JPH0148951B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an adduct of glycidyl acrylate or glycidyl methacrylate (hereinafter both will be collectively referred to as glycidyl (meth)acrylate) and rosin.

Conventionally, a manufacturing method using a diluent such as microcrystalline wax has been proposed for the glycidyl (meth)acrylate-rosin adduct;
The use of a mixture of glycidyl acrylate and a rosin adduct is limited, and removing the diluent from this mixture is extremely complicated and impractical. It is possible to react in bulk without using a diluent as described above, but rosin has a softening point.
Solids at temperatures above 70°C become fluid and mixable when heated above 130°C, but reactions at such high temperatures often cause gelation. Generally, such gelation can be prevented to some extent by adding a polymerization inhibitor such as hydroquinone, but it cannot be completely prevented.

The present inventors demonstrated that without using a reaction solvent (meta)
While investigating various ways to obtain a glycidyl acrylate-rosin adduct, we discovered that gelation can be achieved by keeping the ratio of the number of epoxy groups in glycidyl (meth)acrylate to the carboxyl groups in rosin at a certain constant ratio. The present invention was achieved by discovering that a glycidyl (meth)acrylate-rosin adduct can be easily obtained without any reaction. That is, the present invention
Glycidyl (meth)acrylate-rosin addition characterized by maintaining the ratio of the number of carboxyl groups to epoxy groups at 1.00 or more in the absence of a reaction solvent when glycidyl (meth)acrylate and rosin are reacted. It is the method of manufacturing things.

The glycidyl (meth)acrylate of the present invention is
It can be obtained by saponifying a halohydrin ester obtained by the reaction of (meth)acrylic acid and epihalohydrin with an alkali, or by reacting an alkali metal salt of (meth)acrylic acid with epihalohydrin.

The rosin of the present invention is a resin contained in raw pine resin and tall oil, and is mainly composed of a mixture of monovalent carboxylic acids having an alkylhydrophenanthrene nucleus represented by C ₂₀ H ₃₀ O ₂ These include natural rosins such as gum rosin, tall oil rosin, and udon rosin, and modified rosins such as hydrogenated rosin, disproportionated rosin, and dimerized rosin.

The amount of epoxy groups in the above-mentioned glycidyl (meth)acrylate is usually expressed as epoxy equivalent (weight per epoxy group), and the amount of carboxyl group in rosin is expressed as carboxyl equivalent (weight per 1 carboxyl group). It is expressed as Further, the amount of carboxyl group is often expressed in terms of acid value (KOHmg/g), but the following relationship exists between it and carboxyl equivalent.

Carboxyl equivalent = 56100/acid value The reaction between glycidyl (meth)acrylate and rosin in the present invention is promoted by a basic substance such as a tertiary amine or a quaternary ammonium salt.

Examples of tertiary amines include triethylamine, tributylamine, dimethylbutylamine, and dimethylbenzylamine, and examples of quaternary ammonium salts include tetramethylammonium iodide, tetraethylammonium iodide, tetrabutylammonium iodide, and trimethyl iodide. Examples include butylammonium, tetraethylammonium bromide, tetrabutylammonium bromide, triethylbenzylammonium chloride, triethylallylammonium chloride, and tetraethylammonium benzoate. The amount added is suitably in the range of 0.1 to 5.0 g, preferably 0.5 to 2.0 g per equivalent of epoxy group.

The gelation that occurs during the reaction between glycidyl (meth)acrylate and rosin is thought to be caused by (1) polymerization of vinyl groups, and (2) reaction between hydroxyl groups and epoxy groups. The gelation caused by thermal polymerization of vinyl groups in (1) above can be prevented by a radical polymerization terminator such as hydroquinone or air. In the present invention, a polymerization inhibitor is added to the reaction system for this purpose.
It is good to add in a range of 10 to 2000 ppm, preferably 50 to 500 ppm. In order to suppress the reaction between hydroxyl groups and epoxy groups in (2) above, in the present invention, the ratio of the number of carboxyl groups to epoxy groups is set to 1.00 or more to facilitate the main reaction of ring-opening esterification by both groups. This is intended to suppress the side reaction of ring-opening etherification between the generated hydroxyl group and epoxy group. If the ratio of the above two numbers is less than 1.00, the reaction (2) above tends to occur, causing gelation. The upper limit of the ratio of both numbers may be such that the acid value of the product does not cause any practical problems, and for this purpose, it is preferable that the ratio of both numbers is in the range of 1.00 to 1.10.

The reaction temperature of the present invention is 100-200℃, preferably
The temperature ranges from 120 to 160°C. The reaction time varies depending on various conditions such as the type and amount of catalyst used and the reaction temperature, but is usually in the range of 1 to 5 hours.

The glycidyl (meth)acrylate-rosin adduct of the present invention has a polymerizable vinyl group, so it can be homopolymerized, but it can also be copolymerized with other vinyl monomers, so it can be used to modify vinyl resins. It has uses such as agents.

Examples will be explained below.

Example 1 340 g of tall oil rosin (Harima Kasei Kogyo Co., Ltd. "Hartall Rosin WW") (carboxyl group 1.01 equivalent) was heated and melted at 150°C, cooled to 130°C, and 1.0 g of triethylamine was added while stirring. ,
142 g of glycidyl methacrylate (1.00 equivalent of epoxy group) containing 0.10 g of hydroquinone was added dropwise over about 1 hour. After the addition, the reaction temperature was maintained at 125-135°C. One hour after dropping, the acid value of the reactant was 11.3.
It became 8.9 in 2 hours, and when it reached 8.0 after 3 hours, it was cooled to room temperature. The product is a pale yellow-brown semisolid substance, with hydroxyl ^groups and
Carboxyl group at 172cm ^-1 , 1240cm ^-1 and 1040cm ^-1
Characteristic absorption of ester groups was observed in the product, and it was confirmed that it was a ring-opened ester compound.

Comparative Example 1 335 g of tall oil rosin (carboxyl group 1.00 equivalent) and 0.11 g of hydroquinone used in Example 1
Contains 156g of glycidyl methacrylate (epoxy group
1.10 equivalents) was used to react in the same manner as in Example 1, but gelation occurred approximately 1.5 hours after dropping.

Example 2 Disproportionated rosin (“Bandes G” manufactured by Harima Kasei Kogyo Co., Ltd.). 386 g (carboxyl group 1.10 equivalent) was heated at 160°C.
1.0 g of benzyltriethylammonium chloride after heating and melting at 140°C and stirring.
was added, and then 128 g of glycidyl acrylate (1.00 equivalent of epoxy group) containing 0.15 g of hydroquinone was added dropwise over about 1 hour, and then the reaction temperature was raised to 140 ml.
It was maintained at ±5°C. Two hours after the dropwise addition, the acid value of the reactant decreased to 12, so it was cooled to room temperature. The product is a pale yellow-brown semi-solid material, which in the infrared spectrum shows
Hydroxyl group at 3500 cm ^-1 , carbonyl group at 1720 cm ^-1 ,
Absorption due to ester groups was observed at 1240 cm ^-1 and 1040 cm ^-1 , confirming that it was a ring-opened ester product.

Claims (1)

[Claims] 1. Glycidyl (meth)acrylate, which is characterized in that when reacting glycidyl acrylate or glycidyl methacrylate with rosin, the ratio of the number of carboxyl groups to epoxy groups is maintained at 1.00 or more in the absence of a reaction solvent. Method for manufacturing rosin adducts.