JPS6099112A - Preparation of hydrocarbon resin having high acid value - Google Patents

Abstract

PURPOSE:To obtain the titled resin easily in high yield, providing an adhesive having improved adhesiveness because it has high acid value and a polar group, by reacting a specific fraction prepared by refining of petroleum, etc. with an unsaturated dicarboxylic acid anhydride under heating. CONSTITUTION:(A) A fraction having a boiling point range of -20-280 deg.C preared by refining of petroleum or by cracking of petroleum (preferably a fraction having a boiling point range of 140-280 deg.C, consisting essentially of aromatic hydrocarbon) is reacted with (B) an alpha,beta-unsaturated dicarboxylic acid anhydride (preferably maleic anhydride) under heating preferably at 150-250 deg.C, to give the desired resin. Control of acid value is preferably carried out by combination of a molar ratio of the component B to the unsaturated component in the component A and the reaction temperature. EFFECT:Providing a coating compound having improved pigment dispersibility. Having improved compatibility with epoxy resin, etc.

Description

[Detailed description of the invention] Regarding the manufacturing method.

Traditionally, carboxyl groups have been incorporated into hydrocarbon resins for the purpose of improving various physical properties of hydrocarbon resins, such as improving the adhesion of adhesives containing hydrocarbon resins to metals, and improving the pigment dispersibility of inks and paints. Attempts have been made to introduce

For example, according to Japanese Patent Publication No. 56-19287, the boiling point range of petroleum M# or produced by thermal decomposition of petroleum is 12.
A method for producing a silicic acid-modified resin by adding an unsaturated acid or an unsaturated acid anhydride to a fraction having a temperature of 0 to 280° C. and carrying out cationic polymerization is disclosed.

However, in such a method, the acid value of the resulting resin is only about a few dozen, and it is not possible to obtain a resin with a high acid value, and it also has the disadvantage that emulsions are likely to be formed in the decatalyst step.

1. Japanese Patent Publication No. 47-47994 states that the boiling point range obtained by petroleum refining or thermal decomposition of petroleum is 140 to 2.
It is disclosed that a modified resin can be obtained by adding an unsaturated carboxylic acid or its anhydride to a resin obtained by polymerizing a 20'C fraction using a 7-Riedel-Crafts type catalyst. .

However, in this method, the reactivity between the hydrocarbon resin and the α,β-unsaturated dicarboxylic acid anhydride is not good, so the reaction is required at high temperature and for a long time, so the hue and softening point of the resin are maintained. It is difficult to produce resins with high acid values of 100 or more.

The present inventors have made various studies with the aim of solving these drawbacks and providing a method for producing a hydrocarbon resin having a high acid value, and as a result they have arrived at the present invention. In other words, the present invention deals with
A method for producing a hydrocarbon resin having a high acid value by adding an α,β-unsaturated dicarboxylic acid anhydride to a fraction having a boiling point within a temperature range of 0 to 280°C and carrying out a heating reaction. The main points are as follows.

In particular, the present invention applies to a fraction having a boiling point within a temperature range of -20 to 280°C, which is produced in petroleum refining or thermal decomposition of petroleum, in a molar ratio of 0. The feature is that 1 to 2.0 times as much α,β-unsaturated dicarboxylic acid anhydride is added and the reaction is carried out by heating.

The distillate (hereinafter referred to as cracked fraction) with a boiling point within the temperature range of -20 to 280°C that is produced during petroleum refining or thermal decomposition of petroleum used in the present invention refers to 4J at 20~280°
A total fraction having a boiling point range of 14° C. or a fraction obtained by processing such as distillation, for example, a fraction mainly consisting of aliphatic hydrocarbons having a boiling point range of 20° to 100° C.
It includes any fraction mainly consisting of aromatic hydrocarbons having a boiling point range of 0 to 280"C or a mixture of these in an appropriate ratio, but especially 140 to 280"C.
Most preferred are aromatic hydrocarbon-based fractions having a boiling range of .degree.

As the α,β-unsaturated dicarboxylic acid anhydride used in the present invention, maleic anhydride, itaconic anhydride, citraconic anhydride, etc. can be used, but it is particularly preferable to use maleic anhydride.

The temperature of the heating reaction used in the present invention is 70 to 300°c1.
In particular, it is suitably within the range of 150 to 250'c. If the temperature is lower than 70°C, the reaction rate will be slow and a very long reaction time will be required, and if the acid anhydride content is too small, the product yield will drop significantly, so it is not industrially practical.

Furthermore, if the reaction temperature exceeds 300°C, the resin deteriorates and black carbon-like substances are likely to be produced, which is not preferable. There are no particular restrictions on the reaction pressure and reaction time, but the pressure is, for example, normal pressure to 2.0 kg/cIftG.

The time is preferably 0.5 to 24 hours, for example.

In the raw reactant, the amount of α,β-unsaturated dicarboxylic anhydride added to the cracked fraction is within the range of 0.1 to 2.0 times in molar ratio to the unsaturated component in the cracked fraction. It is necessary. If the amount added is 0.1 times or less, it will not only lower the acid value of the resulting resin to less than 100, but also stagnate the progress of the entire reaction and at the same time reduce the yield of the product. When the reaction temperature is lower than 200°C, the yield is extremely reduced, and the amount added is 2.
Setting it to 0 times or more means that the acid value of the resin obtained is 270 to
However, the acid value does not increase even though the amount added is increased, and rather, the acid value increases due to the increase in the amount of acid anhydride remaining as an unreacted product. None of this is appropriate as it would increase the disadvantages.

The acid value of the hydrocarbon resin obtained by the method of the present invention is approximately in the range of 100 to 300, but the acid value is controlled by α, β-unsaturated dicarbonate relative to the unsaturated component in the cracked fraction of the raw reactant. This can be carried out by a combination of the molar ratio of the acid anhydride and the reaction temperature. The reaction temperature was set to 20
When lowered to 0'C, the unsaturated components in the cracked fraction and α,
Since both components of the β-unsaturated dicarboxylic acid anhydride tend to react in a substantially constant molar ratio, a resin with a constant acid value is obtained as a result. However, when the reaction temperature is raised to 200°C, the above tendency weakens, and in fact, the component with a higher concentration among the two components tends to react more, and as a result, the higher the resin A resin with a low acid value can be obtained.

As explained above, in the production method of the present invention, an appropriate amount of α,β-unsaturated dicarboxylic acid anhydride is added to the cracked fraction produced by petroleum refining or thermal decomposition of petroleum, and the mixture is heated at an appropriate reaction temperature. Since it consists of a reaction, the amount of acid anhydride added and the reaction temperature can be appropriately selected depending on the homopolymerizability of the cracked fraction and the copolymerizability of the acid anhydride. This makes it possible to easily and efficiently produce a hydrocarbon resin having an arbitrary acid value within the range of .

The resin obtained in this way has a high acid value and polar groups, so adhesives containing this resin have good adhesion to metals, etc., and inks and paints containing this resin also have pigment dispersion. Good properties.

Further, this resin has good compatibility with resins having polar groups such as epoxy resins, alkyd resins, phenol resins, and polyesters.

EXAMPLES Next, the present invention will be specifically illustrated by examples, but the scope of the present invention is not limited thereby.

Table 7-1 Composition side Example 1 of a cracked fraction having a boiling range of 140 to 280°C A boiling point range of a cracked fraction having a composition shown in Table 1 obtained by thermal decomposition of petroleum is 140 to 280°C 1 t of 480 liters of aromatic unsaturated hydrocarbon-containing fraction and 1969 liters of maleic anhydride
After charging into a stainless steel autoclave and thoroughly purging with nitrogen, the temperature was 240°C and the pressure was a s kq/c'r/I.
G for 3 hours.

After the reaction, the reaction product was transferred to a vacuum distillation apparatus and heated to 10m+J.
(g, 200°C, distill off unreacted materials for 3 hours, acid value: 260°, softening point: 141°C, 2 hues (guard-boo color number,
Resin 456 having 16 (the same applies hereinafter) was obtained.

Example 2 The same operation as in Example 1 was performed except that the amount of maleic anhydride used was 989, and the acid value was 256. Softening point 142°C
220 pieces of resin having 9 hues and 13 colors were obtained.

Example 3 The same operation as in Example 1 was performed except that the reaction temperature was 150°C, the pressure was t s kg, and AmeG was used to obtain resin 6009 having an acid value of 258°, a softening point of 142°C, and a hue of 10. .

Example 4 In Example 1, the aromatic unsaturated hydrocarbon-containing fraction was added to 6
00 g, maleic anhydride was 409, and the reaction temperature was 230°C.
190 g of gζ resin was obtained.

Comparative Example 0 Production of Hydrocarbon Resin Fraction 10009 containing aromatic unsaturated hydrocarbons having the composition shown in Table 1 and having a boiling point range of 140 to 280°C, obtained by thermal decomposition of petroleum, was transferred to a 2-ton glass separator. The mixture was placed in a blue flask, and after being sufficiently purged with nitrogen, the temperature was raised to 40° C., and 5 portions of boron trifluoride phenolate were added dropwise over 1 hour while stirring.

After the dropwise addition was completed, the reaction was continued for an additional 2 hours.

After completion of the reaction, 500g of IJium aqueous solution
was added and stirred for 30 minutes to stop the reaction.

After the reaction was stopped, the mixture was allowed to stand for 1 hour to separate into an oil phase and an aqueous phase.

The oil phase was transferred to a 1 t separable flask, and unreacted substances were distilled off under a nitrogen stream to obtain 540 g of hydrocarbon resin.

1 ton of 480 g of resin obtained by modification of 0.0 hydrocarbon resin and 120 g of maleic anhydride.
After charging in a stainless steel autoclave and thoroughly purging with nitrogen, it was heated at 240°C, 9 pressure, 1.5 kg, and 5
Allowed time to react.

After the reaction, the temperature was 10 mHg in the same manner as in Example 1.

Unreacted substances were distilled off at 200° C. for 5 hours to obtain 565 g of resin.

The acid value of this resin is 81. Softening point is 143℃9 Hue is 16
Met.

Patent applicant: Toyo Soda Kogyo Co., Ltd.

Claims (1)

[Claims] 1. A product produced by petroleum refining or thermal decomposition of petroleum.
For a fraction having a boiling point range within the temperature range of 0 to 280°C,
A method for producing a hydrocarbon resin having a high acid value, which comprises adding an α,β-unsaturated dicarboxylic acid anhydride and carrying out a heating reaction. 2.120 produced by petroleum refining or thermal decomposition of petroleum.
The fraction having a boiling point range within the temperature range of ~280°C is 1
2. A process according to claim 1, wherein the fraction has a boiling point range of 40 to 280<0>C. 5. The method according to claim 1 or 2, wherein the α,β-unsaturated dicarboxylic acid anhydride is maleic anhydride. 4. The amount of α,β-unsaturated dicarboxylic anhydride added is
A patent that has a molar ratio of α1 to 2.0 times the unsaturated component in a fraction having a boiling point within the temperature range of -20 to 280°C, which is produced by thermal decomposition of petroleum. The method according to claim 1.