JPS58154720A - Production of polysulfoxide carbonate - Google Patents

Abstract

PURPOSE:To produce the title polymer excellent in impact resistance, heat resistance, light fastness, chemical resistance, etc., without any environmental pollution, by reacting a dihydroxydiaryl-sulfoxide compound with a compound having an N, N'-carbonyl bond. CONSTITUTION:A dihydroxyidaryl sulfoxide compound (e.g., 4,4'-dihydroxy- diphenyl sulfoxide) is reacted with a compound having an N, N'-carbonyl bond, e.g., N, N'-carbonyldiimidazole. The use of compond B which has a reactivity equal to that of phosgene can eliminate countermeasures against toxicity and equipment corrosion caused by unreacted phosgene and hydrogen chloride gas formed and facilitate the production of a polysulfoxide carbonate excellent in cracking resistance, impact resistance, heat resistance, light fastness, chemical resistance, etc.

Description

[Detailed description of the invention] [Technical division to which the invention pertains] The present invention relates to a method for producing polysulfoxide carbonate, and particularly to a method for producing polysulfoxide carbonate, which has excellent properties such as crack resistance, impact resistance, heat resistance, light resistance, and chemical resistance. This invention relates to a new method for easily producing polysulfoxide carbonate having nine-dimensional properties.

[Technical background of the invention and its problems]

Polysulfoxide carbonate resins currently being produced experimentally are produced by the so-called solvent method shown below. This is a method of causing a reaction. Although the polysulfoxide carbonate polymer produced by this method has some of the superior properties of polysulfoxide carbonate, the method is limited to the production of relatively low molecular weight products and cannot produce high molecular weight products. It is difficult to obtain. Moreover, since the polymerization reaction is a heterogeneous interfacial polymerization, the reaction is complicated, and the steps after the reaction are extremely diverse, such as purification of the polymer, removal of the solvent, solidification of the polymer, and even drying. It is difficult to always obtain products of constant quality due to the various characteristics of polysulfoxide carbonate (
heat resistance, chemical resistance, weather resistance, mechanical properties, etc.) have not been fully utilized until now. Therefore, many methods have been proposed to improve these. That is, the method for producing polysulfoxide carbonate, conventionally called the solvent method, uses a typical dioxydiaryl sulfoxide-based organic compound, 4,4'-dio-xydiphenyl sulfoxide: p Ho-@-S-■- A method is used in which OH is dissolved in a solvent such as an alkaline halogenated hydrocarbon or a heterocyclic compound, and highly reactive phosgene (CoC72) is blown into the solution in gaseous form.This reaction is expressed by the following reaction formula ( It is thought that the process will proceed as shown in 1).

nHo-@-8-@ -OH+nC0Cj2 (The number of moles of n' (positive number) indicates the degree of polymerization in the case of polysulfoxide carbonate.) In the solvent method, phosgene, which is a highly poisonous gas, is Since hydrochloric acid gas is produced as a by-product as a reaction product, the needs are complex and diverse, such as countermeasures against poisonous gases, treatment of unreacted phosgene, countermeasures against corrosion of equipment due to hydrochloric acid, and desalination process for hydrochloric acid treatment. Furthermore, there were many extremely inconvenient manufacturing facilities.

[Purpose of the Invention] The present inventors have focused on this point and, as a result of various studies, have developed a completely new idea by using an antimetal material equivalent to phosgene in place of phosgene, thereby improving the above-mentioned drawbacks of the solvent method and handling the compost. The aim is to easily produce improved polysulfoxide carbonates without post-processing problems or pollution.

[All of the Inventions] That is, the present invention relates to a method for producing siborisulfoxide carbonate by reacting a dioxydiarylsulfoxide compound with a compound having an N,N'-carbonyl bond.

The dioxydiaryl sulfoxide that can be used in the present invention is not limited to the above-mentioned 4,4'-dioxydiphenyl sulfoxide; for example,
4. l-Dioxy-3,3'-dichlorodiphenyl sulfoxide, 4,4'-dioxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dioxy-
τ-Bromodiphenylsulfoxide, 4,4'-dihydroxy-3,3', 5,5'-tetrachlorodiphenylsulfoxide, 3,3'-dioxydiphenylsulfoxide, 3,3'-dioxy- 4,1-diethyldiphenyl sulfoxide, 3,3'-dioxy-2,2'-dibromsulfoxide, 3,3'-
Examples include diphenyl-4-chloro-4'-methylsulfoquinide.

Further, compounds having the same properties as phosgene that can be used in the present invention include, as specific examples, N,N'-carbonyludimidazur, N,N'-carbonyludivirol,
N,N'-carbonyl-citriasol, N,N'-
Carbonyl-diindole, N,N'-carbonyl-dibenzifdazole, N,N'-carbonyl-dibenztriazole, N,N'-carbonyldibrin, N,
N'-carbonyldibridine, N,N'-carponyl-diplatiazine, N,N'-carbonyl-dibroline, N,N'-carponyl-divirazole.

Examples include N,N'-dipyrrolidine, N,N'-carbonyldibrin, N,N'-carbonyl-2-pyrrolidone, and the like. However, the present invention is not limited to the above compounds (all compounds having an N,N'-carbonyl bond can be used).Compared to phosgene, these N,N'-carbonyl compounds have The N,N'-carbonyl compound having various characteristics extremely advantageous in the production of polysulfoxide carbonate as shown in Table 1 below is used, and dioxy as a reactant is used. In the present invention's synthesis method of polysulfoxide carbonate resin using diaryl sulfoxide, a petro compound is produced as a by-product along with polysulfo oxide carbonate. However, the by-product hetero compound is a colorless solid, and it cannot be synthesized from polysulfoxide carbonate resin. easy to separate, and N, N'
- Features include being able to be reused as a raw material for carbonyl compounds [Effects of the invention] As stated above, <9 synthesis methods using conventional phosgene (9)
Comparing the reaction formula (1)) with the synthesis method using the N,N'-carbonyl compound of the present invention, the superiority of the present invention is clarified as follows.

(1) Since there is no need to pollute the environment due to toxicity, there is no need for countermeasures against poisonous gases, and a relatively simple reaction device is sufficient.

(2) Since it is a solid and easy to handle, homogeneous reactions can be carried out in a medium such as pyridine, hydrogen chloride, etc., and the synthesized polycarbonate becomes homogeneous. And transesterification method, which is a solvent-free synthesis method, can be applied.

(3) The heterocyclic compound as a by-product is easy to recover, and N,
Becomes a raw material for N'-carbonyl compounds and is recycled (4)
Since no hydrochloric acid gas is generated, hydrochloric acid + alkali → desalination process can be omitted, and there is no risk of corrosion due to hydrochloric acid gas, making it possible to reduce manufacturing costs. There are many ripple effects, or benefits, such as the benefits of modifying polycarbonate.

[Embodiments of the invention]

The superior modifications of the present invention to these roses will be explained below with reference to Examples.

Example 1゜4.4'-dihydroxydiphenyl sulfoxide 4
7 g K pyridine (medium II) 1051! was added, and a solution of Ag N,N'-carbonyl-diimidazole dissolved in 80 g of pyridine was added dropwise over 1 minute to the stirred solution. After the mixed solution was equalized and the temperature was raised to a certain temperature, the pyridine solvent began to distill out and a viscous liquid remained after 150 minutes. At this point, when the vacuum It was turned off and the temperature was increased to 150° C., distillation of imidazole started and the distillation was completely stopped at 150°C. Further 250°0
After several hours of stirring, stirring became difficult, so the reaction was stopped and the temperature was gradually returned to normal pressure and room temperature. Since a highly viscous polymer was obtained in the reaction vessel, the viscosity was measured and a highly viscous polysulfoxide carbonate with a specific viscosity of 91.02 (N-methylpyrrolidone) was obtained.

Example 2 52 g of 4.4'-dihydroxy-3,3-dimethyl-diphenyl sulfoxide and 12 pyridine (II medium)
og and N,N'-carbonyl- in the same manner as in Example 1.
When 40 g of triazole was added and the same operation was performed, a highly viscous polymer was obtained after the triazole was distilled out. When the viscosity of this substance was measured, it was found to be a highly viscous polymer with a specific viscosity of 0.98. there were. When the melting point was measured, it was found to be as high as 190°C, indicating that it has excellent heat resistance. At the same time, chemical resistance and light resistance tests were conducted, and it was found that these properties were significantly superior to conventional polycarbonate.

Claims (1)

[Claims] A method for producing polysulfoxide carbonate, which comprises reacting a dioxysulfoxide compound with a compound having an N,N'-carbonyl bond.