JPS5847026A - Production of aromatic sulfide polymer - Google Patents

Abstract

PURPOSE:To obtain the titled polymer at a high converssion, by reacting simple sulfur with a polyhalogen-substituted aromatic compound in the simultaneous presence of an alkali metal formate and a caustic alkali at a specified ratio in an organic solvent. CONSTITUTION:The titled polymer is produced by adding simple sulfur (A), a polyhalogen-substituted aromatic compound (B) (e.g., 1,4-dichlorobenzene), an alkali metal formate (c) (e.g., HCOONa) and a caustic alkali (e.g., NaOH) at a ratio (g. eq. ratio) of 1:0.8-1.2:0.8-1.5:1.3-2.5, in an organic solvent (e.g., hexamethylphosphoric triamide) and reacting the mixture at 100-300 deg.C. It is possible to carry out normal polymerization smoothly by removing excessive oxygen which is generated during the reaction and inhibits the polymerization by the use of component C as a reducing agent. It is also possible to decrease the amount of component C to about a half by the addition of component D, which converts the formed CO into component C.

Description

[Detailed description of the invention]

The present invention relates to a method for producing aromatic sulfide polymers using elemental sulfur as a sulfur source. l! Specifically, elemental sulfur, a polyhalogen-substituted aromatic compound having two or more halogen substituents, an alkali gold rj4 salt of formic acid as a reducing agent, and a strong alkali as a carbon dioxide gas scavenger are used. The present invention relates to a method for producing an aromatic sulfide polymer, which is characterized in that the aromatic sulfide polymer is simultaneously coexisted in an organic solvent at a certain ratio and allowed to react. In recent years, thermoplastic resins with high heat resistance have been increasingly required for mechanical parts and electronic equipment parts, and aromatic sulfide polymers are one of the resins that can meet this demand. In the production method of aromatic sulfide polymer, sulfur raw material,
As a manufacturing method using sulfur, which is the cheapest as it is, as the main raw material, the following is disclosed. Namely, ■ Elemental sulfur, dichlorpeneze/and one inorganic group (
A method of simultaneously melting and reacting mainly N(lcO8) without a solvent (U.S. Patent No. 2515188, U.S. Patent No. 2
No. 558,941) and (2) a method in which elemental sulfur, dichlorobenzene and an inorganic base (mainly Nσ2COI) are reacted in a polar solvent (US Pat. No. 5,878,176). In both of these methods, excess oxygen is stoichiometrically expressed as shown in the above formula.

The fact that [0] is generated is K. (Here, X, Ar and M are each a halogen atom,
shall represent aromatic rings and alkali metals. ) This excess oxygen (0) causes a side reaction with sulfur atoms bonded to the ends or inside of the simple sulfur 1 polymer, or with hydrogen atoms bonded to the polymer or solvent molecules, such as oxidation reactions and hydrogen abstraction reactions. , condensation cyclization reactions, etc., and further accompanying reactions such as 52-order reactions, etc., are thought to occur, and as a result, smooth polymerization reactions are inhibited, and the polymer product becomes pitch-like and carbonized. Therefore, according to the conventional production method, the presence of this excess oxygen inhibits the normal polymerization reaction, so firstly, the polymerization yield is low (neglect and only a product with a low molecular weight can be obtained); In some cases, there are problems in that the polymer tends to become pitch-like or carbonized.As a result, it has been difficult to obtain a practical aromatic sulfide polymer from the viewpoint of physical properties. As a means of solving the drawbacks of this method, he discovered that by coexisting with an appropriate amount of reducing agent to remove excess oxygen and then carrying out the polymerization reaction, the polymerization reaction could proceed extremely quickly and smoothly. The present inventors first made the normal polymerization reaction proceed smoothly by reacting elemental sulfur, a borono-10-substituted aromatic compound, and an alkali metal formate as a reducing agent in an organic solvent. We have developed a method to synthesize group sulfide polymers. %・S+x・X-Ay-X+2aHcOOM4 +Ar
-8+3+ 2 WMX + auto + ncOt
+ acO Furthermore, the inventors found that the Cow produced in this method slightly hinders the increase in the yield of sulfur at the end of the stage of heavy production, and succeeded in controlling this effect by coexisting with an appropriate amount of acetic alkali. The main mechanism of the polymerization is presumed to be as follows. %-8+ n-X-AT-X + 2 f&-HCoo
M + 23 ・MOH→ +Ar-8%+ 2s・M
X+ 2rL-HzO+ a・MtcOi+ n・c. Excess oxygen can thus be removed as water, while the CO2 produced can be removed as carbonic acid 1. It is also thought that this small amount of water combines with the carbonate produced. Furthermore, the inventors have discovered that the alkali metal salt of formate (H
It has been discovered that the amount of alkali metal formate used can be reduced by half by recycling it. The present invention is based on these discoveries, and the polymerization mechanism is presumed to be as follows. ss + 5X-Ay -X + sHcOOM +
5 nMOH-* (-Ay-8+s+ 2 sMX
+2 aHzO+ nM2cOa or more, by using approximately 3 gram equivalents of alkali metal formate in combination with 1 gram equivalent of alkali metal formate, excess oxygen and generated CO2 can be reduced.
Harmful side reactions caused by this were prevented, and the amount of alkali metal formate was reduced, making it possible to efficiently produce aromatic sulfide polymers. Furthermore, since the water produced is a small amount, it hardly inhibits the reaction. Furthermore, a method for producing an aromatic swift polymer using NazS.9H10 as a sulfur raw material is also known. (U.S. Patent No. 5,554,129, U.S. Patent No. 39)
19177 etc.), in this method Na2f3*9H20
There are five problems in that the water of crystallization contained in the water must be removed. The present invention will be explained in detail below. As elemental sulfur, which is one of the raw materials for the polymerization method of the present invention, any of orthorhombic sulfur, monoclinic sulfur, or amorphous sulfur can be used. The polyhalogenated aromatic compound that can be used as a reaction starting material in the present invention is represented by the following formula. (A) (B) X is CI,
Halogen selected from the group consisting of By, I or F, especially CI and By. Y is selected from the group consisting of -R, -OR and -Coo)i (R is selected from the group consisting of H, alkyl, cycloalkyl, aryl, aralkyl). ! selected from the group consisting of alkyl, aryl, aralkyl). In formula (A), m and l are each 2rFlt≦b. An integer of 0≦ru≦4. In formula (B), α and b are respectively 2≦α≦8゜0≦b≦
In the integer formula (C) of 6, c, d, g and f each satisfy 1≦C9d≦
5.0≦−1f≦4 integer. In formula (D)! , A, and Jo are each 1≦l. Mu≦5, 0≦1. An integer with ≦4. Preferred compounds of the above general formula are those containing 2 to 3 halogen atoms, and particularly preferred are those containing 2 to 3 halogen atoms.
It contains halogen atoms. Examples of polyhalogen-substituted aromatic compounds having the above general formula that can be used in the method of the present invention include the following. 1.4-')l lorbenzene, 1.3-dichlorobenzene, 2,5-dichlorotoluene, 1.4-cyfurombenzene1eSg5-trichlorobenzene, 1.4-dichloronaphthalene, 1-methoxy/- 2,5-dichlorobenzene, 4,4'-dichlorobiphenyl, 3,5-dichlorobenzene M, fragrance M, p. p'--,; l lordiphenyl ether, 3.5'
-dichlorodiphenylsulfone, 3,3'-dichlorodiphenylsulfoxide, 3,3'-dichlorodiphenylsulfone, etc. Chlorbenzene, 1,3.5
-Trichlorobenzene and 5,3'-dichlorodiphenylsulfone are preferably used. Alkali metal formate 1 as a reducing agent that is used as an excess oxygen scavenger when coexisting during the reaction, which is a feature of the present invention!
(expressed as HCOOM) is a neutral inorganic salt usually produced industrially by reacting CO with MOW (power alkaline). The alkali metals corresponding to MK in the chemical formula HCOOM include Li and N.
a, K or RA can be used. From an economic standpoint, Na is most preferred. In addition, R-COOM (
In the method of the present invention, a strong alkali is used to collect carbon dioxide gas produced during the reaction, and in particular, an alkali metal hydroxide of KLi, Nα, K or Rh. is preferred. Cα, M! ,
Although hydroxides or oxides of alkaline earth metals such as Bα are effective to some extent, they are not preferred because they may cause harmful side reactions such as reacting with raw material sulfur to form insoluble salts. Elemental sulfur is used as a medium for the polymerization reaction of the present invention. An organic solvent that can completely or partially dissolve a polyhalogen-substituted aromatic compound, an alkali metal salt of formic acid as a reducing agent, and a power alkali for ill gas collection, and which does not contain active hydrogen. is used. The solvent containing active hydrogen itself may inhibit polymerization, or the solvent generated by the reaction of active hydrogen may cause secondary harmful reactions. Organic solvents that can be used in the present invention include amides such as HMPA (hexamethylphosphoric triamide), NMP (N-methylpyrrolidone), TMU (tetramethylurea), and DMA (dimethylacetamide), and etherified polyethylenes such as polyethylene glycol dialkyl ether. Examples include glycol and sulfoxides such as tetramethylene sulfoxide. Among them, HMPA or NM
P has high chemical stability and is particularly preferred. The amount of organic solvent used in the reaction system in the polymerization method of the present invention is desirably within the range of 0.02 to 5 parts per 1 part of elemental sulfur (Durham). If the amount of solvent is more than this, the concentration of the reactant becomes too low, resulting in a significant decrease in the reaction rate, which is not desirable from an economic standpoint. On the other hand, if the amount of the solvent is less than this range, the dissolution of sulfur, formate, and alkali will be insufficient, and the smooth progress of the reaction may be significantly delayed. In the method of the present invention, the mutual charging ratio of elemental sulfur, polyno-10-substituted aromatic compound, alkali gold-11 formate salt as a reducing agent, and alkali as a carbon dioxide gas scavenger is Durham equivalent to 1 unit of elemental sulfur. and polyhalogen-substituted aromatic compound 0.8 to 1.2, preferably 0.9 to 1.1. Formic acid alkali metal salt Q, 8-15, preferably Q, 9-t2. The alkali is used in a ratio of 1.6 to 2.5, preferably 1.4 to t7 (however, alkali metal formate #A1 mol - 2
shall be calculated as gram equivalents). If it deviates from these mutual ranges, there is a possibility that the excess reaction raw material components will inhibit the normal polymerization reaction. caustic alkali i
A major feature of the present invention is that by using about 5 times the gram equivalent of alkali metal formate XtJI, the amount of alkali metal formate can be reduced relative to elemental sulfur. In particular, elemental sulfur, polyhalogen-substituted aromatic compounds, alkali metal salts of formate, and alkalis have a Durham equivalent of 1 s Q
, 9-t1: α9-1.2 + 14-t7 is preferred because the smoothest polymerization reaction is carried out. It is necessary that these four components coexist and react in the above-mentioned organic solvent in Waretani. By causing these reaction materials to coexist simultaneously, the reaction proceeds extremely quickly and smoothly. The polymerization reaction temperature is preferably within the range of 100 to 300°C. At temperatures below 100°C, the reaction rate is markedly reduced, which is unfavorable from an economical point of view, and at temperatures above 300°C, abnormal side reactions may occur in the solvent 1 polymer. Especially from 150
A temperature range of 280°C is preferred for smooth reaction. In the method of the present invention, a conventional polymerization method such as a patch method, two-batch method, or a continuous method can be used for the reaction. In addition, in a batch system, a split charging system can be used in which all reaction raw materials are charged in several batches at the same composition ratio. In the method of the present invention, an anhydride can be used as a reducing agent.Therefore, there is no need for any dehydration step as in the case of NaS・9H-0' The split charge method is a particularly effective means for controlling the reaction heat. It also has major advantages over the polymerization method, such as no energy or time required for dehydration. After the reaction is completed, the coalescence is usually recovered by adding a precipitant such as water, ether, halogenated hydrocarbon, aromatic or aliphatic hydrocarbon to the reaction mixture to precipitate the polymer and inorganic salts, and separating the polymer and inorganic salts. This can be done by washing with water and drying. Appropriate selection of polyhalogenated aromatic compounds. Polymers with branched molecules or copolymers containing two or more different reactive units can be obtained by combining them. For example, as a polyhalogenated aromatic compound as a reaction raw material,
If dichlorobenzene and some amount of trichlorobenzene are used in combination, a phenyl/sulfide polymer with branched molecules can be obtained. <Ittp, +S- when used in combination with y-dichlorolucifersulfone
A copolymer containing single unit ik1 can be obtained. Polymers obtained by the method of the present invention can be obtained using this technique.
It can be formed into a variety of useful articles using known forming techniques. Suitable molding methods include injection molding, pressure molding, single revolution extrusion molding, and similar molding methods. By curing these molded products after molding, they can be made into molded products with higher heat resistance. The polymer of the present invention may be filled with a powder filler such as carbon smoke, calcium carbonate powder, silica powder, titanium chloride powder, or a fibrous filler such as carbon fiber, glass fiber, asbestos, or polyaradide fiber. I can do it. The polymer of the present invention may be used in combination with one or more synthetic resins such as polycarbonate, polyphenylene oxide, polysulfone, polyarylene, polyacetal, polyelectrode, boriaelectrode, polyester, polyδ tyrene, and ABS. You can also. Examples 1 to 7 The polymerization reaction apparatus used was an autoclave made of 1O8 US304 with an internal volume of 300 cm and equipped with an electromagnetic stirrer. For polymerization, predetermined amounts of solvent and various reagents were charged into the autoclave, and the inside of the autoclave was heated with N! Completely replace with gas,
The reaction was carried out by heating to a predetermined temperature while stirring. After the reaction is completed, the autoclave is cooled and the reaction solution Ik* is added with water to precipitate the polymer, separated, and the resulting cake is washed 6 times with hot water and once with acetate, and once at 70°C. The polymer was recovered by drying. The polymerization yield is determined by the amount recovered.
・Calculated based on the amount of sulfur charged. Based on the above polymerization method, the raw material composition 2 reaction conditions were changed [The results of polymerization are summarized in Table 1 (Examples 1 to 2).
7). However, dichlorobenzene IkDcB,) dichlorobenzene TCB, N-medelvirolidone=kNMP. It was abbreviated as hexamethylphosphate triamide tHMPA. Further, the Durham equivalent number of the polyhalogenated aromatic compound is a value calculated based on the assumption that 1 mole/number of halogen substituents is 1 gram equivalent. Comparative Examples 1 to 4 Comparative Examples 1 to 4 corresponding to Example 1 are collectively shown in Table 2. The experimental conditions were the same as in Example 1 except for the charging composition. Comparative Example 1 is a case in which formic acid is not present, and the decomposition reaction also occurs and the yield is lower than in Example 1. In Comparative Examples 2 and 3, either no alkali was added or the amount added was insufficient, and the yields were low in both cases. Comparative Example 4 uses CHi/cooNa, which is a salt without reducing power, instead of formate, which is a reducing salt.
However, the yield is low. Procedural amendment January 21, 1980 Patent Application No. 144989 2, Title of invention Process for producing aromatic sulfide polymer 3, Relationship with the person making the amendment Case Applicant 4, Agent Tokyo Room A, 2-6-2 Marunouchi, Chiyoda-ku, Tokyo 401 Phone: 216-2588 (3297) Patent Attorney Takuo Adachi
. 5. Date of amendment order Showa year, month, day, 6.
Subject of amendment Contents of amendment (1) in Column 2 of Detailed Description of the Invention in the Specification, page 7 of the specification, line 2, “5 grams” rt
s-gram,” I correct it. 12>, the 15th member, line 15, “5x grams” is replaced with “
15x grams,” I corrected. that's all

Claims (5)

[Claims] (1), elemental sulfur, borino-rogen substituted aromatic compound,
Alkali metal salts of formic acid and alkali, 110.8
-t2: 0.8-15: 15-2.5 (Durham equivalent ratio) coexist simultaneously in an organic solvent, and 100
A method for producing an aromatic sulfide polymer, characterized in that the reaction is carried out at a temperature of ~300°C. (2), elemental sulfur, borino-rogen substituted aromatic compound,
Alkali metal salt of formic acid and alkali, 1:Q, 9
Production of an aromatic sulfide polymer according to claim 1, wherein the reaction is carried out at a ratio of ~1.1:0.9~t2:i, 4~t7 (Durham equivalent ratio) and at a temperature of 150~280°C. Method. (3), 110% organic solvent per gram equivalent of elemental sulfur
The method for producing an aromatic sulfide polymer according to claim 1 or 2, wherein 2 to 5 polymers are used. (4) A method for producing an aromatic sulfide polymer according to any one of claims 1 to 6, which uses sodium formate as the alkali gold salt of formic acid. (5) A method for producing an aromatic sulfide polymer according to any one of claims 1 to 4, wherein hydric soda is used as the hydric alkali.