JPS6227434A - Homo-and copoly-polyarylene sulfide containing keto group and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to linear homopolymers and copolymers of polyarylene sulfides having carbonyl groups and optionally further ether groups and/or sulfone groups attached to aromatic groups.

Aromatic polyether- and -thioetherketones represented by the general formula are known (U.S. Pat. No. 3,442,85
Specification No. 7 and German Patent Application Publication Tube 2.164.2
(See specification No. 91). Both of these polymers are crystalline and have such high melting points (T = 367 or 352°C) that they are difficult to process by conventional means.

Polyarylene sulfides are likewise known (U.S. Pat. No. 2,538,941, U.S. Pat. No. 2,513.1).
Specification No. 88 and German patent application publication tube 1°468.
(See specification No. 782). These compounds can be produced by reacting a dihalogenated aromatic compound with an alkali metal or alkaline earth metal sulfide without a solvent or in a polar solvent. It is advantageous to use alkali metal carboxylates as activators (German Patent No. 2 453,739, German Patent Application Publication No. 2)
, 623.363, U.S. Patent No. 4,038,2
59 and 4,038,263). Organic thio compounds can also be used instead of alkali metal sulfides.

The method of German Patent Application No. 1,620,923 requires that during the dehydration of water-containing alkali metal sulfides, hard hydrochloric agglomerates are formed which do not react completely even under vigorous reaction conditions. It has the disadvantage of being

Generally, the polyphenylene sulfides thus produced must also be subjected to a curing step following polycondensation in order to improve their properties (e.g., U.S. Pat. No. 3,717,62
(Specification No. 0, Specification No. 3,524,835 and Specification No. 3,839,301).

In this case, through a crosslinking reaction, a high molecular weight sufficient for use is obtained. However, this means that there is now a risk of losing thermoplasticity. An increase in molecular weight can also be achieved by the combined use of tri- and polyhalogenated aromatic compounds and the resulting crosslinking (German Patent Applications 2,817,731 and 3,205,996). (See specification).

According to the prior art, high molecular weight polyarylene sulfides suitable as molding materials can usually be obtained in two steps or with the addition of crosslinking agents. However, in the two-step process, at the high temperatures required to completely remove water, a reaction between the solvent and water occurs, producing hydrogen sulfide and changing the stoichiometry of the reaction. It has the disadvantage of being uncontrollably disturbed.

German Patent No. 2,453,749 (U.S. Pat. No. 3□919.177) describes a method for producing p-phenylene sulfide polymers, in which p-dihalogen -Hensen 230-450℃
The S-containing compound is reacted with the S-containing compound in the presence of an organic amide, an alkali metal carboxylate and optionally a base.

German Patent Application No. 2,749,645 describes polyethers obtained by the condensation reaction of bisphenols with dihalogenated benzene compounds or by the condensation reaction of halogenated phenols. According to claims 3 and 5, it is also possible to use thiophenol as the copolymerizable monomer.

It is surprising that there is no experimental description for this purpose in the above specification. This is because, as is well known, thiophenols are extremely easily oxidized.

Furthermore, sulfur-containing polymers are known which are based on 4.sup.4"-difluorobenzophenone, hydroquinone and thiophenol and which can be prepared only at great expense and which are prepared in the presence of alkali metal carbonates. The disadvantage is a low reaction rate requiring temperatures above 300°C (European Patents No. 0.001,879 and European Patent No. 0.0
No. 10,868 and U.S. Pat. No. 4,176,222).

It is an object of the present invention to make available mono- and copolymeric polyarylene sulfides with improved material properties. Another object is to simplify and improve the process for producing such polyarylene sulfides.

The inventors have found that mono- and copolymer polyarylene sulfides having repeating units of the formula % can be readily obtained.

This polymer also has the formula %formula% It may have a repeating unit represented by

In this case, Ar is a group represented by , and X and Y are an ether group, a thioether group, a carbonyl group or a sulfone group. n has the meaning of O or 1.

Furthermore, other repeating units may be included by incorporating a portion of bisthiofert or bisfert ions instead of sulfide ions (see below).

Advantageously, the polyarylene sulfide repeat unit is represented by 2.

The subject of the present invention is a process for the preparation of mono- and copolymer polyarylene sulfides according to claims 1 to 9, as well as the polymers according to claims 10 to 12.

The softening point of such new polymers is generally above 300°C. The polymer is obtained by reacting a sulfide-releasing reagent, an inorganic base, a difunctional aromatic ketone and optionally another difunctional aromatic compound. Therefore, polyarylene sulfides of the aforementioned type having a softening point of about 280°C are not within the scope of the claims.

As sulfide-releasing reactants I it is possible to use alkali metal and alkaline earth metal sulfides, elemental sulfur, xanthogenates, thiocarbamates, thioamides or thiocarbamates and mixtures thereof. It is also possible to use mixtures of the compounds just mentioned and up to 50 mol .chi. of alkali metal bisthiofertes or alkali metal bisphenolates.

Particular preference is given to using sodium sulphide.

When using alkali metal sulfides or mercaptides as sulfide-releasing reactants, oligomers and polymers can be formed directly. However, if other sulfide-releasing compounds are used, it is necessary to add base (2). Suitable bases are, for example, alkaline earth metal hydroxides and monocarbonates. Up to 10 moles of ■, based on 1 mole of sulfide-releasing reactant I, can be used.

The homopolymers are difunctional with the general formula % where l1al is fluorine or especially chlorine and Ar is a difunctional aromatic residue represented by 2 below. It is obtained by reacting the aromatic ketone (1) with the above-mentioned sulfur-containing compound (1), optionally in the presence of an inorganic base (2).

Of course, it is also possible to start from an isomer mixture of formula (1).

The copolymer contains at least 1 mol χ, in particular at least 10 mol χ of at least - type of difunctional aromatic ketones.
and 2 TV up to 99mol 2, tlal-8r
-X-(8r-Y)+%-Ar-Hal or V,
Hal-Ar-X-8r-(yL-Ar-X-A
r-)1al difunctional aromatic compound. In this case Hal is fluorine or especially chlorine. Ar, χ, y and n have the meanings previously given.

Particularly preferred difunctional compounds include 4,4'-dichlorodiphenylsulfone and 4,4'-dichlorobenzophenone and 1,3-bis(chlorophenylsulfonyl)benzene.

Particularly advantageous difunctional compounds include: 4.4'-bis(p-chlorophenylsulfonyl)biphenyl, 4.4"-bis(chlorophenylsulfonyl)diphenyl ether, 44'-bis <p-chlorobenzoyl)biphenyl and 4.4″-bis(p-chlorobenzoyl)diphenyl ether.

The reaction is generally carried out in solution. Polar, aprotic, high-boiling solvents, such as tertiary amides, N-substituted lactams, tetrasubstituted ureas, N-substituted cyclic imides, dialkyl-
, diarylsulfones, tertiary arylsulfonic acid amides, 1-alkyl- and/or 1-aryl-1
-Oxophosphoranes and mixtures thereof are preferred. Especially N-methylpyrrolidone, diphenylsulfone,
N,N-dimethylformamide and especially N,N-dimethylbenzamide are suitable. When using diphenylsulfone, which is solid at room temperature, another solvent,
For example, it is advantageous to use 1,2-dichlorohenzene. The solvent/solids-volume ratio is between 1:1 and 20:1.

The final stage of the reaction is advantageously carried out under water-free conditions. It is particularly advantageous to remove water by distilling the alkali metal sulfide containing water of crystallization together with compounds capable of forming azeotropic conditions, such as toluene, anisole or di-n-butyl ether. This dehydration can also be carried out in situ. Optionally, it is also possible to dehydrate the salt beforehand in the organic reaction medium under reduced pressure.

Another advantageous variant is to start directly from the alkali metal sulfide in the hydrated state and carry out the azeotropic dehydration simultaneously with the reaction.

In this case, it is advantageous to add an entrainer (1) and a salt (2) which is at least somewhat soluble in the organic reaction medium.

Suitable salts in this sense include alkali metal salts of aliphatic, aromatic, or araliphatic or dicarboxylic acids having up to 10 carbon atoms.
Alkali metal and alkaline earth metal salts of mono- or disulfonic acids in which the monovalent or divalent residues to which the monovalent or divalent residues are attached have up to 10 carbon atoms; - and alkaline earth metal bromides or iodides, tetrasubstituted phosphonium bromides or iodides, in which the respective substituent is an organic residue of up to 16 carbon atoms.

The amount of such salt is between 1 and 20 oz, especially between 10 and 150 oz, based on the molar amount of alkali metal sulfide used.

The azeotropic agent ■ has a boiling point of 40 to 160 at standard pressure.
Suitable are ethers, alkanes, cycloalkanes, and alkylaromatics which are at . Particularly suitable are cyclohexane and di-n-butyl ether, especially toluene, xylene and heptane. The amount of entrainer 1 depends on the amount of water to be removed from the circulation system as well as on the embodiment of the process.

The reaction should be carried out, for example, in an atmosphere of an inert gas, such as nitrogen gas, to avoid the introduction of air. It is therefore advantageous to remove dissolved oxygen from the solvent used.

When relatively large amounts of S-containing compounds are used, it is advantageous to add alkylating, acylating or arylating agents just before the end of the reaction in order to improve the thermal properties of the polymer. It is.

Suitable alkylating agents are alkyl halides having 1 to 3 carbon atoms, such as methylene chloride or ethylene bromide, dimethyl sulfate or arylsulfonic acid alkyl esters whose constituent alcohols have up to 3 carbon atoms.

Particularly suitable acylating agents are acetyl chloride, acetic anhydride and benzoyl chloride.

Suitable arylating agents include aromatic halogenated compounds activated by C-- and SO,- groups, such as 4-chlorodiphenylsulfone or 4-chlorobenzophenone. In addition, the above-mentioned difunctional aromatic compound■
, ■ or V are also suitable.

The two-step reaction format is illustrated below: 1. First, remove oxygen from the solvent used.

2. Next, dehydrate the sodium sulfide.

3. Add the difunctional aromatic ketone (1) and optionally the difunctional aromatic compound (2) or (2) and heat to the desired reaction temperature under a protective gas atmosphere.

4. Hold the mixture at this temperature for up to 36 hours.

5. An alkylating agent, acylating agent or esterifying agent may be added depending on the case.

6. Precipitate the product and boil with polar solvent.

However, it is particularly advantageous to carry out the process in one step. According to this, starting directly from a mixture consisting of a water-containing alkali metal sulfide I, an inorganic base II, a difunctional ketone ■, a difunctional aromatic compound ■ or ■, a salt ■ and an azeotropic agent ■, The mixture is heated, the water being first removed from the circulation by means of an entrainer, then the entrainer is distilled off and the reaction is carried out to completion at elevated temperature. Alternatively, only components (1), (2), and (2) may be introduced first, and the aqueous solutions of components (1), (2), and (2) may be added to such an extent that the water added dropwise into the reaction vessel is removed from the circulation system at the same time as the azeotropic agent. good.

The resulting product has a molecular weight of 2,000 to 500,000. If high molecular weights are desired, such as those desired for injection molding, extrusion or film production, it is advantageous to carry out the reaction under conditions in which the resulting polymer remains in solution during all stages of the reaction. This means carrying out the reaction at elevated temperatures, using solvents with good solubility for the polymer, such as dimethylbenzamide, and/or using difunctional compounds ■ or ■ in addition to the ketone Hm. are doing.

Low molecular weight products can be used, for example, as components of polymer blends or as components of coatings of suitable hardness.

Relative viscosity η,. The measurement of 6 is carried out analogously to DIN 53,728 by dissolving 0.5 g of the substance in 100 cm' of concentrated sulfuric acid and then measuring at 25°C.

T, -values are Perkin-Elm
er) Measure using a calorimeter DSC-IB. The values listed were obtained during the second heating.

20.00 g of Na, 5-xllzO (90.4 mm
ol; NazS-content 35.3χ) at 220°C initially.
Dehydrate under reduced pressure. 32.09 g (90,4
After addition of 4,4'-dichloroisophthalophenone (mmol) and 120 ml of dimethylbenzamide (fresh, degassed), stirring is continued for 9 hours at 230'C under a nitrogen atmosphere.

This mixture is mixed with the same volume of ethanol after cooling;
The residue was filtered with suction and each
Boil with ml ethanol and water. ηra
d=0.20, T, =317°C, T.

= 116℃ and has the following repeating unit 27.1
g of polymer is obtained.

As in Example 1, 20.00 g Na2
Dry S-XH20 (90.4 mmol), 16.
05 g (45,2 mmol) of 4,4'-dichloroisophthalophenone and 16.05 g (45,2 mmol)
) in 120 ml of dimethylbenzamide at 230° C. under a nitrogen atmosphere for 9 hours. After the same work-up as in Example 1, η−d= 0.34, T-=303
℃, Tg・151℃ and 2 with the following repeating units
6.85 g of polymer are obtained.

50χ 50χ 1 juice J As in Example 1, 20.00 g of Na2
Dry S ・XH20 (90.4 mmol), 25.
71 g (72,4 mmol) of 4,4"-dichloroterephthalophenone and 5.20 g (18,1 mmol)
2 in 120 ml dimethylbenzamide with a mixture consisting of 4,4'-dichlorodiphenyl sulfone.
Stir at 60°C under nitrogen atmosphere for 6 hours. '7r*d=0.23, T-□3 in the same post-processing as in Example 1
67°C, T9 =205°C and 25.5 g of polymer with the following repeating units are obtained.

80χ 20χ Run■'' As in Example 1, 20.00 g of Naz
Dry S-xllzO (90.4 mmol), 15.
25 g (42,95 mmol) of 4,4”-dichloroisophthalophenone, 15.25 g (42,95 mmol)
) 4,4′-dichloroterephthalophenone and 2.
A mixture consisting of 26 g (4,50 o.l.) of 4,4'-bis(p-chlorobenzenesulfonyl)biphenyl and 120 m of 2.3
Stir at 0° C. under nitrogen atmosphere for 9 hours. After the same post-processing as in Example 1, ηred = o.

42, T, ·298°C, T9·158°C, and 26.6 g of polymer having the following repeating units are obtained.

Approximately 5.0χ Implementation ■ 100.00 g of Na25-
0 mmol), 4.0 g of sodium carbonate and 33.
90 g of 4,4°-dihydroxydiphenylsulfone m
: Calcium salt (103°85 mmol) - prepared according to German Patent No. 2.425.166 - 100 m! After addition of water, 184.48 g of 4,4'-dichloroterephthalophenone (519.24 mmol), 30
4 in a vigorously stirred and boiling mixture consisting of 0 g diphenyl sulfone and Loom 1 xylene.
Add dropwise over time and simultaneously remove the land water from the circulation system. Stirring is continued at 230° C. for 2 hours, at 270° C. for 5 hours and at 330° C. for 4 hours while distilling off the xylene. then 30
Cool to 0°C and add 50g of 4°4' during 15 minutes.
-dichlorodiphenylsulfone with 20 ml of dimethylbenzamide and 5 m! ! solution in anisole was added dropwise and stirred for 15 minutes, then initially 300 m
1 of dimethylbenzamide and then 600 ml of ethylene glycol.

The mixture is filtered hot at 100 DEG C. with suction and the residue is boiled twice with acetone and twice with water.

η□ad,07,T,·362°C and 177 g of an almost white powder with the following repeating units was obtained.

80 χ

Claims (1)

[Claims] 1) In producing single and copolymer polyarylene sulfide, the polymer has a repeating unit represented by the formula (Ar-CO-Ar-CO-Ar-S) and I, sulfide-releasing reactant, optionally 50 mol%
II, optionally an inorganic base, III, a compound of the formula Hal-Ar-CO-Ar-CO-Ar-Hal, where Hal is fluorine or especially chlorine; Ar is a difunctional aromatic ketone represented by the following difunctional aromatic group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼.) is the following formula IV, Hal-Ar-X-(Ar-Y)_n-Ar-Ha
l or V, Hal-Ar-X-Ar-(Y)_n-A
r-X-Ar-Hal, in which Hal and Ar have the meanings already given above, n is 0 or 1 and X and Y are respectively -O-, -S-, -CO- and -SO_2- group.) is obtained by reacting another difunctional aromatic compound represented by
A method for producing the above polymer. 2) The method according to claim 1, wherein the reaction is carried out in a polar solvent at a temperature of 120 to 350°C in the absence of oxygen. 3) Claim 2 in which the reaction is carried out in the absence of water
The method described in section. 4) The method according to any one of claims 1 to 3, wherein an alkali metal sulfide is used as the sulfide-releasing reactant (I). 5) A process as claimed in claim 4, in which a total of 1 mol of difunctional starting compound (III) and optionally 0.8 to 1.2 mol of sodium sulfide, based on IV, are used. 6) The reaction was carried out in dimethylbenzamide as a solvent for 20
6. The method according to claims 1 to 5, which is carried out under atmospheric pressure at a temperature of 0 to 260<0>C. 7) The method according to any one of claims 1 to 6, in which an alkylating agent, acylating agent, or arylating agent is used immediately before the end of the reaction. 8) A monohydric sulfide-releasing reactant (I), an inorganic base (II), a difunctional aromatic ketone (III), a difunctional aromatic compound that is at least partially soluble in the organic reaction medium ( The salt (VII) of IV or V) and the entrainer (VI) are first introduced, - the temperature is raised, the water being first removed from the circulation by the entrainer and then the entrainer is distilled off; 8. The process according to claim 1, wherein the polycondensation is carried out to completion at high temperatures. 9) Introducing components III, IV and VI first and component I
, II and VII are added to such an extent that the water added dropwise leaves the circulation system substantially simultaneously with the entrainer. 10) I, sulfide-releasing reactant, optionally 50
Up to mol% of bisthiophenolates or mixtures with bisphenolates and II, inorganic bases, and formulas obtained by reacting with compounds represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , chemical formula, table, etc. ▼ A polymer polyarylene sulfide having a repeating unit represented by . 11) having a repeating unit represented by (Ar-CO-Ar-CO-Ar-S) and 1. a sulfide-releasing reactant, optionally up to 50 mol% of bisthiophenolate or bisphenolate; II, optionally an inorganic base; III, a mixture of the formula Hal-Ar-CO-Ar-CO-Ar-Hal, where Hal is fluorine or especially chlorine and Ar is a difunctional aromatic Difunctional aromatic ketones represented by the group group ▲Mathematical formulas, chemical formulas, tables, etc.▼ or ▲Mathematical formulas, chemical formulas, tables, etc.▼ and, in some cases, the following formula IV, Cl-Ar-X--Cl V , Hal-Ar-X-Ar-(Y)_n-Ar-X-
Ar-Hal, in which Hal and Ar have the meanings already given above, n is 0 or 1 and X and Y are respectively -O-, -S-, -CO- and -SO_
2-part. ) A copolymer polyarylene sulfide obtained by reacting another difunctional aromatic compound represented by: 12) having a repeating unit represented by (Ar-CO-Ar-CO-Ar-S) and I, a sulfide-releasing reactant, optionally 50 mol%
II, optionally an inorganic base, III, a compound of the formula Hal-Ar-CO-Ar-CO-Ar-Hal, where Hal is fluorine or especially chlorine; , Ar is a difunctional aromatic group represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and in some cases, Ar is a bifunctional aromatic ketone represented by the following formula IV. , Hal-Ar-X-(Ar-Y)_n-Ar-Ha
lV, ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In both formulas, Hal and Ar have the meanings already given above, n is 0 or 1, and X and Y are respectively -O-, -S -, -CO-, and -SO_2- groups.) A copolymer polyarylene sulfide obtained by reacting other bifunctional aromatic compounds represented by the following.