JPS601226A - Production of polyketone sulfide carbonate - Google Patents

Abstract

PURPOSE:To produce the titled high-MW polymer of excellent heat resistance safely and simply, by adding a specified compound to a dihydroxy sulfied compound and reacting the mixture with an N,N'-carbonyl compound. CONSTITUTION:The titled polymer is produced by reacting a mixture of (A) a dihydroxy sulfide compound (e.g., 4,4'-dihydroxy-diphenyl sulfied) and (B) a dihydroxy ketone compound (e.g., 4,4'-dihydroxydiphneyl ketone) with (C) a compound having an N,N'-carbonyl bond (e.g., N,N'-carbonyldiimidazole). Conventionally, phosgene is reacted with compound A, but there are problems of toxicity and corrosiveness, and no stable product can be obtained. The use of compound C and the addition of component B having a ketone skeleton having a strong interaction with a sulfide make it possible to obtain the titled high-MW polymer of excellent heat resistance without a problem of toxicity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical field to which the invention pertains] 1. The present invention relates to a method for producing polyketone sulfide carbonate, and more particularly, to a method for producing polyketone sulfide carbonate.

The present invention relates to a new and simple method for producing polyketone sulfide carbonate, which has excellent properties such as heat resistance, crack resistance, weather resistance, and chemical resistance.

[Prior art and its problems]

Conventionally, as a method for producing polyketone sulfide carbonate resin, the solution lid method shown in the following is known. That is, it is produced by allowing phosgene (cocz) to act as an esterifying agent on a mixture of a dihydroxydiaryl sulfide compound and a solvent. This production method involves converting 4,4'-dihydroxydiphenyl sulfide, which is represented by the typical linear formula % as a dihydroxydiaryl sulfide compound, into a halogenated hydrocarbon or a halogenated hydrocarbon treated with an alkali such as sodium hydroxide treated methylene chloride.

For example, 1 is dissolved in a solvent such as a heterocyclic compound such as tetrahydrofuran (THF) or pyridine, and highly reactive phosgene (Co(J2)) is blown into the solution in gaseous form.This reaction is expressed by the linear equation It is thought that the process will proceed as follows.

The polysulfide carbonate produced by the above reaction has a relatively low molecular weight, and it is difficult to obtain a high molecular weight carbonate with excellent physicochemical properties. In addition, since phosgene, which is a highly poisonous gas, is used as a raw material and hydrogen chloride gas is produced as a by-product of the reaction, it is necessary to take measures against poisonous gases, treat unreacted phosgene, and prevent corrosion of equipment due to hydrogen chloride.

There is a problem in that a desalination step and the like are required after hydrogen chloride removal treatment using an alkali. Furthermore, the complexity of the polymerization reaction due to the heterogeneous interfacial polymerization of gaseous phosgene and sweat/liquid, and the removal of the solvent.

Since there are various processing steps such as drying, purification, and solidification of the polymer after the reaction is completed, there are problems such as difficulty in obtaining a product with stable quality. Furthermore, the synthesized P8dC has high crystallinity and undergoes a phase transition (crystallization), becomes polycrystalline and becomes brittle, and at the same time its heat resistance properties are significantly impaired due to its low glass transition point. polysulfide carbonate.

Even though it has the excellent performance mentioned above (rigidity, side weatherability - side impact resistance, etc.), it has rarely been put to practical use until now. This is because it has the problems listed above.

[Purpose of the invention]

The present invention was made to solve these problems, and its purpose is to provide a safe and simple method.

It is an object of the present invention to provide a method for producing polyketone sulfide carbonate having a polymer W having excellent heat resistance. As a result of various studies under such circumstances, the present inventors found that
We came up with the idea of using a compound with an N,N-carbonyl bond as a substitute for phosgene, and by adding a dihydroxydiphenylketone compound with a ketone skeleton that has a strong interaction with sulfides, we have achieved excellent heat resistance. The inventors came up with the idea of obtaining a carbonate with a certain amount of carbonate, and completed the present invention.

[Summary of the invention]

Namely, the method for producing polyketone sulfide carbonate of the present invention is characterized by reacting a dihydroxy sulfide compound and a dihydroxy ketone compound to form a compound having an N,N-carbonyl bond. Below, the manufacturing method of the present invention will be explained in more detail.

The production method of the present invention can employ a solution polymerization method like the conventional method, and can also employ a bulk polymerization method.

In the solution polymerization method, for example, it is possible to employ the following method. That is, first, a dihydroxysulfide compound, a dihydroxyketone compound, N, N''
A mixture consisting of a compound having a -carbonyl bond and a solvent is stirred at room temperature to make it homogeneous, then gradually warmed and continued stirring at about 50 to 70°C for 3.0 to 6.0 hours. Then, a solvent is added and the mixture is gradually heated, and the solvent and reaction by-products are removed while stirring is continued. Further 30-0.
After reducing the pressure to 1% Hg and distilling off 1 reaction by-product, under stirring,
When the reaction is continued by heating to 200 to 280°C, the desired high molecular weight polyketone sulfide carbonate is obtained.

In addition, in the case of bulk polymerization, for example, an N,N-carbonyl compound is mixed with a dihydroxysulfide compound and a dihydroxyketone compound, and a 70 to 100"O
The mixture was allowed to react for 2.0 to 8.0 hours with stirring, and after it was completely melted, the temperature was gradually lowered and pressure reduction started.

Furthermore, the temperature is 200 to 280°C, and the degree of vacuum is 30 to 0.
．． A high molecular weight polyketone sulfide carbonate can be obtained by continuing the reaction at one concentration of Hg for more than ten hours.

In any of the above-mentioned polymerization methods, the sum of the moles of the dihydroxysulfide compound and dihydroxyketone compound used and the compounding ratio of the compound having an N,N-carbonyl bond are approximately 1 molar, and the esterifying agent is It is preferable to use a large amount.

The multicyclic compounds having nitrogen ring members, which are byproducts of the first reaction produced in the production method of the present invention, are all solid at room temperature, so they can be removed from the first reaction system by sublimation under reduced pressure and distillation. It is something to remove.

Dihydroxysulf used in the present invention (wherein,
R1, R, 2, R, and R4 may be the same or different and each represents a hydrogen atom, ), a rogene atom, and a carbon atom number of 1 to
represents an alkyl group having 4 and a nitro group, and n is 0 or 1. ) and the following general formula [1) % formula % (1) (wherein R and R may be the same or different,
An alkyl group having 1 to 4 carbon atoms, n is
0 or 1. ) Dihydroxydialkyl sulfide compounds represented by:

As a dihydroxydiaryl sulfide compound, 1
For example, 4.4'-dihydroxydiphenyl sulfide, 4.4-dihydroxy-3-nitrodiphenyl sulfide, 4. 4-Shihi)”.

xy-3,3-dini-10 diphenyl sulfide.

4. Monosulfide compounds such as 4-dihydroxy-3-methyldiphenyl sulfide and 3,3-dihydroxydiphenyl sanitrodinoenyl sulfide;
4-dihydroxydiphenyl sulfide, 4.4-dihydroxy-3-nitrodiphenyl disulfide, 4
, 4-dihydroxy-3,3-dinitrodiphenyl disulfide, and 3,3'-dihydroxy-4,4-dinitrodiphenyl disulfide. In addition, as a dihydroxydialkyl sulfide compound, 1, for example, di(human tetraxymethyl)
sulfide, di(hominid xyethyl) sulfide,
Examples include di(hydroxypropyl) sulfide, dihydroxy-ethylmethyl sulfide, dihydomethylpropyl sulfide, dihydroxy-ethylpropyl sulfide, and one or more dihydroxy sulfide compounds selected from the above-mentioned dihydroxy sulfide compounds are used. . In addition, the dihydroxyketone compound used in the present invention has the following general formula (where R2, R, , and R4 may be the same or different; Number 1
4) and the following general formula (wherein R and R may be the same or different, and a carbon atom Examples include dihydroxydialkyl ketone compounds represented by (representing an alkyl group having numbers 1 to 4).

As a dihydroxydiarylketone compound.

For example, 4,4-dihydroxydiphenylketone.

4, 4-dihydroxy-3-nitrodiphenylketone, 4.4-dihydroxy-3,3-dinitrodiphenylketone, 4.4-dihydroxy-3-methyldiphenylketone, 3.3-dihydroquine diphenylketone, 3,
4-dihydroxydiphenylketone, 3.3-dihydroxydiphenylketone):/, 3.3'-di, doki, /-
Examples include benzophenone compounds such as 4.4'-di-resifnylketoy.

Further, as the dihydroxydialkyl ketone compound, for example, di(hydroxydimethyl)ketone.

Di(human tetraxydiethyl/l/)ketone, di(hydroxydipropyl)ketone, dihydroxy(ethyl).

methyl) ketone, dihydroxy(methyl, propy/I/
) ketone, dihydroxy (ethyl, propyl) ketone, etc., and one or more types selected from the above-mentioned dihydroxy ketone compounds are used.

Furthermore, any compound having an N,N-carbond used in the present invention can be used, and it is particularly preferable to use a compound having a heterocyclic group containing nitrogen as a ring member. Such compounds include 1, for example, N, N-
Carponyl-diimitasole, N,N-carbonyl-dipyrrole, N1bonyl-diindole, N,N-carponyl-dibenzimitasole, N,N-carbonyl-dibenztriazole, N,N-carbonyl- Jibrin,
J N-carbonyl-dibipericin, IN, iN-carbonyl-dibrathiazine, N,N'-carbonyl-dibroline, N,N-carbonyl-dipyrazole, N,N-
Carbonyludipyrrolidine, N.

2-pyrrolidone, etc., and one selected from the group consisting of these or 211i or more is used.

As the melt to be used in the solution polymerization method of the present invention, any material can be used as long as it dissolves the dihydroxy sulfide compound, dihydroxy ketone compound, and/or compound having an N,N-carbonyl bond. Yes, for example.

Multicyclic compounds such as tetrahydrofuran (THF), pyridine, sulfolane, dioxane, and tetrahydrothiophene, or methylene chloride, ethylene chloride:/, 1.
1-dichloroethylene, )! One or more types selected from the group consisting of 1 to 3 carbon atoms such as hydrogenated hydrocarbons such as ethane, carbon tetrachloride, trichloroethylene, and bromoethane. is used.

Further, as a further feature of the present invention, by using the carbonate esters shown below, the esterification reaction can be carried out extremely smoothly. The carbonate ester compounds include diphenyl carbonates such as diphenyl carbonate, 4-dihydroxydiphenyl carbonate, and 4.4-dimethyldiphenyl carbonate, dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and ethyl methyl carbonate, and phenyl methyl carbonate. ,? , -), acylphenyl carbonates such as phenylethyl carbonate.

Cyclic carbonates such as ethylene carbonate and propylene carbonate are included.

J scale or 2$ selected from the group consisting of these! i version is used.

〔Effect of the invention〕

The compound having an N,N-carbonyl bond used in the present invention has the characteristics shown in the following table in terms of polysulfide carbonate production, compared to phosgene.

The method of the present invention for producing polyketone sulfide carbonate from a dihydroxy compound and a compound having an N,N-carbonyl bond, which has the advantages described above, has various characteristics as shown below.

(1) Since non-toxic compounds are used, there is no need to worry about environmental pollution. Therefore, countermeasures against poisonous gases are not required, and a relatively simple reaction apparatus is sufficient.

(2) Since the raw material is solid, it is easy to handle, and the reaction proceeds uniformly in solvents such as ants, THF, pyridine, or halogenated hydrocarbons, and the resulting polyketone sulfide carbonate is also homogeneous. be.

(3) Since the heterocyclic compound, which is a reaction by-product, is a colorless solid, it can be easily separated from the polyketone sulfide carbonate resin.

Since it becomes a thick phase of a compound having an N-carbonyl bond, it is possible to set up a recycling mechanism.

(4) Since hydrogen chloride gas is not generated, alkali treatment and desalination steps can be omitted, and there is no risk of corrosion due to hydrogen chloride gas, allowing cost reductions in processes and equipment.

(5) The synthesized polymer has excellent heat resistance due to the interaction between carbonyl groups and sulfide groups.

The polyketone sulfide carbonate obtained by the production method of the present invention has the characteristics described above.

Various uses can be expected by utilizing its characteristics.

[Embodiments of the invention]

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 218g and 4,4-dihydroxydiphenylketone 21
4g of N,N-carbonyldiimidazole-325
Then, 100 g of dry tetrahydrofuran (THF) solvent was added as a solvent, and the mixture was stirred at room temperature. After the solution became homogeneous, it was gradually brought to the R edge, and at 67]
THF was distilled out and a viscous solid solution was obtained. Next, the pressure was reduced to about 50 mm) and the waste was gradually heated.
Distillation of imidapool started at around 80°C. When the temperature was further increased, almost no imidazole was distilled out at about 120° C., and a liquid with high viscosity was obtained. Subsequently, the degree of softening was increased (01/I-1 g), and when the mixture was heated for about 4 hours, stirring became impossible and a highly viscous polyketone sulfide carbonate resin which was solid at room temperature was obtained. Regarding such polyketone carbonate pine resin, viscosity measurement (solvent:
Methylene chloride) was conducted, and it was confirmed that it had a specific viscosity of 0.89 (average molecular weight approximately 17,000). Regarding the above resin, engineering R spectrum.

After conducting NMR spectrum and elemental analysis,
It was confirmed that it has a carbonyl bond, a carbonate bond, and a sulfide.

Example 2 250 g of methyl diphenyl ketone and 255 g of 4,4-dihydroxy 3% 3,5.5-tetramethyl diphenyl sulfide were added with N,N-carbonyl lyazole 4.
When the same procedure as in Example 1 was carried out by adding 09 g of diethyl carbonate and 100 g of diethyl carbonate as a solvent, a highly viscous substance was obtained.

When the viscosity of the substance with 7 ha was measured in the same manner as in Example 1, the specific viscosity was 0°76 (average molecular B approximately 1 (S,
000).

Further, the super fat obtained above was molded together with a conventional polycarbonate resin to prepare the following test pieces. The weather resistance (heat resistance) and heat resistance (thermal deformation severity - [stress 18.6 kg/cm]) of each test
As a result of the test, the product of the present invention showed the following results compared to before the test:
It was confirmed that there was almost no change, and it was significantly superior to conventional products.

240g of nylketone and 4,4-dihydroxy-2゜2-
N to 245 g of dichlorodiphenyl sulfide.

360 g of N-carbonyldiimidazole was added, followed by 100 g of dehydrated dimethyl carbonate, and the mixture was stirred until a homogeneous solution was obtained. After that, the same operation as in Example 1 was performed, and high-viscosity bone material was obtained.

When the viscosity of this substance was measured in the same manner as in Example 1, the specific viscosity was 0.66 (average molecular weight approximately 11.00
0).

The structure of the above-mentioned polymeric substance was identified by IJ elemental analysis and NMR, and it was confirmed that it was a polyketone sulfide carbonate resin. Furthermore, when we conducted a combustion test on this resin, it was found to have strong self-extinguishing properties, and was given a UI rating of ■.
It showed the highest flame retardancy of -0.

Claims (1)

Claims: (1) A method for producing polyketone sulfide carbonate, which comprises reacting a dihydroxy sulfide compound, a dihydroxy ketone compound, and a compound having an N,N-carbonyl bond. (2) A production method in which the molar ratio of the dihydroxysulfide compound to the dihydroxyketone compound is between 1.0 and 0.01. (5) A production method in which the reaction is carried out by a bulk polymerization method.