JP2015196758A - Method for producing petroleum resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a petroleum resin capable of giving a petroleum resin particularly excellent in low odor and further excellent in color tone even without performing hydrogenation.SOLUTION: Provided is a method for producing a petroleum resin comprising: a first step of obtaining a post-polymerization mixture including a petroleum resin obtained by polymerizing hydrocarbon monomers with a metal halide compound as a catalyst, a volatile component including at least either a polymerization solvent or an unreacted monomer and a catalyst residue; a second step of obtaining a catalyst residue-removed mixture by adding water to a mixture after polymerization obtained by the first step, precipitating the catalyst residue and removing the same; a third step of obtaining an adsorption-treated mixture by contacting the catalyst residue-removed mixture obtained by the second step with an adsorbent to obtain an adsorption-treated mixture; and a fourth step of heating the adsorption-treated mixture obtained by the third step, thus volatilizing the volatile component from the adsorbent-treated mixture and thereafter recovering the petroleum resin from the remaining component.

Description

  The present invention relates to a method for producing a petroleum resin. More specifically, the present invention relates to a method for producing a petroleum resin that can provide a petroleum resin that is particularly excellent in low odor and excellent in color tone without hydrogenation.

  For example, a hot-melt type comprising a thermoplastic polymer compound such as ethylene-vinyl acetate copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer and a tackifier. Adhesives are used in various fields.

  As a tackifier contained in such a hot-melt adhesive, for example, a rosin resin, a terpene resin, a petroleum resin, and hydrogenated products thereof are used. Among these, petroleum resins are preferably used because they are particularly suitable for industrial production and have high quality stability. Petroleum resins are usually produced by polymerizing specific fractions in petroleum refining using a metal halide compound such as aluminum chloride as a polymerization catalyst.

  When a hot-melt adhesive containing a petroleum resin is used for sanitary goods such as disposable paper diapers and sanitary napkins, it is required that the odor is small and the color tone is excellent.

  However, general petroleum resins have odors and are not good in color tone, such as being dark, and also deteriorate in color tone when heated for hot melt bonding. Therefore, it was unsuitable for use as a tackifier for obtaining a hot melt adhesive. Therefore, when using a petroleum resin as a hot melt adhesive for sanitary goods, for example, as disclosed in Patent Document 1, hydrogenation is performed on the petroleum resin to obtain a hydrogenated petroleum resin. It has been attempted to reduce odor and improve color tone. However, in order to obtain such a hydrogenated petroleum resin, there has been a problem that a hydrogenation step is required and the production cost increases.

  Accordingly, various studies have been conducted on methods for obtaining petroleum resins that are excellent in low odor and color tone without hydrogenation. For example, Patent Document 2 discloses that a petroleum resin having a good color tone and an improved odor can be obtained by adding a hindered phenol-based antioxidant or a hindered amine-based antioxidant to a petroleum resin. ing.

  However, even when the technique disclosed in Patent Document 2 is used, the degree of improvement in odor and color tone may still be insufficient, and further improvement has been eagerly desired.

JP 2002-88116 A JP 2006-274191 A

  The present invention has been made in view of such a situation, and is a method for producing a petroleum resin that can give a petroleum resin that is particularly excellent in low odor and also excellent in color tone without hydrogenation. The purpose is to provide.

  As a result of intensive research to achieve the above object, the present inventors have polymerized hydrocarbon monomers using a metal halide compound as a catalyst, and then removed catalyst residues from the resulting mixture by a specific method. When the adsorbent is brought into contact with the mixture and the petroleum resin is recovered from the mixture in contact with the adsorbent, it gives a petroleum resin that is particularly excellent in low odor and color even without hydrogenation. I found that I can do it. The present invention has been completed by further studies based on this finding.

  Thus, according to the present invention, a hydrocarbon monomer is polymerized using a metal halide compound as a catalyst, and a petroleum resin obtained by polymerizing the hydrocarbon monomer, at least one of a polymerization solvent and an unreacted monomer is used. A first step of obtaining a post-polymerization mixture comprising a volatile component comprising: and a catalyst residue; adding water to the post-polymerization mixture obtained in the first step to precipitate the catalyst residue; A second step of obtaining a catalyst residue removal mixture by removing, a third step of contacting the adsorbent with the catalyst residue removal mixture obtained in the second step to obtain an adsorbent treatment mixture, A fourth step of recovering the petroleum resin from the remaining components after volatilizing the volatile components from the adsorbent treatment mixture by heating the adsorbent treatment mixture obtained in the third step. A method for producing a petroleum resin is provided.

  According to the present invention, a petroleum resin that is particularly excellent in low odor and excellent in color tone can be produced without hydrogenation.

  The first step in the method for producing a petroleum resin of the present invention comprises a step of polymerizing a hydrocarbon monomer using a metal halide compound as a catalyst to polymerize the hydrocarbon monomer, a polymerization solvent and an unreacted solvent. This is a step of obtaining a post-polymerization mixture containing a volatile component containing at least one of the reactive monomers and a catalyst residue.

  The hydrocarbon monomer used in the present invention is not particularly limited as long as it is mainly composed of unsaturated hydrocarbon compounds and can be used in the production of petroleum resins. A fraction containing an unsaturated hydrocarbon compound obtained by reforming and having an boiling point in the range of −20 ° C. to 280 ° C. can be used. Specifically, as a raw material for the aliphatic petroleum resin, a C5 fraction having a boiling point of 100 ° C. or lower and a C9 fraction having a boiling point range of 140 to 220 ° C. obtained by distilling a fraction having a boiling point of −20 ° C. to 280 ° C. of the cracked oil. Examples thereof include a mixture of a C5 fraction and a C9 fraction, a fraction obtained by mixing a C5 fraction and / or a C9 fraction with another aliphatic olefin, a diolefin, and the like.

  Examples of unsaturated hydrocarbon compounds contained in the C5 fraction include linear monoolefins such as 1-butene, 2-butene, 1-pentene, 2-pentene, methylbutene, methylpentene, hexene; cyclopentene, methylcyclopentene, Cyclic monoolefins such as cyclohexene; Chain conjugated dienes such as 1,3-butadiene, isoprene, 1,3-pentadiene and 1,3-hexadiene; Cyclic conjugated dienes such as cyclopentadiene and methylcyclopentadiene: 1,2-butadiene , Non-conjugated dienes such as 1,4-pentadiene; Examples of unsaturated hydrocarbon compounds contained in the C9 fraction include aromatic vinyls such as styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, and indene; cyclic unsaturated hydrocarbons such as dicyclopentadiene. And so on.

The metal halide compound used for polymerizing the hydrocarbon monomer is not particularly limited as long as it can obtain the target petroleum resin by polymerizing the hydrocarbon monomer. From the viewpoint of having, it is preferably a halide of an element belonging to Group III of the periodic table or a complex thereof. Specific examples of such metal halide compounds include aluminum trichloride (AlCl ₃ ), aluminum tribromide (AlBr ₃ ), gallium trichloride (GaCl ₃ ), boron trifluoride diethyl ether complex (BF ₃ .Et ₂ O). Of these, AlCl ₃ or BF ₃ .Et ₂ O is preferably used from the viewpoint of versatility.

  The amount of the metal halide compound used is not particularly limited, but is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the hydrocarbon monomer used for the polymerization. is there.

  The metal halide compound can be used as a catalyst in combination with a halogenated hydrocarbon for the purpose of improving the activity as a catalyst. The halogenated hydrocarbon used for this purpose is a halogenated hydrocarbon in which a halogen atom is bonded to a tertiary carbon atom, or a halogenated hydrocarbon in which a halogen atom is bonded to a carbon atom adjacent to a carbon-carbon unsaturated bond. Is preferred. Specific examples of the halogenated hydrocarbon in which a halogen atom is bonded to a tertiary carbon atom include t-butyl chloride, t-butyl bromide, 2-chloro-2-methylbutane, and triphenylmethyl chloride. Specific examples of the halogenated hydrocarbon in which a halogen atom is bonded to a carbon atom adjacent to the carbon-carbon unsaturated bond include benzyl chloride, benzyl bromide, (1-chloroethyl) benzene, allyl chloride, 3-chloro-1 -Propine, 3-chloro-1-butene, 3-chloro-1-butyne, cinnamon chloride.

  When the halogenated metal compound and the halogenated hydrocarbon are used in combination, the halogenated hydrocarbon is used in a molar ratio with respect to the metal halide compound, preferably 0.05 to 50, more preferably 0.1 to 10. It is a range.

  In polymerizing a hydrocarbon monomer using a metal halide compound as a catalyst, the method of mixing the hydrocarbon monomer and the metal halide compound is not particularly limited, and any method may be used. For example, the hydrocarbon monomer may be added to the reactor in which the metal halide compound is present in a batch, in portions, or continuously, or the hydrocarbon monomer is present. The metal halide compound may be added to the reactor all at once, in portions, or continuously.

  The polymerization reaction of the hydrocarbon monomer may be performed in the absence of a solvent or in the presence of a solvent, but from the viewpoint of better controlling the polymerization reaction, the polymerization reaction is preferably performed in the presence of a solvent. The type of the polymerization solvent is not particularly limited as long as it does not inhibit the polymerization reaction, but saturated aliphatic hydrocarbons or aromatic hydrocarbons are preferable. Examples of the saturated aliphatic hydrocarbon used as a polymerization solvent include n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, n-heptane, 2-methylhexane, 3-methylhexane, and 3-ethyl. Carbon such as pentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2,2,3-trimethylbutane, 2,2,4-trimethylpentane, etc. C5-C10 chain saturated aliphatic hydrocarbons; C5-C10 cyclic saturated aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane. As an aromatic hydrocarbon used as a polymerization solvent, C6-C10 aromatic hydrocarbons, such as benzene, toluene, xylene, are mentioned, for example. A polymerization solvent may be used individually by 1 type, and may be used as a 2 or more types of mixed solvent. Although the usage-amount of a polymerization solvent is not specifically limited, It is preferable that it is 10-1000 weight part with respect to 100 weight part of monomer mixtures used for a polymerization reaction, and it is more preferable that it is 50-500 weight part. In addition, like a general C5 fraction or C9 fraction, a mixture of an unsaturated hydrocarbon compound and a saturated hydrocarbon compound is added to the polymerization reaction system, and the unsaturated hydrocarbon compound is used as a monomer component. The saturated hydrocarbon compound may be used as at least a part of the polymerization solvent.

  When a polymerization solvent is used in the first step in the method for producing a petroleum resin of the present invention, it is removed as a volatile component to be removed from the adsorbent treatment mixture in a third step described later. Become.

  The polymerization temperature for carrying out the polymerization reaction is not particularly limited, but is preferably in the range of -20 to 100 ° C, and preferably in the range of 35 to 85 ° C. If the polymerization temperature is too low, the polymerization activity may be reduced and the productivity may be inferior. If the polymerization temperature is too high, the color tone of the resulting petroleum resin may be inferior. The pressure for performing the polymerization reaction may be atmospheric pressure or increased pressure. The polymerization reaction time can be appropriately selected, but is usually selected in the range of 10 minutes to 12 hours, preferably 30 minutes to 6 hours.

  As described above, when a hydrocarbon monomer is polymerized using a metal halide compound as a catalyst, a volatile property including a petroleum resin obtained by polymerizing the hydrocarbon monomer and at least one of a polymerization solvent and an unreacted monomer. A post-polymerization mixture containing the components and catalyst residues can be obtained.

  In the second step of the method for producing a petroleum resin of the present invention, the catalyst residue is removed by adding water to the post-polymerization mixture obtained in the first step to precipitate the catalyst residue and removing it. This is a step of obtaining a mixture.

  The water added to the mixture after polymerization may be pure water, but is preferably water in which an alkaline component such as ammonia or sodium hydroxide is dissolved in order to precipitate the catalyst residue efficiently. In addition, an alcohol such as methanol may be added together with water for the purpose of reducing the catalyst residue remaining in the post-polymerization mixture after removing the catalyst residue (catalyst residue removal mixture) as much as possible.

  The amount of water to be added to the mixture after polymerization is not particularly limited. For example, it is added in an equimolar range or more with respect to the metal halide compound used in the first step, and preferably used in the first step. It is added in a large excess relative to the metal halide compound. The temperature of the water to be added is not particularly limited, for example, selected from the range of 20 to 80 ° C. The reaction time after the addition of water is not particularly limited, for example, selected from the range of 0.1 to 2 hours Is done.

  The method for adding water is not particularly limited, and it may be added all at once, dividedly or continuously.

  As described above, when water is added to the post-polymerization mixture obtained in the first step, a catalyst residue is precipitated. By removing the catalyst residue according to a conventional method such as filtration or centrifugation, a catalyst residue-removed mixture from which the catalyst residue has been removed from the post-polymerization mixture can be obtained.

  The third step in the method for producing a petroleum resin of the present invention is a step of obtaining an adsorbent-treated mixture by bringing the adsorbent into contact with the catalyst residue removal mixture obtained in the second step.

The adsorbent used in the present invention is not particularly limited, and may be a chemical adsorbent or a physical adsorbent. Examples of chemical adsorbents used include basic zinc carbonate, zinc oxide, zinc sulfate, zinc laurate, zinc stearate, zinc myristate and other zinc-based adsorbents, zirconium oxide, zirconium hydroxide, zirconium phosphate, etc. Zirconium-based adsorbents, manganese-based adsorbents such as manganese dioxide, cobalt-based adsorbents such as cobalt chloride, copper-based adsorbents such as copper chloride and copper oxide, and amine-based adsorbents such as polyamine compounds. Examples of physical adsorbents that can be used include zeolite adsorbents that are collectively called hydrous aluminosilicate minerals such as sodium aluminum silicate, silicon dioxide, magnesium oxide, silica gel, silica / alumina, aluminum silicate, and activated alumina. Acid clay, activated clay, dosonite compounds, hydrotalcite compounds and the like. One adsorbent may be used alone, or two or more adsorbents may be used in combination. When two or more adsorbents are used in combination, two or more chemical adsorbents may be used in combination, two or more physical adsorbents may be used in combination, or one or more chemical adsorbents may be used. An adsorbent and one or more physical adsorbents may be used in combination, for example, a chemical adsorbent may be supported on the physical adsorbent. In particular, from the viewpoint of obtaining a petroleum resin excellent in low odor, among these adsorbents, it is preferable to use a chemical adsorbent, more preferably a zinc-based adsorbent, and basic zinc carbonate is used. Is particularly preferred.

  The method for bringing the catalyst residue removal mixture into contact with the adsorbent is not particularly limited. For example, the catalyst residue removal mixture and the adsorbent coexist in an appropriately selected container, and a batch treatment method in which the adsorbent is stirred and contacted as necessary, or the packed column is filled with the adsorbent in advance. And a continuous treatment method in which the catalyst residue removal mixture is circulated and contacted.

  The amount of adsorbent used when the catalyst residue removal mixture and the adsorbent are contacted by a batch processing method is not particularly limited, but is usually 0.01 to 100 parts by weight of petroleum resin contained in the catalyst residue removal mixture. 5.0 parts by weight, preferably 0.03 to 3.0 parts by weight, and more preferably 0.05 to 2.0 parts by weight.

  The temperature at which the catalyst residue removal mixture and the adsorbent are brought into contact with each other is not particularly limited, but is usually selected in the range of 10 to 70 ° C, and the treatment time is not particularly limited, but is usually 0.1 to 2 hours. Selected by range.

  When the catalyst residue removal mixture and the adsorbent are brought into contact with each other by a batch processing method, the adsorbent can be removed from the catalyst residue removal mixture by filtration or the like, if necessary. If there is no problem in using the petroleum resin even if the adsorbent remains, the adsorbent may be used for the next step without removing the adsorbent from the catalyst residue removal mixture.

  As described above, when the adsorbent is brought into contact with the catalyst residue removal mixture containing the petroleum resin obtained in the second step and the volatile component containing at least one of the polymerization solvent and the unreacted monomer, the adsorbent A processing mixture is obtained. In the method for producing a petroleum resin of the present invention, it is necessary to bring the adsorbent into contact with the catalyst residue removal mixture before the volatile components are volatilized and removed. In this way, hydrogenation is not performed. In both cases, it is possible to provide a petroleum resin which is particularly excellent in low odor and further excellent in color tone. If contact with the adsorbent is performed only on the post-polymerization mixture before removing the catalyst residue, the catalyst residue may adversely affect the adsorbent, and the resulting petroleum resin may not be sufficiently improved in low odor and color tone. is there. In addition, even if the adsorbent is not contacted with the catalyst residue removal mixture and is removed after volatilizing and removing the volatile components, the resulting petroleum resin may not be sufficiently improved in low odor and color tone. is there.

  The fourth step in the method for producing a petroleum resin of the present invention is a step of recovering the petroleum resin from the remaining components after volatilizing the volatile components from the adsorbent treatment mixture.

  The method for volatilizing the polymerization solvent and the unreacted monomer, which are volatile components, from the adsorbent-treated mixture is not particularly limited, and may be a conventional method. For example, a method of heating while blowing an inert gas such as nitrogen and a steam distillation method can be exemplified. The temperature for volatilizing the volatile component may be determined according to the boiling point of the volatile component and is not particularly limited, but is usually selected in the range of 40 to 300 ° C. When the volatile component is removed from the adsorbent treatment mixture, the remaining component is usually only the petroleum resin, so that the solid petroleum resin can be obtained by cooling the component.

  The petroleum resin obtained by the method for producing a petroleum resin of the present invention as described above may be subjected to a post-reaction such as a hydrogenation reaction or an acid modification reaction as necessary. However, since the petroleum resin obtained by the method for producing a petroleum resin of the present invention is excellent in low odor and color even without being subjected to a hydrogenation reaction, the production process is simplified and the production cost of the petroleum resin is reduced. From the viewpoint of reducing the size, it is preferably used as a non-hydrogenated petroleum resin that has not been subjected to a hydrogenation reaction.

  In the method for producing a petroleum resin of the present invention, it is possible to obtain a petroleum resin excellent in color tone even in a non-hydrogenated petroleum resin state. For example, the Gardner color number of a 50 wt% toluene solution is 3.0. The following petroleum resin can be obtained, and it is also possible to obtain a petroleum resin that is 2.5 or less.

  Although the weight average molecular weight (Mw) of the petroleum resin obtained with the manufacturing method of the petroleum resin of this invention is not specifically limited, Usually, it is 1000-10000, Preferably it is 1500-7000, More preferably, it is 1800-5500. . Moreover, although average molecular weight (Mz) is not specifically limited, Usually, it is 2000-20000, Preferably it is 2500-15000, More preferably, it is 3000-10000. The ratio of the Z average molecular weight to the weight average molecular weight (Mz / Mw) is also not particularly limited, but is usually 1.2 to 4.0, preferably 1.4 to 3.5, and more preferably 1.5. ~ 3.0. In addition, the weight average molecular weight (Mw) and Z average molecular weight (Mz) of petroleum resin can be calculated | required as a polystyrene conversion value by the measurement of a high performance liquid chromatography.

  The softening point of the petroleum resin obtained by the method for producing a petroleum resin of the present invention is not particularly limited, but is preferably 60 to 140 ° C, more preferably 70 to 130 ° C, and 80 to 120 ° C. More preferably.

  Various additives such as an anti-aging agent, an ultraviolet absorber, and a wax may be added to the petroleum resin obtained by the method for producing a petroleum resin of the present invention, if necessary.

  The use of the petroleum resin obtained by the method for producing a petroleum resin of the present invention is not particularly limited, and includes a tackifier, a binder resin, a compatibilizing agent, an adhesive modifier, a road surface marking display material modifier, It can be applied to conventional petroleum resin applications such as road pavement material modifiers, rubber molding modifiers, ink modifiers, paint modifiers, plastic modifiers and the like without any particular limitation. However, since the petroleum resin obtained by the method for producing a petroleum resin of the present invention is particularly excellent in low odor and color tone, it is suitable for use as a tackifier, and sanitary items such as disposable paper diapers and sanitary napkins. The use of adhesives used as articles as tackifiers is particularly suitable.

  Hereinafter, although this invention is demonstrated based on a more detailed Example, this invention is not limited to these Examples. In the following, “part” and “%” are based on weight unless otherwise specified. Moreover, the test and evaluation were performed according to the following description.

[Softening point]
It measured according to JIS K 6863.

[Molecular weight]
It calculated | required as a standard polystyrene conversion value by the gel permeation chromatography analysis. In addition, gel permeation chromatography analysis uses "HLC-8320GPC" manufactured by Tosoh Corporation as a measuring device, and a column using three connected "TSKgel SuperMultipore HZ" manufactured by Tosoh Corporation, with tetrahydrofuran as a solvent. And 40 ° C. and a flow rate of 1.0 ml / min.

(Solution hue)
A 50% toluene solution of petroleum resin immediately after production was prepared, and the Gardner color number of this solution was measured according to JIS K0071-2. The smaller the value, the better the hue.

[Solution hue after heating at 200 ° C. for 3 hours]
The petroleum resin immediately after production was allowed to stand in an oven at 200 ° C. for 3 hours and then allowed to cool, and then a 50% toluene solution was prepared. The Gardner color number of this solution was measured according to JIS K0071-2. The smaller the value, the better the hue.

[Odor after heating]
The odor after heating of the petroleum resin was evaluated by a sensory test according to the 6-step odor intensity display method in the odor smell measurement method published by the Odor Control Research Association. Specifically, first, 0.2 g of petroleum resin was placed in a 20 ml heat-resistant container, which was sealed with a lid. The heat-resistant container containing the petroleum resin was placed in an oven and heated at a temperature of 140 ° C. for 2 hours, and the odor after heating was confirmed. This odor was confirmed by a panel of 6 people who were not used to the odor of petroleum resin (that is, they did not touch the odor of petroleum resin in their daily lives). Also, the odor-smelling sample order should be random, based on the following indicators: a value in 0.5 increments (ie, for example, “0” for odorless, intermediate between odorless and finally recognizable odor) For example, “0.5”).
0: Odorless 1: Smell finally recognized (detection threshold concentration)
2: A weak odor that tells what smell it is (cognitive threshold concentration)
3: Smell that can be easily detected 4: Strong odor 5: Strong odor In addition, the results of the sensory test exclude the maximum and minimum values of the 6 panel judgment values, respectively, and the remaining 4 judgment values. Obtained by averaging. The smaller the sensory test value, the better the low odor.

[Example 1]
After charging 15.4 parts of cyclopentene, 46.3 parts of cyclopentane, and 1.2 parts of aluminum trichloride in a reaction vessel, 107.4 parts of a hydrocarbon mixture having the composition shown in Table 1 below was added over 60 minutes. Were continuously added and polymerization was carried out at 70 ° C. After completion of the addition of the hydrocarbon mixture, 4 parts of a 1: 1 mixture of 28% aqueous ammonia and methanol in a weight ratio was added to the reaction solution, and the resulting precipitate was separated by filtration. Then, after adding 1.00 parts of basic zinc carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) as an adsorbent to the filtrate (1.20 parts with respect to 100 parts of petroleum resin considering the yield of petroleum resin) By heating while blowing nitrogen, the volatile component (polymerization solvent and unreacted monomer) is volatilized. Further, by blowing saturated steam from 240 ° C., the remaining volatile component is volatilized. Removed. After confirming that there was almost no oil layer in the distillate of the volatilized component, blowing of saturated steam was stopped and the melt was taken out. By allowing the melt to cool, a pale yellow resinous petroleum resin was obtained with a yield of 83%. The obtained petroleum resin had a softening point of 93 ° C., a weight average molecular weight (Mw) of 2200, a Z average molecular weight (Mz) of 3700, and an Mz / Mw of 1.68. The obtained petroleum resin was evaluated for the solution hue, the solution hue after heating at 200 ° C. for 3 hours, and the odor after heating. The Gardner number of the solution hue was 2.5, and the solution after heating at 200 ° C. for 3 hours. The hue was 5.0, and the sensory test evaluation value of the odor after heating was 1.8. In addition, Table 2 summarizes the addition time, type and amount of adsorbent added during the production of petroleum resin, the solution color, the solution color after heating at 200 ° C. for 3 hours, and the odor after heating. .

[Examples 2 to 5]
In the same manner as in Example 1, except that the type and amount of adsorbent added to the filtrate (the amount with respect to 100 parts of petroleum resin in consideration of the yield of petroleum resin) were changed as shown in Table 2, A resin was obtained and evaluated. The evaluation results of the solution hue, the solution hue after heating at 200 ° C. for 3 hours, and the odor after heating are summarized in Table 2. In Table 2, “zirconium-based adsorbent” is “Kesmon NS-80E” manufactured by Toa Gosei Co., Ltd., and “zeolite-based adsorbent” is a polyamine compound-containing zeolite manufactured by Kyoritsu Pharmaceutical.

[Comparative Example 1]
A petroleum resin was obtained and evaluated in the same manner as in Example 1 except that no adsorbent was added to the filtrate. Table 2 summarizes the evaluation results of the solution hue, the solution hue after heating at 200 ° C. for 3 hours, and the odor after heating at 200 ° C. for 3 hours.

[Comparative Example 2]
Without adding an adsorbent to the filtrate after separating the precipitate, basic zinc carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) 0 with respect to 100 parts of the petroleum resin melt immediately after stopping the blowing of saturated steam. Example 1 except that 0.12 part of zirconium adsorbent (“Kesmon NS-80E” manufactured by Toa Gosei Co., Ltd.) and 0.12 part were added and stirred for 5 minutes, and then the melt was allowed to cool. In the same manner as above, petroleum resin was obtained and evaluated. Table 2 summarizes the evaluation results of the solution hue, the solution hue after heating at 200 ° C. for 3 hours, and the odor after heating at 200 ° C. for 3 hours.

[Comparative Example 3]
A petroleum resin was obtained and evaluated in the same manner as in Comparative Example 2 except that the type and amount of the adsorbent added to the petroleum resin immediately after stopping the blowing of saturated steam were changed as shown in Table 2. . The evaluation results of the solution hue, the solution hue after heating at 200 ° C. for 3 hours, and the odor after heating are summarized in Table 2.

  As can be seen from Table 2, the petroleum resin obtained by the method for producing a petroleum resin of the present invention (Examples 1 to 5) is excellent in color tone and excellent in low odor regardless of immediately after production and after heating. On the other hand, petroleum resins obtained without using any adsorbent (Comparative Example 1) and petroleum resins obtained by adding an adsorbent to petroleum resin after volatilizing volatile components (Comparative Examples 2, 3 ) Was inferior in color tone and low odor than the petroleum resin obtained by the method for producing a petroleum resin of the present invention.

Claims (1)

A petroleum resin obtained by polymerizing a hydrocarbon monomer using a metal halide compound as a catalyst to polymerize the hydrocarbon monomer, a volatile component containing at least one of a polymerization solvent and an unreacted monomer, and a catalyst A first step of obtaining a post-polymerization mixture comprising a residue;
A second step of obtaining a catalyst residue removal mixture by adding water to the post-polymerization mixture obtained in the first step to precipitate and remove the catalyst residue;
A third step of contacting the adsorbent with the catalyst residue removal mixture obtained in the second step to obtain an adsorbent treatment mixture;
A fourth step of recovering the petroleum resin from the remaining components after volatilizing the volatile components from the adsorbent treatment mixture by heating the adsorbent treatment mixture obtained in the third step;
A method for producing a petroleum resin.