JPS5867727A - Manufacture of polyarylene sulfide - 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 a method for producing polyarylene sulfide.

Polyarylene sulfides are known (see 1 U.S. Pat. No. 2.5!113,941 and λ'51 to 188
), they can be prepared from the corresponding haloaromatic and alkyl metal sulfides V or alkaline earth metals sulfides Y. The reaction can be carried out using the reactants as is. , or a polar solvent can also be used. That is, according to the method described in U.S. Pat. No. 4,354,129, monomeric and polymeric sulfides contain double bonds between adjacent ring atoms and are substituted by at least one atom. It is prepared by reacting a 1m cyclic compound with an alkali metal sulfone in a polar solvent such as an amide 1 lactam or sulfone at elevated temperature.The polyhene compound is used as a branching agent. be able to.

In DE 2.45 to 749, carboxylates are claimed as reaction promoters, and in addition to alkali metal sulfides, organothio compounds are also claimed as sulfur donors, DE 2. .624365
According to U.S. Pat.

N-methylpyrrolidine and alkali metal hydroxide complete the catalyst system.

Combinations of alkali metal carbinates and alkali metal carboxylates are described in US Pat. No. 4.03 &259, and lithium halides are described in US Pat. No. 40342.
b No. 5, it is used as a catalyst for the production of polyphenylene sulfy F.

German Published Patent No. 2.62 to 562 or U.S. Patent No. 40
In S&262, lithium halides or alkali metal xylates are used as catalysts for the production of arylene sulfy Y polymers. N-methylpyrrolidine and alkali metal hydroxide complete the catalyst system.

National Publication No. 333 or U.S. Patent No. 4.
According to No. 064114, lithium acetate is used as a catalyst for the production of arylene sulfide polymers. N
-alkyl bio9)P and, if appropriate, alkali metal hydroxides and/or alkali metal carbonates as bases;
Complete the catalyst system.

Alkali metal sulfonates are disclosed in U.S. Patent No. 405a260.
Lithium carbonate and lithium borate are also claimed in US Pat. No. 4 (ls9.518).

Polyarylene sulfides with reduced melt fluidity can be treated with tri(alkali metal) phosphate catalysts (German Published Patent Application No. 2.93 to 710) or alkali metal phosphonate catalysts (German Published Patent Application No. 2.950°797). It can be manufactured using

In DE 2.621555 the dehydration which is customary before the reaction with the zohaloaromatic 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. No. 717.62
No. 0, No. 4524,835 and No. 4859,301), this step is intended to improve the properties of the polymer by chain extension and branching reactions.

Without a curing step, p-z rifhenylene sulfur generally has a low melt viscosity and is not thermoplastically processable.

According to U.S. Pat. No. 4,919,177, nine p-polyphenylene sulfides produced without prior curing are melt-spun under selected conditions and with the help of a catalytic lithium carboxylate. It is intended to be used as a fiber. In U.S. Pat. No. 4.114947 or DE 2.81 Suf. 51, calcium can be obtained without a curing step by hardening with a certain amount of residual water and if appropriate in the presence of xylate. It is stated that the p-polyphenylene sulfide obtained can be extruded, spun into a single fiber, and shaped.

The present invention involves the condensation of a branched 4-arylene sulfide V with high melting degree and high molecular weight in a solvent containing dihalo-nobenzene and polyhalogenobenzene and an alkali metal sulfide. or alkaline earth metal sulfide 102~CL
It is based on the principle that the reaction is carried out in the presence of 3 moles (per mole of alkali metal sulfide). The resulting damaged polyarylene sulfide can be shaped, extruded and spun into fibers without post-curing treatment. These have substantially improved first mechanical properties compared to polyarylene sulfide V which has been commercially available in the past.

The subject of the present invention is that &) 50 to 0% - corresponds to formula (1) [wherein X is fluorine, X% bromine or chlorine; θ~50chi is 21 [1 in the formula! has the same meaning as above, and R1 may be the same or different, and hydrogen, 0, to 03.
Alkyl, ○, ~0 ■ Cycloalkyl% Oe ~ 0 Also aryl 101 ~ 0 No. Alkyl or 0! ~0roaralkyl, and/or the two groups R1 can be linked to form an aromatic or heterocyclic ring, and at least one group R1 is always different from hydrogen] JIC equivalent Tb dihalogen Benzene, b) -1" (L1 to 2.4 mol S, tFf or α4 to 2-0 mol-, relative to dihalogenobenzene, formula
Xn...@(m) [wherein, mr is an aromatic or heterocyclic group having 6 to 24 carbon atoms and at least 43 free valences, and I has the same meaning as above. and O) an alkali metal sulfide, preferably sodium or potassium sulfide or a mixture thereof, tFP
preferably in the form of a hydrate or an aqueous mixture, if appropriate together with an alkali metal hydroxide; React in amide or lactam ~ Provided that the molar ratio of a) and C) is (L85:1~t, 15:1
% preferably in the range of α95 to α06:1)
The molar ratio of
0 to 285° C. and the reaction is carried out at 2 to 30 mol (relative to the alkali metal sulfide) of formula (IV) or (
V) Alkali metal sulfide and/or alkaline earth metal sulfide “Rose” (IV), M#80.
(V) [where %M stands for alkali metals - in particular lithium, sodium and potassium - and MI stands for alkaline earth metals %%! 1. Process for preparing branched, high molecular weight polyarylene sulfides with high melt viscosity in the presence of danesium and calcium.

Alkali metal sulfates are preferably used, and among these, sodium sulfide and potassium sulfide are particularly preferably used. The sulfide 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 sulfuric acid V 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 is used to regenerate the alkali metal sulfide. Add the material stoichiometrically to the page. If appropriate, instead of the alkali metal hydroxide it is also possible to add compounds which cleave or form the alkali metal hydroxide under one reaction condition.

Lithium sulfide V, sodium sulfide monopotassium sulfide and rubidium sulfide, preferably sodium sulfide and potassium sulfide V are examples of alkali metal sulfides used. Mixtures of alkali metal sulfides can also be used.

An example of a suitable alkali metal hydroxide is lithium hydroxide.
Sodium hydroxide and potassium hydroxide, and mixtures thereof.

The alkali gold maple sulfide and/or alkali metal sulfide or alkaline earth metal sulfide may be dehydrated in one or more stages - for example by distilling off the water from the reaction solution. is the formula (1
) and (3) the alkali metal sulfide and alkali metal sulfide or alkaline earth metal sulfide which should be completed before addition of the p-zohalo compound can be partially dehydrated together or separately. .

The reactants can be combined in essentially any desired form, and the p-aromatics of formula (1) and (1) and the polyhaloaromatics of formula <m> are together or separately 1 successively 1 part at a time or directly 1% alkali metal sulfide solvent or a part thereof to and alkali metal sulfide or alkaline earth metal sulfide of formula (■) and (to). I can do it.

However, one alkali metal sulfide together with a solvent or a part thereof, and the sulfides of formulas CP, I') and (to), one compound of formulas (1) and (3) and -rehalor
It is also possible to add it to aromatics (1).

Any other combination of one reactant is also possible, including the ability to combine all reactants directly.

Examples of p-tz haloaromatics of formula (1) that can be used according to the invention are: 1)-1'fluorobenzene, p-zokdhunzene, p-sotu, rombenzene 1p-shortbenzene, 1- Fluoro-4-chlorobenzene% 1-fluoro-4-10benzene, 1-chloro-4-10benzene% 1-/lo-4-iodobenzene, and 1-bromo-4-iodobenzene. These can be used alone or mixed with each other. Preferred are monozochlorobenzene and p-dichlorobenzenetheal.

Examples of p-haloaromatics of formula 0 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-pa rubenzene% 1,2,4.5-tetramethyl-3,6-dichlorobenzene% 1-cyclohexyl-2,5-dichlorobenzene% 1-phenyl-2,5-1'chlor Benzene-1-benzyl-2,5
-dichlorobenzene, 1-phenyl-2,5-dibromobenzene, 1-P-) lylu-2.5-N chlorobenzene% 1-1>-) di-2,5-dibu-tetrampenzene, and 1- Hexyl-2,5-dichlorobenzene. These can be used alone or in combination with each other.

Examples of polyphenoroaromatics of formula (III) that can be used according to the invention are 1,2,3-trichlorobenzene,
1,2.4-) dichlorobenzene, 1,2.4-triptetrabenzene, 1*2*4-) rhodobenzene
1e! S,5-)dichloro-2,4,6-)limethylbenzene ~ 1.2.3-)dichlorna7talene,1@
2.4-) IJ-dichloronaphthalene, 1.2.6-) dichloronaphthalene, 2.5.4-)! llortoluene%
2*4ets-trichlorotoluene, 1,2. ! 1.4
-tetrachlornaphthalene, 1,2,4.5-tetraflulbenzene, 2.2',4,4#-tetrachlorobiphenyl and 1,! 1,5-trichlortriazine.

Generally, polar solvents that are sufficient to dissolve one organic and inorganic reactant 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 can 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, which are defined as lactams in the present case, additionally contain an alkyl group having 1 to 6 carbon atoms on the nitrogen atom.

Examples of suitable solvents are %M, N'-(/methylacetoamyl, M, Ml-diethylacetoanod, M,
N',-diglobylacetamide, H, M1. t/Methylbenzoic acid amide, caprolactam% y-Methylcaglolactam, N-ethylcaglolactam, N-isoglopylcactam% N-yne! Circaglolactam, N
- Probylcaglolactam, N-Butylcaglolactam, Summer - Cyclohexylcaglolactam, N-Methyl-2
-pyrrolidone, N-ethyl-2-pyrrolidone, M-isopropyl-2-pyrrolidone-N-imbutyl-2-pyrrolidone, N-zolobyl-2-pyrrolidof-pyrrolidone, N-cyclohexyl-2-pyrrolid 7%
N-1+-5-methyl-2-pyrrolidone 1N-cyclohexyl-2-pyrrolidone, N-methyl-5-methyl-
2-humantfflJton, N-methyl-3,4.5-)dimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, X-isopropyl-2
-Piperidone% N-isobutyl-piperidone, N-
Methyl-6-methyl-2-piperidone s”-1f-5
-ethyl-2-piperidone 1W-methyl-2-oxo-
Hexamethyleneimine and Fuki-ethyl-2-oxo-hexamethyleneimine.

Mixtures of the abovementioned solvents can also be used.

The condensation reaction temperature is generally from 160 to 300°C, preferably from 200 to 285°C.The reaction time is up to 10 hours, but preferably from 12 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.

The dihalonobenzene and the hyalkali metal sulfide are reacted in equimolar amounts as far as possible.

Therefore, the molar ratio of zohalonepenzene/alkali metal sulfuric acid V is preferably in the range of Fi[L95:1 to t05:1. However, the sound (L85:1~t15
: You can use Jin that extends to a range of 1.

The polyhaloaromatics of the formula (III) which can be used according to the invention may be present in amounts up to a few molar based on the moiety of dihalo-nobenzene, depending on the reaction conditions, or together with p-zohalo-nobenzene. Although it can be added separately, generally 1 to 2.4 mol-1 cL to the dacha 1:Ir nobenzene, preferably α4-z.

・The molar ratio is sufficient.

The amount of solvent can be selected within wide limits but is generally from 2 to 15 moles per mole of alkali metal sulfide.

Treatment of the reaction mixture can be carried out in various ways.

The polyarylene sulfite can be separated off from the reaction solution by conventional methods, such as filtration or centrifugation, directly or after addition of water, for example.

Filtration is generally followed by a water wash to remove inorganic components such as alkali metal sulfides and alkali metal chloride V that may be attached to the monopolymer.

In addition to this washing, it is of course also possible to carry out washing or extraction with other washing liquids.

Polymers can also be prepared by removing the solvent from the reaction space and washing as described above.

The polyarylene sulfuric acid according to the invention can be prepared by adding one other polymer, a pigment and a filler, such as graphite, to a metal powder.
Glass powder may be mixed with ground quartz or glass fibers or polyarylene sulfide with customary additives, such as customary stabilizers or mold release agents.

Generally, the melt fluidity of 4-arylene sulfide is
Measured at 516° C. using a 15-mm weight according to Te M12!58-70 and expressed in %t/10 min.

However, in the case of high melting indexes, this measurement becomes problematic due to the high flow rate of the polymer melt.

Therefore, the melt viscosity % m (pas) of the % polymer melt is -
With the help of Instron rotational viscometer 1 shear force y (pm
) was determined at 306°C.

In the case of this method, the melt viscosity is 10-1 to 10? pa,s
can be measured accurately within a very wide range. In the case of an instrumental viscometer, the polymer is melted between a fixed grate 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. An S 2501j viscometer from Instrument Ron was used: 2 cone and plate diameters.

The melt viscosity measured at shear force τ=10”l)a is shown.

In the present invention, p-polyarylene sulfide has KTh immediately after separation from the reaction mixture, and general K(L5X10'~
5X10'l)! L@11 and above, preferably t
, with a melt viscosity of 5X10m~1 (1'paes), which can be directly processed by extrusion, injection molding or other conventional processing methods to produce automobile parts, armatures, electronics) by conventional methods. o Two engineering parts such as switches, electrical nozzles 1 Chemical resistant parts and equipment such as pump howling and pump impellers - Etching Blood leakage 1 Sealing washers 1 Office equipment and communication equipment parts, household goods, pulp % - You can make bearing parts, etc.

Example 1 This example is based on U.S. patent 'l, s, s
54°129 is described.

Sodium sulfide trihydrate 129F (Na, equivalent to 111 mol) and N-methyl-2-pyrrolidone 300f were placed in an autoclave equipped with a stirrer. The mixture was flushed with nitrogen and warmed to 202°C. During this operation, a total of 10 - of water was discharged. The mixture was then cooled to about 160°C and N-methyl-2-
Pirridone approx. 5 or medium p-Zokuda Rubenzene 147F (
e1 mol) was added. The reaction mixture with an initial pressure of nitrogen 2
．． Warm to 245° C. over 50 minutes under 5 pearls and maintain this temperature for 3 hours. After the mixture was cooled to room temperature, a gray solid was separated and carefully washed with water to remove any inorganic components.

The product was dried under vacuum at 80° C. to give poly P-7 ethylene sulfide 1oα3F (93%) with the following properties:
Obtained: Melt viscosity + 711 = 45 pl@.

At (τ=IO”P), thermoplastic processing was not possible without curing.

Example 2 Sodium sulfide hydrate 19t4F (t455 mol) and sodium sulfide hydrate (N&tBOs@
7 ft to) 1 & 9 F (5 moles vI relative to the moles of sodium sulfide) and a suitable amount of sodium hydroxide to neutralize the sodium hydrogen sulfide contained in the mixture, are first added to N-methylpyrrolidone. 50
It was introduced during 0f. When the mixture is slowly heated to 175°C, a distillate containing mainly water is produced.
I got a score of 0-.

Then N-methylpyrroliV7p-t/'chlorobenzene 22 a 5 f (1,50 mol) and 1,2.4-
After a total addition of 2.72 f (1005 moles) of trichlorobenzene and addition of the autoclave, the reaction mixture was brought to 200-270 DEG C. over a period of 90 minutes and maintained at this temperature for 20 minutes.

After the reaction was completed, the autoclay was cooled to 150° C., the pressure was released, and the reaction mixture was taken out. The produced p-polyphenylene sulfur P was separated, and the salts adhering to it were carefully removed with water. After drying, the % p-polyphenylene sulfide was isolated as an off-white solid. Melt viscosity also = 1450 pa-a (rz 10” I)a)*
Example 5 According to Example 2 except using 10 mol of sodium sulfide hydrate, melt viscosity also = 18001) ILφ
(τ Engineering 10 Tomi Pa).

Example 4 1.2.4-) Lichlorpe/Zen&54t (α0195
ft* ftj melt viscosity η, = 2200 pa-s (rz1o”pa) according to Example 2, except using

Example 5 Example 2 was followed except that 20 mol of sodium sulfide hydrate was used. Melt viscosity Vm=2550 p&am
(rx=10”pa).

Example 6 Potassium sulfite hydrate K180s・2H,02a
Example 2 was followed except that sr (10 ml 96 per mole of sodium sulfur V) was used.

Melt viscosity 1. x= 1900 paell (Tx=r
10"I")e%Ph1llips for comparison
Commercially available non-heat treated p-polyphenylene sulfy%R7tOn M from P@troleumaomp,
The melt viscosity of
a) was therefore substantially lower than the melt viscosity of p-polyphenylene sulfide described in the Examples of the invention.

The commercially available thermoplastically processable p-polyphenylene sulfide RytOn R4 from Phllillipa Petrol*um Oomp was probably obtained by further thermal post-treatment. Despite this further post-treatment, 1 this commercially available thermoplastically processable p-polyphenylene sulfide has inferior mechanical properties to the inventive p-polyphenylene sulfide, in which p-polyphenylene sulfide is obtained directly in one step. (See Table 1)
.

Claims (1)

[Claims] t, a) 50 to 100 moles corresponds to the formula ■ [in the formula, X is fluorine to bromine or Fiiodine] and D to 50- corresponds to the formula I has the same meaning as above, and R1 may be the same or different, and hydrogen to 0, ~ 0 snow,
Alkyl%O,,aR・cycloalkyl-06~0 snow 4
Aryl 101~0 snow 4 alkaryl or 0. ~0 Aralkyl and/or the two groups R1 can be linked to form an aromatic or heterocyclic ring, and at least one group R1 is always different from hydrogen]K equivalent f zohalo-nobenzene b) α1 to 2.4 mole for zohalo-nobenzene, formula ■ murXn 0. H,, (II) [wherein, m r
is an aromatic or pericyclic group having 6 to 24 carbon atoms and at least 3 free valences, X is as defined above) 1 and n are 5 or 4. mr aromatic compound and C) alkali metal sulfide are reacted in d) a polar solvent, provided that the molar ratio of a) to C) is α85:1 ~
The range KTo of t15:1 and the molar ratio of C) to d) is 1
:2 to 1:15, the polycondensation time is up to 10 hours, and the polycondensation temperature is maintained at 160 to 300°C,
Then, the reaction was carried out with 2 to 3
1. A method for producing a high molecular weight branched polyarylene sulfide, which is carried out in the presence of 0 mol-0 alkali metal sulfide and/or alkaline earth metal sulfide. 2. The process according to claim 1, using p-dichlorobenzene or p-dibromobenzene as component a).
2. The method according to claim 1, which uses the polyhalo aromatic compound of (2). Table 1. The method according to claim 1, wherein 2 to 30 mol of sodium sulfide or potassium sulfide is used per alkali metal sulfur V. 5. The method according to claim 1, wherein 2cutam and/or ami-V in which nitrogen is completely alkylated is used as a solvent.