JPS59174622A - Preparation of polyketone carbonate - Google Patents

Abstract

PURPOSE:To prepare a polyketone carbonate having excellent impact strength and heat resistance, etc., safely and easily, by adding a compound having N,N'- carbonyl bond as an esterification agent to a dihydroxyketone compound. CONSTITUTION:A dihydroxyketone compound (e.g. 4,4'-dihydroxybenzophenone) is added with equimolar amount of a compound having N,N'-carbonyl bond (preferably a compound having a hetrocyclic group containing nitrogen atom as a ring member, e.g. N,N'-carbonyl-diimidazole), and the objective polyketone carbonate is obtained preferably by the solution polymerization or bulk polymerization of the mixture.

Description

[Detailed description of the invention] [Technical field to which the invention pertains] The present invention relates to a method for producing polyketone carbonate,
More specifically, the present invention relates to a new and simple method for producing polyketone carbonate having excellent properties such as impact resistance, heat resistance, crack resistance, and weather resistance.

[Technical Background of the Invention and its Problems] Conventionally, the following solution polymerization method has been known as a method for producing polyketone carbonate resin. That is, it is produced by allowing phosgene (COCl2) to act as an esterifying agent on a mixture of a dihydroxydiarylketone compound and a solvent. In this production method, 4,4'-dihydroxydiphenylketone represented by the following formula, which is a typical dihydroxydiarylketone compound, is treated with an alkali-treated halogenated hydrocarbon such as sodium hydroxide-treated methylene chloride, or , tetrahydrofuran (THF), a heterocyclic compound such as pyridine, etc., and phosgene (COCA!2), which is highly reactive, is blown into the solution in gaseous form. This reaction is thought to proceed as shown in the following equation.

The polyketone carbonate produced by the above reaction is
It 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.
There are problems in that it is necessary to treat unreacted phosgene, prevent corrosion of the equipment due to hydrogen chloride, and perform a desalination process after hydrogen chloride removal treatment using an alkali. Furthermore, the polymerization reaction is complex due to the heterogeneous interfacial polymerization of gaseous phosgene and a solution, and the processing steps after the reaction are diverse, such as removing the solvent, drying, purifying, and solidifying the polymer. from,
There are problems such as difficulty in obtaining products with stable quality.

Despite polyketone carbonate having the above-mentioned excellent properties (heat resistance, weather resistance, impact resistance, etc.), there are 1 reasons why it has hardly been put to practical use until now.
This is because it has the problems listed above.

[Object of the Invention] The present invention was made to solve these problems, and its purpose is to provide a safe and simple method for producing polyketone carbonate having a high molecular weight.

Under such circumstances, as a result of various studies, the present inventors came up with the idea of using a compound having an N,N'-carbonyl bond as a substitute for phosgene, and completed the present invention. .

[Summary of the Invention] That is, the method for producing polyketone carbonate of the present invention includes:
It is characterized by reacting a dihydroxyketone compound with 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, the following method can be employed. That is, first, a mixture consisting of a dihydroxyketone 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 a temperature of about 100°C to 3. 0-6
．． Continue stirring for 0 hours. Next, add solvent, gradually warm up, and continue stirring to remove solvent and reaction by-products. Further, the pressure is reduced to ~0.1 Hg to distill off the reaction by-products, and the reaction is continued by heating to 200-280°C with stirring to obtain the desired high molecular weight polyketone carbonate.

In addition, in the case of bulk polymerization, for example, a dihydroxyketone compound and an N,W-carbonyl compound are mixed,
React for 2.0 to 3.0 hours under stirring at 70 to 100°C, and after completely melting, gradually raise the temperature and start reducing pressure.
Vacuum degree 30-0. A high molecular weight polyketone carbonate is obtained by continuing the reaction at lllllHg for more than ten hours.

In any of the above-mentioned polymerization methods, it is preferable that the dihydroxyketone compound used and the compound having an N,N'-carbonyl bond be used in equimolar amounts.

The reaction by-products of the heterocyclic compounds produced in the production method 1 of the present invention, which have nitrogen as a ring member, are all solid at room temperature, so they can be removed from the reaction system by sublimation under reduced pressure. Dihydroxyketone used in the present invention (in the formula, 几1.几2.R3 and R4 may be the same or different and are hydrogen atoms) ・Rogen atom, carbon atom number 1 It represents a group selected from the group consisting of an alkyl group having ~4 and a nitro group. ) Dihydroxydialkyl ketone compounds shown in the following are exemplified.

Examples of dihydroxydiarylketone compounds include 4,4'-dihydroxydiphenylketone, 4,4'
~dihydroxy-3-nitrodiphenylkatone, 4
．． 4'-dihydroxy-3,3'-dinitrodiphenylketone, 4.4'-dihydroxy-3-methyldiphenylketone, 3. :('-dihydroxydiphenylketone, 3.4'-dihydroxydiphenylketone.

3, :(-dihydroxydiphenylketone, 3.3'
Examples of benzophenone compounds such as -dihydroxy-4,4'-dinitrodiphenyl ketone and dihydroxydialkyl ketone compounds include di(hydroxydimethyl)ketone, di(hydroxydiethyl)ketone, di(hydroxydipropyl)ketone, dihydroxy (Ethyl, methyl) ketone, dihydroquine (methyl, propyl) ketone, dihydroxy (ethyl, propyl) ketone, etc. Are the dihydroxyketone compounds mentioned above selected? 1 type also works 2 fl! The above are used. Furthermore, the compounds having an N,N'-carbonyl bond used in the present invention include ',N-1-K
Any compound having a bond 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, for example, N,N'-carbonyl-diimidazole, N,N
'-Carponyl divirol, N,N'-carbonyl-ditriazole, N,N'-carbonyl-diindole, N,N'-carbonyl-dibenzimidazole,
N,N'-carbonyl-dibenztriazole, N,N
'-Carbonyl-dibrin, N,N'-carbonyl-dibiberidine, N,N'-carbonyl-dibrathiazine, N,N'-carbonyl-dibroline, N,N'-carbonyl-divirazole, N, N'-Carponyl Divirolidine, N, N'-Carponyl Divirolidine, N
, N'-carbonyl-di-2-pyrrolidone, etc., and one or more kinds obtained from the group consisting of these are used.

As the solvent used in the solution polymerization method of the present invention, any solvent can be used as long as it dissolves the dihydroxyketone compound and/or the compound having an N,Y-carbonyl bond, such as tetrahydrofuran. (THF), pyridine.

Heterocyclic compounds such as sulfolane, dioxane, tetrahydrothiophene, or methylene chloride, ethylene chloride, 1,1-dichloroethylene, trichloroethane, 1
Examples include halogenated hydrocarbons having 1 to 3 carbon atoms, such as carbon dioxide, trichloroethane, and bromoethane, and one or more selected from the group consisting of these are used.

[Effects of the Invention] The compound having an N,M-carbonyl bond used in the present invention has advantages as shown in the following table in comparison with phosgene in producing polyketone carbonate.

The method of the present invention for producing a compound having an N,N'-carbonyl bond and a siboriketone carbonate on a dihydroxyketone compound has various characteristics as shown below.〇(1) ) Since non-toxic compounds are used, there is no need to worry about environmental pollution. Therefore,
No measures against poisonous gases are required, and a relatively simple reaction apparatus is sufficient.

(2) Since the raw materials are solid, they are easy to handle;
In a solvent such as THP, pyridine or a halogenated hydrocarbon, the reaction proceeds uniformly, and the resulting polyketone carbonate is also homogeneous.

(3) Since the heterocyclic compound, which is a reaction by-product, is a colorless solid, it is easy to separate from the polyketone carbonate resin, and it is recycled because it becomes a raw material for a compound having an N,N'-carbonyl bond. Mechanism settings are possible.

(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.

The polyketone 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 characteristics.

EXAMPLES Below, the present invention will be described in more detail with reference to Examples.

[Example 1 of the invention 45 g of 4.4'-dihydroxybenzophenone [,N,
36 g of N'-carbonyl-diimidazole was added, and 50 g of THF was further added as a solvent, followed by stirring at room temperature.

After the solution became homogeneous, the temperature was gradually raised to 67°.
THF was distilled off at C to obtain a viscous solid solution.

Next, the pressure was reduced by about 40 degrees HgK, and the temperature was gradually raised, and the distillation of imidazole started at around 80°C. Further, when the temperature was continued to rise, at about 120"O, a portion of the imidazo was almost no longer distilled out, 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 polyketone carbonate resin that was solid at room temperature was obtained.

Regarding such polyketone carbonate resins.

When the viscosity was measured using an Ubbelohde viscometer (solvent: methylene chloride), it was confirmed that the product had a specific viscosity of 0177 (average molecular weight approximately 13ρOO). Regarding the above resin, IR spectrum, NMR spectrum,
And when elemental analysis was performed, it was confirmed that it had a carbonyl bond and a carbonate bond.

Example 2 40 g of N,N'-carbonyl-triazole was added to 750 g of ゜keto, and 52 g of THF was further added as a solvent, and the same operation as in Example 1 was performed to obtain a highly viscous substance.

When the viscosity of this substance was measured in the same manner as in Example 1, the specific viscosity was 0.78 (average molecular weight approximately 18.00
0).

Furthermore, the resin obtained above was molded together with a conventional polycarbonate resin to prepare a test piece. Weather resistance (weather meter - 10,000 hours) and heat resistance (heat distortion temperature = 180°C [stress 18.6 kg gβ) of each test piece
]) When a test was conducted, it was confirmed that the product of the present invention showed almost no change compared to before the test, and was significantly superior to the conventional product.

Example 3 95 g of 4,4'-dihydroxy-2,2'-dichlorodiphenylke) y 50 g of KN,N'-carbonyl-diimidazole was added, and dehydrated tetrahydrofuran (T
HF) and stirred until a homogeneous solution was obtained. When the temperature was raised to 70° C. over about 60 minutes, THF gradually began to distill out. Sara K, 7
Stir for about 60 minutes at 5°C, and when THF gradually stops distilling out, add sulfolane (6p:260
℃) was gradually added dropwise. After dropping sulfolane over about 15 minutes, 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 50111 Hg, sulfolane was distilled out, followed by imidazole distillation. When the degree of vacuum was subsequently increased to 10 Hg, imidazole was distilled out, leaving behind a viscous liquid. Further, when heating and stirring were continued, the viscosity increased at 270° C. and stirring became impossible, so heating was stopped.

Regarding the obtained high viscosity material, Example 1. When the viscosity was measured in the same manner as above, it was confirmed that the product had a specific viscosity of 1.10 (average molecular weight approximately 21,000).

In addition, the structure of the above polymer substance is IR, NMl'L.

When fixed by elemental analysis, it was confirmed that it was a polyketone carbonate resin.

Agent Patent Attorney Noriyuki Chika (1 other person) 163-

Claims (1)

[Claims] (1) A method for producing polyketone carbonate, which comprises reacting a dihydroxyketone compound with compounds having an N,N'-carbonyl bond. # (2) When a compound with N,N'-carbonyl bond is nitrogen