JPS6138922B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention involves cracking and distilling a fraction having a boiling point within the range of 140 to 240°C among cracked oil fractions obtained by thermally decomposing petroleum. polymerize,
The present invention relates to a method for producing a hydrocarbon resin having excellent weather resistance and suitability for top coating. A method for producing hydrocarbon resins by polymerizing unsaturated hydrocarbon-containing fractions obtained during thermal decomposition of petroleum products in the presence of a Friedel-Crafts type catalyst is well known. At this time, if a large amount of dicyclopentadiene (DCPD) is present in the raw material oil, the hydrocarbon resin polymerized using it will have a high bromine number, and when used as a paint, it will have poor topcoat compatibility. However, the weather resistance will deteriorate. Furthermore, if the polymerization temperature is high as a condition for producing the resin, the molecular weight of the resin obtained will be low, the overcoat compatibility and weather resistance will be poor, and the hue will also be poor. On the other hand, if the temperature is too low, the resulting resin will have a high molecular weight and will have good overcoat compatibility and weather resistance, but will have a high softening point and will be difficult to use as a paint. Furthermore, when the amount of conjugated diolefin in the polymerization raw material exceeds wt%, the resulting resin has good overcoat compatibility, but has poor weather resistance and poor solubility. Furthermore, if the aromatic unsaturated component in the polymerization raw material is less than 30%, the molecular weight of the resin obtained by polymerization will be low, and if this is used in a paint, satisfactory results will not be obtained in terms of top coat compatibility and weather resistance. do not have. The present inventors have discovered that the material has excellent weather resistance and topcoat compatibility, which are important physical properties for paints, and has a softening point of 110 to 140.
As a result of studying methods for producing hydrocarbon resins for paints in the temperature range of 140 to 240 degrees Celsius, we found that conjugated diolefins in the fraction with a boiling point of 140 to 240 degrees Celsius are less than 1wt% aromatic. We have discovered that the above objectives can be achieved by polymerizing the group unsaturated hydrocarbon component at 30 to 55 wt%, adjusting the concentration of DCPD in the raw material and the polymerization temperature during polymerization using this within a certain range. . That is, it is essential that the DCPD concentration and polymerization temperature fall within a range that satisfies the following equation. x/10-2<y<-x/4+20 where x is the polymerization temperature (℃) and y is the DCPD concentration (wt
%). However, y is greater than 0. In order to adjust the raw material oil so that it has the above-mentioned composition range, for example, it can be thermally decomposed under pressure, and then the boiling point range can be adjusted by fractional distillation. Examples of the polymerization catalyst used in the present invention include Friedel-Crafts type catalysts such as boron trifluoride or its phenol and ether complexes, and aluminum trichloride. The resin can be obtained by a general method, except that the raw material oil adjusted to the above range is used and the polymerization temperature is in the range of 0 to 60°C. After the reaction is completed, the mixture is deactivated by adding water, alkaline aqueous solution, etc. to the reaction product according to a conventional method, and then deashed by washing with water, etc., and unreacted hydrocarbon oil is distilled off. The polymer can be obtained in a yield of 35-55% based on the raw material oil used. The features of the present invention are listed below. (1) By adjusting the DCPD concentration in the raw material oil and the polymerization temperature, it is possible to obtain a resin with excellent weather resistance and topcoat compatibility, which are important physical properties for paints. (2) Even if the raw material oil components vary greatly, the desired resin can be obtained by using the above method, that is, by using one in which the raw material composition is adjusted. (3) Resin with good color and solubility can be obtained by decomposing and refining raw material oil. Examples will be shown below, but these are just examples, and the present invention is not limited to these examples unless it goes against the spirit thereof. In the Examples and Comparative Examples, the hydrocarbon resins were evaluated by the following method. (1) Softening point Measured by the ring and ball method according to JIS K-2531. (2) Color: 5 g of hydrocarbon resin was dissolved in 5 g of toluene, compared with Gardner standard color, and expressed as Gardner value. (ASTM D-1544-58T) (3) Bromine number Measured by ASTM D-1158-57T. (4) Paint Preparation Method After mixing hydrocarbon resin, linseed oil, and mineral spirits in the specified proportions, add and disperse the dryer, Bengara, calcium carbonate, and glass beads in the specified amounts in that order, then add an anti-settling agent and heat at 45℃. A uniform composition was prepared by standing for 2 hours. (5) Weather resistance of coating film A coating test report was prepared from the coating prepared in (4) according to the method described in JIS K-5400. The test method was performed using a Sunshine Weatherometer at a black panel temperature of 65℃ and a spray cycle.
An accelerated deterioration test was conducted under conditions of 18 min/2 hr and a light resistance time of 100 hr. As a result, changes in appearance were displayed in the following four stages. A: No cracks were observed at all. B: Cracks of about 1 mm are observed in some parts. C: Cracks of about 5 mm are observed in some areas. D: Many cracks are observed throughout. This evaluation represents the weather resistance of the coating film. (5) Topcoat compatibility The paint prepared in (4) was applied using a 4 mil doctor blade, and after drying, oozing of the topcoat (White Marine Paint, manufactured by Shinto Paint Industry KK) was observed. Judgment was made by the number of times of coloring. A: Number of times oozing was observed: 9 to 10 times B: 〃 5 to 8 times C: 〃 4 times or less Example 1 A cracked oil fraction with a boiling point range of 140 to 240°C was heated under pressure.
After thermally decomposing DCPD, the low boiling point fraction and high boiling point fraction were removed to prepare the polymerization component composition shown in Table 1. Put 500g of this raw oil into the 2 separable flask.
Polymerization was carried out at 20°C for 1 hour. The catalyst is 2.5g of boron trifluoride phenol complex (30% concentration)
was added to the reaction system within 30 minutes after the start of the reaction. Note that the polymerization was performed under a dry nitrogen atmosphere. After the polymerization was completed, 250 g of 1% caustic soda and 250 g of xylene were added to the polymerization reaction solution to neutralize it, the aqueous layer was separated, and the oil layer was washed with the same amount of water. The obtained oil layer was heated to 180 to 190°C in a nitrogen stream, and unreacted oil was distilled off. Table 1 shows the results of measuring various physical properties of the resulting resin. Example 2 The raw material oil prepared in the same manner as in Example 1 to have the polymerization component composition shown in Table 1 was operated in accordance with Example 1. The physical properties of the obtained resin are shown in Table 1. Example 3 All operations were carried out in accordance with Example 1, except that raw oil prepared to have the polymerization component composition shown in Table 1 in the same manner as in Example 1 was polymerized at 40°C. The physical properties of the obtained resin are shown in Table 1. Example 4 The same procedure as in Example 3 was carried out, except that 2.0 g of a catalyst was added to a raw material oil prepared in the same manner as in Example 1 to have the polymerization component composition shown in Table 1. The physical properties of the obtained resin are shown in Table 1. Comparative Examples 1, 2, 5 The raw material oil prepared in the same manner as in Example 1 to have the polymerization component composition shown in Table 1 was operated in accordance with Example 3. The physical properties of the obtained resin are shown in Table 1. Comparative Example 3 All operations were carried out in accordance with Example 1, except that raw material oil prepared to have the polymerization component composition shown in Table 1 in the same manner as in Example 1 was polymerized at 50°C. The physical properties of the obtained resin are shown in Table 1. Comparative Example 4 All operations were carried out in accordance with Example 1, except that raw material oil prepared to have the polymerization component composition shown in Table 1 in the same manner as in Example 1 was polymerized at 65°C. The physical properties of the obtained resin are shown in Table 1. 【table】

Claims (1)

[Claims] 1. Of the cracked oil fractions produced during the thermal decomposition of petroleum, the boiling point fraction within the range of 140 to 240°C is decomposed and distilled to contain conjugated diolefins of 1 wt% or less, aromatic A fraction containing 30 to 55 wt% of unsaturated hydrocarbon components and dicyclopentadiene adjusted to the range expressed by the formula below is used as a raw material, and is polymerized at a temperature of 0 to 60°C in the presence of a Friedel-Crafts type catalyst. A method for producing a hydrocarbon resin characterized by x/10-2<y<-x/4+20 (y>0) y: dicyclopentadiene concentration wt% x: polymerization temperature ℃