JPH0160171B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyarylene sulfide. Polyarylene sulfides are known (see US Pat. Nos. 2,538,941 and 2,513,188). They can be prepared from the corresponding halogenoaromatic and alkali metal sulfides or alkaline earth metal sulfides. The reaction can be carried out using the reactants as they are, or a polar solvent can also be used. Thus, according to the method described in U.S. Pat. No. 3,354,129, monomeric and polymeric sulfides contain at least one double bond between adjacent ring atoms and are substituted by at least halogen atoms. They are prepared by reacting certain cyclic compounds with alkali metal sulfides in polar solvents such as amides, lactams or sulfones at elevated temperatures. Polyhalogen compounds can be used as branching agents. In DE 2453749, carboxylates are claimed as reaction promoters and, in addition to alkali metal sulfides, organothio compounds are also claimed as sulfur donors. German Published Patent No. 2623363 or US Patent No.
According to No. 4038261, lithium chloride or lithium carboxylate can be used as catalysts for the production of arylene sulfide polymers. N-methylpyrrolidone and alkali metal hydroxide complete the catalyst system. Combinations of alkali metal carbonates and alkali metal carboxylates are disclosed in U.S. Pat. No. 4,038,259.
Also, lithium halide is covered by U.S. Patent No.
No. 4038263, it is used as a catalyst for the production of polyphenylene sulfide. German Published Patent No. 2623362 or US Patent No.
No. 4,038,262, lithium halides or alkali metal carboxylates are used as catalysts for the production of arylene sulfide polymers. N-methylpyrrolidone and alkali metal hydroxide complete the catalyst system. German Published Patent No. 2623333 or US Patent No.
According to No. 4064114, lithium acetate is used as a catalyst for the production of arylene sulfide polymers. N-alkylpyrrolidone and, if appropriate, alkali metal hydroxide and/or alkali metal carbonate as base complete the catalyst system. Alkali metal sulfonates are described in U.S. Pat. No. 4,038,260, and lithium carbonate and lithium borate are described in U.S. Pat.
It is claimed in No. 4039518. Polyarylene sulfides with reduced melt flowability can be produced using tri-(alkali metal) phosphate catalysts (German Published Patent No. 2930710) or alkali metal phosphonate catalysts (German Published Patent No. 2930797). Can be done. In DE 2 623 333, the dehydration which is customary before the reaction with the dihalogeno aromatic in a polar solvent is carried out in two stages. First, the catalytic lithium acetate hydrate is dehydrated, and in the subsequent second step, the sodium sulfide dihydrate is dehydrated. Generally, P-polyphenylene sulfide is subjected to a further curing step following the reaction (U.S. Pat.
3717620, 3524835 and 3839301). This step is intended to improve the properties of the polymer by chain extension and branching reactions. Without a curing step, P-polyphenylene sulfide generally has a low melt viscosity and is not capable of thermoplastic processing. According to U.S. Pat. No. 3,919,177, P-polyphenylene sulfide produced without prior curing is melt spun into fibers under selected conditions and with the aid of catalytic lithium carboxylate. It is intended that In US Pat. No. 4,116,947 or DE 2,817,731 P-polyphenylene sulfate obtained without a curing step is disclosed by using a certain amount of residual water and, if appropriate, in the presence of carboxylates. push out the id,
It states that it can be spun into fibers and shaped. The present invention is characterized in that branched polyarylene sulfide with high melt viscosity and high molecular weight is condensed with dihalogenobenzene and polyhalogenobenzene and alkali metal sulfide in a certain solvent, and further the reaction is carried out with alkali metal sulfite and/or It is based on the principle that the process is carried out in the presence of 0.02 to 0.3 moles of alkaline earth metal sulfite (per mole of alkali metal sulfide). The resulting polyarylene sulfide can be shaped, extruded and spun into fibers without post-curing treatment. These have substantially improved mechanical properties compared to previously commercially available polyarylene sulfides. The subject of the invention is that (a) 50 to 100 mol % of formula (I) [wherein X is fluorine, chlorine, bromine or iodine; preferably chlorine or bromine] and 0 to 50% corresponds to the formula ^[ _{wherein , _ _
C6} - _C24 aryl, _C7 - _C24 alkaryl or
C ₇ -C ₂₄ aralkyl, and/or the two radicals R ¹ can be linked to form an aromatic or heterocyclic ring, and at least one radical R ¹ is always different from hydrogen. Corresponding dihalogenobenzene, (b) 0.1 to 2.4 mol %, preferably 0.4 to 2.0 mol %, based on the dihalogenobenzene, of the formula Ar an aromatic or heterocyclic group having 3 free valences, X being as defined above, and n=3 or 4; and (c) an alkali metal sulfide, preferably sodium. or potassium sulfide or a mixture thereof, preferably in the form of a hydrate or aqueous mixture, if appropriate together with an alkali metal hydroxide; (d) a polar solvent, preferably an amide or a lactam;
Particularly preferably the reaction is carried out in an amide or lactam in which the nitrogen is completely alkylated, provided that the molar ratio of (a) and (c) is in the range from 0.85:1 to 1.15:1, preferably from 0.95 to 0.05:1. and (c) and (d)
in the range of 1:2 to 1:15, the polycondensation time is up to 10 hours, preferably 0.2 to 5 hours, and the polycondensation temperature is 160 to 300°C, preferably 200°C.
~285° C. and the reaction is carried out with 2 to 30 mol % (based on the alkali metal sulfide) of the alkali metal sulfite and/or alkaline earth metal sulfite of formula () or (V) M ₂ SO ₃ () , M′SO ₃ (V) [wherein M represents an alkali metal, especially lithium, sodium and potassium, and M′ represents an alkaline earth metal, especially magnesium and calcium]. This is a method for producing a branched high molecular weight polyarylene sulfide having a physical viscosity. Alkali metal sulfites are preferably used,
Among them, sodium sulfite and potassium sulfite are particularly preferably used. The sulfite according to the invention is normally used in the form of its hydrate or its aqueous solution, but it can also be used in that form if the commercially available form is anhydrous. The alkali metal sulfides, preferably potassium sulfide and sodium sulfide, are preferably used in the form of their hydrates or aqueous mixtures. However, they may also be prepared directly from hydrogen sulfide and the corresponding alkali metal hydroxide or from alkali metal hydrogen sulfide and the corresponding alkali metal hydroxide according to a stoichiometric reaction in a reaction solution. Mixtures of alkali metal sulfides can also be used. If alkali metal hydrogen sulfide is contained in the alkali metal sulfide as an impurity or is generated during the reaction, depending on the proportion of alkali metal hydrogen sulfide in the reaction solution, alkali metal hydroxide may be added to regenerate the alkali metal sulfide. is further added stoichiometrically. If appropriate, instead of the alkali metal hydroxides it is also possible to add compounds which cleave or form alkali metal hydroxides under the reaction conditions. Lithium sulfide, sodium sulfide,
potassium sulfide and rubidium sulfide,
Preferably sodium sulfide and potassium sulfide are examples of alkali metal sulfides used. Mixtures of alkali metal sulfides can also be used. Examples of suitable alkali metal hydroxides are lithium hydroxide, sodium hydroxide and potassium hydroxide,
and mixtures thereof. The alkali metal sulfide and/or alkali metal sulfite or alkaline earth metal sulfite can be dehydrated in one or more stages, for example by distilling off the water from the reaction solution. Partial dehydration is the P- of formulas (I) and ()
This should be completed before addition of the dihalogeno compound. The alkali metal sulfide and alkali metal sulfite or alkaline earth metal sulfite can be partially dehydrated together or separately. The reactants can be combined in essentially any desired manner. The P-dihalogenoaromatics of formulas (I) and () and the polyhalogenoaromatics of formula (), together or separately, successively, in part or directly, are combined with an alkali metal sulfide, a solvent or a portion thereof, and can be added to alkali metal sulfites or alkaline earth metal sulfites of formulas () and (V). However, if the alkali metal sulfide together with the solvent or a part thereof and the formulas () and (V)
It is also possible to add sulfites of formula (I) and () to the compounds of formula (I) and () and to polyhalogenoaromatics (). It is also possible to combine all reactants directly. Any other combination of reactants is also possible. Examples of P-dihalogenoaromatics of formula (I) that can be used according to the invention are P-difluorobenzene,
P-dichlorobenzene, P-dibromobenzene,
P-diiodobenzene, 1-fluoro-4-chlorobenzene, 1-fluoro-4-bromobenzene, 1-chloro-4-bromobenzene, 1-chloro-4-iodobenzene and 1-bromo-4-iodobenzene It is. These can be used alone or mixed with each other. The preferred one is P
-dichlorobenzene and P-dibromobenzene. Examples of P-halogeno aromatics of formula () that can be used according to the invention are 2,5-dichlorotoluene,
2,5-dichloroxylene, 1-ethyl-2,5
-dichlorobenzene, 1-ethyl-2,5-dibromobenzene, 1-ethyl-2-bromo-5-chlorobenzene, 1,2,4,5-tetramethyl-
3,6-dichlorobenzene, 1-cyclohexyl-2,5-dichlorobenzene, 1-phenyl-
2,5-dichlorobenzene, 1-benzyl-2,
5-dichlorobenzene, 1-phenyl-2,5-
They are dibromobenzene, 1-P-tolyl-2,5-diglolbenzene, 1-P-tolyl-2,5-dibromobenzene, and 1-hexyl-2,5-dichlorobenzene. These can be used alone or in combination with each other. Examples of polyhalogenaromatics of formula () that can be used according to the invention are 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,
4-tribromobenzene, 1,2,4-triiodobenzene, 1,3,5-trichloro-2,4,
6-trimethylbenzene, 1,2,3-trichloronaphthalene, 1,2,4-trichloronaphthalene, 1,2,6-trichloronaphthalene, 2,
3,4-trichlorotoluene, 2,4,6-trichlorotoluene, 1,2,3,4-tetrachloronaphthalene, 1,2,4,5-tetrachlorobenzene, 2,2',4,4'- They are tetrachlorophenyl and 1,3,5-trichlorotriazine. Generally, polar solvents that allow the organic and inorganic reactants to dissolve sufficiently under the reaction conditions can be used for the reaction. However, amides and lactams can be used with preference; N-alkylated amides and lactams are particularly preferred. In the context of the present invention, lactams are lactams of C3-C5 amino acids which optionally have substituents in the carbon skeleton, such as C1-C5 alkyl groups, which are inert under the reaction conditions. In the context of the present invention, N-alkyl lactams are defined as lactams in the present case, but
Furthermore, the nitrogen atom has an alkyl group having 1 to 6 carbon atoms. Examples of suitable solvents are N,N'-dimethylacetamide, N,N'-diethylacetamide, N,
N'-dipropylacetamide, N,N'-dimethylbenzoic acid amide, caprolactam, N-methylcaprolactam, N-ethylcaprolactam, N
-isopropylcaprolactam, N-isobutylcaprolactam, N-propylcaprolactam,
N-butylcaprolactam, N-cyclohexylcaprolactam, N-methyl-2-pyrrolidone,
N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-cyclohexyl-2-
pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone,
N-methyl-3-methyl-2-pyrrolidone, N-
Methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-
2-piperidone, N-isopropyl-2-piperidone, N-isobutyl-2-piperidone, N-
Methyl-6-methyl-2-piperidone, N-methyl-3-ethyl-2-piperidone, N-methyl-
2-oxo-hexamethyleneimine and N-ethyl-2-oxo-hexamethyleneimine. Mixtures of the abovementioned solvents can also be used. The condensation reaction temperature is generally 160-300°C, preferably
The temperature is 200-285℃. The reaction time is up to 10 hours, preferably 0.2 to 5 hours. It is advantageous to increase the reaction temperature stepwise during this period. Since the condensation temperature is generally higher than the boiling point of the solvent, additional pressure is naturally required. Dihalogenobenzene and alkali metal sulfide are reacted in equimolar amounts as far as possible.
The dihalogenbenzene/alkali metal sulfide molar ratio is therefore preferably in the range 0.95:1 to 1.05:1. However, it is 0.85:1 ~
It can be expanded to a range of 1.15:1. The polyhalogenoaromatics of the formula () which can be used according to the invention can be used in amounts of up to a few mol %, based on the fraction of dihalogenobenzene, depending on the reaction conditions.
It can be added together with the dihalogenobenzene or separately, but as a rule a proportion of 0.1 to 2.4 mol %, preferably 0.4 to 2.0 mol %, based on the dihalogenobenzene, is sufficient. The amount of solvent can be selected within a wide range, but generally 2
~15 moles. Treatment of the reaction mixture can be carried out in various ways. The polyarylene sulfide can be separated from the reaction solution in conventional manner, for example by filtration or centrifugation, directly or after addition of water, for example. This is generally followed by a water wash to remove inorganic components such as alkali metal sulfides and alkali metal chlorides that may be attached to the polymer. In addition to or following this washing, it is of course also possible to carry out washing with other washing liquids or extraction. Polymers can also be produced by removing the solvent from the reaction space followed by washing as described above. The polyarylene sulfide according to the invention can be combined with other polymers and pigments and fillers, such as graphite, metal powders, glass powders, ground quartz or glass fibers, or with the usual additives for polyarylene sulfides, such as It may be mixed with conventional stabilizers or mold release agents. Generally, the melt flowability of polyarylene sulfide is measured in accordance with ASTM 1238-70 at 316°C using a 5 kg weight and is expressed in g/10 min. However, in the case of high melting indexes, this measurement becomes problematic due to the high flow rate of the polymer melt. Hence, the melt viscosity of the polymer melt in nm (pas)
was determined at 306 °C as a function of shear force τ(pa) with the help of an Instron rotational viscometer. In this method, the melt viscosity is 10 ^-1 to ^{10 7} pa・s
can be measured accurately within a very wide range. In the Instron viscometer, the polymer is melted between a fixed plate and a rotatable cone, and the torque of the cone is measured. From torque, angular viscosity and equipment data, melt viscosity as a function of shear force can be calculated. A model 3250 viscometer from Instron was used: cone and plate diameter 2 cm. The melt viscosity measured at shear force τ=10 ² pa is shown. In the present invention, the P-polyarylene sulfide is generally 0.5×
10 ³ to 5×10 ⁵ pa・s and more, preferably
It has a melt viscosity of 1.5×10 ³ to 10 ⁴ pa·s. It can be directly processed by extrusion, blow extrusion, injection molding or other conventional processing methods to produce automotive parts, armatures, electronic parts such as switches, electrical panels, chemical resistant parts and devices such as It can make pump housings and pump impellers, etched bath dishes, sealing washers, office equipment and communication equipment parts, household goods, valves, ball bearing parts, etc. Example 1 This example is based on U.S. Pat. No. 3,354,129 for comparison.
describes the production of polyphenylene sulfide according to No. 129 g of sodium sulfide trihydrate (equivalent to 1 mole of Na ₂ S) in an autoclave equipped with a stirrer.
and 300 g of N-methyl-2-pyrrolidone were added.
Flush this mixture with nitrogen and slowly
It warmed up to 202 degrees Celsius. During this operation, a total of 10 ml of water
leaked out. The mixture is then cooled to approximately 160°C,
147 g (=1 mol) of P-dichlorobenzene in about 50 g of N-methyl-2-pyrrolidone were added. The reaction mixture was warmed to 245° C. under an initial pressure of 2.5 bar of nitrogen over 30 minutes and maintained at this temperature for 3 hours.
After the mixture was cooled to room temperature, a gray solid was separated. Next, this was carefully washed with water to remove mixed inorganic components. The product was dried under vacuum at 80°C to give 100.3 g of poly-P-phenylene-sulfide with the following properties:
(93%) was obtained: melt viscosity ηm = 4.5 pa・s (τ =
10 ² pa), thermoplastic processing was not possible without hardening. Example 2 191.6 g (1.455 mol) of sodium sulfide hydrate and 18.9 g of sodium sulfite hydrate (Na ₂ SO ₃ .7H ₂ O) (5 mol % based on the number of moles of sodium sulfide) A suitable amount of sodium hydroxide to neutralize the sodium hydrogen sulfide contained in the mixture was first introduced into 500 g of N-methylpyrrolidone. By slowly heating the mixture to 175°C, 35.0 ml of distillate containing water as a main component was obtained. 220.5 g (1.50 mol) of N-methylpyrrolidone P-dichlorobenzene and 2.72 g (0.005 mol) of 1,2,4-trichlorobenzene were then added and, after adding the autoclave, the reaction mixture was heated at 200 ml for 90 minutes. The temperature was brought to ~270°C and maintained at this temperature for 20 minutes. After the end of the reaction, the autoclave was cooled to 150°C, the pressure was released and the reaction mixture was taken out. The p-polyphenylene sulfide formed was separated and carefully removed by the attached salt. After drying, p-polyphenylene sulfide was separated as an off-white solid. Melt viscosity η _n =1450pa・s
(τ=10 ² pa). Example 3 Example 2 was followed except that 10 mol% of sodium sulfite hydrate was used. Melt viscosity η _n =
1800 pa・s (τ=10 ² pa). Example 4 1,2,4-trichlorobenzene 3.54g (0.0195
Example 2 was followed except that mol) was used. Melt viscosity η _n =2200 pa·s (τ = 10 ² pa). Example 5 Example 2 was followed except that 20 mol% of sodium sulfite hydrate was used. Melt viscosity η _n =
2350pa・s (τ=10 ² pa). _Example 6 Potassium sulfite hydrate _K2SO3・
Example 2 was followed except that 28.3 g of 2H ₂ O (10 mole % based on moles of sodium sulfide) was used.
Melt viscosity η _n =1900 pa·s (τ = 10 ² pa). For comparison, the melt viscosity of Ryton, a commercially available non-heat treated P-polyphenylene sulfide from Phillips Petroleum Comp., is η _n =
3.5 pa·s (τ=10 ² pa) and thus substantially lower than the melt viscosity of P-polyphenylene sulfide described in the examples of the invention. Commercial thermoplastically processable P-polyphenylene sulfide from Phillips Petroleum Ccmp.
Ryton R4 was probably obtained by further thermal post-treatment. Despite this further post-treatment, this commercially available thermoplastically processable P
-Polyphenylene sulfide is P-polyphenylene sulfide according to the present invention, in which P-polyphenylene sulfide is directly obtained in one step.
- Has poorer mechanical properties than polyphenylene sulfide (see Table 1). 【table】

Claims (1)

[Claims] 1 (a) 50 to 100 mol% of formula I [wherein X is fluorine, chlorine, bromine or iodine] and 0-50% of the formula [In the formula, X has the same meaning as above, and R ¹ may be the same or different, and hydrogen, C ₁
~ _C20 alkyl, _C5 ~ _C20 cycloalkyl, _C6 ~
C ₂₄ aryl, C ₇ ~C ₂₄ alkaryl or C ₇ ~
C ₂₄ aralkyl and/or two groups R ¹
can be linked to form an aromatic or heterocyclic ring and at least one group R ¹ is always different from hydrogen], (b) 0.1 to 0.1 for dihalogenobenzene; 2.4 mol%
of the formula ArXn ... () [wherein Ar is an aromatic or heterocyclic group having 6 to 24 carbon atoms and at least 3 free valences, X is as defined above, and n is 3 or 4] and (c) an alkali metal sulfide are reacted in (d) a polar solvent, provided that the molar ratio of (a) to (c) is from 0.85:1 to
in the range of 1.15:1 and the molar ratio of (c) to (d) is 1:
in the range of 2 to 1:15, the polycondensation time is up to 10 hours, and the polycondensation temperature is maintained at 160 to 300 °C,
The reaction is then carried out with 2 to 30 mol% of alkali metal sulfite and/or
or in the presence of an alkaline earth metal sulfite. 2. The method according to claim 1, wherein p-dichlorobenzene or p-dibromobenzene is used as component (a). 3 0.4 to 2.0 mol% relative to dihalogenobenzene
A method according to claim 1, using a polyhalogeno aromatic compound of the formula. 4. The method according to claim 1, in which sodium sulfite or potassium sulfite is used in an amount of 2 to 30 mol % based on the alkali metal sulfide. 5. The method according to claim 1, wherein a lactam and/or amide in which nitrogen is completely alkylated is used as a solvent.