DE1570803A1 - Process for the preparation of polyarylsulfones - Google Patents

Description

The invention relates to the production of polyarylsulfones from aromatic sulfonyl halides.

Polyarylsulfones with repeating units of the formula: -Ar-SO ₃ can be prepared by adding a reactant of the formula: H-Ar-SO ₃ .X and / or an equal molar mixture of reactants of the formulas: X.SO ₃ -Ar- SO ₃ .X and H-Ar-H with 0.05 to 5% (based on the weight of the reactants) antimony pentachloride or an iron salt soluble in the polymerization mixture is fused. In these formulas, X represents a halogen atom (preferably chlorine), and Ar represents a divalent aromatic radical, which is preferably derived from benzene, a polynuclear hydrocarbon with at most two aromatic rings, or from a compound of the formula:

-Y- / S (D

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(where Y is a direct bond or -0-, -S-, -SO-, T-g -CO-, a divalent hydrocarbon radical or «inen Represents a glycol residue and the benzene rings each carry one of the two valence bonds of the radical Ar) or derived from ring substitution derivatives thereof, Ar in the various units of the chain of the polymer thus obtained can be different. *

Potyarylsulfones are generally strong thermoplastic substances with a high softening point. Those that have units of the formula:

(U)

λ 2 · ~ * t Ix

where R, R, R ^J and R preferably represent hydrogen atoms but can also represent halogen atoms or alkyl or alkoxy groups with a maximum of 4 carbon atoms, and where Z represents an O or S atom and possibly a direct bond in some units.

co. In the production of polyaryisulfones according to this'

- * Up to now the procedure has been the use of diluents ^ been avoided because the presence of a diluent

the reaction was slowed down and the

produced low molecular weight products.

The polymerization in the presence of, for example, H * -tro- BATH ORIGINAL

methane or 1,1-dioxothiolane (cyclic tetramethylene sulfone) gave products that were also active after reaction times of 6 hours or more a reduced viscosity of only 0.041 and 0.07, respectively.

However, if the polymerization is carried out without a diluent, there are many disadvantages. For example, as the polymerization proceeds, the mixture loses its fluidity until it finally forms a solid mass despite the progressive increase in temperature. In order to then achieve products with a high molecular weight, it may be necessary to stop the reaction, grind the solid product to a powder and then continue the polymerization in the solid phase. Such a two-step process is cumbersome and uneconomical. Furthermore, at the high temperatures which are necessary for the production of products with a high molecular weight , there is a risk of crosslinking if a disulfonyl halide is present among the reactants. Another disadvantage is that volatile reactants are lost during the reaction at these high temperatures.

° It has now surprisingly turned out that

^ that these poly ary isulfones are not above 160 ° C

cn lying temperature can be successfully established if the

- * reactants in a nitrobenzene of the formula:

Are dissolved, where A is a hydrogen or halogen atom or

represents an alkyl, cyano or nitro group and A represents a hydrogen or halogen atom or an alkyl group, the alkyl groups each having at most ¹ l carbon atoms. It is preferred to use nitrobenzene itself, since this is available in practice and is liquid at the corresponding temperatures.

The reaction is carried out at a temperature not exceeding 160 ° C., because at higher temperatures the reaction product is generally formed in a substantially discolored state. The preferred temperature range is from 100 to I ¹ JO ⁰ C. At these temperatures the products are discolored little or not at all. Temperatures below 100 ^° C. even down to 20 ^° C. can indeed be used, but result in longer reaction times.

The nitrobenzene thinner or solvent is preferred used in amounts not exceeding 5 parts by weight Mean per part by weight of the respondents. The usage Not only is larger amounts of the diluent uneconomical but also leads to products of lower molecular weight. On the other hand, the mixture can when used from a very small amount of the diluent solidify during the polymerization, especially when products of -. high molecular weight are to be produced. This is how it works ■> It is difficult to remove the product from the structure, as a result can also be damaged. So there will be 0.75 to 3 parts by weight per part by weight of polymerizable reaction participants

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I O / UO

preferably used .. The use of equal parts of diluent and Monomer has given very good results.

As a result of the use of a diluent according to the invention, catalysts other than antimony pentachloride and the iron salts soluble in the polymerizable mixture can also be used. In addition to antimony pentachloride and ferric chloride as well as ferric fluoride, ferrobromide, ferroiodide, ferric orthophosphate and ferro- and ferricetoacotonates, other Lawis acids can be used, which are a cationic sulfonylium type - (Ar-SO ₂ ) from an aromatic sulfone ( Ar-SO ₂ .X) are able to produce. Such Lewis acids are, for example, among the higher halides, in particular the fluorides and chlorides of the elements of variable valency occurring in groups IV in VIII of the table of the periodic table. Antinone pentachloride and ferric chloride are particularly effective. However, molybdenum pentachloride and oxamyl hexachloride are also good, and titanium tetrafluoride, ornamental tetrachloride and antimony pentafluoride and others are effective catalysts. The optimal amount of the catalyst is usually equal to the minimum amount or slightly more that is sufficient to allow the polymerizable monomers to completely convert into the polyarylsulfones; larger amounts have no further advantage in terms of reaction rate or increase in molecular weight and can possibly cause difficulties in removal from the product. The optimal amount depends on the catalyst. For example, ferric chloride is used

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in an amount of preferably at least 0.25 moles per 100 moles the polymerizable reactants, and antimony pentachloride is preferably used in an amount of at least 0.5 moles per 100 moles.

The manufacture of high molecular weight products is achieved with greater certainty when a small molar excess of the disulfonyl halide X.SO ₂ -Ar-SO ₃ .X is used. This applies to the use of a mixture of X.SO ₃ -Ar-SO ₂ X and H-Ar-H as well as to the use of H-Ar-SO ₃ .X.

The polymerization is generally impaired by moisture, so that it is kept low.

The physical properties of the products depend on their molecular weight and the starting material. Through appropriate Wäilder respondents and the conditions you can but high molecular weight polyarylsulfones, more excellent thermal stability and high softening point. The amorphous polymers are in a number of organic solvents dissolvable, and they are usually strong, often transparent, and stable for long periods of time when molten. You are therefore extremely suitable for plastic deformation processes such as Injection, pressing and extrusion. They can also be poured or spun as a solution to create films or threads.

When polymerizing in the presence of , a diluent 009815/1693

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medium, the products can already be obtained in solution, so that they can be deashed immediately if necessary, which can be done, for example, by treatment with a chelating agent for the catalyst. The use of a diluent has the further advantage that the reaction between a disulfonyl halide of the formula X.SO ^ Ar-SO ₂ .X and a compound of the formula H-Ar-H takes place without the formation of crosslinked products, as would otherwise occur without a diluent and tend to arise at the higher temperatures. The use of the disulfonyl halide also has technical advantages because its production is simpler and cheaper than that of the monosulfonyl halide of the formula H-Ar-SO ₂ .X. .

The invention is illustrated below by means of examples. All of the specified viscosity measurements represent a water-reduced viscosity, which was measured in each case with a solution of the polymer (Ig) in dimethylformamide (100 cm ^) at 25 ^° C.

example 1

16.8 g of diphenyl ether - ^ - sulfonyl chloride were dissolved in nitrobenzene (27.8 g). This solution (6 cnr) was poured into a heated at 120 ⁰ C flask equipped with a stirrer, a condenser and a suitable for passing dry nitrogen over the mixture inlet. The solution was then 10 minutes at 120 ° C under a nitrogen

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atmosphere, whereupon ferric chloride (62.5 mg; 0.385 millimoles) was added as 1 cnr of a 6.25 w / v solution in nitrobenzene. After a further 4 hours the flask was cooled and the solution was diluted by the addition of 20 cubic inches of dimethylformamide. The solution was then poured into methanol, causing the polymer to precipitate. The solid v / urde filtered off, washed with methanol and dried for 48 hours at 150 ⁰ C under an absolute pressure of 0.1 Torr. The product had a reduced viscosity of 0.42.,

Example 2

Three further? Polymerizations were carried out, and the resulting polymers v / ere as isolated in Example 1, the difference being that initially more nitrobenzene was used and that the solutions were maintained after the addition of ferric chloride longer to 120 ⁰ C. The overview shows the amounts of additional nitrobenzene, the polymerization times and the reduced viscosities of the products in comparison with the product according to Example 1:

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additional
liitrobenzene Polymerization
Time 0 min decreased
Viscosity O cm ⁵ 4 h 10 min 0.42 4 cm ³ 5 h 30 min 0.34 8 cm ³ 6 h 0 min 0.24 12 cm ³ 25 h 0.19

Thus, by using larger amounts of the diluent, the molecular weight of the polymeric product would be increased is decreased, and this decrease is not compensated for by increasing the response time.

Example 3

Five further polymerizations were carried out as in Example 1, but at 80, 100, 130, 150 and 180 ° C., respectively. The product was brought to a volume of 30 cm with fresh dry liitrobenzene and then cooled to room temperature and then washed 4 times with 5% hydrochloric acid solution. then the product was washed with water and poured into methanol to precipitate the polymer, which is then as in Example 1 was filtered off, washed and dried. In each case one sample was molded by compression molding at 29O ° C under a press

2
pressure of 31.5 kg / mm and processed into a film in a 3-minute pressing process. With the eye, it was found that the sample prepared at 150 ⁰ C had a darker color and that produced in the at l80 ° C a significant dete-

the color had changed.

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- 10 - Example k

4 polymerization flasks were set up, each containing diphenyl wire (1.702 g; 10.0 millimoles), diphenyl ether-M ¹ -disulfonyl chloride (3 * 672 g; 10.0 millimoles and nitrobenzene (10 cm) 120 ⁰ C. and stirred under a nitrogen atmosphere. the solutions were given various amounts of ferric chloride (as a solution in nitrobenzene) according to the table below. After 22 hours, the polymers were isolated by the solutions were respectively poured into methanol and the product filtered off, washed with fresh methanol and then ^{dried under 0.2 torr for 24 hours at 150 °} C. The polymer yields and the reduced viscosities are shown in the table:

Ferric chloride additive

polymer
yield decreased
Viscosity 4.7 g 0.18 4.8 g 0.17 4.7 g 0.07 4.6 g 0.22

8.1 mg (0.05 millimoles) 16.2 mg (0.10 millimoles) 32.1 » _m g (0.20 millimoles) 68.4 mg (0.42 millimoles)

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example 5

A solution of diphenyl ether (C, 8o8 g; 40.0 Milliinol) and diphenyl ether-4, i \ '-disulfonylchlorid (14.688 g; '10, 0 ITilliinol) in nitrobenzene (20 cm) v / urde 5 minutes at 130 ⁰ C. heated. Ferric chloride (64.8 mgs 0.400 millimoles) was then added as 3.81 cm ^{5 of} a 1.7 weight / volume solution in nitrobenzene to cause the polymerization. During the entire reaction, nitrogen was continuously withdrawn from a bottle of liquid nitrogen and passed over the mixture. On analysis it was found that it contained 1,300 parts by volume v / ater per million parts by volume. After the polymerization, the product was isolated by pouring the solution into ethanol and filtering off the solid, washing it with fresh ethanol and drying it at 150 ° C. under an absolute pressure of 0.2 torr for 24 hours, resulting in a polymer with a reduced viscosity of 0.18.

When the procedure was repeated, the nitrogen supply to the reaction vessel was first through one containing phosphorus pentoxide Headed on vermuculite-filled - »6 cm tower. All connections were made with copper pipe to prevent the penetration of Moisture through the pipe wall into the nitrogen inflow to bring a hindrance. When analyzing the treated Nitrogen was found to contain only 9 parts by volume of water per million parts by volume of nitrogen. In this case had the polymeric product had a reduced viscosity of "0.56.

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- ■ 12 -

Example C

Diphenyl (3, dinghy ¹ g; 20,0Millimol)! V / urde in Mitrobenzol (10 cm ^) with excess diphenyl ether ^{1, 1} J'-disulfonyl chloride (7 ^ 13 g; 20.2 llillimol) at 130 ⁰ C dissolved under an atmosphere of dry nitrogen (ie nitrogen less than about 50 parts v / water per million parts by volume). The solution was stirred for 5 minutes, (32 mg, ¹ J; 0.200 mmol) followed by ferric chloride as 1.91 cnr a 1.7 wt / volfl-solution was added urr to initiate the polymerization. After 3.5 hours the solution was diluted with nitrobenzene (10 cm) and stirred. One half of the resulting solution was separated udd cooled, while the other half was kept total of 22 hours .on 1'3O ⁰ Q *. The two isolated and dried polymeric products had reduced viscosities of 0.70 and 1.9, respectively, and were both in cold nitrobenzene and in cold dimethylformamide. completely dissolvable.

Comparatively v / urde diphenyl ether in the same manner with diphenyl ether ^1! Heated V-disulfonyl without diluent, in which ferric chloride was used (119 mg) al3 catalyst and the final temperature is about 235-2 ^{1 0} C was JO. Hach '..' ashing and drying, the separated, polymeric product had an ef.:s ^ O ^ -iger. Content of substance that was insoluble in nitrobenzene and dimethylformamide. The soluble fraction had a reduced viococity of 0.31.

009815/1693

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1.2 Diphenoxyäthan (4.286 g; 20.0 mmol) and diphenyl ether 4,4 ^l rdia0fonylchlorid (7,342 g; 20.0 millimoles) was dissolved (10 cnr) in nitrobenzene, and the solution heated to 130 ⁰ C under a dry nitrogen atmosphere became. After minutes, perrichloride (32.4 mg; 0.200 millimoles) was added as 1.80 cnr of a 1.8 wt / total solution in nitrobenzene. The mixture was kept I ¹ IO minutes at this temperature, whereupon nitrobenzene (90 cm) was added and the solution was cooled to room temperature. The solution was then washed 4 times with 5% strength hydrochloric acid solution with vigorous stirring and twice with distilled water and then poured into stirred methanol to precipitate the product. The product was washed further with methanol and then dried ^{at 150 ° C. for 24 hours.} The resulting polymer (9.8 g) had a reduced viscosity of 0.71. Upon analysis, it was found to contain 0.0033 »iron and Ο, Ο75ί ashes. The polymer was easily processed into almost transparent films by compression molding at 250 ° C. When examined with X-rays, the polymer was found to be amorphous.

Example 8

Dibenzofuran (3.364 g; 20.0 millimoles) and diphenyl ether-4,4'-disulfonyl chloride (7.432 g; 20 millimoles) was dissolved in nitrobenzene (10 cnr) and heated to 120 ° C under a dry Heated nitrogen atmosphere. The solution was 4 minutes at this Stirred temperature Then ferric chloride (28 mg; 0.17 milli-

^009815/1693 ·, «OKCtNAL

was added INOL) than 0.7 cnr a 4.0 wt / Vols solution in Mitrobenzol maintained and the reaction mixture v / eitere22 hours to 120 ⁰ C. Nitrobenzene (100 cnr) was added and the product was isolated as in Example 7. This resulted in an amorphous polymer (8.7 g) with a reduced viscosity of 0.48. Colorless films could be produced therefrom by compression molding at 310 ^° C. using a compression pressure of 31 * 5 kg / mm.

Example 9

1,2-Diphenocyethane (2.210 g; 10.3 millimoles) and Dipheny1-4,4'-disulfonyl chloride (3.522 g; 10.5 millimoles) were added in Nitaxkenzol (10 cnr) dissolved and heated to 120 ° C under dry Heated nitrogen. Ferrichloride (8 mgs 0.05 millimoles) was added as 0.2 cnr of a 4.0 cew / volume solution in nitrobenzene. After 17 hours at 12p ° C, the product was obtained by adding of dimethylformamide (40 cnr) and pouring the solution into stirred methanol. Received after washing and drying an amorphous polymer (5.1 g) which had a reduced viscosity of 0.21.

Example 10

Dipheny1-4,4'-disulfonyl chloride (3.522 gj 10.5 mmol) and dibenzofuran (1.682 g; 10.0 mmol) were dissolved in nitrobenzene 10 cnr) and heated at 120 ⁰ C under dry nitrogen. Ferric chloride (8mg; 0.05 millimoles) was used as. 0.2cm 'one

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Ί, Ο wt / vol2 solution in nitrobenzene was added. Three minutes after the addition of the catalyst, the polymer began to precipitate out of the solution and after 16 hours at 120 ^° C. the mixture was diluted with dimethylformamide and then filtered. The precipitate was thoroughly washed with methanol and then dried. When examined by X-rays, the polymer (3.1 g) was found to be crystalline. It was insoluble in any common solvent.

Example 11

Diphenyl ether (17.02 g; 100 Killimol) and diphenyl ether I.lp-disulfonyl chloride (37.065 g; 101 MillimQl) nitrobenzene dissolved in viurden (50 cnr) and heated to 130 ⁰ C under dry nitrogen, followed by ferric chloride (97 mg; 0, 60 millimoles) was added as a solution in 5 g of nitrobenzene. After 3.5 hours, a sample was removed from the reaction vessel and diluted with further nitrobenzene, whereupon the product was precipitated by pouring into methanol. After drying, the polymer had a reduced viscosity of 0.70. The remainder of the reaction mixture was allowed to polymerize for a total of 6.75 hours. This resulted in a product which, after isolation, washing and drying, had a reduced viscosity of 1.18 _e .

Example 12

Diphenyl ether (3 ¹ I ₁ Oi g; 200 millinoles) and diphenyl wires

M'-disulfonyl chloride (7 * 1.13 gi 202 Killimol) were in:, 'itro-

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benzene (100 cm) dissolved at 130 ⁰ C under dry nitrogen. After 6 minutes, ferric chloride (304 mg; 1.87 mi.llimole) was added as a solution in 18 g of nitrobenzene and the mixture was allowed to polymerize for 5.5 hours. The viscous product was cooled, diluted with nitrobenzene (800 cm) and then vigorously stirred with 100 cnr of a 5N hydrochloric acid solution. After separating the aqueous layer, washing with hydrochloric acid was repeated 4 times. The solution was then washed once with a 5.5% sodium carbonate solution and once with water. The nitrobenzene solution was then poured into methanol to precipitate the polymer. The polymer was filtered off and extracted with methanol for 2Ί hours. Subsequently, it was Ί8 hours, dried at 170 ⁰ C under an absolute pressure of 0.2 Torr. The polymer (87 g) had a reduced viscosity of 0.70. From a sample of the polymer v / urde a film having a thickness of 0.127 mm produced kg / mm by compression molding at 300 ⁰ C under a pressure of 31.5. At 20 ^° C. the film had a yield point

of 10.05 kg / mm.

Example 13

Diphenyl ether (17.02 g; 100 Iiillinol) and diphenyl-4,4 ¹ -disulfonylohlorü (35, ¹ JO g; 106 mmol) (50 cm *) is dissolved in nitrobenzene and heated to HLO ⁰ C with stirring under dry nitrogen. Ferric chloride (137 mg; 0.84 milliir.ol) was added as 8.10 cm ^{3 of} a 1.69% by weight solution in nitrobenzene.

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injected by means of a hypodermic syringe. After 6 Stundden polymerization was dissolved by adding molten Diphenylähter (1 cnr) to a standstill, after which the mixture a further 17 hours at ⁰ C was stirred IJJO. It was then poured into a soaking vat in methanol, whereupon the solid was filtered off, suspended in fresh methanol and refluxed for 24 hours. The product was filtered off and 17 hours at 10O ⁰ C in vacuum dried to give a polymer gave (44.9 g) having a reduced viscosity of 0.55.

The polymer was processed by compression molding into blocks measuring 5 »O8 2.54 1.27 cm and into 0.18 mm thick films at 280, 300, 320, 1340 and 360 ° C. The color of the fabrics became progressively deeper as the temperature increased. The films produced at 280 and 300 ⁰ C had little internal stress, and the generated at 36O ⁰ C pointed decomposition numerals.

Example 14

Diphenyl ether-4-sulfonyl chloride (107.48 g; 400 millimoles) was dissolved in nitrobenzene (100 cm) and the solution was ^{brought into equilibrium at 120 °} C. Antimony pentachloride (ο.39 cur; 3.05 millimoles) was used as 30 cm 'of a 1,3-Voljč solution in nitrobenzene was added and the mixture was stirred for 4 hours at 120 ⁰ C. the reaction was stopped by the addition of aniline (5 cnr) in nitrobenzene (100 cnr), and the mixture was stirred for a further hour at 120 ^° C. The solution was poured into a soaking vat in methanol, and the precipitated one

_{Product was treated twice} with hot methanol MArN -. "," .., ..

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and then washed with acetone and plug in! Dried 2Ί hours at 190 ⁰ C under 0.1 Torr. This resulted in a polymer (89 g) with a reduced viscosity of 0.72. It was processed by compression molding at 2 ¹ JO ⁰ C to form sheets with dimensions of 7 * 62 5.08 χ 0.32 cm.

comment

The table below gives the amounts of nitrobenzene in parts by weight per part by weight of the polymerizable reactant (Monomers) again, those in the above examples taking into account the additional introduced with the catalyst Kitrobenzene were used. The table also shows the respective amount of the catalyst in moles per 100 moles of the polymerizable reactants, v / obei as a catalyst antimony pentachloride in Example 14 and ferric chloride in the other Bn !, was used ..

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Examples Parts nitrobenzene per
Part monomer 1 2.1 CVJ 3.1 4.3 5.4 3 2.1 2.2 5 1.33 . 6th l-, 32 7th 1.22 8th 1.19 9 2.13 10 2.35 11 1.20 12th 1.28 13th 1.33 14th 1.45

19 moles of catalyst per mole of monomer

2.9 2.9 2.9

0.25 0.50 1.00 2.11 0.50 o, 50 0.50 0.13 0.24 0.21 0.30-0.17 0.41 0.76

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Claims (7)

Claims 1. Process for the preparation of polyaryisulfones with repeating units of the formula -Ar-SO ₃ - from a reactant of the formula H-Ar-SOp.X and / or a mixture of reactants of the formulas X.SOp- _v Ar-SOp.X and H-Ar-H, where X is a halogen atom and Ar is a divalent aromatic radical, characterized in that the polymerization takes place at a temperature not above 160 ° C. in solution in a nitrobenzene of the formula: is carried out, where A ^x is a hydrogen or halogen atom or an alkyl, cyano or nitro group and A represents a hydrogen or halogen atom or an alkyl group, the alkyl groups in each case at most ¹ J carbon atoms possess, and wherein a Lewis acid is used as catalyst which is able to produce a cationic sulfonylium species - (Ar-SOp) ⁺ from an aromatic sulfonyl halide SOg.X) dissolved in a nitrobenzene of the above formula. 2. The method according to claim 1, characterized in that 0.75 to 3 parts by weight of the nitrobenzene are used per part by weight of the polymerizable reactants. 009815/1693 BATH ORIGINAL 3. The method according to claim 1 or 2, characterized in that nitrobenzene is used as the solvent. 4. The method according to any one of claims 1 to 3 »thereby characterized in that the polymerization takes place at 100 to 140 ° C. 5. The method according to any one of claims 1 to ^, characterized characterized in that as a catalyst antimony pentachloride or an iron salt soluble in the polymerization mixture in one Amount of from 0.05 weight percent to 5 weight percent of the polymerizable reactants is used. 6. The method according to claim 5, characterized in that the catalyst is antimony pentachloride in an amount of raLiidesstens 0.5 moles per 100 moles of the polymerizable reactants is used. 7. The method according to claim 5 »characterized in that ferric chloride is used as the catalyst in an amount of at least 0.25 mol per 100 mol of the polymerizable reactants _t . 3> \ D 009815/1693