JPS5855445A - 2-methylpropylene glycol di(meth)acrylate - Google Patents

Abstract

NEW MATERIAL:2-Methylpropylene glycol di(meth)acrylate of the formula (R is H is or methyl). USE:Useful as a raw material or intermediate for thermosetting coating materials, adhesives, photosensitizers, crosslinking agents, modifiers of copolymers, etc. PROCESS:An acid chloride of acrylic or methacrylic acid is dehydrochlorinated with a glycol to give a compound of the formula. For example, 2-methylpropylene glycol and a tertiary amine, e.g. pyridine or triethylamine, in a molar amount of twice that of the 2-methylpropylene glycol are reacted with the acid chloride of acrylic or methacrylic acid in a molar amount of twice of the 2- methylpropylene glycol in a solvent, e.g. benzene or ether. The compound of the formula is characterized by the following facts compared with glycol di(meth) acrylate: The polar effect due to the electron releasing effect of the methyl group, eliminative effect of the hydrogen atom (in the methine group) joined to the same carbon atom as the methyl group by the covalent bond or the high reactivity of the polymerizable double bonds at both ends.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention provides novel diacrylate or dimethacrylate c
(hereinafter abbreviated as di(meth)acrylate).

Generally, most glycol di(meth)acrylate-F is synthesized by reacting acrylic acid or methacrylic acid with glycol.

The above-mentioned glycols known so far include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, phlopylene gelicol, I,! -Fujire y y y Ko-J/, 1s4-
Futhylene gelicol, neopentyl glycol, 1.
6-hext)fV7 glycol, etc.

These glycol di(meth)acrylates have two heavy metal vinyl groups in one molecule, so they can be used as thermosetting paints,
It is used in a wide range of applications as raw materials and intermediates for adhesives, nonwoven fabric binders, photosensitive agents, paper processing agents, copolymer modifiers, crosslinking agents, etc., but glycol di(meth) is the most suitable for each application. ) K to obtain acrylate
The type of glycol must be carefully selected. The present inventors conducted extensive research to expand the range of selection, and as a result, 2-methylpropylene glycol di(meth)acrylate, synthesized using 2-methylpropylene glycol as the glycol, is a completely new compound. In addition, they also discovered that they have unique properties compared to conventionally known glycol di(meth)acrylates, leading to the present invention.

That is, the present invention provides a novel 2-methylpropylene glycol di(meth)acrylate represented by the general formula (R in the formula is hydrogen or a methyl group).

2-Methylpropylene glycol, which is the glycol component of 2-methylpropylene glycol di(meth)acrylate produced by 1jllK, can be produced industrially by the oxidation reaction of isobutyne or the oxo reaction of allyl alcohol. Characteristics include that it is asymmetric with respect to the main chain of the molecule because it has one methyl group on the carbon atom in the position, and that it is highly chemically reactive because both terminal hydroxyl groups are primary. It is a glycol with

In general, methods for synthesizing glycol-based (meth)acrylates include (1) dehydrochlorination reaction between an acid chlorophyte of acrylic acid or methacrylic acid and glycol, (2) a reaction between a glycol monoacrylate rust conductor and an acid g2ide of acrylic acid or methacrylic acid. (3) a transesterification reaction between a lower alkyl ester of acrylic acid or methacrylic acid and glycol; and (4) a direct dehydration reaction between acrylic acid or methacrylic acid and glycol.

The 2-methylpropylene glycol di(meth)acrylate of the present invention is the above-mentioned (1), (2), (3) and (4).
), but to specifically describe the reaction (1) as an example, 2-methylpropylene glycol and 2 times the mole of pyridine or a tertiary amine such as triethylamine are mixed with a stirring blade. Ether, benzene, toluene, stored in a reactor equipped with
Pour into a solvent such as aromatic hydrocarbons such as xylene or aliphatic or alicyclic hydrocarbons such as hexane or cyclohexane, and slowly add 2-methylpropylene while stirring and maintaining the temperature at 0 to 10°C. After dropping 0 drops of acrylic acid chloride or methacrylic acid chlorophyte of glycol, it was allowed to fully react for 5 to 8 hours.
The generated ammonium hydrochloride is removed from the reaction mixture by random means. Next, the solvent is distilled off from the KF liquid by vacuum distillation, and the residue is then vacuum distilled to obtain the objective 2-methylpropylene glycol di(meth)acrylate as a colorless and transparent liquid. Compounds can be identified by infrared absorption spectroscopy, nuclear magnetic resonance spectroscopy, elemental analysis, etc.

2-Methylpropylene glycol di(meth)acrylate obtained by the present invention has a side chain methyl group in the glycol group, so it has a polar effect due to the electron pushing action of the methyl group, and has the same covalent bond to the li atom as the methyl group. Thermosetting paints are developed by utilizing characteristics different from conventionally known glycol group (meth)acrylates, such as the detachment effect of hydrogen atoms (methine hydrogen atoms) and the high reactivity of polymerizable double bonds at both ends. It can be widely applied as a raw material or intermediate for adhesives, photosensitizers, crosslinking agents, copolymer modifiers, etc. The present invention will be explained in detail by examples below, but the present invention is not limited by these. Parts in the examples refer to parts by weight; infrared absorption spectra are based on IR Mu-2 lid manufactured by JASCO Corporation, and magnetic resonance spectra are measured using 0-45. I (measured using Lfi).

Example 1 501 parts of 2-methylpropylene glycol and 101 parts of ethyl alcohol were stirred vigorously using 101 parts of dry ether as a solvent, and the reaction vessel was cooled with ice water to maintain the reaction temperature at 0 to 10°C. , acrylic acid rx, 9
100 parts of hydride was slowly added dropwise. After dropping, ii
Stirring was continued for 5 hours at a warm temperature and after confirming that the reaction had progressed sufficiently, the triethylamine hydrochloride was separated from the reaction mixture P, the P solution was washed with water until it became neutral, and it was dried over magnesium oxide anhydride. After filtration, the solution was distilled off under reduced pressure to obtain 102 parts of a pale yellow liquid substance. When cuprous chloride S@, which is known as a polymerization inhibitor, was added to this substance and vacuum distilled, a colorless and transparent liquid substance 90s was obtained (71'C,
7511g) e The structural formula of the liquid substance obtained after 5K is based on principal analysis,
Infrared absorption spectrum, nuclear magnetic resonance spectrum 2-
It was confirmed that it was methylpropylene glycol diacrylate.

Elemental analysis Actual value Calculated value o
40.55 60.601 (6,9
27,12 Infrared IImWk yield spectrum 1720 ex-' shows carbonyl group of ester moiety, 1
Absorption derived from the terminal vinyl group is shown at 6403-' and from the carbonylmethyl group at 1420a11-'.

Nuclear magnetic resonance spectrum 5.70-6.50 ppm olefin proton
6H4,10pI) II Methylene proton 412.25 H) ■ Methylene proton
1H1,05pp job Methyl proton
5H Example 2 50 parts of 2-methylpropylene glycol and 6 parts of acrylic acid
2 parts to 10 G parts of dry benzene, 065 parts of 2,6-di-t-butyl-p-cresol as a polymerization inhibitor and 4.0 parts of p-toluenesulfonic acid as a dehydrating agent,
The mixture is refluxed for 5 to 8 hours using benzene, an organic solvent that forms an azeotrope with water and substantially separates the water. Thereafter, the reaction mixture was washed with water until it became neutral, dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain 85 parts of a pale yellow liquid substance. 5 parts of steel chloride, known as a polymerization inhibitor, was added to this substance and vacuum distilled to obtain 80 parts of a colorless and transparent liquid substance (74°C, 15°C).
．． 5.jig) *The structural formula of the liquid material thus obtained showed exactly the same spectrum data as in Example 1, and thus it was confirmed that it was 2-methylpropylene glyco-kX) acrylate.

Example S 116 parts of 2-methylpropylene glycol and 116 parts of ethylamine were stirred vigorously using 100 parts of dry ether as a solvent. 116 parts of acid Ωride was slowly added dropwise. After 6 drops, stirring was continued for 5 hours using an electric appliance to confirm that the reaction had progressed sufficiently, and the hydrochloride of triethyl ai) was removed from the reaction mixture door to door. Then, the P solution was washed with water until it became neutral, dried over anhydrous magnesium sulfate, and the IW medium was distilled off under reduced pressure to obtain 110s of a pale yellow liquid substance. 5 m of di-chlorinated steel, known as a polymerization inhibitor, was added to this substance, and 95 parts of a colorless and transparent liquid substance was obtained by vacuum distillation (62°C/
2■Hg).

The structural formula of the liquid substance obtained in this way was determined by elemental analysis.
2- from infrared absorption spectrum and nuclear magnetic resonance spectrum
II&I determined that it was methylpropylene glycol dimethacrylate.

Elemental analysis Actual value Calculated value 0 4 5.4 2 6 5
．． 7 0H7,928,02 Infrared absorption spectrum 172051-' shows carbonyl group of ester bond, 14
42cIlr' K-terminal vinyl group, 1420cm1 (indicates absorption derived from carbonylmethine group).

Nuclear magnetic resonance spectrum 5.84 ppwr olefin proton
4H4・1 4 ppm methylene proton
4H2,2S pp grave methine proton
IHl, 95 $1p■ Methyl proton
6Hs, o o ppm methyl proton
5th day applicant representative old SS

Claims (1)

[Claims] t 2 represented by the general formula (a in the formula is water or a methyl group)
-Methylpropylene glyc; -di(meth)acrylate