JPS5876423A - Preparation of polysulfide carbonate - Google Patents

Abstract

PURPOSE:To obtain the titled resin having a high molecular weight safely and easily, by reacting a dihydroxysulfide compound with a compound having an N, N'-carbonyl bond as a esterifying agent. CONSTITUTION:(A) A dihydroxysulfide compound e.g. 4,4'-dihydroxydiphenyl sulfone, is reacted with (B) a compound having an N,N'-carbonyl bond preferably in an equimolar amount. For example, a mixture of the compounds (A) and (B) with a solvent, e.g. tetrahydrofuran or pyridine, is subjected to the solution polymerization at room temperature -70 deg.C under stirring, and then heated to distill away the solvent and by-product, or subjected to the mass polymerization at 200-280 deg.C and 30-0.1mm.Hg vacuum degree for some ten hours to give the aimed titled resin. EFFECT:The method is hygienic due to neither toxic phosgen to be used nor formation of hydrogen chloride gas. The reaction by-products are easily removed.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polysulfide carbonate, and more specifically, the present invention relates to a method for producing polysulfide carbonate, which has excellent properties such as impact resistance, heat resistance, crack resistance, weather resistance, and chemical resistance. This invention relates to a new and simple manufacturing method.

Conventionally, the following solution polymerization method is known as a method for producing polysulfide carbonate resin. That is, it is produced by allowing phosgene (COCJ?2) 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 a typical dihydroxydiaryl sulfide compound represented by the following formula %, into a halogenated hydrocarbon treated with an alkali such as sodium hydroxide treated methylene chloride, or For example, phosgene (C
OClt) is injected in gaseous form. This reaction is thought to proceed as shown in the following equation.

The polysulfide carbonate produced by the above reaction has a relatively low molecular weight, and it is difficult to obtain a high molecular weight product with excellent physicochemical properties. In addition to using phosgene, which is a highly poisonous gas, as a raw material, hydrogen chloride gas is produced as a by-product of the reaction. Therefore, countermeasures against poisonous gases, treatment of unreacted phosgene, prevention of corrosion of equipment due to hydrogen chloride, and removal of hydrogen chloride using alkali. There is a problem in that a desalination step, etc. after the drying process is required. Furthermore, the complexity of the polymerization reaction due to the heterogeneous interfacial polymerization of gaseous phosgene and a solution, and the processing required after the reaction is completed, such as removal of the solvent, drying of the cage, purification, solidification, etc. There are problems such as it being difficult to obtain.

The reason why polysulfide carbonate has hardly been put into practical use until now, even though it has the excellent properties mentioned above (heat resistance, chemical resistance, weather resistance, impact resistance, etc.) This is because it has the problems listed above.

The present invention was made to solve these problems, and its purpose is to provide a safe and simple method for producing polysulfide carbonate having a high molecular weight.

Under such circumstances, the present inventors have conducted various studies and have come up with the idea of using a compound having an N,N'-carbonyl bond as a substitute for phosge/, and have completed the present invention. Ta.

That is, the method for producing polysulfide carbonate of the present invention is characterized by reacting a dihydroxysulfide compound and 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 the mineral solution electrolysis method as well as the conventional method, and can also employ the bulk polymerization method.

In the hot tub polymerization method, for example, the following method can be employed. That is, first, a mixture consisting of a dihydroxysulfide compound, a compound having an N,N'-carbonyl bond, and a solvent was stirred at room temperature to make it homogeneous, and then gradually heated to about 50 to 70°C.
Continue stirring for 0-6.0 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.

After further reducing the pressure to 3G to 0.1 mIHl and distilling off the reaction by-products, the reaction is continued by heating to 2G and 0 to 280°C with stirring to obtain a high molecular weight polysulfide carbonate.

(9) When using the bulk polymerization method, for example, a dihydroxinal 7-idized metal compound and an N,N'-carbonyl compound are mixed, and 2.0 to 3.
After reacting for 0 hours and completely melting, the temperature is gradually raised and pressure reduction is started. And furthermore, the temperature is 200-28
By continuing the reaction at 0° C. and a vacuum degree of 30 to 0 J-0 for more than ten hours, p high molecular weight polysulfide carbonate is obtained.

In any of the above-mentioned polymerization methods, it is preferable that the dihydroxysulfide compound used and the metal compound having an N,N'-carbonyl bond be used in an isotropic amount.

Since the reaction by-products, the heterocyclic compounds having nitrogen as ring members, produced in the production method of the present invention are all solid at room temperature, they can be removed from the reaction system by sublimation and distillation under reduced pressure. It is something to do.

The dihydroxy sulfide compound used in the present invention includes the following general formula CI) (wherein R11 &, R
s and circles may be the same or different and represent a hydrogen atom, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a nitro group, and n is , 0 or 1 ◎) and the following general formula (1) % formula % (1) (wherein 8 and R' may be the same or different) Dihydroxydialkyl sulfide compounds are often mentioned (representing an alkyl group having 1 to 4 carbon atoms, where n is 1).

As a diaryl sulfide compound,
For example, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3-nitrodiphenyl nalfide, 4,4'-dihydroxy-3,3/-dinitoditzeel sulfide, 4,4'-dihydroxy-3 -Methyl diphenyl sulfide, s, s'-dioxidiphenyl sulfide, 3,4'-dihydroxydiphenyl sulfide, 3,3'-dihydroxydiphenyl sulfide, 3,3'-dihydroxydiphenyl sulfide
-4,4'-cinitrodiphenylsaldihydroxydiphenyl disulfide, 4,4'-dihydroxy-3
-Disulfide compounds such as Nitota diphenyl disulfide, 4,4'-dihydroxy-3,3'-dinitrodi7el disulfide, 3,3'-dihydroxy-4,4'-dinitrodiphenyl disulfide, etc. Can be mentioned. Examples of dihydroxydialkyl sulfide compounds include di(hydroxymethyl) sulfide, di(human tetraxyethyl) sulfide, di(hydroxypropyl) sulfide, dihydroxy-ethylmethyl sulfide, dihydro-tetraxymethylpropyl sulfide, and dihydroxy-ethylpropyl sulfide. Examples include vir sulfide, and one or more selected from the above-mentioned dihydroxy sulfide compounds are used.

Any compound having a bond can be used, especially %O having a heterocyclic group having nitrogen as a ring member.
is preferable. Examples of darkening compounds include N,N'-carbonyl-dazole, N,N'-
Carboeludipyrrole, N,N'-*rubonyludipyrrole, N,N'-1yrubonyludiindole, N,N'-*rubonyludipendazole, N,
N'-carbonyl-dibenztriazole, N,N'-
carbonyl-dibrin, N,N'-carbonyl-dipiperidine, N,N'-carbonyl-digutthiazine, N,
N'-carbonyl-dibutetraphosphorus, N,N'-carpoerudipidzole, N,N'-carpoerudivireridine, N,N'-carbonyl-dibipurine, N,N'-
Examples include carbonyl-di'2-bi-tetralidone, and one or more selected ones from the group consisting of these are used.

The solvent used in the 0*m heavy feeding method of the present invention includes the above-mentioned dihydroxysulfide compound and/or N, N
'Any substance can be used as long as it dissolves the compound having a Karl bond, such as heterocyclic compounds such as tetrahydrofuran (THF), pyridine, sulfolane, dioxane, tetrahydrothiophene, or methylene chloride. , halogenated hydrocarbons having 1 to 3 carbon atoms such as ethylene chloride, 1,1-dichloroethylene, trichlorethane, carbon tetrachloride, trichloroethylene, bromoethane, etc., and nine selected from the group consisting of these. One or more types may be used.

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

The method of the present invention for producing polysulfide carbonate from a metal compound having an N,N'-carbonyl bond and a dihydrotetraxysulfide compound, which has the advantages listed above, has various characteristics as shown below. be.

(1) Since non-toxic compounds are used, there is no need to worry about environmental pollution. There is no need for rounding or countermeasures against poisonous gases, and the reaction equipment can be relatively simple.

0) The raw material is solid, easy to handle, and T
The reaction proceeds uniformly in a solvent such as HF, pyridine, or a hydrocarbon-based solvent, and the resulting polysulfide carbonate is not homogeneous.

(3) The heterocyclic compound, which is a reactant, is a colorless solid, so it can be easily separated from the polysulfide carbonate resin, and it contains N.

Since N'-L is a raw material for a compound having an L bond, a recycling mechanism can be set up.

0) Since no hydrogen chloride gas is generated, alkali treatment and desalination steps can be omitted, and there is no risk of corrosion due to hydrogen chloride gas, allowing for shutdown of processes and equipment.

The polysulfide carbonate obtained by the production method of the present invention having the above-mentioned characteristics can be expected to have various uses by utilizing its properties.
! i! I will clarify.

Example 1 4.4'-dihydroxydiphenylsulfone 48N,
N,N'-carbonyl-diimidazole 36jF was added, and THF 50 Ii was further added as a solvent, followed by stirring at room temperature. After the solution became homogeneous, the temperature was gradually raised, and THF was distilled out at 66°C, yielding a viscous solid solution. Next, the pressure was reduced to about 30 ml, and the temperature was gradually raised to about 70° C., at which point distillation of imidazole started.

Further, the temperature was continued to be raised for nine more times, and no imidazole was distilled out at about 120° C., and a liquid with high viscosity was obtained. Subsequently, when the mixture was heated under reduced pressure for 4 hours, stirring became impossible and a highly viscous polysulfide carbonate resin that was solid at room temperature was obtained.

When the viscosity of this polysulfide carbonate resin was measured using an Ubbelohde viscometer (solvent: methylene chloride), the specific viscosity was 0.76 (average molecular weight approximately 1).
2,000).

Further, when the above resin was subjected to IR subexyl and elemental analysis, it was confirmed that the resin contained sulfide and carbonate bonds.

4. 40 g of N,N'-carbonyl-triazole was added to 52 jl of 4'-dihydroxy-3,3'-dinitrodiphenyl sulfide, and 5s of THF was added as a solvent.
When I was added and the same operation as in Example 1 was performed, a highly viscous substance was obtained.

When the viscosity of this substance was measured in the same manner as in Example 1, the specific viscosity was 0.77 (average molecular weight approximately 13.0
00).

Furthermore, the resin obtained above was cured together with a conventional polycarbonate resin to prepare a test piece.
Its chemical resistance (acetone, THF.

Judgment after immersion in methanol solvent at 75°C for 30 days) and heat resistance (heat distortion temperature -! 1 g G'C)
[Stress 18.6 kll/cd)] was tested and it was confirmed that there was almost no change in the product of the present invention compared to before the test, and it was significantly superior to the conventional product. Ta.

4. Add N,N'-diigidazole 501 to 100 I of 4'-dichlorodiphenyl sulfide, and add dehydrated tetrahydro 7 run (T
HF) 1 o MI was added dropwise and stirred until a homogeneous solution was obtained. After that, gradually warm it up to 65% over about 60 minutes.
When the temperature was raised to ℃, THF gradually began to distill out.

Further, stirring was continued for about 100 minutes at 65°C, and when THF stopped distilling out, sulfolane (bp: 2
60°C) was gradually added dropwise. After dropping sulfolane over about 1 second, the temperature was raised to 150° C. over about 150 minutes, and a portion of sulfolane and imidazole began to distill out. When the pressure was reduced to approximately 50 to 2 x 10-"wrHI, imidazole and sulfolane distilled out in a short time, leaving a viscous liquid behind. Further, when heating and stirring were continued, the viscosity decreased at 230°C. Since stirring became impossible due to the increase, heating was stopped.

The obtained high viscosity substance was subjected to viscosity measurement (solvent: N-methylpyrrolidone) in the same manner as in Example 1, and the specific viscosity was 1.02 (average molecular weight approximately 19.500).
When the structure of the above-mentioned polymeric material was identified by IR, elemental analysis, and NMR, it was confirmed that it was a polysulfide carbonate resin. In addition, hardening of materials that cause
When the solvent resistance of the material was investigated, it was confirmed that it was not attacked by organic solvents such as acetone and THF.

4.4'-Dihydroxy-3,3'-dimethoxy diphenyl sulfide 90 j' KN, N'-Carponyl dipyrazole 501 was added and the reaction was carried out in the same manner as in Example 3, and the specific viscosity was 1. A high molecular weight polysulfide carbonate resin having an average molecular weight of 0.01 (average molecular weight approximately 19,000) was obtained.

Claims (1)

[Claims] (1) S', Vt 7-ide compound in IPEI, and N
, a compound having an N'-car-nyl clamp.
m construction method. (The manufacturing method according to claim S, wherein the compound having an N, N'-1 l-1 nyl bond has a heterocyclic group containing nitrogen as a ring member. The manufacturing method according to claim 1, which is carried out legally. (4) In the solution polymerization method, a dihydroxy sulfide compound and a compound having an N,N'-car-nyl bond are first heated at room temperature. solution polymerization at about 70°C, then
4. The manufacturing method according to claim 3, which is carried out by heating and then distilling off the common medium and reaction by-products under reduced pressure. (5) The manufacturing method according to claim 1, wherein the reaction is carried out using a bulk polymerization method.