JPS5849339A - 2-methylpropylene glycol monoacrylate - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula (R is H or CH3). USE:A raw material or intermediate for thermosetting coating compound, adhesives, crosslinking agents, etc. PROCESS:For example, equimolar amounts of 2-methylpropylene glycol and a tertiary amine(e.g., pyridine, triethylamine) are poured to a solvent(e.g., ether, benzene, hexane), and (meth) acrylic acid chloride in an amount equimolar with 2-methylpropylene glycol is slowly added dropwise to it at 0-10 deg.C with stirring. The reaction is carried out for 5-8hr after the addition of (meth) acrylic acid chloride the prepared ammonium hydrochloride is removed, the filtrate is distilled under reduced pressure and distilled in a vacuum, to give a compound shown by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a new acrylate product.

Generally, most glycol monoacrylates are 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, propylene glycol, 1,3-butylene glycol, 1,4-phthylene gelicol, neopentyl glycol, 1.6' -A-
Xamethylene glycol etc. are used. These glycol monoacrylates share a polymerizable vinyl group and an active hydroxyl group in one molecule, so they can be used in thermosetting paints, adhesives, nonwoven fabric binders, modifiers for copolymers for paper processing, ion exchange resins, and dental materials. It is used in a wide range of applications as a raw material and intermediate for crosslinking agents, fiber treatment agents, etc., but the type of glycol must be carefully selected to obtain the most suitable glycol monoacrylate for each application. No.

As a result of intensive research to expand the range of selection, the present inventors discovered that 2-methylpropylene glycol monoacrylate, which was synthesized using 2-methylpropylene glycol as the glycol, was a completely new compound. It was discovered that it has unique properties compared to conventionally known glycol monoacrylates, leading to the present invention.

That is, the present invention provides the general formula CH2=CRCO2CH2CH, CH20H, (1)C
A novel glycol monoacrylate represented by H3 (R in the formula is hydrogen or methyl group) is provided.

2-Methylpropylene glycol, which is the glycol component of 2-methylpropylene glycol monoacrylate according to the present invention, can be produced industrially by the oxidation reaction of isobutyne or the oxo reaction of allyl alcohol, but due to its chemical structure, , it has one methyl group at the 2-position carbon atom, so it is asymmetrical with respect to the main chain of the molecule, and the hydroxyl groups at both ends are both primary, so it is highly chemically reactive. It is a glycol with special characteristics.

Generally speaking, glycol monoacrylate is synthesized by reacting methyl methacrylate with ethylene oxide.
-Excluding examples in which hydroxyethyl methacrylate is synthesized, (1) Aku IJ) dehydrochlorination reaction of acid chloride of chloric acid or methacrylic acid with glycol, (2)
Synthesis methods include (3) a transesterification reaction between a lower alkyl ester of acrylic acid or methacrylic acid and a glycol, and (3) a direct dehydration reaction between acrylic acid or methacrylic acid and a glycol.

Although the 2-methylpropylene glycol monoacrylate of the present invention can be synthesized by any of the reactions (1), (2), and (3) above, the reaction (1) will be specifically described as an example. 2-Methylpropylene glycol and an equimolar amount of tertiary amine such as pyridine or triethylamine are stored in a reactor equipped with stirring blades, and aromatic hydrocarbons such as ether, benzene, toluene, xylene, or hexane or cyclohexane. The mixture is poured into a solvent such as a hydrocarbon such as 2-methylpropylene glycol, and an equimolar amount of acrylic acid chloride or methacrylic acid chloride as 2-methylpropylene glycol is slowly added dropwise from the surface while stirring and maintaining the temperature at 0 to 10°C. After the dropwise addition, the reaction mixture is sufficiently reacted at room temperature for 5 to 8 hours, and then the ammonium hydrochloride produced by filtration is removed from the reaction mixture.

Next, the solvent of liquid j' is distilled off under reduced pressure.

Thereafter, the residue is vacuum distilled to obtain the desired colorless and transparent liquid 2-methylpropylene monoacrylate. ``Nuclear compounds can be determined by infrared absorption spectroscopy, nuclear magnetic resonance spectroscopy, elemental analysis, etc.

2-Methylpropylene glycol monoacrylate obtained by the present invention has a side chain methyl group in the glycol component, so there is a polar effect due to the electron pushing action of the methyl group, and a hydrogen atom covalently bonded to the same carbon atom as the methyl group. Utilizing the separation effect of (methane hydrogen atoms) or the high reactivity of terminal polymerizable vinyl groups and terminal hydroxyl groups, it has a wide range of applications as raw materials and intermediates for thermosetting paints, adhesives, crosslinking agents, etc. Be expected.

The present invention will be explained in detail below with reference to Examples, but the present invention is not limited thereto.

In addition, parts in the examples mean parts by weight, infrared absorption spectra were measured using JASCO IRA-2 model, and nuclear magnetic resonance spectra were measured using JEOL C-60HL model.

Example-1゜50 parts of 2-methylpropylene glycol and 56 parts of triethylamine were stirred vigorously using dry ether as a solvent, and the reaction vessel was cooled with ice water to bring the reaction temperature to 0 to 0.
505 parts of acrylic acid chloride are slowly added dropwise while maintaining the temperature at 10°C. After completing the dropwise addition, continue stirring at room temperature for 5 hours to confirm that the reaction has progressed sufficiently, and then remove the triethylamine hydrochloride from the reaction mixture and add f.
The liquid was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain 70 parts of a pale yellow liquid substance. 3 parts of cuprous chloride, which is known as a polymerization inhibitor, was added to this substance and vacuum distilled to obtain 58 parts of a colorless and transparent liquid substance (
56°C/2ml II Hg). The structural formula of the liquid substance obtained in this way was determined by elemental analysis, infrared absorption spectrum, and
Elemental analysis of 2-methylbroville from nuclear magnetic resonance spectrum Actual value Calculated value C58,0+ 58.32) (8,62
8,39 Alcoholic hydroxyl group+ in infrared absorption spectrum 3100-3650 cm'
Nuclear magnetic resonance spectrum showing absorption derived from carbonylmenane group at 715.1725cm-' + 4 ]Ocm-' carbonyl group of ester bond 2.15 ppm methyl proton
1) 11.05 ppm Methylproto7
3H Example-2 50 parts of 2-methylpropylene glycol and 56 parts of triethylamine were vigorously stirred using dry ether as a solvent, and the reaction vessel was cooled with ice water to bring the reaction temperature to 0 to 5.
While maintaining the temperature at °C, 58 parts of methacrylic acid chloride is slowly added dropwise. After the completion of the dropwise addition, stirring was continued for 5 hours at room temperature and after confirming that the reaction had progressed sufficiently, the triethylamine hydrochloride was separated from the reaction mixture, and the liquid fl was dried over anhydrous magnesium sulfate. After 3 days,
The solvent was distilled off under reduced pressure to obtain 68 parts of a pale yellow liquid substance. This substance is added with 3 parts of cuprous chloride, known as a polymerization inhibitor, and vacuum distilled to form a colorless and transparent liquid substance.
(56°C/2+++ mHg).

The structural formula of the liquid substance obtained in this way was determined by elemental analysis.
From infrared absorption spectrum and nuclear magnetic resonance spectrum, 2.
-Methylpropylene/methacrylate was confirmed.

Elemental analysis Actual value Calculated value C60,4960,74 H9,108,92 Infrared absorption spectrum 310 (alcoholic hydroxyl group at 1-3650 cm-1 1720 cm-1 carbonyl group of ester bond 164
Nuclear magnetic resonance spectrum showing absorption derived from the terminal vinyl group at 0□-1 5.28 ppm Olefin proton 2
H4, 18ppm methylene proton
4H3,75-3.95 pI)m Hydroxyl proton IH (disappeared by heavy water exchange) 1.96 ppm
Methyl proton 3H1,00ppm
Methyl proton 3H patent applicant Daicel Chemical Industries, Ltd.

Claims (1)

[Claims] 2 represented by the general formula CH2"CRCO2CH2CHCH20HzeCH3 (R in the formula is hydrogen or a methyl group)
-Methylpropylene glycol monoacrylate