JP2955352B2 - Bis (imidocarbonyl) compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel bis (imidocarbonyl) compound and a method for producing the same.

These bis (imidocarbonyl) compounds can be used as modifiers and stabilizers for various resins, and further include unsaturated polyester, epoxy, urethane, urethane / urea,
It can be used as a release agent for heat effect resin such as urea phenol resin.

[Conventional technology]

Conventionally, for example, in the field of release agents, when injection molding a resin, it is generally important that a molded product is easily released from a mold, and in order to achieve these objects, various external Not only release agents but also internal release agents have been developed. Among the release agents, fatty acids or fatty acid metal salts are usually used as the internal release agent. For these release agents, depending on the resin to be molded, it is necessary that the internal release agent is dissolved in the raw material, or for coating after molding, the release agent attached to the resin surface is washed with an organic solvent. It is hoped that it can be removed. However, these fatty acids or metal salts of these fatty acids have various problems to be improved in terms of solubility in resin raw materials, solubility in various organic solvents used for washing after molding, and the like. .

[Problems to be solved by the invention]

The object of the present invention is, for example, when used as a release agent, the problems described above, namely, poorly soluble in resin raw materials,
An object of the present invention is to provide a novel compound having excellent releasability used for various resins, which has improved insolubility in various organic solvents used for washing a molded product, and an inexpensive production method thereof. .

[Means for solving the problem]

The present inventors have conducted intensive studies to achieve the above object, and as a result, completed the present invention.

That is, the present invention provides the following general formula (I) Wherein R ₁ is a C ₈ -C ₃₀ aliphatic saturated or unsaturated hydrocarbon, R ₂ is a compound having a formula weight of 14-1000 which may contain up to 15 O atoms and / or tertiary N atoms. illustrates one divalent hydrocarbon group. Further, X and Y represents an oxygen atom or N-R _3, may be the same, good .R ₃ be different is a hydrogen atom or, more than 15 O contain atoms and / or tertiary N atom a monovalent hydrocarbon radical is a good formula weight 15 to 1000. However, X, R ₃ when Y is N-R ₃ simultaneously in the same, A bis (imidocarbonyl) compound represented by the following formula (II), (III) or (IV) (Wherein R ₁ and R ₂ have the same meanings as in formula (I), and R ₄ and R ₅ each independently contain a hydrogen atom or a group containing 15 or less O atoms and / or tertiary N atoms. Shows a monovalent hydrocarbon group having a good formula weight of 15 to 1000) (Wherein, R ₁ and R ₂ have the same meaning as in formula (I)) (Wherein, R ₁ and R ₂ have the same meanings as in formula (I), and R ₄ has the same meanings as in formula (II)). The compound of the present invention comprises trimellitic anhydride and a compound represented by the general formula (V) R ₁ -NH ₂ (V) wherein R ₁ represents a C ₈ -C ₃₀ aliphatic saturated or unsaturated hydrocarbon. General formula (VI) obtained by reacting an aliphatic primary amine represented by the formula in an organic polar solvent. (Wherein, R ₁ has the same meaning as in formula (V)) and an imide carboxylic acid represented by the following general formula (VII): HX-R ₂ -YH (VII) (wherein R ₂ is 15 or less) O atom and / or tertiary N
A divalent hydrocarbon group having a formula weight of 14 to 1000 which may contain atoms is shown. Also, X and Y represents an oxygen atom or N-R _3, may be the same or different. R ₃ is a hydrogen atom or up to 15 O atoms and / or tertiary N
A monovalent hydrocarbon group having a formula weight of 15 to 1000, which may contain atoms, is shown. However, X, Y are in same R ₃ in the case of N-R ₃ simultaneously, or different or may be) by the formula reacting an active hydrogen compound represented (I)
And a method for producing a bis (imidocarbonyl) compound represented by the formula: The bis (imidocarbonyl) compound represented by the general formula (II), (III) or (IV) is represented by the following formula (VIII), (IX) or (X) (Wherein, R ₂ has the same meaning as in formula (VII), and R ₄ and R ₅ each independently represent a hydrogen atom or a formula amount that may contain up to 15 O atoms and / or tertiary N atoms. HO—R ₂ —OH (IX) (wherein R ₂ has the same meaning as in formula (VII)) (Wherein, R ₂ has the same meaning as in formula (VII), and R ₄ has the same meaning as in formula (VII)
I) having the same meaning), which is obtained by reacting a compound represented by the following formula with an imidocarboxylic acid represented by the general formula (VI).

The feature of the bis (imidocarbonyl) compound of the present invention is that
For example, when used as a mold release agent during resin molding, it shows excellent mold release properties, and also has excellent solubility in resin materials and good cleaning properties with organic solvents when adhered to the resin surface after resin molding. That is.

Hereinafter, the method for producing the bis (imidocarbonyl) compound of the present invention will be specifically described.

In the present invention, the imide carboxylic acid represented by the general formula (VI) is obtained by reacting trimellitic anhydride with an aliphatic primary amine represented by the formula (V) in an organic polar solvent. Reaction of trimellitic anhydride with an aliphatic primary amine to produce an amic acid as an intermediate (hereinafter referred to as the first-stage reaction), and furthermore, an intramolecular dehydration reaction of the amic acid is performed to obtain a compound represented by the general formula It comprises a stepwise reaction of a reaction for producing the imidocarboxylic acid represented by (VI) (hereinafter, referred to as a second-stage reaction).

As the aliphatic primary amine used, an amine having a C _{8 to} C ₃₀ saturated or unsaturated aliphatic carbon chain, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, icosylamine, isododecylamine, Isotetradecylamine, isohexadecylamine, isooctadecylamine, isoicosylamine, oleylamine, aminododecene, aminoeicosene and the like.

The amount of the primary amine used may be at least equimolar to the trimellitic anhydride, and is preferably 1 to 2 moles.

In the production of imidocarboxylic acid, the organic polar solvent used is an organic polar solvent whose functional group does not react with an amine or acid anhydride, and is inert to the system and a solvent that dissolves the product. In addition, the reactants must dissolve at least one, and preferably both.

Solvents used in the first-stage reaction include N, N-dimethylacetamide, N, N-dimethylformamide, N-
Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, cresol hexamethylphosphoramide, tetramethylurea, dimethylsulfoxide, dimethylsulfone, Examples include tetramethylene sulfone, dimethyltetramethylene sulfone, and the like. These solvents can be used alone or in combination with other solvents, and further in combination with a non-polar solvent such as benzene, toluene, xylene and cyclohexane.

Further, as the solvent used in the reaction of the second step in the present invention, any solvent can be used as long as the solvent does not react with the intermediate amide acid and can be heated to a temperature required for dehydration imidization, for example, 300 ° C. However, the organic polar solvent capable of dissolving the intermediate is preferable from the viewpoint of simplicity of handling operation and the like.

The amount of the solvent used in the reaction is not particularly limited, but usually 1 to 10 times the weight of the raw material is sufficient.

In carrying out the reaction, the method of charging the raw materials is not particularly limited, but the first-stage reaction is preferably carried out under substantially anhydrous conditions, and the water contained in the solvent is azeotropically removed in advance. After the removal by the above method, the raw material is preferably charged under a nitrogen atmosphere.

In the first-stage reaction, the reaction temperature is usually 50 ° C or lower, preferably 20 to 25 ° C. Also, the reaction time is usually 0.
5 to 15 hours is enough.

In the second-stage reaction in which the amide acid obtained in the first-stage reaction is heated to be dehydrated and imidized, the reaction temperature is usually 100.
300300 ° C., preferably 130-250 ° C. The reaction time varies depending on the type of solvent and the reaction temperature, but usually 1 to 5 hours is sufficient.

The end point of the reaction can be determined by infrared absorption spectrum and high performance liquid chromatography.

After completion of the reaction, the product precipitated by cooling is separated by filtration, or the reaction solution is directly discharged into water and separated to obtain an imidocarboxylic acid represented by the general formula (VI).

Next, in the method of the present invention, the obtained imidocarboxylic acid is reacted with an active hydrogen compound represented by the general formula (VII), (VIII), (IX) or (X) to obtain a compound represented by the general formula (I): (I
A bis (imidocarbonyl) compound represented by I), (III) or (IV) is obtained.

Examples of the active hydrogen compound defined by the general formula (VIII) include ethylene diamine, propane diamine, propylene diamine, butane diamine, pentane diamine, hexane diamine, heptane diamine, octane diamine, decane diamine, dodecane diamine, tetradecane diamine, hexadecane diamine, Alkanediamines such as octadecanediamine and eicosanediamine, N, N'-
N-alkyl-substituted polyethylene polyamine compounds such as dialkylethylenediamine, N, N ', N "-trialkyltriethylenetetramine, oligoethylene glycol bis (2-aminoethyl ether), oligoethylene glycol bis (3-aminopropyl ether) And the like, and oligoethylene glycol bis (N-alkylaminoalkyl ethers) which are N-alkyl-substituted compounds of those compounds, and oligopropylene glycol bis (2-aminoethyl ether) , Such as oligopropylene glycol bis (3-aminopropyl ether), and oligo-substituted N-alkyl-substituted compounds of those compounds B propylene glycol bis (N- alkylaminoalkyl ethers), and the A up.

As the active hydrogen compound defined by the general formula (IX),
Alkanediols such as ethylene glycol, propanediol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, decanediol, dodacandiol, tetradecanediol, hexadecanediol, octadecanediol, eicosandiol, and the like, Oligoethylene glycols, oligopropylene glycols,
Dialkanolamines such as diethanolamine and dipropanolamine, N-methyldiethanolamine, N
N-alkyldialkanolamines such as -ethyldiethanolamine, N-methyldipropanolamine and N-ethyldipropanolamine, and further, ethylene oxide and propylene oxide are added to the terminal -OH group of the N-alkyldialkanolamine. And the like.

As the active hydrogen compound defined by the general formula (X),
Alkanolamines such as ethanolamine, aminopropanol and aminobutanol, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, N-ethylpropanolamine and the like;
-Oligoethylene glycol mono (aminoalkyl ethers) such as alkylaranolamines, oligoethylene glycol mono (2-aminoethyl ether) and oligoethylene glycol mono (3-aminopropyl ether), and N- Oligoethylene glycol mono (N-alkylaminoalkyl ethers) which are alkyl-substituted compounds, oligopropylene glycol mono (2-aminoethyl ether), oligopropylene glycol mono (3-aminopropyl ether)
And the like, and oligopropyne glycol mono (N-alkylaminoalkyl ethers) which are N-alkyl-substituted compounds of these compounds.

A method for producing a bis (imidocarbonyl) compound represented by the general formula (I) by reacting these active hydrogen compounds with an imide carboxylic acid represented by the general formula (VI) comprises a method comprising the steps of: Is obtained by heat dehydration. At this time, benzene, toluene, xylene, cyclohexane or the like may be used without any problem by using an organic solvent which is inert to the reaction system.

When the diol represented by the general formula (IX) is used as a raw material, the reaction is promoted using an acid catalyst represented by sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, and naphthalenesulfonic acid. Can be.

When an active hydrogen compound having low reactivity is used as a raw material, the carboxylic acid group of imidocarboxylic acid is converted to an inorganic acid such as phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, thionyl chloride, sulfuryl chloride, and phosgene. After the compound is converted to a carboxylic acid chloride, the desired product can be obtained by reacting with an active hydrogen compound in the presence of a suitable base.

The amount of the active hydrogen compound used is desirably 0.1 to 0.8 times the mol of the imidocarboxylic acid. If it is less than 0.1 mole, it is difficult to remove unreacted imide carboxylic acid, and if it exceeds 0.8 mole, the yield of bis-form becomes extremely low.

The reaction temperature is 100 ° C when dehydrating by heating without a catalyst.
The temperature range is preferably from 0 ° C to 200 ° C in the case where a catalyst is used or the reaction is carried out after derivation to an acid halide compound.

The reaction time is 1 to 20 hours in the former case and 1 to 10 hours in the latter case.

The end point of the reaction can be determined by infrared absorption spectrum and high performance liquid chromatography.

After completion of the reaction, the product precipitated by cooling is filtered off or the organic solvent used in the reaction is distilled off to obtain the desired bis (imidocarbonyl) compound.

Further, when a high-purity bis (imidocarbonyl) compound is required, it can be purified by recrystallization or sludge using an appropriate organic solvent.

[Action]

The bis (imidocarbonyl) compound of the present invention thus obtained is easily soluble in an organic solvent. For example, when used as a mold release agent in molding a resin, the bis (imide carbonyl) compound exhibits extremely excellent mold release properties. It is a compound shown.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 A reactor equipped with a stirrer, a reflux condenser, a Dean-Stark water separator and a nitrogen inlet tube was charged with 400 ml of N, N-dimethylacetamide and 100 ml of toluene, and water in the solvent was removed by azeotropic dehydration. After removal, the mixture was cooled to room temperature and charged with 80 g of trimellitic anhydride under a nitrogen atmosphere. To this solution, at room temperature, 112 g of stearylamine was added in 300 ml of toluene.
l, A solution dissolved in 130 ml of N, N-dimethylacetamide was added dropwise over 2 hours. Then, the mixture was stirred at room temperature for 10 hours.
Thereafter, reflux was carried out at 150 to 170 ° C. for about 5 hours until water disappeared. After completion of the reaction, the mixture was cooled, and the precipitated solid was separated by filtration and dried to obtain imidocarboxylic acid as a white solid.

Yield: 171.9 g (93% yield) Melting point: 127-130 ° C. Example 2 500 ml of toluene obtained in Example 1 in a reactor equipped with a stirrer, a reflux condenser, a Dean-Stark water separator and a nitrogen inlet tube. 200 g of imidocarboxylic acid, 14 g of ethylene glycol and 1 g of p-toluenesulfonic acid were charged and refluxed for 3 hours. After completion of the reaction, the organic layer was washed with warm water at 70 ° C. and separated to remove the acid catalyst. After cooling, the precipitated crystal was separated by filtration and dried to obtain the desired bis (imidecarbonyl) compound. Obtained.

Yield 125g (61% yield) Melting point 91-94 ° C The results of elemental analysis and mass spectrometry (Ms) of the obtained compound were as follows.

Elemental analysis (C ₅₆ as _{H 84 N 2 O 8) C} H N calc (%) 73.64 9.27 3.07 Analytical values (%) 73.51 9.43 3.15 Ms (FD Method): 913 (M +) Example 3 a stirrer, a reflux A reactor equipped with a condenser, a Dean-Stark water separator, and a nitrogen inlet tube was charged with 750 ml of toluene and 200 g of the imidocarboxylic acid obtained in Example 1, and heated at 70 ° C.
To dissolve. 75 g of thionyl chloride was added dropwise thereto, and the mixture was stirred at 70 ° C. for 3 hours, and then excess thionyl chloride was distilled off under reduced pressure together with toluene. 500 ml of toluene was added to the obtained reaction mixture, and the mixture was heated to 70 ° C. N, N'-
20 g of dimethylethylenediamine was added, and the mixture was stirred at 70 ° C. for 2 hours. Furthermore, 47.9 g of triethylamine was added, and 70 ° C
For 2 hours. After completion of the reaction, the organic layer was washed with warm water at 70 ° C. to remove triethylamine hydrochloride. The solid obtained by distilling off toluene was sludged with methanol to obtain a target bis (imidocarbonyl) compound.

Yield: 164 g (Yield: 77%) Melting point: 130.5-132 ° C. The results of elemental analysis and mass spectrum (Ms) of the obtained compound were as follows.

Elemental analysis (C ₅₈ H ₉₀ N ₄ as O ₆₎ C H N calc (%) 74.16 9.66 5.96 Analytical values (%) 74.00 9.53 5.55 Ms (FD Method): 939 (M +) Example 4 stirrer, reflux A reactor equipped with a condenser, a Dean-Stark water separator, and a nitrogen inlet tube was charged with 700 ml of toluene and 180 g of the imidocarboxylic acid obtained in Example 1, and heated at 70 ° C.
To dissolve. 70 g of thionyl chloride was added dropwise thereto, and the mixture was stirred at 70 ° C. for 3 hours. Then, excess thionyl chloride was distilled off under reduced pressure together with toluene. 800 ml of toluene was added to the obtained reaction mixture, and the mixture was heated to 70 ° C. N, N ',
Add N ″ -trimethyldiethylenetriamine 20 g, and add 70 ° C.
For 2 hours. Further, 43 g of triethylamine was added, and the mixture was stirred at 70 ° C. for 2 hours. After the reaction is completed, the organic layer is
To remove the hydrochloride of triethylamine. The solid obtained by distilling off toluene is sludged with methanol to give the desired product bis (imidocarbonyl).
The compound was obtained.

Yield: 165 g (yield: 82%) Melting point: 95-97 ° C. The results of elemental analysis and mass spectrum (Ms) of the obtained compound were as follows.

Elemental analysis (C ₆₁ H ₉₇ N as ₅ O ₆₎ C H N calc (%) 75.53 9.81 7.03 Analytical values (%) 73.05 9.53 7.35 Ms (FD Method): 996 (M +) [Effect of the Invention The present invention Is a new type of screw that has improved solubility in resin materials and organic solvents, and has excellent release properties, for example, when used as a release agent during resin molding. An (imide carbonyl) compound and a method for producing the same are provided.

Claims (4)

(57) [Claims] 1. The compound of the general formula (I) Wherein R ₁ is a C ₈ -C ₃₀ aliphatic saturated or unsaturated hydrocarbon, R ₂ is a compound having a formula weight of 14-1000 which may contain up to 15 O atoms and / or tertiary N atoms. X and Y each represent an oxygen atom or NR ₃
And may be the same or different. R ₃ represents a hydrogen atom or a monovalent linear hydrocarbon group having a formula weight of 15 to 1000 which may contain up to 15 O atoms and / or tertiary N atoms. However, when X and Y are simultaneously N—R ₃ , R ₃ may be the same or different.) 2. A compound of the general formula (II) (Wherein R ₁ and R ₂ have the same meanings as in formula (I), and R ₄ and R ₅ each independently contain a hydrogen atom or a group containing 15 or less O atoms and / or tertiary N atoms. And a monovalent chain hydrocarbon group having a good formula weight of 15 to 1000). 3. A compound of the general formula (III) (Wherein R ₁ and R ₂ have the same meanings as in formula (I)). 4. A compound of the general formula (IV) (Wherein R ₁ and R ₂ have the same meanings as in formula (I), and R ₄ is a hydrogen atom or 15 or less O atoms and / or tertiary N
A monovalent linear hydrocarbon group having a formula weight of 15 to 1000 which may contain an atom).