JPH05163268A - New maleimide compound derivative and its production - Google Patents

Abstract

PURPOSE:To provide a new compound having high melting point and excellent fluidity and useful as a moldability-improving agent for thermoplastic resin, etc. CONSTITUTION:The compound of formula I (R<1> is H or methyl; R<2> and R<3> are H, alkyl, cycloalkyl or aryl; X is H, alkyl, halogen or hydroxy). The compound is produced by the addition reaction of a maleimide compound of formula II (R<4> is H, 1-5C alkyl, cycloalkyl, etc.) with an aromatic vinyl compound of formula III (R<5> to R<7> are H or 1-5C alkyl; R<8> is aryl) in the presence of a polymerization inhibitor (e.g. p-t-butylcatechol) optionally in a solvent (e.g. toluene) at 60-150 deg.C. The amount of the compound of formula II is 0.1-2mol based on 1mol of the compound of formula III and that of the polymerization inhibitor is 0.05-5wt.% based on the sum of the compounds of formula II and formula II. The compound of formula I can be produced from an inexpensive raw material in high yield at a low cost.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel maleimide compound derivative synthesized from an aromatic vinyl compound and a maleimide compound. INDUSTRIAL APPLICABILITY The novel maleimide compound derivative of the present invention has a high melting point and good fluidity, and thus is a compound useful as, for example, an agent for improving fluidity or moldability of a thermoplastic resin having excellent heat resistance.

[0002]

2. Description of the Related Art Conventionally, a maleimide copolymer has been obtained by polymerizing an aromatic vinyl compound and a maleimide compound. Further, it is useful that a low molecular weight petroleum resin or a low molecular weight compound having a specific ring structure is useful as a processability improver.
No. 192141.

[0003]

DISCLOSURE OF THE INVENTION While studying the polymerization of an aromatic vinyl compound and a maleimide compound, the inventors of the present invention caused a Dales-Alder addition reaction between the aromatic vinyl compound and the maleimide compound to give a novel compound. Found to generate. As a result of investigating the physical properties of this novel compound, it was found that it is a low molecular weight compound, has a high melting point, and exhibits good fluidity when melted. A low molecular weight compound having such physical properties is not found in a chemical agent added to a resin in the related art, and is improved in performance of a synthetic resin, for example, when it is compatible with the synthetic resin, it easily flows. Also, it is useful for improving the moldability of a synthetic resin, for example, it becomes a lubricant even if they are not compatible, and facilitates molding. The low molecular weight compound generally shows good compatibility with the synthetic resin.

The present invention is a low molecular weight compound having a relatively high melting point, and by exhibiting good fluidity when melted,
The first object is to provide a novel maleimide compound derivative useful for improving the fluidity and moldability of synthetic resins such as thermoplastic resins, and it is economical to use such a derivative in high yield and at low cost. A second object is to provide a manufacturing method that can be obtained in a targeted manner.

[0005]

In order to solve the above-mentioned first problem, the present invention provides a novel maleimide compound derivative represented by the following structural formula.

[0006]

[Chemical 3]

In this structural formula, R ² , R ³ and X are specifically as follows. R ² and R ³
Then, the alkyl group preferably has 1 to 6 carbon atoms, and if the number of carbon atoms is larger than this, heat resistance may be reduced. The cycloalkyl group is preferably a cyclohexyl group. The aryl group preferably has 6 to 12 carbon atoms, and if the aryl group has more carbon atoms than this, heat resistance may decrease. In the substituted aryl group, one or more hydrogen atoms in the aryl group are alkyl groups (for example, having 1 to 1 carbon atoms).
3), substituted with one or more of halogen, hydroxyl group, carboxyl group and nitro group. Specific examples of R ² and R ^{3 which} are substituted aryl groups include a methylphenyl group, a 2-bromophenyl group, a 2-chlorophenyl group, a p-hydroxyphenyl group and a nitrophenyl group.

X is hydrogen, an alkyl group, a halogen or a hydroxyl group. Here, the alkyl group has 1 carbon atom
The range of 5 to 5 is preferable, and if the number of carbons is larger than this, the heat resistance may decrease. Specific examples of X include a methyl group, a bromo group, a chloro group, a hydroxyl group and the like. The compound represented by the above structural formula has a melting point of 15
The temperature is 0 to 350 ° C., and the viscosity sharply decreases at a temperature equal to or higher than the melting point, and the liquid becomes a low viscosity liquid.

In order to solve the second problem, the present invention provides a novel maleimide compound derivative represented by the above structural formula by subjecting an aromatic vinyl compound and a maleimide compound to an addition reaction in the presence of a polymerization inhibitor. The manufacturing method to obtain is provided. The maleimide compound used in the present invention has the following formula:

[0010]

[Chemical 4]

Compounds represented by, for example, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-tertiarybutyl. Maleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide,
Examples thereof include N-bromophenylmaleimide, N-naphthylmaleimide, N-laurylmaleimide, 2-hydroxyethylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide and N-nitrophenylmaleimide. It is possible to use one or more of these.

The aromatic vinyl compound used in the present invention has the following formula:

[0013]

[Chemical 5]

Compounds represented by, for example, styrene; o-methylstyrene, m-methylstyrene, p-
Methylstyrene (o-, m-, p-methylstyrene is also called vinyltoluene), 1,3-dimethylstyrene,
2,4-dimethylstyrene, ethylstyrene, p-third
Alkyl styrenes such as primary butyl styrene; α-methyl styrene, α-ethyl styrene, α-methyl-p-methyl styrene; vinylnaphthalene; o-chlorostyrene,
Examples thereof include halogenated styrenes such as m-chlorostyrene, p-chlorostyrene, and 2,4-dibromostyrene; halogenated alkylstyrenes such as 2-methyl-4-chlorostyrene, and one or two of these. The above can be used. From the viewpoint of the balance between productivity and physical properties, styrene, vinyltoluene and α-
It is desirable to use at least one selected from the group consisting of methylstyrene.

The method for producing the novel maleimide compound derivative of the present invention is not particularly limited, but the following method is advantageous in high yield and economically. That is, it is a method of heating and mixing an aromatic vinyl compound and a maleimide compound in the presence of a polymerization inhibitor. In particular, by pre-charging a part or all of one raw material in the reaction system in advance, and by sequentially dropping the remaining raw material,
The novel maleimide compound derivative of the present invention can be efficiently produced. When the maleimide compound is a solid at room temperature, an organic solvent can be used if necessary.

The polymerization inhibitor used in this reaction is not particularly limited as long as it can inhibit radical polymerization, and specific examples thereof include diphenylpicrylhydrazyl, chloranil, 2,4. -Dimethyl-6
-T-butylphenol, dibutyldithiocarbamic acid copper (II) salt, manganese acetate, chromium acetate, 1,3,5-triphenylverdazyl, 2,2,6,6-tetramethyl-4-piperidone-1-oxyl, Nitrosobenzene,
Dichloronitrosobenzene, methyl-α-nitrosoisopropyl ketone, iron chloride; p-benzoquinone, methyl-
Benzoquinones such as p-benzoquinone, 2,5-dimethyl-p-benzoquinone, methoxy-p-benzoquinone, chloro-p-benzoquinone and 2,5-dichloro-p-benzoquinone; hydroquinone, 2,5-di-t- Hydroquinones such as butylhydroquinone and hydroquinone monomethyl ether; pt-butylcatechol, 3-
Catechols such as phenylcatechol and catechol;
Amines such as di-p-fluorophenylamine, p-phenyldiamine and thiodiphenylamine; tri-p-
Examples include nitro compounds such as nitrophenylmethyl, m-dinitrobenzene, dichloronitrophenol, dinitrotoluene, nitrophenol, and 1,3,5-trinitroanisole, which can be used alone or in combination of two or more. It will be done. In the present invention, preferred among the above-mentioned polymerization inhibitors are benzoquinones, hydroquinones and catechols.

The amount of the polymerization inhibitor added varies depending on the conditions such as the type of the polymerization inhibitor used and the reaction temperature. To obtain the compound of the present invention in a high yield, an aromatic vinyl compound and a maleimide compound are used. It is preferable to appropriately set it in consideration of not increasing the production amount of the copolymer. In particular, in order to reduce the decrease in the yield of the compound of the present invention due to the production of a polymer due to a thermal polymerization reaction or the like which is a side reaction during the addition reaction, the aromatic compounds present in the reaction system It is preferable to add it so as to be 0.05 to 5 wt% with respect to the total amount of the vinyl compound and the maleimide compound. If the amount of the polymerization inhibitor used is more than this range, it tends to remain in the subsequent steps, which is not economical.

In the addition reaction, a non-reactive solvent can be used if necessary. Examples of such a solvent include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons that are liquid at room temperature such as hexane and heptane. Etc. The solvent may be a single solvent or a mixed solvent of two or more kinds.

In the production of the maleimide compound derivative of the present invention, the maleimide compound and the aromatic vinyl compound are contained in an amount of 0.1 to 2.0 mol, preferably 0.2 to 1 mol, of the maleimide compound with respect to 1 mol of the aromatic vinyl compound. Used in a ratio of 0.0 mol. Unreacted maleimide compound may remain in the reaction system if the maleimide compound is in excess of the above range, and the purification step may be complicated, and if the amount is too small, the compound of the present invention relative to the total amount of the maleimide compound and the aromatic vinyl compound used. The yield may be low.

The above addition reaction is carried out, for example, in the range of 60 to 150.
0.5-10 at a temperature of 80 ° C, preferably 80-120 ° C.
It is carried out for an hour, preferably 1 to 5 hours. The atmosphere during the reaction is not particularly limited, but when using a polymerization inhibitor whose polymerization suppressing effect is improved by the coexistence of oxygen, it is preferable to exist in the presence of oxygen within a range avoiding the explosion range. To collect the product from the reaction solution by carrying out the reaction as described above, for example, unreacted raw materials and an organic solvent are distilled off, concentrated, washed with a solvent such as toluene and then filtered and dried. The method of doing is adopted. When the product precipitates during the reaction, it can be more effectively obtained by filtration and washing, and the reaction residual liquid can be recovered and reused to further increase the yield.

The product thus obtained is confirmed to be a maleimide compound derivative represented by the above structural formula by elemental analysis, nuclear magnetic resonance (NMR) analysis, infrared (IR) analysis and mass spectrometry. The collected maleimide compound derivative is, for example, a thermoplastic resin (for example,
Vinyl chloride resin, chlorinated vinyl chloride resin, ABS resin,
Polyamide resin, etc.) is uniformly mixed with a kneader or roll and used to improve the fluidity of the resin. The use is not limited to this.

[0022]

The compound represented by the above structural formula has a ring structure composed of a maleimide compound and an aromatic vinyl compound as a constitutional unit and thus has a high melting point. Since it is a low molecular weight compound, it has good fluidity when melted. .. Moreover, since it has a structural unit derived from a maleimide compound and an aromatic vinyl compound as a structural unit and is a low molecular weight compound, it has good compatibility with a thermoplastic resin.

By subjecting the maleimide compound and the aromatic vinyl compound to the addition reaction in the presence of the polymerization inhibitor, the compound represented by the above structural formula can be obtained at a high yield and economically.

[0024]

EXAMPLES Specific examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples.
In the following, "parts" means "parts by weight" unless otherwise specified.
"%" Means "% by weight". The products obtained in the following Examples and Comparative Examples were subjected to elemental analysis and NMR.
Analysis, IR analysis and mass spectrometry were performed to investigate its chemical structure.

NMR analysis was performed using deuterated chloroform (C
The measurement was carried out in DCl ₃ ) using tetramethylsilane as a standard substance, and ¹ H-NMR spectrum and ¹³ C-NMR were obtained.
The spectrum was obtained. The nuclear magnetic resonance apparatus used was VXR
It was −300S (manufactured by Varian Co., Ltd.). For IR analysis, an infrared analyzer (FT / I
R-3, manufactured by Shimadzu Corporation).

Mass spectrometry was carried out using an M-2000A mass spectrometer (Hitachi Ltd.). Example 1 N-phenylmaleimide 120 in a 1 liter flask
g, 80 g of toluene, and pt which is a polymerization inhibitor
-Butylcatechol (3.6 g) was charged, and the temperature was raised to 110 ° C while nitrogen gas containing 7 vol% oxygen was bubbled through the reaction system at 20 ml / min. The maleimide was completely dissolved in toluene to give a pale yellow homogeneous solution. After the temperature of this solution became stable, 100 g of styrene was uniformly added dropwise over 2 hours. A white precipitate was formed as the reaction proceeded. After the dropping was completed, the reaction was continued at 110 ° C. for another 2 hours. After cooling the reaction solution to room temperature, the precipitate was filtered off, washed with a small amount of toluene, and dried under reduced pressure to obtain 148 g of a white powder [compound (1)]. The yield was 67%.

The obtained compound (1) is subjected to elemental analysis, mass analysis, ¹ H- and ¹³ C-NMR analysis and infrared spectrum analysis, and is a compound represented by the following structural formula (1) It was confirmed. As a result of mass spectrometry, the molecular weight was 450. Elemental analysis values are shown in Table 1, ¹ H-NMR spectrum is shown in FIG. 1, ¹³ C-NMR spectrum is shown in FIG.
The infrared spectrum is shown in FIG.

[0028]

[Chemical 6]

Table 1 ------------- Elemental analysis value (mol%) of compound (1) C H N ---------- −−−−−−−−−−−−−−− Calculated value 74.70 4.89 6.23 Measured value 74.97 4.81 6.23 −−−−−−−−−−−−−−− −−−−−−−− (Note) The calculated value was obtained as C ₂₈ H ₂₂ N ₂ O ₄ .

The structure of compound (1) was determined as follows. From the elemental analysis and the mass spectrometry, the molecular formula C ₂₈ H ₂₂ N
₂ O ₄ is introduced. On the other hand, in the infrared spectrum, 1780
The presence of a carbonyl group (C = O) derived from the imide groups in cm ^-1 and 1700 cm ^-1 is derived. In ¹ H-NMR, two kinds of methylene (CH ₂ ) and four kinds of methine (CH)
And the aromatic ring hydrogen number 14 are shown. ^{In 13} C-NMR, two kinds of methylene (CH ₂ ) and four kinds of methine (C
H) and four carbonyl groups are shown.

Example 2-α-methylstyrene 113 instead of 100 g of styrene
The same operation as in Example 1 was carried out except that g was used to obtain 140 g of a white powder [compound (2)]. The yield was 55%. The obtained compound (2) was analyzed by the same method as in Example 1 and as a result, it was found to be a compound represented by the following structural formula (2). The infrared spectrum of the compound (2) is shown in FIG.

[0032]

[Chemical 7]

Example 3 A 1-liter flask was charged with 120 g of N-cyclohexylmaleimide, 80 g of toluene, and 3.6 g of t-butylcatechol as a polymerization inhibitor, and oxygen 7 vol% was added.
The temperature was raised to 110 ° C. while bubbling nitrogen gas containing 20 ml / min into the reaction system. The N-cyclohexylmaleimide was completely dissolved in toluene to form a slightly yellow homogeneous solution. After the temperature of this solution has stabilized, styrene 100
g was evenly added dropwise over 2 hours. No precipitate was formed even if the reaction proceeded. After the dropping was completed, the reaction was continued at 110 ° C. for another 4 hours. Then, toluene and unreacted raw materials were distilled off from the reaction solution under reduced pressure, and the obtained slightly yellow solid was dissolved in hot methanol. Some insoluble matter is filtered off,
The filtrate was cooled, and the precipitated white powder was filtered off, washed with a small amount of methanol and dried under reduced pressure to obtain 120 g of a white powder [compound (3)]. The yield was 55%.

Regarding the obtained compound (3), Example 1
As a result of analysis by the same method as described above, it was found to be a compound represented by the following structural formula (3). The infrared spectrum of the compound (3) is shown in FIG.

[0035]

[Chemical 8]

Compounds (1) to (1) obtained in the above Examples
Regarding (3), the melting point was examined, and the results are shown in Table 2. The molecular weight is also shown in Table 2. The melting point is measured by a melting point measuring device [BUECHI 510], Buki Laboratories-
Technique AGE (BUECHI LABORATORIUMS-TECHN
Manufactured by IK AG).

Table 2 Physical Properties of Compounds (1) to (3) Compounds Molecular Weight Melting point [° C.] --- ----------------------- Example 1 (1) 450 214-215 Example 2 (2) 462 291-292 Example 3 (3) 464 192 to 193 −−−−−−−−−−−−−−−−−−−−−−−−−− Reference Example Polychlorinated vinyl chloride resin (“HA-51 manufactured by Sekisui Chemical Co., Ltd.”
K ", chlorination degree 67%, polymerization degree 1000) 100 parts were dissolved in tetrahydrofuran 900 parts. Dissolve evenly,
It became a colorless and transparent solution.

After air-drying this solution at room temperature, it was dried in a vacuum dryer at 1 mmHg and 120 ° C. for 8 hours to obtain a transparent film resin [resin (1)]. Resin (1) was measured by melt flow measuring device (Shimadzu flow tester (FL
The melt viscosity at 180 ° C. under a load of 100 kg was measured by OWTESTER CFT-500) and found to be 2.5 million poise. On the other hand, 100 parts of polychlorinated vinyl chloride resin and Example 1
3 parts of the compound (1) obtained in (1) was dissolved in tetrahydrofuran in the same manner and dried to obtain a transparent film resin [resin (2)]. When the melt viscosity of the resin (2) was measured under the same conditions as those of the resin (1), it was 700,000 poise, and the fluidity was significantly improved as compared with the resin (1).

[0039]

According to the present invention, a maleimide compound derivative having a high melting point and excellent fluidity is provided. Also,
This derivative is excellent in compatibility with a synthetic resin such as a thermoplastic resin and has a great effect of improving the fluidity thereof. According to the present invention, such a novel maleimide compound derivative can be obtained at a high yield and economically.

[Brief description of drawings]

FIG. 1 ¹ H-NM of compound (1) obtained in Example 1.
It is an R spectrum.

FIG. 2 ¹³ C-NM of compound (1) obtained in Example 1
It is an R spectrum.

FIG. 3 is an infrared spectrum of the compound (1) obtained in Example 1.

FIG. 4 is an infrared spectrum of compound (2) obtained in Example 2.

5 is an infrared spectrum of the compound (3) obtained in Example 3. FIG.

Claims (2)

[Claims] 1. A novel maleimide compound derivative represented by the following structural formula. [Chemical 1] 2. A process for producing a novel maleimide compound derivative represented by the following structural formula by subjecting an aromatic vinyl compound and a maleimide compound to an addition reaction in the presence of a polymerization inhibitor. [Chemical 2]