JPH0211634A - Production of polyarylene sulfone - Google Patents

Abstract

PURPOSE:To make it possible to use inexpensive monomer materials and to perform a direct polymerization reaction, catalyst recovery, etc., by performing a specified polymerization reaction in the presence of a catalyst selected from among tungstic acid, molybdic acid and a heteropoly-acid. CONSTITUTION:In the production of a polyarylene sulfone comprising repeating units of formula I (wherein Y is a direct bond, -O-, -S-or a group of formula II; Z is -CO-, -SO2 or a group of formula II; and R1 and R2 are each H, a halogen atom, a 1-3C alkyl or a 1-3C haloalkyl), any polycondensation reaction selected from among a polycondensation reaction (A) of an aromatic compound of formula VI or the like with sulfuric acid, a polycondensation reaction (B) of an aromatic compound (B) of formula VII (wherein the sulfonic group-free benzene ring is one in which the ring hydrogen para to -Y- is unsubstituted; and Y is as defined in formula I), etc., and a polycondensation reaction (C) of an aromatic disulfonic acid of formula VIII (wherein Y is as defined in formula I) or the like with an aromatic compound of formula VI or the like is performed in the presence of a catalyst selected from among tungstic acid, molybdic acid and a heteropoly-acid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application J] The present invention relates to a method for producing poly-7lylsulfones.

[Prior art and its problems] The polyaryl sulfones obtained by the present invention are highly heat-resistant thermoplastic resins C'' and are excellent in high-temperature creep properties, N flammability, dimensional stability, chemical resistance, etc. Electricity
It is used in a wide range of fields such as electronic parts, automobile parts, and medical equipment.

Conventionally, methods for producing polyarylsulfones include (1) polycondensation of an aromatic disulfonyl halide and an aromatic compound under a Lewis acid catalyst such as anhydrous aluminum chloride, or polycondensation of an aromatic disulfonyl halide and an aromatic compound under a Lewis acid catalyst such as anhydrous aluminum chloride; (British Patent No. 1016245, British Patent No. 1060546, British Patent No. 1109842, etc.), (2) Forming other bonds such as an ether bond with an aromatic compound that already has a sulfonyl bond. In particular, there is a method of polycondensation. For example, a method of polycondensing 4.4--dichlorodiphenylsulfone and 4.4-dihydroxydiphenylsulfone or 4-chloro-4-hydroxydiphenylsulfone in the presence of an alkali metal (
British Patent No. 1078234, British Patent No. 1133561,
No. 1177183, No. 1153035), etc. are known.

However, method (1) inevitably has the disadvantage that the aromatic sulfonyl halides used as raw materials are hydrolyzed during handling and storage, and separation of the catalyst is complicated. In addition, the method (2) has problems such as it is difficult to commercially obtain raw gemstones and, moreover, it is expensive.

Therefore, there is an industrial need for a method for producing polyarylsulfones in which the raw material monomers are easily available and inexpensive, and the handling and polymerization methods are easy.

[Problem to be Solved by the Invention] As a result of intensive study to propose a method that satisfies such demands, the present inventors have discovered that a specific catalyst can achieve the desired purpose. , completed the present invention based on this knowledge.

The present invention is directed to the production of novel polyarylsulfones, which are industrially extremely advantageous, by direct polymerization of industrially available and inexpensive raw materials. The purpose is to provide an A construction method.

[Means for Solving the Problems 1] The method for producing polyarylsulfones according to the present invention is to prepare polyarylsulfones consisting of repeating units represented by general formula (1) by the following (△), (B) or A special feature characterized in that, in preparing the product by the polycondensation reaction according to (C), one or more catalysts containing tungstic acid, [from liver consisting of livenic acid and their heteropolyacids] are used. Each represents a direct bond, -O--S- or -502-. R1 and R2 may be the same or different and each represents hydrogen, halogen, an alkyl group having 1 to 3 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms. ] (A) A polycondensation reaction between at least one aromatic compound represented by general formula (II) or its nuclear-substituted derivative and sulfuric acid.

O3H [In the formula, it is assumed that the nuclear hydrogen atom at the para position to -Y- at J3 in the benzene ring having no sulfonic acid group is not substituted. Y has the same meaning as the general formula (I>).] (C) At least one aromatic disulfonic acid or its nuclear substituted derivative represented by the general formula (IV) and the general formula (I
A polycondensation reaction with at least one aromatic compound represented by I) or its nuclear-substituted derivative.

[In the formula, the nuclear hydrogen atom at the para position to -Y- is not substituted. Y has the same meaning as in general formula (I). ] (8) Polycondensation reaction using at least one aromatic monosulfonic acid represented by general formula (III) or its nuclear substitution derivative.

] As the aromatic compound represented by general formula (II) or its nuclear substituted derivative, biphenyl, diphenyl ether,
Diphenyl sulfide, diphenylmethane, 2,2-diphenylpropane, 1,1-diphenylethane, dichlorodiphenylmethane, 2.2-diphenylhexafluoropropane, 2゜2-diphenylhexachloropropane, 4-phenoxybiphenyl, 1,4 -bis(phenoxy)benzene, 4,4--diphenylbiphenyl, 4゜4--diphenyldiphenyl ether, 4.4=-diphenyldiphenylsulfone, 4,4--diphenylbenzophenone, 3.3--diphenylbenzophenone, 2
, 2-bis(biphenyl)propane, 3-methyldiphenyl ether, 3-chlordiphenyl ether, 3,3
--dimethyldiphenyl ether, 2,2'-dichlorodiphenyl ether and the like.

Similarly, the aromatic sulfonic acids represented by the general formula (I[I) or (IV) or their nuclear substituted derivatives include monosulfonated products of the aromatic compounds represented by the above (n) or their nuclear substituted derivatives, and Examples include disulfonated compounds.

However, the present invention is not limited to the above examples.

Examples of the catalyst according to the present invention include tungstic acid, molybdic acid, and heteropolyacids thereof. The heteropolyacid referred to herein is a condensed acid consisting of two or more types of oxyacids, and the polyacid atoms include tungsten and molybdenum, and the heteroatoms include the following various types.

That is, in the heteropolyacid of tungstic acid (the heteroatoms include PXAS, Si, Ti, Go, Fe, B
, ■, Be, I, Ni, Ga, etc., and specific examples of the heteropolyacid of tungstic acid include those having the following structural formula.

+13 [PW12040], 113 A 5W12040] 1-I Si W1204o] H4T I W12040] H5COW1204Q] H5FeW1204o+5 [BW1204o], H3[VW1204o, H6[B eWg 03 1], H6 [T eW6 024 Ko, Town■ W6024], 1”4 N! W6024H6], -GaW602
4H6], H6P2 W18062], Town AS2 W18062], H7PW11033], In addition, the heteroatoms in the heteropolyacid of molybdic acid include P, As, Si, Ge, TCc, Th, Mn,
Examples include Ni, Te, I, Co, Cr, Fe, Qa, etc., and specific examples of the heteropolyacid of molybdic acid include those having the following structural formula.

H[PMO12040], H3[A SM O120401, H4[S! M O12040], H4GeMO12040], H4T i M O12040] ・I''B
08MO12042], HB TFIM012042], HPM01103g], H7[ASMO11039], H3GeMO11039], 116 MnMOg 032], 1'6 NiMO9032], TeMO6024], HIMOe024] , H3C0M06024H6], HC0M06024H6], H3FeMo6 o24H6], Town GaMo6024H6], To14 N! Mo 6 o24H6]
, H6P2 MOH3062]・To16 [A82 M0180B2]・Furthermore,
Mixed coordination heteropolyacids in which two or more types of each atom are coordinated, such as H[PMOW11040], H4[PReW11040], H4[PVMO1104ol, H5[PV2 MO10040], etc., can also be used. All of these heteropolyacids exemplified above are known. From the viewpoint of ease of synthesis or availability, heteropolyacids containing P or 3i as heteroatoms are preferred, particularly 12-tungstrine I'm (H[PWl, 204o]
), 12-tungstosilicic acid (H3[S! W120
40]), 12-Molybdoline M (1-13[PM
o12040]) etc. are more preferable.

Further, the tungstic acid, molybdic acid, or a heteropolyacid thereof used as the catalyst may be a hydrate, and furthermore, a compound capable of producing the tungstic acid, molybdic acid, or a heteropolyacid thereof in the reaction system. It may be in the form of Examples of such compounds include salts of alkali metals such as potassium and sodium, heavy metal salts such as cobalt, nickel, manganese, and copper, and salts such as an[nium] salts. MC! ! It may be in the form of oxides, chlorides, and sulfides represented by 6 and σMS3 (M=W or MO).

The catalysts exemplified above may be used alone or in combination of two or more.

From the viewpoint of reactivity and selectivity, heteropolyacids are preferred.

The manufacturing method according to the present invention is generally carried out as follows. That is, in reaction (A), an aromatic compound, fj!
Charge iM and a catalyst, aromatic monosulfonic acid and catalyst in reaction (B), aromatic disulfonic acid, aromatic compound and catalyst in reaction (C), respectively, into a reactor,
The reaction is carried out at 60 to 280°C while removing the water produced. Methods for removing water produced by the reaction include a method of introducing a gas such as nitrogen gas into the reaction solution, a method of removing it by reacting under reduced pressure, and a method of removing water by reacting under reduced pressure, and an inert solvent such as n-octane. Examples include a method in which water is added and the azeotropic water is phase-separated and removed.

The reaction temperature varies depending on the type of aromatic compound, desired reaction time, etc., but is usually in the range of about 60 to 280°C, preferably in the range of 100 to 230°C. If the reaction temperature is below 60°C, it is difficult to obtain a practical reaction rate;
At temperatures exceeding 280°C, it is difficult to obtain a high polymer due to deactivation of the catalyst.

The reaction time depends on the amount of catalyst, the type of aromatic compound, the reaction temperature, etc., but is usually about 1 to 50 hours.

In reaction (A), the aromatic compound and sulfuric acid are used in equimolar amounts. The amount of the catalyst to be used is selected from a wide range as long as it is an effective amount to exhibit the activity, but from the viewpoint of reaction rate and economy, it is preferably about 0.1 to 30% by weight based on the sulfuric acid. is advantageously about 1 to 15% by weight.

The amount of the catalyst used in reaction (B) is about 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the aromatic monosulfonic acid.

In reaction (C), aromatic disulfonic acid and aromatic compound are used in equimolar amounts, and the catalyst is aromatic disulfone M1.
It is advantageous to add about 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, per part by weight of 0.00 weight.

Although the present invention can be carried out without a solvent, the viscosity may increase as the reaction progresses, making stirring and rapid processing difficult, so in such a case, an organic solvent may be used.

The organic solvent that can be used is not particularly limited as long as it does not react with the substrate and is an aromatic compound, but usually,
N-methyl-2-pyrrolidone (hereinafter abbreviated as rNMPJ), N,N-dimethylace1-amide (hereinafter rDM
It is abbreviated as AcJ. ), N,N-dimethylformamide, dimethyl sulfoxide and the like are preferred.

According to the method of the present invention, polyarylsulfones of various molecular weights can be prepared by appropriately selecting various conditions such as reaction substrate, reaction temperature, and reaction time. It is also possible to adjust the molecular weight of the target product by adding a compound capable of stopping growth, such as an aromatic compound, during the reaction.

The reaction solution obtained as described above is poured into water, and the produced solid is filtered off and dried to obtain a polymer.

The catalyst can be recovered and reused by concentrating the mother liquor after filtering off the polymer and extracting it with a suitable solvent such as diethyl ether.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Diphenyl ether 17.0 g (0.10 mol), 98
% sulfuric acid 10.0g (0.10 mol), 12 tungstrine M (H3PW1204o-3ot-+20) 1.0
0g and NMP20m, 200d with nitrogen gas introduction pipe
The mixture was charged into a reactor and heated to 180° C. with stirring under a nitrogen stream. The reaction was carried out for 8 hours while cooling and removing produced water entrained by nitrogen gas. Thereafter, the reaction solution was poured into 350 d of water, and the produced solid was filtered off and dried under reduced pressure to form a polyester. -23.7g is 1q. As a result of measurement, the intrinsic viscosity of this product was 0.51 (0.59/+1 concentration in NMP, 30'C, hereinafter the same). In addition, the molecular weight in terms of borisdylene measured by GPC (the same applies hereinafter) is Mn
16,000 (Mw38.000).

Example 2 Diphenyl ether-4-sulfonic acid 25.0y (0,
10 mol), 12-tungstosilicic acid (1'4 Si
W1204o・24 ト120) 2. 5
g, DMA C20ml! and n-octane 5mi
was charged into a 200 m reactor, and the temperature was raised to 170°C while stirring. The reaction was carried out for 12 hours while removing azeotropically produced water from the system. Then, the reaction solution was poured into 350 ml of water, the solid produced was filtered off, and then dried under reduced pressure to form a polymer 2.
3.29 was obtained. As a result of the measurement, the intrinsic viscosity of this material is
It was 0.67. Moreover, its molecular weight is Mn19,00
0 (Mw45,000).

Example 3 Schiffnyl ether-4,4-disulfonic acid 16.5
9 (0.05 mol), diphenyl ether 8.50y
(0.05 mol), 12-tungstrine 13.3 g
and NMP30d were charged into a 200d reactor, Example 1
React and treat in the same manner as above to obtain 1q of polymer 23.59. As a result of measurement, the intrinsic viscosity of this product was 0.54.

Example 4 2.2-diphenylpropane 19.69 (0.10 mol), 98% sulfuric acid 10.03 (0.10 mol) and 12-
1.50% of tungstosilicic acid was charged into a reactor, and the temperature was raised to 200'C with stirring under a nitrogen stream. Polymer 26.3SF was reacted and treated in the same manner as in Example 1 to obtain one digit of polymer 26.3SF. As a result of measurement, the intrinsic viscosity of this product was 0.73.

Example 5 Diphenylmethane 16.8Ij (0.10 mol), 98
% sulfuric acid 10.0q (0.10 mol) and 12-lybdophosphoric acid (13PM○12040 hydrate) 1.50y
was charged into a reactor and reacted in the same manner as in Example 4 to form polymer 23. I got OtJ. The intrinsic viscosity of this material is 0.57
Met.

[Effects of the Invention] According to the production method of the present invention, an excellent polyaryl that can be widely used industrially and is produced by directly polymerizing it using industrially easily available and inexpensive 7-mer as a raw material. Sulfones can be easily produced. Moreover,
The catalyst used can be easily recovered and C1 reused.

Patent applicant: Shin Nihon Rika Co., Ltd.

Claims (1)

[Claims] 1. Polyarylsulfones consisting of repeating units represented by general formula (I) as shown below (A), (B) or (
Polyarylsulfones characterized in that one or more catalysts selected from the group consisting of tungstic acid, molybdic acid and their heteropolyacids are used in the production by the polycondensation reaction according to C). Production method. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, Y is a direct bond, -O-, -S-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc. Represents ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. here,
X and X' may be the same or different, and each
Direct bond, -O-, -S- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Z is a direct bond,
-CO-, ▲Mathematical formulas, chemical formulas, tables, etc.▼, or-
Represents SO_2-. R_1 and R_2 may be the same or different and each represents hydrogen, a halogen, an alkyl group having 1 to 3 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms. ] (A) A polycondensation reaction between at least one aromatic compound represented by general formula (II) or its nuclear-substituted derivative and sulfuric acid. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, it is assumed that the nuclear hydrogen atom at the para position to -Y- is not substituted. Y has the same meaning as in general formula (I). ] (B) A polycondensation reaction using at least one aromatic monosulfonic acid represented by general formula (III) or its nuclear substitution derivative. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [In the formula, in the benzene ring that does not have a sulfonic acid group,
It is assumed that the nuclear hydrogen atom at the para position to -Y- is not substituted. Y has the same meaning as in general formula (I). ] (C) at least one aromatic disulfonic acid represented by general formula (IV) or a nuclear substituted derivative thereof, and general formula (II)
A polycondensation reaction with at least one aromatic compound represented by the formula or its nuclear substituted derivative. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) [In the formula, Y has the same meaning as in the general formula (I). ]