JPS62167773A - Crown ether (meth)acryloyl compound - Google Patents

Abstract

NEW MATERIAL:A crown ether (meth)acryloyl compound expressed by formula I (R is H, CH3 or C2H5; n is 1 or 2; Q is formula II when n is 1 and formula III when n is 2; m is 0 or 1). EXAMPLE:A crown ether acryloyl compound expressed by formula IV. USE:Capable of readily homopolymerizing or copolymerizing in the presence of a polymerization catalyst to form a transparent thermoplastic polymer containing the crown ether and having expected uses as a raw material for synthetic resins of optical members since the compound is supposed to have a high refractive index. PREPARATION:A crown ether, e.g. a compound expressed by formula V or VI, is reacted with an ester or halide of an unsaturated carboxylic acid to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel polymerizable compound that is expected to be applied as a raw material for synthetic resins containing crown ether (meth)7 spider crown ether.

[Prior art] Crown ether is basically (CI2GH20)n
It is a monocyclic, macrocyclic polyether with the structure of
Other applications are being attempted in a wide range of fields, such as use as a phase transfer catalyst.

Among macrocyclic polyethers, macrocyclic bicyclic diamino polyethers having a nitrogen atom in the structure H1M5 are called cryptands, and are known to be complexes with various metal salts as described above. It is a compound.

Regarding crown ether products resulting from the reaction of cryptand with other compounds, and methods for producing the same, there are many proposals regarding analytical reagents, and this is because cryptand exhibits the above-mentioned properties. However, there are few proposals regarding polymerizable or curable compounds containing cryptand. Such curable compounds include, for example, crown ether epoxy compounds reacted with epoxy compounds, which are cured with a curing agent and used for molding,
In JP-A No. 5, it was discovered that it was useful as a compound for other resins.
It is disclosed in Japanese Patent No. 8-57378.

[Problems to be Solved by the Invention] Although the crown ether epoxy compound described above can be cured by reacting with a curing agent to form resins in various forms,
The resin is thermosetting.

Therefore, there is no known compound that contains a crown ether and has polymerizability and exhibits thermoplasticity as a monopolymer.

The objective of the present invention is to provide a novel compound containing a crown ether, which is suitable for molding optical members that require excellent optical properties and which can be used as a thermoplastic polymer. That is.

[F stage for solving problems] The present invention is based on the general formula (wherein, R is H, i13, C2h, n is an integer of 1 or 2, Q is a crown ether, and n is 1). It is a crown ether (meth)acryloyl compound represented by (1m indicates the !i! number of O or 1).

The crown ether (meth)acryloyl compound of the present invention can be obtained by reacting a crown ether produced by a known method with an ester of an unsaturated carboxylic acid or a halide of an unsaturated carboxylic acid.

The crown ether used here is 1, for example, They can be used with commercially available products.

Further, the specific ester of unsaturated carboxylic acid or /\ride of unsaturated carboxylic acid used is as follows.

shih2=sheet t, ;ut, L
;112 = t, ;-subr.

These are (meth)acrylic acid esters or (meth)acrylic acid halides.

The reaction method depends on whether a (meth)acrylic acid ester or a halide as exemplified above is used as a raw material, which is selected according to the crown ether (meth)acryloyl compound as the desired reaction product, and the catalyst, reaction conditions, etc. be slightly different.

When (meth)acrylic acid ester is used, it is preferable to react in the presence of a catalyst.

Examples of catalysts include e-sulfuric acid, concentrated phosphoric acid, polyphosphoric acid,
The reaction in which a catalytic amount of para-toluenesulfonic acid, litharge, etc. is added can be carried out in a solvent system in which the crown ether is dissolved in an organic solvent capable of dissolving the crown ether, for example, tetrahydrofuran, but it is not necessary to use a solvent. Crown ether and (meth)acrylic acid ester can be directly reacted in a solvent-free system. In the case of a reaction in a solvent system, it is preferable to gradually heat the reaction temperature to raise the temperature to 71 degrees to the boiling point of the (meth)acrylic acid ester or solvent, and carry out the reaction while refluxing them. In the reaction of 1, it is preferable to gradually raise the reaction temperature so that the alcohols produced are distilled out of the reaction system as the reaction progresses.Therefore, it is preferable to raise the temperature sufficiently to carry out these reactions. Preferably,
Considering these conditions, the reaction temperature is 50°C to 200°C.
°C, preferably 30 °C to 150 °C, the reaction time is
1 to 8 hours is sufficient in the temperature range specified in E.
After the reaction, in a solvent-based reaction, the solvent and the alcohols produced during the reaction are distilled off, and the resulting product is poured into cooled petroleum ether, for example.
Precipitate the desired crown ether (meth)acryloyl compound.

It can be precipitated and separated.

・Also, when using (meth)acrylic acid halide, 1
The reaction system may be either a solvent system or a non-solvent system as in the case of the ester in L. Also, a catalyst may not be used, and if the reaction is carried out in the presence of a catalyst, for example, pyridine , :・Y-based soda, :-Y-based potash, etc. are added in a catalyst amount. The inside of the reaction system is preferably kept in a dry atmosphere to prevent moisture from entering. 6. The reaction temperature is the same as that for the esters mentioned above. Under the conditions, the hydrogen halide gas generated during the reaction is released from the reaction system and separated, and the reaction temperature is 50°C to 200°C, preferably 30°C to 150°C.
The reaction time is 30 minutes to 5 minutes in this temperature range. After one reaction, if the reaction is a solvent system, the solvent is distilled off.

The desired crown ether (meth)acryloyl compound is precipitated by pouring the reaction product thus obtained into, for example, n-hegisan.

1 fll can be precipitated.

The (meth)acrylic ester or halide to which a polymerization inhibitor is added is preferably used, since it prevents polymerization during the reaction.

The charging ratio (molar ratio) of crown ether (meth)acrylic acid ester or halide is based on the reaction, for example,
Since the following formula is followed for methyl acrylate, are the two moles equivalent?

Alternatively, 2 moles of (meth)acrylic ester or halide may be used per 1 mole of crown ether, or it is preferable to use a slight excess of (meth)acrylic ester or halide.

The crown ether (meth) 7 represented by the general formula +1ij according to the present invention is soluble in common organic solvents and has a polymerizable group in one molecule, so it can be used as a common polymerization catalyst 1 such as benzoinosyl peroxide. The presence of peroxides allows for chemical hardening. Therefore, it is assumed that monopolymerization of the crown ether (meth)acryloyl compound alone or in combination with other transparent nail platform compounds results in a colorless and transparent polymer with a high refractive index. Because
As a synthetic resin raw material for optical components. Expected to apply 5″-
[Example] Example 1 Methyl acrylate (contains a small amount of phenothiazine as a polymerization inhibitor) 18.8 parts (small amount, one round) and the following formula, Cryptand (゛Cryptofix 122
": Merck & Co. product) 2B, 2 parts were charged into a reactor, and 0.5 part of para-toluenesulfonic acid was added as a catalyst. The temperature inside the reactor was gradually raised by heating with stirring, and the reaction was started. Methanol generated as the reaction progresses is distilled out of the reaction system, and the temperature inside the reactor is maintained at about 90°C, and when the reaction time from the beginning reaches 4 hours,
The heating was stopped and the reaction was terminated by cooling to room temperature.
The reaction product was taken out from the reactor, poured into cooled petroleum ether, and the white precipitate that precipitated was collected.
5.8 parts of a white solid product were obtained.

The melting point of the obtained white product is 18.7°C to 13.7°C, and in IR analysis, its IR chart is as shown in Figure 1, and the single element analysis value is as follows. It was confirmed that the compound was a crown ether acryloyl compound represented by the following formula.

0% N% N% Theoretical value 58.38 8.11 7.57 Actual side Ill1i 58.43 8
．． 05 7.55 Example 2 Acrylic acid chloride (contains trace amount of polymerization inhibitor) 1
9.0 parts, and Cryptand similar to Example 1 (“Cryptofix 122”: Merck & Co. product) 26.
Charge 2 parts into a reactor, install a calcium chloride pipe in the reactor to prevent moisture from entering the reactor, and after purging the inside of the reactor with dry air, gradually heat it from room temperature. After the 0 reaction, the reaction was carried out for 2 hours while refluxing at about 80°C and removing the generated hydrogen chloride gas from the reactor.
Cool to room temperature and remove one reaction product from the reactor;
The oil was poured into 200ml of cooled n-hexane, and the white precipitate that precipitated was collected to obtain 35.6 parts of a white solid product.

The melting point of the obtained white product was 18.8°C to 19.6°C, and the IR analysis confirmed that it was the same crown ether acryloyl compound as in Example 1. Furthermore, the results of single-element analysis were as follows, which confirmed that the compound was a diaphragm compound.

0% N% N% Theoretical value 58.38 8.11 7.57 Actual value 58.44 8.06 7.54 Reference example Cryptand used in Examples 1 and 2 (“Cryptofix 122”: Merck & Co. product) A chart based on IR analysis is shown in Figure 2.

[Effect of the Invention 1 The crown ether (meth)acryloyl compound of the present invention is a new compound. The compound mentioned above depends on the presence of a polymerization catalyst F
It is easily polymerized by a polymerization reaction, and can be a homopolymer or a copolymer with other polymerizable polymers. It is assumed that these polymers are transparent, malleable and W-like polymers, and have a high refractive index. Therefore, the compound of the present invention is expected to be applied as a raw material for synthetic IIM of optical members.

[Brief explanation of drawings]

Figure 1 is an IR chart of the crown ether acryloyl compound produced in Examples 1 to 2 of Kibasu 1, and Figure 2 is an IR chart of the cryptand compound in the reference example.
It is a chart.

Claims (1)

[Claims] General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R is H, CH_3, C_2H_5, n is an integer of 1 or 2, Q is a crown ether, and when n is 1▲ A crown ether (meth)acryloyl compound represented by ▼, when n is 2, ▲, where n is 2, ▲, where m is an integer of 0 or 1).