KR100186809B1 - Polymeric composition and components thereof - Google Patents

Abstract

The present invention relates to a polymer composition consisting of a phenol / formaldehyde system and a polyarylsulfone having an epoxy pendant or terminal group, a new epoxy terminated polyarylsulfone and a new crosslinked epoxy terminated polyarylsulfone. These compositions may or may not be reinforced with fibers and / or other fillers.

Description

Polymer Compositions and Their Components

The present invention relates to thermosetting compositions made from aromatic polymers having reactive groups and to methods of making such polymers.

U.S. Application No. 4448948 describes polyethersulfones and polyetherketones with relatively low molecular weights terminated with glycidyloxy end groups and methods for making these polymers. These polymers are described as crosslinkable using conventional epoxy crosslinking reagents such as diaminodiphenyl sulfone.

EP 311349 describes, among others, polymer compositions having a polyarylsulfone component and a thermosetting resin component. The thermosetting component may be selected from epoxy resins, bismailimide resins or phenol-formaldehyde resins and the preferred polyarylsulfone polymers have a special general formula, preferably the reactive end groups, in particular -OH and -NH ₂ Having end groups.

The polymer composition according to the present invention consists of a polyarylsulfone and phenol / formaldehyde (PF) thermoplastic system composed of reactive epoxy groups which, when containing reinforcing fillers such as glass fibers or carbon fibers, have surprisingly greatly enhanced physical properties.

Suitable PF systems include both Novolac and Resol type PFs.

These epoxy groups can be attached to the polymer chain as end groups or as pendant groups or both.

When the epoxy group is an end group, the number of such end groups per polymer chain is preferably between 1.5-2.5 and an average of 1 ± 0.2 at each end site of each chain in a given polymer sample is very suitable.

Preferred polymers for use in the compositions of the present invention consist of E and E ¹ units linked by ether and / or thioether contention, where E is a divalent aromatic radical having a sulfone group and E ¹ is optionally a sulfone group and It is a bivalent aromatic radical which has a terminal group of general formula (I).

[Wherein k is an integer of 1-3 selected according to G,

G is a direct bond or the following general formula (II)

J is at least one residue selected from divalent phenol residues, aminophenol residues or aromatic diamine residues, preferably residues of formula (III)

-PhAPh-(III)

Ph is phenylene, especially 1, 4- phenylene; And

A is a direct bond,-0-, -S-, -SO-, -CO-, -CO _2- , SO ₂ -or C _1-6 hydrocarbon]

In the preferred polymer compositions of the invention the polysulfone units E and E ¹ are independently selected from the general formula (IV) radicals;

-(PhSO ₂ Ph) _n- (Ⅳ)

┌─

In which Ph is phenylene, in particular 1, 4-phenylene and optionally

Unobstructed such as halogen, alkyl or alkoxy

Having up to four substituents;

N is 1-2 and can be a fraction;

└─

Optionally small amounts are selected from radicals of the general formula (V):

(Ph) _a (V)

[Wherein a is 1-3 and can be a fraction, and these phenylenes are linearly bonded or fused to each other via a single bond or a divalent group other than SO ₂ ]

Fraction refers to the average value for a given polymer chain that includes units having various n or a values.

In a preferred polymer composition of the present invention, the relative proportion of repeating units of polyarylsulfone is, on average, the extent to which at least two (PhSO ₂ Ph) n units are continuously connected in each polymer chain, each of 1: 99-99: 1 In particular, between 10: 90-90: 10 is preferred. Generally, the ratio is in the range of 25-50 (Ph) _{a and the} remainder (PhSO ₂ Ph) n.

Preferred polyarylsulfones for use in the polymer composition of the present invention are units of the following general formula (VI) or units of the following general formula (VII).

X Ph SO ₂ Ph X Ph SO ₂ Ph (“PES”) (Ⅵ)

X (Ph) a X Ph SO ₂ Ph (“PES”) (Ⅶ)

[Wherein X is O or S and may vary from unit to unit.

The ratio of (VI) to (i) is preferably between 10: 90-80: 20, particularly preferably 10: 90-55: 44.

The relative ratio of repeating units of polyarylsulfone can be expressed as a weight percentage of 100 times (weight of SO ₂ ) / (weight of average repeating units). The preferred content of SO ₂ is at least 20%, preferably 23% -30%. When a = 1 this value corresponds to a PES / PEES ratio of at least 20:80, preferably 35: 65-65: 35.

This ratio is limited to the above units only. In addition to these units, polyarylsulfones may comprise up to 50%, in particular up to 250 mole%, of other repeating units; In that case, the preferred range of contents (if used) is for the entire polymer. Examples of such units were as follows.

┌─

Wherein A ¹ is a direct bond and is O, S, CO or a divalent hydrocarbon

Radicals.

└─

When polyarylsulfone is the product of nucleophilic synthesis, the units thereof are, for example, bisphenols and / or the corresponding bistyols or phenol-thiols;

Hydroquinone,

4, 4′-dihydroxybiphenyl,

Lesosinol,

Dihydroxynaphthalene (2, 6 and other isomers),

4, 4'- dihydroxydiphenyl ether or thioether,

4, 4'- dihydroxybenzophenone,

2, 2'-bis (4-hydroxyphenyl) propane or methane;

It may be derived from one or more.

If bistiol is used it may be made on its own, ie a dihalide, for example as described below, may react with alkali sulfide or polysulfide or thiosulfate.

Examples of such other units are those having the following general formula;

┌─

Wherein X is independently CO or SO ₂ ;

Ar is a divalent aromatic radical;

M is an integer of 0-3 if X is non-zero when X is SO ₂ .

└─

It is preferred that Ar ¹ is at least one divalent aromatic radical selected from phenylene, biphenylene or terphenylene. A special unit where m is greater than zero has the following general formula:

When the polymer is a product in the synthesis of nucleophilic materials, these units may comprise at least one dihalide,

For example, 4, 4'- dihalobenzophenone,

4, 4′-bis (4-chlorophenylsulfonyl) biphenyl,

1, 4-bis (4-halobenzoyl) benzene,

4, 4′-bis (4-halobenzoyl) biphenyl

It may be selected from.

These can of course be derived in part from the bisphenols of interest.

This polyarylsulfone may be a product made by synthesis method using nucleophilicity from halophenone and / or halothiophenol. In any nucleophilic synthesis, halogens such as chlorine or bromine can be activated by the copper catalyst present. Such activation is sometimes unnecessary if the halogen is activated by an electron acceptor group. In any case, fluorides are generally more active than chlorides. For the synthesis using nucleophilicity of polyarylsulfone (hereinafter referred to as nucleophilic synthesis), at least one alkali metal carbonate and aromatic sulfone solvent in an amount up to 10 mol% above the amount is carried out at a temperature of 150-350 ° C. It is desirable to.

If desired, polyarylsulfone may be a product made by electrophilic synthesis.

It is preferred that the polyarylsulfones contain pendant groups and / or terminal groups of the general formula -R ¹ -Z before epoxidation. Wherein R ¹ is a divalent hydrocarbon group, preferably an aromatic hydrocarbon group and Z is a residue of a group with active hydrogen which reacts with a suitable compound containing epoxy to form an epoxy group as described above, in particular R ² is C ₈ Hydrocarbon residue containing -NHR ² , -NH ₂ , -OH or -SH residue.

It is suitable that the number average molecular weight of polyaryl sulfone is between 2000-60000. Preference is given to at least 9000, in particular at least 10000, such as 11000-25000. However, if desired, polymers with molecular weights as small as 3000-9000 may be used in some cases, such as for example to control the final molecular weight of the foamed polymer, which will be described in more detail later.

In order to show the molecular weight, it is convenient to use the converted viscosity measured by the solution made by adding 1 g of a polymer to a 100 ml solution of dimethyl formamide at 25 ° C. The relationship is as follows.

RV 0.15 0.25 0.45 0.92

MW (number average molecular weight) 5000 13000 20000 60000

(In fact, these molecular weights were measured by vapor osmosis and of course, the general error range is about 10%.)

Epoxy groups on the polyarylsulfones of the present invention are usually aromatic

Diamines,

Aromatic mono primary amines,

Aminophenols,

Polyhydric phenols,

Polyhydric Alcohol,

Polycarboxylic acid; From one or more of

It may be derived from an epoxide containing compound which is a derived mono or poly-glycidyl derivative.

Examples of liquids at room temperature include the following: tetraglycidyl diamino diphenylmethane, such as MY 720 ”or MY 721” from Ciba-Geigy with a viscosity of 10-20 Pa s at 50 ° C .; (MY 721 is a low-viscosity form of MY 720 and is designed for use at high temperatures);

Triglycidyl derivatives of p-aminophenol having a viscosity at 0.5 ° C. of 0.55 to 0.85 Pa s (My 0510 ”from Ciba-Geigy); or

Diglycidyl ether of 2,2-bis (4,4′-dihydroxyphenyl) propane with a viscosity at 25 ° C. of 8-20 25 Pa s (Epikote 828 ”from Shell)

The present invention also includes polyarylsulfones as described above having epoxy endgroups wherein the general formula of the epoxy endgroups is as follows:

┌─

K is selected from an integer of 1 to 3 depending on J;

J is a divalent phenol residue, aminophenol residue or aromatic diamine

A residue selected from at least one of the residues;

The residue preferably has the general formula III.

│-Ph A Ph-(Ⅲ)

Ph is phenylene, especially 1, 4- phenylene;

A is a direct bond,-O-,-S-,-SO ₂ -,-CO-,-CO _2-

Or C _1-6 hydrocarbons.

└─

At least one starting polymer having at least one terminal or pendant group of the general formula —R ₁ ZH and wherein E and E ¹ units are linked by ether and / or thioether bonds;

(a) at least one epihalohydrin when G is a direct bond; And

(b) when G is of formula (II), at least one compound of formula IIB:

And polyarylsulfone containing an epoxy group can be prepared.

According to the invention the aromatic polymers also have at least one pendant or terminating group of the formula -R ¹ Z- and the polyarylsulfone chain and the general formula -R ^{1 in} which units E and E ¹ are linked by ether and / or theoether bonds. It consists of a second polyarylsulfone chain having at least one pendant or terminating group which is Z- and linked units E and E ¹ by ether and / or thioether bonds, said chain being a residue of an epoxy group of the general formula (I) Connected by a group of the general formula -R ¹ Z- bound by.

The present invention also relates to a polyarylsulfone chain having at least one pendant or terminating group of the general formula -R ¹ Z- and to which units E and E ¹ are linked by ether and / or thioether linkages of the general formula -R ¹ Z- Provided is a process for preparing the polymers described above, which comprises reacting with a second polyarylsulfone chain having at least one pendant or terminating group, wherein units E and E ¹ are linked by ether and / or thioether bonds.

The relative ratios and initial molecular weights of the two polyarylsulfones are selected depending on the final molecular weight desired.

The ratio of the general formula -R ¹ Z- group to the general formula -R ¹ Z- group connected to the epoxy group of general formula (I) is 10: 90-90: 10, more preferably 20: 80-80: 10. It is especially preferable that it is 70: 30-60: 40.

These polymers show surprisingly significantly improved properties when they contain reinforcing fillers such as carbon fiber or glass fiber, especially when compared to polymers having the general formula -R ¹ Z- end group.

Polyarylsulfones having an epoxy group according to the present invention may be crosslinked with conventional thermosetting epoxy resin systems.

Crosslinked polyarylsulfones are products of at least partial curing of polyarylsulfones having epoxy groups with a curing agent and possibly a catalyst.

The curing agent is preferably an amino compound having a molecular weight of up to 500 per amino group, such as an aromatic amine or guanidine derivative. Specific examples are 3, 3'- and 4, 4'- diaminodiphenylsulfone, methylenedianiline and dicyandiamide. The total amino content of the curing agent is between 70-110% of the stoichiometric amount required of the polyarylsulfone. If necessary, other standard epoxy curing agents such as aliphatic diamines, amides, carboxylic anhydrides, carboxylic acids, phenols or phenol / formaldehyde condensates can be used.

If a catalyst is used, usually derivatives with Lewis acids such as amines such as boron trifluoride, piperidine or methylethylamine are used. Otherwise it may be basic such as imidazole or amine.

The polymer composition of the present invention is particularly suitable for making structures such as load bearing structures or impact resistant structures.

To do this, the composition may include reinforcing agents such as fibers.

In the composites of the invention, the fibers are cut to an average of less than 20 mm, such as about 3-6 mm in length, and added at a concentration of 5-70%, in particular 20-60%. However, in the case of structures it is preferred to use 30-70%, in particular 50-70%, long fibers such as glass fibers or carbon fibers.

This fiber can be organic or inorganic, which is a hard polymer such as polyparaphenylene terephthalamide. Among the inorganic fibers, glass fibers such as E ”or S may be used, or alumina, zirconia, silicon carbide, other ceramic or metal compounds may be used. Very suitable reinforcing fibers are carbon fibers such as graphite. Organic or carbon fibers may or may not be suitable materials for the compositions of the present invention in view of being able to dissolve in the liquid precursor composition without adverse reactions or in terms of adhering to both the thermosetting / thermoplastic composition and the fibers of the present invention. have. In particular, carbon or graphite fibers may or may not be coated with an epoxy resin precursor or preferably a thermoplastic such as polyarylsulfone. It is preferred to apply a material that adheres the inorganic fiber to both the fiber and the polymer composition, for example an organo-silane coupling agent applied to the glass fiber.

The composition is for example a toughening agent glass granules such as a liquid rubber having a reaction group; Rubber particles and rubber coated glass granules may include fillers such as polytetrafluoroethylene, graphite, boron nitride, talc mica and vermiculite, stabilizers such as pigments, nucleating agents and phosphates. The total amount of such materials and fiber reinforcements should be such that the composition contains at least 20% by volume of the polymer composition. The percentage of fibers and these other materials is calculated based on the final state of use, such as the total composition cured or crosslinked.

In the composite of the present invention, short single-fiber fibers may be added to the polyarylsulfone solution of the present invention or to the polymer composition containing the polyarylsulfone before evaporating the solvent. However, the preferred composite consists of long fibers which are contacted by passing the long fibers through the polyarylsulfone and its solution, if present. The impregnated fiber reinforcement thus made is used alone or in combination with other materials, such as additional amounts of the same or different polymer or resin precursors or mixtures, to make shaped articles.

In addition, incompletely cured compositions can be made into films using methods such as compression molding, extrusion, solidification-casting or belt-casting, and then the mixture flows over the fibers, penetrates through them and cures, resulting in laminates. It consists of laminating the film on non-woven mats, knitted fabrics or long fibers of relatively short fibers under conditions of sufficient temperature and pressure.

The composites of the present invention may, for example, have a temperature higher than the curing temperature of the thermosetting component or, if already cured, a temperature higher than the glass transition temperature of the mixture, usually at least 150 ° C., generally about 190 ° C. and at least 0.1 MN / m ² , Can be made by compression molding to a pressure of at least 5 MN / m ² or by laminating layers of impregnated fiber reinforcement with a heated roller and then secondary curing to a temperature of about 240 ° C.

The multi-ply laminates thus made are either anisotropic with the fibers oriented parallel to each other or quasi-isotropic with the fibers of each ply oriented at a constant angle, typically about 45 ° C., but 30, 60 with respect to the top or bottom plies. It may be oriented at an intermediate angle of ° or 90 °. It is also possible to use laminates with a medium orientation between anisotropy and quasi-isotropy. Suitable laminates are those of at least 4 ply, preferably at least 8 ply. The number of plies depends on the use of the laminate to be used, such as the required strength, and laminates of at least 32, such as hundreds of plies, are preferred. As mentioned above they can agglomerate in the middle of the layer.

The following examples will illustrate the invention.

In the examples, the bending rate, the stress due to extrusion (yield strength) and the resin cleavage strength and hardness, K _1c and G _1C were measured as follows.

Using a “Instron” model 1122 test instrument with a crosshead speed of 5 mm / min, a uniform sample bent at three points was used and the bending rate was calculated according to the following equation.

E = ¼.F / .L ³ / BW ³

┌─

Where F is the force required for the center of the sample to begin bending.

F / is a slight bend and is less than W / 2.

W is the thickness of the sample,

B is the width of the sample;

L is the spacing between supports

└─

Usually L = 50mm, B = 3mm, W = 10mm.

The compressive stress σy was measured on an Instron machine with crosshead speeds of 5 mm per minute using samples of various sizes.

To determine the breaking strength and hardness, a linear elastic fission machine test bent at three points and notched on one edge is used, and the data are made using an impact device. The maximum value of the splitting strength and the strain energy release rate at the start of splitting is as follows.

G _1C = U _C / BW.

┌─

Where is the equivalence function,

U _C is the energy absorbed in the impact test.

└─

Samples were tested using a mechanized notch with a test rate of 1 ms ⁻¹ at −65 ° C.

Example 1

Heat up to 280 ° C. and hydroquinone (30 moles) and dihydroxydiphenylsulfone (20 moles) in 4,4′-dichlorodiphenylsulfone (50 moles) in potassium carbonate (50 moles) and diphenyl sulfone solvent. And 40: 60 PES: PEES polyarylsulfone samples. A slight excess of 4, 4'-dichlorodiphenylsulfone was used to form -C1 terminal groups on the polymer. During the reaction, m-aminophenol was added to the reaction mixture as an end-capping agent. After cooling, the polymer sample was triturated and washed with acetone, methanol and water and dried until all potassium salts were gone.

RV of the polymer being Sample A was 0.28 (1% solution in dimethylformamide-DMF), Tg was 195 ° C. and the structural formula is as follows.

A portion of Sample A was mixed with diglycidyl ether (Epikote 828 ”from Shell, 2 mole parts) of 2,2-bis (4,4-dihydroxyphenyl) propane. The mixture was warmed by heating to 180 ° C. for 2 hours until the polymer dissolved. After cooling, the reactions were dissolved in dichloroethane (colorless solution) and poured into methanol to precipitate the polymer. The polymer (hereinafter referred to as sample B) was tested by infrared (IR) and nuclear magnetic resonance (nmr) to find that the polymer's structural formula is as follows.

Example 2

Samples A and B in powder form were mixed 50:50 and compression molded at 300 ° C. and 4 tons (pressure) for 15 minutes to form a 2 mm thick film. The hardness of the resulting film was very strong and especially strong compared to similar films made of Sample A (which is brittle at this molecular weight). The film, partly in dichloromethane at room temperature, swelled slightly after 7 days (polyarylsulfone is generally dissolved or greatly swollen in dichloromethane). This film can be melted thermoplasticly.

Sample B did not polymerize uniformly when molded at 300 ° C.

Example 3

At room temperature, PF precondensates (Novolak SFP 118 from ex Schenectady Chemical) (68 g) and hexamethylenetetramine (12 g) samples were mixed with various amounts of polymer samples A and B in 90:10 v / v methylene chloride: methanol. It was. No polymer was mixed in the comparative sample. The mixture was poured into a tray surrounded by molded release paper and the solvent was allowed to evaporate. The remaining solvent was removed in a 60 ° C./0 mmHg vacuum oven.

The material was ground to a powder and then molded into test plaques as follows. The press and metal mold used to make the plaques were heated to 150 ° C. for 1 hour. A vacuum bag was made using a nylon bag film stable up to 260 ° C. Mastic tape was attached to three sides of this bag. The powder molding compound was sandwiched between the preheated mold parts, placed in a bag, sealed and vented. The bag containing the molding was placed on the press and the pressure was increased to the maximum molding pressure (15 tonnes for a 150 mm × 100 mm mold) until the flams appeared. The mold was held at 150 ° C. under vacuum for 15 minutes and then removed and cooled to 50 ° C. before removing the plaque.

The mechanical properties of the two samples are shown in Table 1.

Ductility factor (DF) of all samples is shown in Table 2.

Table 1

Sample 5 9 One Flexure GPa 5.15 5.00 6 Yield strength σy MPa 226 241 343 Fission Strength K _1C MNm ^-1.5 0.63 1.9 0.52 Fission Hardness G _1C KJm ^-2 0.17 0.88 0.07 Ductility (K _1C / y) ² ㎛ 7.8 62 2.2

TABLE 2

Sample % Of A DF Sample % Of B DF One 0 2.2 One 0 2.2 2 10 3.3 5 10 10 3 15 12 6 15 14 4 20 13 7 20 23 - - 8 30 55 5 35 7.8 9 35 62 - - - 10 40 102

It is evident that the hardness of the polymer composition composed of the polyarylsulfone and PF of the present invention was greatly increased as can be seen in the resulting ductility.

Testing the morphology of the molded samples revealed that as the level of polyarylsulfone increased, it changed from uniform to ribbon-like and co-continuous. Simultaneous-continuous morphology is present at least about 20% of the polyarylsulfone weight.

Example 4

Another composition was prepared by the method of Example 3 using various amounts of polymer samples A and B and containing chopped glass fibers (length 3.2 mm, USA, ex Certaineed, aminosilane applied). The ductility (DF) of each sample was measured by measuring the breaking strength and yield strength of the made plaque. The results of both compositions (25% polymer, 40% glass) are listed in Table 3 and all samples and their ductility are shown in Table 4.

The numbers in parentheses thereafter refer to the weight percent of the glass fibers in the composition.

Example 5

A 25-35 wt% solution of polymer was pumped onto a 12K tow spread of Hercules IM7 carbon fiber wound onto a drum to make a prepreg and the drum was cut into pieces of prepreg and dried at room temperature. 24 ply of prepreg in one direction was molded at 320 DEG C and 2.4 MPa for 5 minutes, and then preheated for 15 minutes without applying pressure to form a synthetic plaque. Test plaques were used to measure cleavage hardness (C _1C ). Samples and results are summarized in Table 5.

TABLE 3

Chopped fiberglass 40 32.18 32.2 % Of glass 40 40 40 SFP 118 38.13 30.4 40.5 Hexamethylenetetramine 6.73 5.36 7.16 Sample A 15.14 - - Sample B - 12.06 - % Of polymer 25 25 - Flexure GPa 13.8 12.6 12.6 Yield strength σy MPa 441 450 473 Fission Strength K _1C MNm ^-1.5 5.63 8.45 4.23 Fission Hardness G _1C KJm ^-2 4.48 8.18 2.95 Ductility (K _1C / σy) ² ㎛ 163 353 80

Table 4

% Of A DF (20) DF 40 DF (60) % Of B DF (20) DF 40 DF (60) 0 55 80 95 0 55 80 95 15 49 182 99 15 175 285 293 25 138 151 97 25 178 353 725 35 200 210 144 35 190 321 665

Table 5

polymer Volume fraction of fiber (%) G _1C (2 times average) (KJm ^-2 ) 100% A1 ^1,3 65.2 1.09 100% A ¹ 57.9 1.37 100% A ² 57.3 0.86 67% A / 33% B ² 60.3 2.30 50% A / 50% B ¹ 60.6 1.64 50% A / 50% B ² 63.1 1.95 50% A / 67% B ² 62.8 1.91 33% A / 67% B ² 54.8 2.87 20% A / 80% B ² 57.3 2.65

1-solvent used is 90/10 v / v CH ₂ C1 ₂ / CH ₃ OH,

2-solvent used is 67/33 v / v cyclopentanone / acetone

3-polymer A1 was prepared in the same manner as polymer A, but with an RV of about 0.22.

The present invention relates to thermosetting compositions made from aromatic polymers having reactive groups and to methods of making such polymers.

Claims (4)

Aromatic polymers consisting essentially of polyarylsulfone chains consisting of divalent aromatic radicals E containing sulfone groups, which are repeating units linked by ether and / or thioether bonds, and optionally E ¹ , divalent aromatic radicals containing sulfone groups As a polyarylsulfone chain, pendent or terminating group of the formula-R ¹ Z-(wherein R ¹ is a divalent hydrocarbon group and Z is a residue of a group having active hydrogen reacting with an epoxy-containing compound) An aromatic polymer having at least one of which is connected to at least one second polyarylsulfone chain by said —R ¹ Z — groups bonded together by a residue of a unit of formula (I): [Wherein k is an integer of 1-3 selected according to G, G is a direct bond or the following general formula (II); J is at least one residue selected from divalent phenol residues, aminophenol residues or aromatic diamine residues. Preferred are the residues of formula (III); -PhAPh-(III) Ph is phenylene, especially 1, 4- phenylene; And A is a direct bond,-0-, -S-, -SO-, -CO-, -CO _2- , SO ₂ -or C _1-6 hydrocarbon] A polymer composition composed of the aromatic polymer of claim 6 and a reinforcing filler. A polyarylsulfone chain having at least one pendant or terminating group of formula -R ¹ Z-and repeating units E and E ¹ connected to the epoxy group of formula (I), at least one of a pendant or terminating group of formula -R ¹ Z- And reacting with a second polyarylsulfone chain having repeating units E and E ¹ . Ether and / or thioether bond optionally with an aromatic radical of bivalent E containing repeating units which are, sulfonic group connected consists of E ¹ is an aromatic radical of bivalent containing a sulfonic group, to the reactive epoxy of formula (ⅡA) Polyarylsulfones having end groups. ┌─ Where k is an integer from 1 to 3 selected according to J J is one or more divalent phenol residues, aminophenol residues or aromatics Residues selected from diamine residues, these residues being preferred Preferably, it is a residue of following formula (III). │-PhAPh-(III) │ ┌─ Wherein Ph is phenylene, in particular 1, 4-phenylene, A is a direct bond,-0-,-S-,-SO-,-SO ₂ ,-CO-, -CO ₂ or C ₁ -C ₆ -hydrocarbon. │ └─ └─