JPH04173812A - New methacrylic acid derivative and its polymer - Google Patents

Abstract

NEW MATERIAL:A derivative shown by formula I (R is 1-30C aliphatic group; Ar is 5-14C aromatic group which may contain N, O or S). EXAMPLE:Methacrylic acid cyclohexyldiphenylmethyl ester. USE:A raw material for a polymer useful as an optically resolving agent. PREPARATION:A carboxylic acid ester shown by formula II is allowed to react with a Grignard reagent to give an alcohol shown by formula III, which is then reacted with methacrylic acid chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel methacrylic acid derivative and its polymer, which are extremely useful as, for example, optical resolution agents and resist agents.

[Problems to be solved by conventional techniques and inventions] Conventionally,
A monomer that itself has no asymmetric carbon and does not exhibit optical activity is polymerized using an optically active initiator, and the resulting polymer has an optical rotation that exceeds that due to the optically active group of the initiator used. It is known that there are examples showing luminosity.

For example, an isotact polymer obtained by anionic polymerization of methyl methacrylate using an optically active Grignard reagent exhibits too large an optical rotation, considering that the optical rotation is based solely on the contribution of optically active groups introduced as terminal groups. (Abstracts of the 22nd Annual Meeting of the Chemical Society of Japan (19
69) See page 211).

On the other hand, triphenylmethyl methacrylate is known to produce isotactic polymers regardless of the polymerization conditions due to steric hindrance due to the presence of bulky substituents, and the isotactic chains are tightly formed. It is estimated that it has a helical structure. However, this polymer obtained by polymerization using a common initiator does not exhibit optical activity because the winding direction produces the same number of helices on the left and right sides (J, Po1y...).

Sci., Part B, 6.753 (1968
)reference).

The present inventors have discovered that a highly optically active polymer of triphenylmethyl methacrylate or a derivative thereof can be obtained by polymerizing triphenylmethyl methacrylate or a derivative thereof using an optically active anionic polymerization initiator. I have already filed a patent application for the patent application
No. 29, JP-A-57-209908, JP-A-57-2
(Refer to each publication No. 12143).

An object of the present invention is to provide a polymer of optically active methacrylic acid derivatives different from those mentioned above.

[Means for solving the problem] The present inventors added a bulky substituent to methacrylic acid,
The present invention was completed as a result of intensive research aimed at increasing functionality by polymerizing with a chiral catalyst.

That is, the present invention uses a methacrylic acid derivative represented by the following general formula (1) and this methacrylic acid derivative as a raw material,
The present invention provides an optically active polymer mainly composed of a structural unit represented by the following general formula (2), which is obtained using an optically active polymerization initiator or an optically active catalyst.

CH3 CH2=c C=O R-C-Ar? Ar (However, R is an aliphatic group having 1 to 3 carbon atoms, preferably a cyclic alkyl group or a chain alkyl group having 1 to 20 carbon atoms. Ar is a phenyl group, a naphthyl group, etc. is an aromatic group having 5 to 14 carbon atoms and may contain N, O, and S atoms.) CH.

-(CF12-Ch- C=0 -C-Ar Ar (However, R and Ar have the same meanings as above.) The methacrylic acid derivative represented by the above general formula (1) is represented by the following general formula (3) It is obtained by reacting a carboxylic acid ester represented by the above with a Grignard reagent to obtain an alcohol represented by the following general formula (4), and reacting this alcohol with methacrylic acid chloride.

Ar (3) ArRCOHG
Hz=C I Ar c=.

■ (4).

-C-Ar Ar (In the above series of formulas, R and Ar have the same meanings as above.) The optically active polymer mainly composed of the structural unit represented by the above general formula (2) of the present invention is It is obtained by ionic polymerization using a methacrylic acid derivative represented by the general formula (1) as a raw material and using an optically active polymerization initiator or an optically active catalyst.

Examples of the optically active polymerization initiator or optically active catalyst used here include anionic polymerization initiators comprising an organometallic compound and an asymmetric ligand compound. The organometallic compound may be any compound as long as it can form a complex with the asymmetric ligand compound, and includes an alkali metal, alkaline earth metal, aluminum, or similar metal as a counterion, and carbon, nitrogen, or anion as an anion. Organometallic compounds consisting of oxygen, sulfur, etc. are used. Specifically, N,
Examples include lithium amide of N'-diphenylethylenediamine.

As the asymmetric ligand compound, optically active (+)- or (-)-spartine, (S)-(+)- or (R)-(-) -1(2-pyrrolidinylmethyl)pyrrolidine , (S,S)-(+)- or (R,R)-(
-)-2,3-dimethoxy-1,4-bis(dimethylamino)butane and the like.

A preferred method for preparing the catalyst of the present invention is to mix an organometallic compound and a dehydrated and dried asymmetric ligand compound in an amount equivalent to or slightly more than the organometallic compound in a solvent, for example, a hydrocarbon solvent. The mixture is mixed to form a complex and used as a polymerization catalyst. When polymerizing the methacrylic acid derivative represented by the above general formula (1) using the polymerization catalyst prepared in this way, it is not necessary to use a solvent, but it is also possible to polymerize the methacrylic acid derivative by dissolving it in a solvent. In this case, the solvent used must not inhibit anionic polymerization.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Mecryl cyclohexyldiphenylmethanol was reacted with 2.3g of methyl cyclohexanecarboxylate in ether by adding 2 equivalents of phenylmagnesium bromide, and 3.97g of cyclohexyldiphenylmethanol (yield 92%, melting point 68°C).

After dissolving this in 25++1 of tetrahydrofuran (THF) and cooling to -78°C, 11++1 of a butyllithium/heptane solution was added, and then 25++1 of methacrylic acid chloride was added.
．． Added 8a+1. After the reaction was completed, THF was distilled off, ether was added, and the mixture was washed with a saturated aqueous sodium carbonate solution and a saturated aqueous sodium chloride solution. After further purification by silica gel column chromatography, it was recrystallized from hexane and cyclohexyldiphenylmethyl methacrylate o,! 5o
g (yield 10%, melting point 74.3-75.1°C) was obtained.

The IR spectrum and 'H-NMR spectrum of the obtained cyclohexyldiphenylmethyl methacrylate are shown in FIG. 1 and FIG. 2, respectively.

Example 2 Polymerization of cyclohexyldiphenylmethyl was carried out in a sufficiently dried glass polymerization tube under a nitrogen stream. First, cyclohexyldiphenylmethyl methacrylate 0.
Dissolve 15g in 3L of toluene and heat at -78°C.
It was cooled to Next, the catalyst was prepared by reacting n-butyllithium with an equivalent amount of N,N'-diphenylethylenediamine in hexane at room temperature to synthesize a lithium amide of N,N''-diphenylethylenediamine, and a 1.2-fold equivalent of the asymmetric Ligand compound (+) -1(2-pyrrolidinylmethyl)
A complex was synthesized by adding pyrrolidine.

This was added to a toluene solution of the monomer to initiate polymerization.

After 24 hours, the polymerization was stopped with a small amount of methanol and the polymer was precipitated into 100 ml of methanol. It was immediately centrifuged and vacuum dried at 50°C.

Table 1 shows the yield, optical rotation, degree of polymerization, and tacticity of the obtained polymer.

Example 3 Synthesis of cyclopropyldiphenylmethyl methacrylate Commercially available cyclopropyldiphenylmethanol 5.47 g
was dissolved in 50 ml of THF and diluted with NaH1,
21 g was added and reacted at 50°C for 8 hours. To this was further added dropwise a solution of methacrylic acid chloride 3II+1 in THF under water cooling, and the mixture was stirred for 1.5 hours. After concentration, ether was added, and the mixture was washed with distilled water, saturated aqueous sodium bicarbonate solution, and saturated aqueous sodium chloride solution. After dehydrating the ether solution with anhydrous magnesium sulfate, the ether was distilled off and recrystallized from hexane to obtain 1.85 g of cyclopropyldiphenylmethyl methacrylate (yield 26.1%, melting point 69.7-70.1°C) ) was obtained.

The IR spectrum and 'H-NMR spectrum of the obtained cyclopropyldiphenylmethyl methacrylate are shown in FIG. 3 and FIG. 4, respectively.

Example 4 Mecryl cyclopropyldiphenylmethyl side 1 L
±LL cyclopropyldiphenylmethyl methacrylate 0.15
The same operation as in Example 2 was performed using g.

Table 1 shows the yield, degree of light application, degree of polymerization, and tacticity of the obtained polymer.

Example 5 Cyclopropyldiphenylmethyl methacrylate 0.15
g, as an asymmetric ligand (S,S)-(+)-2,
The same operation as in Example 2 was performed using 3-dimethoxy-1,4-bis(dimethylamino)butane.

Table 1 shows the yield, degree of light application, degree of polymerization, and tacticity of the obtained polymer.

Table 1 Note) a) Optical rotation was determined using JASCO DIP-1 in chloroform.
Measured with 81 DIGITAL POLARIMETER.

b) The degree of polymerization was measured by converting the polymer into polymethyl methacrylate and using gel chromatography.

[Effects of the Invention] The novel polymer of the present invention has optical activity and is very useful as an optical resolution agent and the like.

[Brief explanation of the drawing]

Figure 1 shows the IR spectrum of cyclohexyldiphenylmethyl methacrylate obtained in Example 1, and Figure 2 shows its 'H-
This is an NMR spectrum. Figure 3 shows the IR spectrum of cyclopropyldiphenylmethyl methacrylate obtained in Example 3, and Figure 4 shows its 'H-
This is an NMR spectrum.

Claims (1)

[Claims] 1. A methacrylic acid derivative represented by general formula (1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (However, R is an aliphatic group having 1 to 30 carbon atoms, Ar is an aromatic group having 5 to 14 carbon atoms, N, (O and S atoms may be included.) 2. The compound of the following general formula (2) obtained using the methacrylic acid derivative according to claim 1 as a raw material and using an optically active polymerization initiator or an optically active catalyst. An optically active polymer consisting mainly of the structural units shown. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (2) (However, R and Ar have the same meanings as above.)