JP2002226452A - Compound having two kinds of reactive group and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate of a compound effective for its addition to methyl methacrylate in order to facilitate controlling the polymerization reaction in copolymerization in producing polymethyl methacrylate(PMMA) having crosslinked structure and also markedly improve both the heat resistance and chemical resistance of the resulting PMMA. SOLUTION: This compound having two kinds of reactive groups is shown by the formula (1) (wherein, the isopropenyl group is located on meta-or para- position relative to the other substituent). The other objective method for producing the above compound comprises making a urethanation reaction between 3- or 4-isopropenyl-α,α-dimethylbenzyl isocyanate and ethylene glycol or a monoester thereof in the absence of solvent or in a solvent inert to the raw materials; in the case of using the monoester of ethylene glycol, hydrolyzing the resulting urethnation reaction product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound having two kinds of reactive groups and a method for producing the same. The compound provided by the present invention is useful for improving the heat resistance and chemical resistance of polymethyl methacrylate (hereinafter abbreviated as PMMA).

[0002]

2. Description of the Related Art Generally, plastic materials are lighter in weight than inorganic glass, and are excellent in impact resistance, workability and mass productivity. In recent years, taking advantage of this feature, plastics having excellent transparency have been used in a wide range of fields as a substitute for inorganic glass.

[0003] Above all, PMMA is excellent in transparency, light weight, weather resistance, mass productivity, etc., and is therefore used for lighting covers, signboards, glazing materials for vehicles and buildings, and front panels for instruments and flat panel displays. Widely used as such. However, when used in a vehicle or in the vicinity of a heating element, its heat resistance is inferior to that of a polycarbonate resin or the like, and its chemical resistance is low.

In order to solve these problems, there have been proposed a method of adding cyclohexyl methacrylate to methyl methacrylate for copolymerization, and a method of adding methyl methacrylate to maleic anhydride and styrene for copolymerization (Japanese Patent Publication No. Sho. 58-87104). However, since PMMA has a linear structure, no improvement in chemical resistance is seen.

On the other hand, many methods have been proposed for producing PMMA having a crosslinked structure by copolymerizing methyl methacrylate and acrylate or methacrylate compounds of various polyhydric alcohols (Japanese Patent Application Laid-Open No. 63-75022).
No.). However, in this production method, although heat resistance and chemical resistance are improved, there is a tendency to run away suddenly during the polymerization reaction, so that it is difficult to control the polymerization, to obtain a polymer having a good surface state and a small polymerization distortion. Has a problem such as having a long time, and is not widely used.

[0006]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, it is an object of the present invention to facilitate the control of the polymerization reaction in copolymerization when producing PMMA having a crosslinked structure and to reduce the amount of PMMA obtained by polymerization. An object of the present invention is to provide an intermediate of a compound which is effective to be added to methyl methacrylate for the purpose of greatly improving heat resistance and chemical resistance, and a method for producing the same.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a compound having both an isopropenyl group and a hydroxyl group represented by the formula (1) is
After crosslinking with a compound having a plurality of isocyanate groups, it is copolymerized with methyl methacrylate to form a PMM.
The present inventors have found that PMMA having a crosslinked structure that can easily control the polymerization reaction can be produced while improving the heat resistance and chemical resistance of A, and have completed the present invention.

That is, the present invention provides the following formula (1)

[0009]

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(Wherein the isopropenyl group is located at the meta or para position with respect to the other substituent).

The present invention includes a method for making this compound. That is, the present invention provides 3-isopropenyl-α, α-
Formula (1) characterized in that dimethylbenzyl isocyanate or 4-isopropenyl-α, α-dimethylbenzyl isocyanate and ethylene glycol are subjected to a urethanization reaction without a solvent or in a solvent having no reactivity with raw materials. This is a method for producing the compound represented by the formula (hereinafter, referred to as a first production method).

In this production method, ethylene glycol is used in an amount of 1 to 1 per mol of 3-isopropenyl-α, α-dimethylbenzyl isocyanate or 4-isopropenyl-α, α-dimethylbenzyl isocyanate.
It is preferable that the urethanization reaction is performed by using 0 mol and setting the reaction solution temperature to 20 to 110 ° C.

The present invention also relates to 3-isopropenyl-α,
After subjecting α-dimethylbenzyl isocyanate or 4-isopropenyl-α, α-dimethylbenzyl isocyanate to a monoester of ethylene glycol to a urethanization reaction without a solvent or in a solvent having no reactivity with the raw materials, A method for producing a compound represented by the formula (1), which is characterized by hydrolyzing a product of the urethanation reaction (hereinafter, referred to as a second production method).

In the second production method, a monoester of ethylene glycol is added to 1 mol of 3-isopropenyl-α, α-dimethylbenzyl isocyanate or 4-isopropenyl-α, α-dimethylbenzyl isocyanate. Using 8 to 5 mol, the reaction solution temperature was 20 to 1
It is preferable to perform the urethanization reaction at 10 ° C. It is also preferable that the hydrolysis is performed with an acid or an alkali.

[0015]

Next, the compounds of the present invention will be described in more detail.

In the present invention, 3-isopropenyl-α,
α-Dimethylbenzyl isocyanate or 4-isopropenyl-α, α-dimethylbenzyl isocyanate is commercially available or easily available by synthesis by a known method.

The reaction time of the urethanization reaction is preferably from several minutes to 72 hours, more preferably from several minutes to 12 hours, from the viewpoint of preventing side reactions such as a condensation reaction.

In the first production method, the molar ratio of ethylene glycol to 3-isopropenyl-α, α-dimethylbenzyl isocyanate or 4-isopropenyl-α, α-dimethylbenzyl isocyanate is based on 1 mole of the former. The reaction is preferably carried out using at least 1 mol of the latter. More preferably, it is at least 1.2 mol. By using 1 mol or more of ethylene glycol, the yield of the compound represented by the formula (1) can be improved. In terms of reactivity, the upper limit of the amount of ethylene glycol is not particularly limited. However, from the viewpoint that excess ethylene glycol needs to be removed after the reaction,
The upper limit of ethylene glycol is preferably about 10 mol.
From these viewpoints, based on 1 mol of the isocyanate,
It is more preferable to use 3 to 5 moles of ethylene glycol.

In the second production method, the molar ratio of the monoester of ethylene glycol to 3-isopropenyl-α, α-dimethylbenzyl isocyanate or 4-isopropenyl-α, α-dimethylbenzyl isocyanate is 1 mole of the former. The reaction is preferably carried out using at least 0.8 mol of the latter. More preferably, it is at least 1 mol. By using 0.8 mol or more of the monoester of ethylene glycol, the yield of the compound represented by the formula (1) can be improved. In terms of reactivity, the upper limit of the ethylene glycol monoester is not particularly limited. The upper limit is preferably about 5 mol. From these viewpoints, it is more preferable to use 1 to 2 moles of a monoester of ethylene glycol with respect to 1 mole of the isocyanate.

The monoester of ethylene glycol is not particularly limited, but examples of preferred examples thereof include ethylene glycol monosalicylate, ethylene glycol monoacetate, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. Can be mentioned.

Regarding the hydrolysis method in the second production method. Although there is no particular limitation, preferred examples include a method using an acid or an alkali. Examples of the acid include hydrochloric acid, hydrobromic acid, sulfuric acid and phosphoric acid. Examples of the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium carbonate.

In the first and second production methods, the urethanization reaction may be carried out without a solvent or using a solvent. As the solvent, those which do not react with the raw materials, that is, 3-isopropenyl-α, α-dimethylbenzyl isocyanate or 4-isopropenyl-α, α-dimethylbenzyl isocyanate, and ethylene glycol or a monoester thereof can be used. . Examples of the solvent having no reactivity with the raw materials that can be suitably used in the present invention include methylene chloride, chloroform,
Chlorine-containing organic solvents such as carbon tetrachloride, dichloroethane or tetrachloroethane; esters such as methyl acetate, ethyl acetate or butyl acetate; ethers such as diethyl ether, diphenyl ether, dioxane or tetrahydrofuran; hexane; liquid sulfur dioxide; Carbon sulfide, benzene, toluene, xylene, nitromethane, nitrobenzene, acetonitrile, dimethylformamide, dimethylacetamide or 1,3-dimethyl-2
-Imidazolidinones and the like.

In the first and second production methods, the urethanization reaction may be carried out without a catalyst, or a urethanation-promoting catalyst may coexist. When using a urethane-promoting catalyst, it is preferably 0.1 to 50,000 ppm, more preferably 1 to 50,000 ppm based on the weight of the isocyanate compound.
Use -10000 ppm. The urethanization promoting catalyst is not particularly limited, but dibutyltin dilaurate can be mentioned as an example of the urethanization promoting catalyst that can be suitably used.

In the first and second production methods, the temperature of the reaction solution at the time of performing the urethanization reaction is preferably from 20 to 110 ° C., and more preferably from 20 to 80 ° C. By setting the temperature to 20 ° C. or higher, the reaction time can be prevented from being prolonged, and by setting the temperature to 110 ° C. or lower, generation of by-products can be suppressed.

In the first and second production methods, the compound represented by the formula (1) can be isolated. The method of isolation is not particularly limited, but a preferred method is chromatography. When a product of higher purity is required, it is preferable to crystallize the product after chromatography using no solvent or a hydrocarbon such as pentane or hexane. There is no particular limitation on the amount of the solvent used relative to the crystals, but it is efficient to use, for example, 1 to 10 times (weight ratio) the crystals. The temperature at which the crystallization is performed varies depending on the solvent, but it is preferable that stirring is continued until crystal precipitation in a temperature range from room temperature to a temperature lower than the boiling point of the solvent.

[0026]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited by these examples.

Example 1 Synthesis of N- (3-isopropenyl-α, α-dimethylbenzyl) -2-hydroxyethyl carbamate 20 g of 3-isopropenyl-α, α-dimethylbenzyl isocyanate was added to a reaction solution at a temperature of 40. At 500C, in the presence of 500 ppm of dibutyltin dilaurate (based on the weight of isocyanate), the mixture was dropped into 18.5 g of ethylene glycol, and stirred for 4 hours to cause a urethanization reaction. The reaction mixture was purified by silica gel column chromatography to obtain a colorless syrup. To this was added 40 g of hexane and stirred. The resulting precipitate was collected by filtration and dried to give 20 g of the title compound as a white solid. mp 53.0〜55.1 ℃ ¹ HN.MR (CDCl ₃ , 400MHz) δ1.60-1.70 (6H, m), 2.16
(3H, dd), 3.40 (1H, brs), 3.78 (2H, brs), 4.14 (2H, b
rs), 5.09 (1H, s), 5.25 (1H, brs), 5.35 (1H, dd), 7.2
5-7.38 (3H, m), 7.50 (1H, s). MASS (M ⁺ ) 263. According to the above analysis results, N- (3-isopropenyl-α,
Formation of (α-dimethylbenzyl) -2-hydroxyethyl carbamate was confirmed.

Example 2 Synthesis of N- (4-isopropenyl-α, α-dimethylbenzyl) -2-hydroxyethyl carbamate 4-isopropenyl-α, α-dimethylbenzyl isocyanate was replaced with 20 g of 4-isopropenyl-α, α-dimethylbenzyl isocyanate. Isopropenyl-α, α
The reaction and purification were conducted in the same manner as in Example 1 except for using 20 g of -dimethylbenzyl isocyanate to obtain 20 g of the title compound as a white solid. mp 73.2 ~ 76.0 ℃ ¹ HN.MR (CDCl ₃ , 400MHz) δ1.65 (6H, brs), 2.15 (3H,
dd), 3.50 (1H, brs), 3.78 (2H, brs), 4.14 (2H, brs),
5.09 (1H, s), 5.25 (1H, brs), 5.35 (1H, dd), 7.25-7.
30 (2H, m), 7.30-7.35 (2H, m). MASS (M ⁺ ) 263. According to the above analysis results, N- (4-isopropenyl-α,
Formation of (α-dimethylbenzyl) -2-hydroxyethyl carbamate was confirmed.

Example 3 Synthesis of N- (3-isopropenyl-α, α-dimethylbenzyl) -2-hydroxyethyl carbamate 10.0 g of 3-isopropenyl-α, α-dimethylbenzyl isocyanate, ethylene glycol mono Acetate (Product with monoacetate content of more than 60% by mass)
10 g of dibutyltin dilaurate (1000 ppm by weight of isocyanate) was mixed, and the mixture was stirred for 12 hours while maintaining the reaction solution temperature at 60 ° C. to perform a urethanization reaction. After completion of the reaction, 10 g of the reaction solution was dissolved in 30 ml of toluene, and 40 g of a 10% aqueous sodium hydroxide solution was mixed.
The hydrolysis reaction was performed by stirring for 4 hours while maintaining the reaction solution temperature at 90 ° C. After separating the reaction solution, the toluene layer was concentrated, developed with chloroform by silica gel column chromatography, and the separated liquid was concentrated to obtain 2.6 g of the title compound as a white solid. The analysis results of this compound were consistent with the analysis results described in Example 1.

[Application Examples] Hereinafter, the application of the present invention will be described in detail with reference to application examples, but the present invention is not limited thereto. This application example improves the heat resistance and chemical resistance of PMMA by crosslinking the compound represented by the formula (1) with a compound having a plurality of isocyanate groups and then copolymerizing the compound with methyl methacrylate. PMMA having a crosslinked structure with easy reaction control
Is to be able to be manufactured.

N- (3-isopropenyl-α, α-having both an isopropenyl group represented by the formula (1) and a hydroxyl group.
37.6 g of xylene diisocyanate was added dropwise to 26.3 g of (dimethylbenzyl) -2-hydroxyethyl carbamate while cooling so that the reaction solution temperature became 20 to 40 ° C., and reacted to obtain 63.9 g of a urethane compound (A). Was.

100 g of methyl methacrylate, 10 g of the urethane compound (A), 0.2 g of bis (4-t-butylcyclohexyl) peroxydicarbonate and t
-Butyl peroxyisopropyl carbonate 0.1 g
And defoaming the homogenized solution under reduced pressure.
It was poured into a mold composed of a mm square glass plate and a gasket of vinyl chloride. Then, the mixture was polymerized at 60 ° C. for 3 hours, gradually heated to 70 ° C., once cooled to 45 ° C., heated again at 60 ° C. for 8 hours, gradually heated, and polymerized at 110 ° C. for 1 hour. . The performance evaluation and measurement of the plate-like polymer taken out of the mold were performed by the following methods. As shown in Table 1, good results were obtained in all of the easiness of polymerization, heat resistance, and chemical resistance. (1) Ease of Polymerization The difficulty of a runaway polymerization reaction at the time of gelation at the time of casting polymerization was evaluated in the following stages. ：: does not occur, Δ: frequently occurs, ×: occurs. (2) Heat resistance T is measured by TMA analyzer TAS-300 manufactured by Rigaku Corporation.
The g point was measured. (3) Chemical resistance ASTM D. 543. ：: no change, Δ: swelled, ×: dissolved Created and evaluated. As shown in Table 1, the obtained polymer has heat resistance,
Poor chemical resistance.

Comparative Example 2 A plate polymer was prepared in the same manner as in the application example except that 20 g of ethylene glycol diacrylate was used instead of the urethane compound (A).
An evaluation was performed. The resulting polymer, as shown in Table 1,
It was inferior in ease of polymerization and chemical resistance as compared with the applied examples.

Comparative Example 3 A plate polymer was prepared and evaluated in the same manner as in the application example except that 5 g of triethylene glycol diacrylate was used instead of the urethane compound (A). As shown in Table 1, the obtained polymer was inferior in ease of polymerization, heat resistance and chemical resistance as compared with the applied examples.

[0035]

[Table 1]

From the application examples and the comparative examples, the urethane compound (A) produced using the compound of the present invention represented by the formula (1) is easy to control the polymerization reaction in copolymerization with PMMA, has high heat resistance and It was confirmed that the compound was useful as a compound for improving chemical resistance.

[0037]

According to the present invention, there has been provided a compound represented by the formula (1) which is a novel compound having two kinds of reactive groups, and a production method capable of obtaining this compound in good yield.

This compound is extremely useful as an intermediate of a compound that improves the control of polymerization reaction with PMMA, heat resistance and chemical resistance.

Continued on the front page (72) Inventor Noboru Kawasaki 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc. (72) Inventor Masahiro Shioji 580-32 Nagaura, Sodegaura-shi, Chiba F-term in Mitsui Chemicals, Inc. 4H006 AA01 AA02 AB49 AC41 AC56 BB70 BC10 BC31 BE60 RA10 4J100 AB15Q AL03P BA39Q CA03

Claims (6)

[Claims] (1) Formula (1) (Wherein the isopropenyl group is located at the meta or para position with respect to the other substituent). 2. Isopropenyl-α, α-dimethylbenzyl isocyanate or 4-isopropenyl-
The method for producing a compound according to claim 1, wherein α, α-dimethylbenzyl isocyanate and ethylene glycol are subjected to a urethanization reaction without a solvent or in a solvent having no reactivity with the raw materials. 3. 3-Isopropenyl-α, α-dimethylbenzyl isocyanate or 4-isopropenyl-
The method according to claim 2, wherein the urethanization reaction is carried out by using 1 to 10 moles of ethylene glycol per 1 mole of α, α-dimethylbenzyl isocyanate and setting the reaction solution temperature to 20 to 110 ° C. 4. 3-Isopropenyl-α, α-dimethylbenzyl isocyanate or 4-isopropenyl-
After subjecting α, α-dimethylbenzyl isocyanate and a monoester of ethylene glycol to a urethanization reaction without a solvent or a solvent having no reactivity with the raw materials, hydrolyzing a product of the urethanation reaction. The method for producing a compound according to claim 1, wherein 5. Isopropenyl-α, α-dimethylbenzyl isocyanate or 4-isopropenyl-
5. The method according to claim 4, wherein the urethanization reaction is carried out at a reaction liquid temperature of 20 to 110 [deg.] C. using 0.8 to 5 mol of ethylene glycol monoester with respect to 1 mol of [alpha], [alpha] -dimethylbenzyl isocyanate. 6. The method according to claim 4, wherein the hydrolysis is performed with an acid or an alkali.