. The
polymers of this invention can also be processed together with other thermoplastics or
thermosetting plastics.
The preferred utility of the polyethylene ether block copolymers of this invention is as
matrix resins for the fabrication of fibrous composite systems for which the fibres
conventionally used for reinforcing industrial moulding compounds may be used. These
fibres can be organic or inorganic fibres, natural fibres or synthetic fibres, and can also be
in the form of fibre bundles, of oriented or non-oriented fibres or of endless filaments.
A further preferred utility of the polyarylene ether block copolymers of this invention is
the modification of other plastics materials. These materials may be basically
thermoplastics or therrnosetting plastics. Such systems are especially suitable for use as
matrix resins which are used for fabricating composite components.
To be singled out for special mention is the unexpectedly good solubility of the block
copolymers in numerous conventional organic solvents, for example in fluorinated or
chlorinated hydrocarbons, and the very good stability of the solutions obtained.Representative examples of suitable solvents are polar aprotic solvents such as
N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl
sulfoxide and sulfolane, as well as chlorinated aliphatic hydrocarbons such as methylene
chloride, I ,2-dichloroethane and cyclic ketones such as cyclohexanone and cyclo-
pentanone, and also cyclic ethers such as 1 ,3-dioxolane.
2~52~88
- 15-
In contrast to the starting prepolymers, the novel block copolymers have very good
solubility in, for example, methylene chloride, and form solutions which are stable for
several days. They may therefore be processed from a solution to films or incorporated in
other systems.
Hence the invention also relates to a solution containing ca. 1 to 75% by weight,
preferably 5 to 50% by weight, based on the solution, of a solution of a polyarylene ether
block copolymer of this invention in an organic solvent.
The invention further relates to the use of the polyarylene ether block copolymers or
solutions thereof, for making mouldings, coatings, sheets or fibrous composite structures.
The block copolymers modified in the practice of this invention normally carry
preponderantly phenolic end groups. Further specific end groups can be obtained by
subsequent reactions. For example, alkoxy and acyloxy end groups can be obtained with
an a1kyl halide or with a halide of a monocarboxylic acid. The novel copolymers are
normally amorphous or partially crystalline.
The reduccd viscosities of the prepolymers and polyarylene ether block copolymers are
measured in 1 % solutions in dimethyl formamide (DM~) (1 g of polymer in 100 ml of
DM~),
Preparation of the low molecular polyarylene ethers (prepolymers)
Example A: 626 g (2,5 mol) of 4,4'-dihydroxydiphenylsulfone, 703 g (2.45 mol) of4,4'-dichlorodiphenylsulfone, 363 g (2.625 mol) of K2CO3 and 1400 g of diphenyl
sulfone are heated to 180C in a 101 metal reactor while blanketdng with N2. After the
temperature of the reaction mixture has reached 180C, the batch is stirred for 2 hours.
The water of condensadon formed during the reacdon is continuously removed from the
reaction mixture by disdlladon through a descending condenser. After 2 hours at 180C,
the reaction temperature is raised to 260C stepwise over 2 hours and kept constant at this
temperature for 4 hours. The reaction mixture is then discharged from the reactor through
a bottom blow valve, cooled, and then coarsely ground.
A pordon of the polymer is worked up by extraction (3 x acetone/water = 80/20; 1 x
water). Acetdc acid is added during the aqueous extraction to liberate the OH end groups.
20~2`~88
- 16-
The polyether sulfone is thereafter dried at 110C under vacuum. It has a reduced
viscosiq of llred = 0.33 dVg and has an aromatic end group content of l lO IlVal/g.
Example B: lOS g (0.50 mol) of 4,4'-dihydroxybenzophenone, 140.7 g (0.49 mol) of4,4'-dichlorodiphenylsulfone, 72.5 g (0.525 mol) of K2CO3 and 245.6 g of diphenyl
sulfone are reacted in accordance with the general procedure described in Example A in a
1 I metal reactor (reaction conditions 180 C/2 h; 180-260 C/2 h; 260 C/3.75 h). The
resultant polymer has a reduced viscosity of ~red = Q30 dUg.
Example C: 93.1 g (0.50 mol) of phenylhydroquinonet 140.7 g (0.49 mol) of 4,4'-di-
chlorodiphenylsulfone,72.6 g (0.525 mol) of potassium carbonate and 233.8 g of di-
phenylsulfone are reacted in accordance with the general procedure described in
Examp1e A in a 1 litre metal reactor (reaction conditions: 180C/2 h; 180-260C/2 h;
260C/3 h) and subsequently worked up. The resultant polymer has a llred of 0.26 dl/g.
Example D: 93.1 g (0.50 mol) of 4,4-dihydroxybiphenyl, 140.7 g (0.49 mol) of 4,4'-di-
chlorodiphenylsulfone,72.6 g (0.525 mol) of K2C03 and 223.8 g of diphenyl sulfone are
rcacted in accordance with the general proced0e described in Example A in a I I metal
reactor (reacdon conditions 180 C/2 h; 180-260 C/2 h; 260 C/4 h). The resultant poly-
mer has a reduced viscosity of tl,~d = 0.22 dUg.
Example E: 93.1 g (0.50 l) of 4,4'-dihydroxybiphenyl, 129.22 g (0.45 mol) of
4,4'-dichlorodiphenylsulfone,72.56 g (0.525 mol) potassium carbonate and 222.32 g of
diphenylsulfone are reacted in accordance with the general procedure described in
Example A in a 1 litre metal reactor (reaction conditions: 180C/2 h, 180-270C/2 h,
270Ocn.45 h) and worked up. The resultant polymer has a ~,cd of 0.24 dVg.
Preparation of modified polyarylene ether block copolymers:
E~xam~le 1: 15 g of the reaction mixture prepared according to Example B containing
5.91 g of low molecular polyarylene ether, and 29.4 g of a reaction mixture prepared
according to Example A containing 11.81 g of polyarylene ether, are completely fused in a
glass reactor under nitrogen at 150C/2 h. Then 0.34 g of bisphenol A diglycidyl ether
(epoxide equivalent 175.5-179 g/Val; 1.92 %, based on the total amount of polyarylene
ether) are added dropwise to the me1t. The reaction is terminated 2 h after the addition of
the diglycidyl ether is complete.
-17- 2Q~2~8~
The reacdon mixture is discharged f~m the glass reactor, ground and then worked up by
extraction (3 drnes with acetone/water in the ratio 80:20; once with water). Acedc acid is
added during the extracdon with water to se~ free the OH end groups. The modi~led poly-
arylene eeher block copolymer has a llred Of 0.48 dUg.
Example 2- 22.5 g of the reacdon mixture prepared according to Example B containing
9.0 g of low molecular polyarylene ether, and 22.5 g of the reacdon mixture prepared
according to Exarnple A containing 9.0 g of polyarylene ether, are reacted with 0.36 g of
bisphenol A diglycidyl ether (epoxide equivalent 175.5-179 g/Val; 2.0 %, based on the
total amount of polyarylene ether) in a glass reactor in accordance with the general
procedure described in Example 1. The modified polyarylene ether block copolymer has a
llred of 0.44 dVg.
Example 3: 22.5 g of the reaction mixture prepared according to Exarnple C containing
8.9 g of low molecular polyarylene ether, and æ.s g of the reaction mixture prepared
according to Example A containing 9.0 g of po1yarylene ether, are reacted with 0.27 g of
bisphenol A dig1ycidyl ether (epoxide equivalent 175.5-179 glVal; 1.5 %, based on the
total amount of polyarylene ether) in a glass reactor in accordance with the general
procedure described in Example 1. The modified polyarylene ether block copolymer has a
,ed of 0.45 dVg.
ExamDle 4: 30 g of the reaction mixture prepared according to Example C containing
11.6 g of low molecular polyarylene ether, and 15 g of the reaction mixture prepared
according to Example A containing 6.0 g of polyarylene ether, are reacted with 0.35 g of
bisphenol A diglycidyl ether (epoxide equivalent 175.5-179 glVal; 2.0 %, based on the
total amount of polyarylene ether) in a glass reactor in accordance with the general
procedure described in Example 1. The modified polyarylene ether block copolymer has a
~lrcd of 0.59 dVg.
Example 5: 30 g of the reaction mixture prepared according to Example D containing
11.78 g of low molecular polyarylene ether, and 15 g of the reaction rnixture prepared
according to Example A containing 6.03 g of polyarylene ether, are reacted with 0.32 g of
bisphenol A diglycidyl ether (epoxide equivalent 175.5-179 g/Val; 1.80 %, based on the
total amount of polyarylene ether) in a glass reactor in accordance with the general
-18- 20~2488
procedure described in Example 1. The modi~led polyarylene ether block copolymer has a
llred of 0.67 dVg.
Example 6: 24.9 g of the reaction mixture prepared according to Example A containing
10 g of low molecular polyarylene ether, and 25.65 g of the reaction mixture prepared
according to Example E containing 10 g of polyarylene ether, are reacted with 0.50 g of
dihydroxydiphenylsulfone diglycidyl ether (epoxide equivalent 188.7 g/~al; 2.5 %, based
on the total amount of polyarylene ether) in a glass reactor in accordance with the general
procedure described in Example 1. The modified polyarylene ether block copolymer has a
,ed of 0.36 dVg.
Example 7: 24.9 g of the reaction mixture prepared according to Example A containing
10 g of low molecular polyarylene ether, and 25.7 g of the reacdon mixture prepared
according to Example E containing 10 g of polyarylene ether, are reacted with 0.20 g of
N,N,O-triglycidyl-p-aminophenol (epoxide equivalent 95-107 g/Val; 1.0 %, based on the
total amount of polyarylene ether) in a glass reactor in accordance with the general
procedure described in Example 1. The modified polyatylene ether block copolymer has a
of 0.37 dVg.
Example 8: The polymer synthesised according to Example 1 is added in the form of a
solution in methylene chloride containing 10 parts by weight of polymer to a mixture
consisting of 50 parts by weight of N,N,N',N'-tetraglycidyldiaminodiphenylmethane and
50 parts by weight of N,N,0-triglycidyl-p-aminophenol, and the solvent is removed under
vacuum. After addition of 50 parts by weight of p-diaminodiphenylsulfone, the solution is
fully cured for 2 hours at 160C and for 2 hours at 210C. Specimens are cut from the
sheet so obtained and tested for their flexural strength (= 147 N/mm2) and edge fibre
elongaffon (= 4.7 %).
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