JPS61212536A - Novel acrylate and production thereof - Google Patents

Abstract

NEW MATERIAL:2,5 (or 6)-Dihydroxy-1,6 (or 5)-cyclooctanediyldi-2-propenoate shown by the formula I. USE:Useful as a raw material or an improver for ink, coating compound, adhe sive, covering agent, or molding resin. Useful as an intermediate for a reaction of organic synthesis by using hydroxyl group as a reaction site. Having an advantageous structure with respect to problem of dispersion of photosensitive functional group. The novel substance can be synthesized inexpensively, and is economically and industrially advantageous. PREPARATION:1,2,5,6-Diepoxycyclooctane shown by the formula II or 1,2,5,6- cyclooctanetetraol shown by the formula III as a raw material is reacted with acrylic acid in the presence of a catalyst, to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a novel acrylate compound represented by the formula (2) and a method for producing the same.

The compound represented by formula (1) can be easily homopolymerized or copolymerized with other unsaturated group-containing compounds in the presence of heat, ultraviolet rays, ionizing radiation, or a radical polymerization initiator.

B. Conventional technology Various acrylic esters have been known so far.

For example, monofunctional monomers such as methyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate, etc.
Polyfunctional monomers such as I methylolpropane triacrylate, trimethylolpropane) +7 methacrylate, and pentaerythritol 17 acrylate are generally known. As monofunctional monomer β-hydroxyalkyl acrylates, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, etc. are known.

As a method for producing the above β-hydroxyalkyl acrylate, Japanese Patent Publication No. 44-31472, Japanese Patent Publication No. 45-146
5.Special Publication No. 45-15988, Special Publication No. 45-4oos9
．． @ 1977-28081, JP 47-28082,
The epoxy compound described in JP-A No. 48-28599 and Acryl i1! A method of reacting under a t-catalyst is known, but as in the present invention, a cyclooctane ring is
-Hydroxyalkyl acrylate - A method for introducing it into the root is not yet known.

On the other hand, U.S. Pat.
, 602 is known. This is a tetraester compound containing two or more ac+10yl groups in one molecule, which is obtained by reacting acrylic acid and an acid anhydride of other carboxyl powder with a dieboxide compound in the presence of a catalyst. This is what you get. However, the anhydride of acrylic acid and carboxylic acid used here is extremely expensive and, from an economic standpoint, has poor practicality as a crosslinking agent or resin modifier.

Means, action, and effect for solving the C1 problem In contrast, in the present invention, diacrylate is produced using acrylic acid or acrylic acid ester as a raw material, and these are all industrial raw materials and 1. It can be easily and inexpensively obtained.

Moreover, since the phosphor compound obtained here has acryloyloxy groups at both ends of the molecule, it has a structure that is advantageous in dealing with the problem of dispersing photosensitive functional groups.

This product is useful as a raw material or modifier for inks, paints, adhesives, coatings, and molding resins, and can also be used as a reaction intermediate for organic synthesis by using water groups as reaction sites. can.

What the present invention encompasses is a novel 2,5(!i or 6)-dihydroxy-1,6(
or 5]-cyclooctanediyldi-2-propenoate and its production method. The new compound represented by the chemical formula (1) is represented by the following formula (11).
, 2,5.6-jepoxycyclooctane is used as a starting material.

For the compound represented by formula (II), catalysts known as catalysts for hydroxyesterification of epoxy compounds, such as imidazoles such as 2-methylimidazole, quaternary ammonium salts such as tetramethylammonium chloride, benzyldimethylamine, and By reacting with acrylic acid in the presence of amines such as butylamine or lauric acid esters such as dibutyltin dilaurate (2°5 (or 6) expressed by the formula
-Dihydroxy-1,6 (or 5)-cyclooctanediyl di-2-10 penoate is synthesized.

The reaction temperature is 75 to 75°C from the viewpoint of shortening the reaction time and preventing polymerization.
Advantageously, it is carried out at 120°C.

A polymerization inhibitor is added to prevent thermal polymerization of acrylic acid. Such polymerization inhibitors include nohydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t
-butylphenol, 3-hydroxythiophenol,
α-nitroso-β-naphthol, p-benzoquinone, 2
．． Examples include 5-dihydroxy-p-quinone and copper salts.

The novel compound H represented by the chemical formula (I) (1,2,5,6-cyclooctanetetraol represented by the formula 1111) can also be used as a gold starting material.

In this case, the reaction is promoted by using a catalyst and continuously removing the water produced from the system.

The catalyst used here can be arbitrarily selected from known esterification catalysts such as sulfuric acid, p-toluenesulfonic acid, and boron trifluoride. It is advantageous to use an azeotropic solvent, such as toluene, to completely separate the nine molecules produced by the reaction.

D. Example The present invention will be explained below with reference to Examples.

[Example 1] 1.2,5.6-jepoxycyclooctane (11) 2
10f% p-methoxyphenol 13.5F, 2-
Ethyl-4-methylimidazole 4f'i toluene 30
09Kid solution and reflux with stirring, Aku'I
/I/I! It was dripped at 324ft for 2 hours. After the dropwise addition was completed, the reaction was allowed to continue for an additional hour and then cooled. The reaction mixture was completely neutralized with sodium carbonate saturated water IW solution, and then washed with saturated brine until it no longer showed alkalinity. The solvent was distilled off under reduced pressure.
I got 230, my friend.

[Example 2] 1.2,5.6-jepoxycyclooctane (!I) 2
1 (1% p-methoxyphenol 13.5 f, II ethylbenzylammonium chlora()'1.5?
A solution of 300 fVCIW in toluene was refluxed with stirring and added dropwise over 2 hours. After the dropwise addition was completed, the reaction was allowed to continue for an additional hour and then cooled. The reaction mixture was neutralized with a saturated aqueous solution of sodium carbonate, and then washed with saturated brine until it no longer showed alkalinity. When the solvent was distilled off under reduced pressure, colorless liquid compound (1) 1629 was obtained.

The liquid compound (+)H obtained in the example has a low odor,
It has the following properties.

・Boiling point ('C/Hg per day): 110 ・Infrared absorption spectrum (liquid desert, cm-'') 3440 (OH stretching vibration of secondary alcohol) 2930 (CH stretching vibration) 1720 (C=0 of acrylic ester Stretching vibration] 1628.1615 (CH ro of acrylic ester =
CH-Stretching Vibration) 1405 (CH-Stretching Vibration of Acrylic Acid Ester=CH-
In-plane bending vibration] 1183 (C-〇-stretching vibration of acrylic acid ester) ・Nuclear magnetic resonance spectrum k (“CNMR, 89,55MH
zCDC4,), δ (ppm) a: 130.7 b: 12s,.

e:165. O d: 66.1 ~ 81.3 e: 21.3 ~ 27.8 Procedural amendment written by Shiro Uo July 10, 1985 Commissioner of the Patent Office Manabu Shiga e 1, Indication of the case 1985 Patent Application No. 52866 No. 2, Name of the invention New acrylate and its manufacturing method 3, Relationship with the case of the person making the amendment Patent applicant address 1-4-5 Marunouchi, Chiyoda-ku, Tokyo
Name (234) Sanyo Kokusaku Valve Co., Ltd. 4, Agent address: 16 Kanda Kita Jorimono-cho, Chiyoda-ku, Tokyo
101 English Building 3rd Floor 5, Section 6 of the detailed description of the invention in the specification to be amended, Contents of the amendment Contents of the amendment 1. On page 7, line 13 of the specification, the phrase "after neutralization" has been corrected to "after washing."

2. On page 9, line 4 of the same It says r89,55 J. Corrected to r　22.5J.

Claims (2)

[Claims] (1) An acrylate compound represented by the following chemical formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (2) The following chemical formula ( I
) A method for producing an acrylate compound represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)