JP2015036407A - Catalyst for producing petroleum resin, and method for producing petroleum resin by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new catalyst for producing a petroleum resin, which can allow the petroleum resin to have excellent hue, a high polymerization conversion rate of a monomer in a starting oil and low gel content and the starting oil containing large amounts of dicyclopentadienes to be used, and to provide a method for producing the petroleum resin by using the catalyst for producing the petroleum resin.SOLUTION: The catalyst for producing the petroleum resin comprises a boron trifluoride alcohol complex and phenol. A molar ratio of both of the phenol and the alcohol to the boron trifluoride is 2.5-14.0 and another molar ratio of the phenol to the alcohol is within a range of 0.2-5.5. The method for producing the petroleum resin by using the catalyst for producing the petroleum resin is also provided.

Description

  The present invention relates to a novel catalyst for petroleum resin production and a method for producing petroleum resin using the same, and more particularly, a petroleum resin excellent in hue and raw material monomer conversion and having a low gel content. The present invention relates to a novel petroleum resin production catalyst capable of using a raw oil containing a large amount of dicyclopentadiene and a method for producing a petroleum resin using the same.

  A method of producing a petroleum resin by polymerizing in the presence of a Friedel-Crafts-type catalyst using an unsaturated hydrocarbon-containing fraction obtained during cracking and refining of petroleum as a raw material oil is well known. The unsaturated hydrocarbon-containing fraction at that time is an unsaturated hydrocarbon fraction having a boiling range of 20 to 110 ° C. (sometimes referred to as an aliphatic hydrocarbon fraction or C5 fraction) and a boiling point. Two types of unsaturated hydrocarbon fractions in the range of 140 to 280 ° C. (aromatic hydrocarbon fractions and sometimes C9 fractions) are common, and aliphatic petroleum resins obtained from the C5 fractions An aromatic petroleum resin obtained from the C9 fraction, and an aliphatic / aromatic copolymer petroleum resin obtained by copolymerizing the C5 fraction and the C9 fraction are known. An alicyclic petroleum resin obtained by thermally polymerizing dicyclopentadiene is also known.

  Specific examples of the dicyclopentadiene used as the raw material for the alicyclic petroleum resin include dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, and the like. When the dicyclopentadiene is polymerized in the presence of a Friedel-Crafts-type catalyst, the monomer polymerization conversion rate does not increase, and a large amount of unsaturated bonds exist in the resin. The problem that quality deteriorates occurs. Therefore, when producing an aliphatic petroleum resin, an aromatic petroleum resin, an aliphatic / aromatic copolymer petroleum resin, etc., it is common to produce the dicyclopentadiene by a fraction obtained by removing it by distillation or the like.

  Petroleum resins are generally used in applications such as rubber processing aids, paints, adhesives, inks, and asphalts, and must be compatible with compounds such as rubber and rosin resins that are used in combination with these applications. Therefore, it is desired that the gel content is small.

  As an attempt to improve polymerization activity and resin physical properties when producing a petroleum resin, a method for producing a hydrocarbon resin using boron trifluoride as a main catalyst in the presence of a cocatalyst has been proposed (for example, a patent). Reference 1). In order to improve the hue, a method for producing a petroleum resin in which a C9 fraction and a C5 fraction are polymerized at a low temperature in the presence of a Friedel-Craft type catalyst has been proposed (for example, see Patent Document 2).

  Also, from the viewpoint of utilization of unused fractions, a method for producing a petroleum resin by conducting a polymerization reaction in the presence of a Friedel-Crafts type catalyst using dicyclopentadiene as a raw material has been studied. A method of polymerizing the contained C9 fraction at a low temperature in the presence of boron trifluoride or a boron trifluoride complex (for example, see Patent Document 3), C9 fraction and dicyclopentadiene are Friedel-Crafts type A method of polymerizing in the presence of a catalyst (for example, see Patent Documents 4 to 6), a method of polymerizing a C5 fraction and dicyclopentadiene in the presence of a Friedel-Crafts catalyst (for example, see Patent Document 7), Etc. have been proposed.

  In order to prevent gelation at the time of storage of petroleum resin, a method of adding an amine-based stabilizer to petroleum resin has been proposed (see, for example, Patent Documents 6 and 7).

Japanese Patent Laid-Open No. 56-106912 (see, for example, the claims) Japanese Patent Laid-Open No. 61-197616 (see, for example, the claims) Japanese Patent Laid-Open No. 62-064811 (for example, refer to the claims) Japanese Patent Laid-Open No. 07-033951 (for example, refer to the claims) Japanese Patent Application Laid-Open No. 08-034824 (for example, refer to the claims) Japanese Patent Laying-Open No. 2011-127006 (see, for example, the claims) Japanese Patent Laying-Open No. 2010-006901 (for example, refer to the claims)

  However, in the method proposed in Patent Document 1, although the effect of a single cocatalyst is described, no study has been made on the effect of using a plurality of cocatalysts, and gelation during polymerization is not performed. The petroleum resin that satisfies all of prevention, monomer polymerization conversion improvement, and hue improvement at the same time has not been studied at all. The methods proposed in Patent Documents 2 and 3 have problems in productivity and cost, such as the polymerization at a low temperature, the monomer polymerization conversion rate is reduced, and refrigeration equipment is required. Further, in the methods proposed in Patent Documents 4 and 5, the polymerization catalyst is not described in detail, and it is not possible to satisfy all of the prevention of gelation during polymerization, the improvement of monomer polymerization conversion, and the improvement of hue at the same time. Moreover, in the method proposed by patent document 6, 7, it is for preventing the gelatinization at the time of storage, and no examination is made about the gelation at the time of superposition | polymerization. The polymerization catalyst is not described in detail, and it is impossible to satisfy all of the prevention of gelation during polymerization, the improvement of monomer polymerization conversion rate, and the improvement of hue.

  Therefore, the present invention uses a catalyst for producing a petroleum resin for producing a petroleum resin having excellent hue and monomer polymerization conversion and low gel content, and uses a petroleum resin using the catalyst, particularly a feedstock containing a large amount of dicyclopentadiene. It is an object of the present invention to provide a method for producing a petroleum resin.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a catalyst composition obtained by adding a specific range of phenol to a boron fluoride alcohol complex is excellent in hue and monomer polymerization conversion, and has a low gel content. The present inventors have found that it is useful as a petroleum resin production catalyst for producing a petroleum resin, and has completed the present invention.

  That is, the present invention is a petroleum resin production catalyst comprising a boron trifluoride alcohol complex and phenol, which is a composition of a boron trifluoride alcohol complex and phenol, and the petroleum resin production catalyst is boron trifluoride. The total (molar ratio) of phenol and alcohol to 2.8 to 14.0, and the phenol / alcohol (molar ratio) in this case is in the range of 0.3 to 5.5 The present invention relates to a resin production catalyst and a method for producing a petroleum resin using the same.

  The present invention is described in detail below.

  The petroleum resin production catalyst of the present invention is a novel petroleum resin production catalyst comprising a boron trifluoride alcohol complex and phenol.

  The petroleum resin production catalyst of the present invention is excellent in the monomer polymerization conversion rate of the raw material oil by adding a phenol in a specific range to the boron trifluoride alcohol complex, and the obtained petroleum resin has a color tone. It is an excellent catalyst for providing a petroleum resin with a low gel content. In particular, it is a catalyst for producing a petroleum resin that can use a raw oil containing a large amount of dicyclopentadiene. Here, when a complex in which phenol is not added to the boron trifluoride alcohol complex, for example, a single complex of boron trifluoride alcohol complex is used as a catalyst, the monomer polymerization conversion rate of the raw material oil is inferior, and the obtained petroleum resin is It is inferior in color tone and becomes a petroleum resin with a high gel content. And the tendency becomes more remarkable when using the feedstock containing many dicyclopentadiene.

  In the petroleum resin production catalyst of the present invention, the amount of phenol added to the boron trifluoride alcohol complex is such that the total (molar ratio) of phenol and alcohol to boron trifluoride is 2.5 to 14.0, preferably 2. In this case, the phenol / alcohol (molar ratio) is in the range of 0.2 to 5.5, preferably 0.3 to 3.7. Here, the total (molar ratio) of phenol and alcohol to boron trifluoride is 2.5 to 14.0, and the phenol / alcohol (molar ratio) at that time is in a range other than 0.2 to 5.5. A catalyst having a low monomer polymerization conversion rate is obtained, and the resulting petroleum resin is inferior in hue or has a high gel content.

  Examples of the boron trifluoride alcohol complex constituting the petroleum resin production catalyst of the present invention include boron trifluoride methanol complex, boron trifluoride ethanol complex, and boron trifluoride butanol complex. The concentration of the boron trifluoride alcohol complex is not particularly limited as long as the total of phenol and alcohol (molar ratio) and phenol / alcohol (molar ratio) with respect to boron trifluoride are within the above ranges.

  The amount of phenol constituting the petroleum resin production catalyst of the present invention is such that the total of phenol and alcohol (molar ratio) and phenol / alcohol (molar ratio) with respect to the final boron trifluoride are within the above range. There is no particular limitation.

  As a preparation method of the catalyst for petroleum resin production of the present invention, the total (molar ratio) of phenol and alcohol to boron trifluoride is 2.5 to 14.0, and the phenol / alcohol (molar ratio) at that time is Any method can be used as long as it is 0.2 to 5.5, for example, a method in which a boron trifluoride alcohol complex and phenol are mixed in advance; a raw material oil of petroleum resin, a boron trifluoride alcohol complex and Examples include a method of separately mixing phenol and the like. When the catalyst is prepared in a petroleum resin feedstock, these catalyst feedstocks may be divided and added to the feedstock.

  The petroleum resin production catalyst of the present invention is excellent in molecular weight, softening point, and hue by being used in a polymerization reaction of a raw material oil that is an unsaturated hydrocarbon-containing fraction obtained by, for example, pyrolysis and / or refining of petroleum. Thus, a petroleum resin with a small amount of gel can be produced with high production efficiency.

  As the raw material oil at that time, for example, a C5 fraction having a boiling range of 20 to 110 ° C., a C9 fraction having a boiling range of 140 to 280 ° C., a dicyclopentadiene fraction, etc. obtained by pyrolysis and refining of petroleums, etc. Can be mentioned.

  As the C5 fraction, any fraction can be used as long as it is known as a fraction having a boiling range of 20 to 110 ° C. generally obtained by pyrolysis and refining of petroleums, for example, isoprene. , Conjugated diolefinically unsaturated hydrocarbons having 4 to 6 carbon atoms represented by trans-1,3-pentadiene, cis-1,3-pentadiene, cyclopentadiene, methylcyclopentadiene, etc .; butene, 2-methyl- C 4-6 monoolefinically unsaturated hydrocarbons typified by 1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, cyclopentene and the like; cyclopentane, 2-methylpentane, 3 -Aliphatic saturated hydrocarbons such as methylpentane and n-hexane; and mixtures thereof.

  As the C9 fraction, any fraction can be used as long as it is known as a fraction having a boiling range of 140 to 280 ° C. generally obtained by pyrolysis and refining of petroleum. , Α-methylstyrene, β-methylstyrene, vinyltoluene, indene, vinyl aromatic hydrocarbons having 8 to 10 carbon atoms typified by alkyl derivatives of indene; olefins having 10 or more carbon atoms; 9 or more carbon atoms Saturated aromatics of dicyclopentadiene, such as dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene; mixtures thereof, and the like.

  Any dicyclopentadiene fraction can be used as long as it is generally obtained by pyrolysis and refining of petroleum, and the C9 fraction is further refined, in the C5 fraction. And those obtained by dimerizing and purifying methylcyclopentadiene.

  The petroleum resin obtained using the catalyst for producing a petroleum resin of the present invention is particularly excellent in hue and less gel formation. Therefore, the raw material oil preferably contains 10% by weight or more of dicyclopentadiene. . In this case, the dicyclopentadiene may be any one as long as it is generally known as a dicyclopentadiene obtained by thermal decomposition and refining of petroleum, such as dicyclopentadiene, methyldicyclopentadiene. , Dimethyldicyclopentadiene, mixtures thereof and the like.

  When the C5 fraction is used as the main component as the raw material oil, the resulting petroleum resin is referred to as an aliphatic petroleum resin. When the C9 fraction is used as a main component, the obtained petroleum resin is referred to as an aromatic petroleum resin. When a mixture of the C5 fraction and the C9 fraction (mixing ratio in that case is arbitrary) is used, the resulting petroleum resin is referred to as an aliphatic / aromatic petroleum resin. Furthermore, when dicyclopentadiene is used, the obtained petroleum resin is referred to as an alicyclic petroleum resin.

  The production conditions for producing the petroleum resin are not subject to any limitation other than performing the polymerization in the presence of the catalyst for producing the petroleum resin of the present invention. A petroleum resin can be produced by adding a catalyst for heating and polymerizing by heating.

  The polymerization temperature at that time is arbitrary, and is preferably 0 to 100 ° C., particularly preferably 0 to 80 ° C., because a petroleum resin excellent in hue can be produced with high production efficiency. Here, when producing a petroleum resin having an excellent hue, a low-temperature polymerization method in which the polymerization temperature is less than 0 ° C. is generally used, but the low-temperature polymerization method has a low monomer polymerization conversion rate and a production efficiency. It has the problem of being inferior. By using the petroleum resin production catalyst of the present invention, a petroleum resin excellent in hue can be produced with high production efficiency even under conditions of 0 ° C. or higher. Further, the amount of the catalyst for producing the petroleum resin is arbitrary, and among them, the production method is particularly excellent in production efficiency. Therefore, it is 0.1 to 2 parts by weight with respect to 100 parts by weight of the raw material oil. Preferably there is. Furthermore, the polymerization time is preferably in the range of 0.1 to 10 hours. The reaction pressure is preferably atmospheric pressure to 1 MPa.

  After the polymerization reaction of petroleum resin, it is also possible to remove the catalyst for petroleum resin production, and in that case, it is possible to select a conventional method such as neutralization treatment with a base, washing with water, distillation with a solvent, etc. It is.

  The resulting petroleum resin is excellent in hue and monomer polymerization conversion, and has a low gel content. Particularly, the hue is 10 or less, and the average polymerization conversion of all monomers is 70% by weight or more. Is preferred. Moreover, it is preferable that it has a softening point of 60-160 degreeC, especially 70-150 degreeC. In particular, a petroleum resin having a weight average molecular weight (Mw) of 500 to 5,000 is preferable because of excellent processability.

  A novel petroleum resin production catalyst that has excellent hue and raw material monomer conversion, and can be used for petroleum resins with a low gel content, especially raw oils containing a large amount of dicyclopentadiene, and the same A method for producing a petroleum resin is provided.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention does not receive a restriction | limiting at all by these Examples. In addition, the analysis method of the raw material oil used in the Example and the comparative example and the obtained petroleum resin is as follows.

<Raw oil>
C9 ((A), (B)) fraction (Table 1), dicyclopentadiene fraction (Table 2) with a boiling range of 140-280 ° C obtained by decomposition and purification of naphtha, with a boiling range of 20-110 ° C Each composition of C5 fraction (Table 3) is shown in Tables 1-3. In Tables 1 to 3, DCPD is an abbreviation for dicyclopentadiene and CPD is an abbreviation for cyclopentadiene.

＜石油樹脂製造用触媒成分＞
三フッ化ホウ素メタノール錯体：三フッ化ホウ素５０重量％（ＡＬＤＲＩＣＨ（株）製）。
三フッ化ホウ素ブタノール錯体：三フッ化ホウ素３０重量％（ステラケミファ（株）製）。
フェノール：（和光純薬（株）製、試薬特級)
〜分析方法〜
＜各原料油中の成分分析＞
ＪＩＳ Ｋ−０１１４（２０００年）に準拠してガスクロマトグラフ法を用いて分析した。

<Catalyst component for petroleum resin production>
Boron trifluoride methanol complex: Boron trifluoride 50% by weight (ALDRICH Co., Ltd.).
Boron trifluoride butanol complex: 30% by weight of boron trifluoride (manufactured by Stella Chemifa Corporation).
Phenol: (Wako Pure Chemical Industries, special reagent grade)
~ Analysis method ~
<Ingredient analysis in each feedstock>
It analyzed using the gas chromatograph method based on JISK-0114 (2000).

<Measurement of monomer polymerization conversion>
Based on JIS K-0114 (2000), the total monomer amount in the oil before and after the polymerization was measured by a gas chromatographic method, and the monomer polymerization conversion rate was calculated.

<Measurement of weight average molecular weight (Mw)>
Measurement was performed by gel permeation chromatography according to JIS K-0124 (1994) using polystyrene as a standard substance.

<Measurement of softening point>
It measured by the method based on JISK-2531 (1960) (ring ball method).

<Measurement of hue (Gardner)>
The obtained petroleum resin was measured as a 50 wt% toluene solution according to ASTM D-1544-63T.

Example 1
Mixing 3.00 g of boron trifluoride butanol complex and 1.30 g of phenol (total of phenol and alcohol (molar ratio) to boron trifluoride is 3.2, and phenol / alcohol (molar ratio) is equivalent to 0.5) Then, a catalyst for petroleum resin production was prepared.

  A glass autoclave having an internal volume of 2 liters was charged with 400 g of C9 (A) fraction (see Table 1) obtained by decomposition of naphtha as raw material oil and 100 g of DCPD fraction (see Table 2) (C9 fraction / DCPD). Fraction = 80/20 (wt%)). Next, after heating to 40 ° C. under a nitrogen atmosphere, 4.30 g of the obtained catalyst for producing a petroleum resin (corresponding to 0.86 parts by weight with respect to 100 parts by weight of the raw oil) was added at 40 ° C. Polymerized for 3 hours. The charging conditions (ratio) are shown in Table 4.

  After the completion of the polymerization reaction, a sodium hydroxide aqueous solution was added to neutralize the solution, and then the gel was collected by filtration, dried, and the weight of the gel was measured. In addition, petroleum resin was recovered by distillation of unreacted oil in the oil layer.

  Table 5 shows the physical properties of the obtained petroleum resin. The monomer polymerization conversion was 70%, and the obtained petroleum resin did not contain gel and the hue was excellent at 7.

Comparative Example 1
Mixing 3.00 g of boron trifluoride butanol complex and 16.00 g of phenol (total of phenol and alcohol to boron trifluoride (molar ratio) is 15.0, phenol / alcohol (molar ratio) is equivalent to 6.0) The catalyst was prepared.

  A petroleum resin was produced in the same manner as in Example 1 except that 19.00 g of the obtained catalyst was used. The charging conditions (ratio) are shown in Table 4.

  Table 5 shows the physical properties of the obtained petroleum resin. The monomer polymerization conversion was 60%, and the obtained petroleum resin was bad with a hue of 15.

Example 2
Mixing 4.00 g of boron trifluoride butanol complex and 1.50 g of phenol (total molar ratio of phenol and alcohol to boron trifluoride is 3.0, phenol / alcohol (molar ratio) is equivalent to 0.4), A catalyst for petroleum resin production was prepared.

  A glass autoclave having an internal volume of 2 liters was charged with 400 g of a C9 (B) fraction (see Table 1) and 100 g of a C5 fraction (see Table 3) obtained by cracking naphtha as a raw oil (C9 fraction / C5). Fraction = 80/20 (wt%)). Next, after heating to 40 ° C. in a nitrogen atmosphere, 5.50 g of the obtained petroleum resin production catalyst (corresponding to 1.10 parts by weight with respect to 100 parts by weight of the raw oil) was added at 40 ° C. Polymerized for 2 hours. The charging conditions (ratio) are shown in Table 4.

  After the completion of the polymerization reaction, a sodium hydroxide aqueous solution was added to neutralize the solution, and then the gel was collected by filtration, dried, and the weight of the gel was measured. In addition, petroleum resin was recovered by distillation of unreacted oil in the oil layer.

  Table 5 shows the physical properties of the obtained petroleum resin. The monomer polymerization conversion was 85%, and the obtained petroleum resin did not contain gel and the hue was excellent at 7.

Example 3
A glass autoclave with an internal volume of 2 liters was charged with 300 g of a C9 (B) fraction (see Table 1) and 200 g of a C5 fraction (see Table 3) obtained by cracking naphtha as a raw oil (C9 fraction / C5). Fraction = 60/40 (% by weight)). Except that, petroleum resin was produced in the same manner as in Example 2. The charging conditions (ratio) are shown in Table 4.
Table 5 shows the physical properties of the obtained petroleum resin. The monomer polymerization conversion was 86%, and the obtained petroleum resin did not contain a gel and had an excellent hue of 6.

Comparative Example 2
Use 4.00 g of boron trifluoride butanol complex and 0.40 g of phenol (total of phenol and alcohol (molar ratio) to boron trifluoride is equivalent to 2.4, phenol / alcohol (molar ratio) equivalent to 0.1) A petroleum resin was produced in the same manner as in Example 3 except that. Table 4 shows the preparation conditions.

  Table 5 shows the physical properties of the obtained petroleum resin. The monomer polymerization conversion was 64%, the obtained petroleum resin did not contain gel, and the hue was 11.

Example 4
A glass autoclave with an internal volume of 2 liters was charged with 300 g of a C9 (B) fraction (see Table 1) and 200 g of a C5 fraction (see Table 3) obtained by cracking naphtha as a raw oil (C9 fraction / C5). Fraction = 60/40 (% by weight)). Next, after heating to 40 ° C. in a nitrogen atmosphere, 4.00 g of boron trifluoride butanol complex and 1.20 g of phenol (the total (molar ratio of phenol and alcohol to boron trifluoride) is 2.9, phenol / Alcohol (molar ratio corresponding to 0.3) was added and polymerization was carried out at 40 ° C. for 2 hours. The charging conditions (ratio) are shown in Table 4.

  Table 5 shows the physical properties of the obtained petroleum resin. The monomer polymerization conversion was 75%, and the obtained petroleum resin did not contain gel and the hue was excellent at 6.

Comparative Example 3
Use 4.00 g of boron trifluoride butanol complex and 20.00 g of phenol (total of phenol and alcohol (molar ratio) to boron trifluoride is 14.2 and phenol / alcohol (molar ratio) is equivalent to 5.6) A petroleum resin was produced in the same manner as in Example 4 except that. Table 4 shows the preparation conditions.

  Table 5 shows the physical properties of the obtained petroleum resin. The monomer polymerization conversion was 66%, and the obtained petroleum resin did not contain gel and the hue was 14.

Example 5
2.40 g of boron trifluoride methanol complex and 1.70 g of phenol (total of phenol and alcohol (molar ratio) to boron trifluoride is equivalent to 3.1, phenol / alcohol (molar ratio) is equivalent to 0.5) A petroleum resin was produced in the same manner as in Example 4 except that. Table 4 shows the preparation conditions.

  Table 5 shows the physical properties of the obtained petroleum resin. The monomer polymerization conversion was 89%, and the obtained petroleum resin contained no gel and the hue was 7.

Example 6
After adding 3.50 g of phenol to the raw material oil first, boron trifluoride methanol complex 2.40 g (total (molar ratio) of phenol and alcohol to boron trifluoride is 4.2).
A petroleum resin was produced in the same manner as in Example 4 except that phenol / alcohol (molar ratio corresponding to 1.0) was added. Table 4 shows the preparation conditions.

  Table 5 shows the physical properties of the obtained petroleum resin. The monomer polymerization conversion was 86%, and the obtained petroleum resin contained no gel and the hue was 7.

Example 7
Mixing 3.00 g of boron trifluoride butanol complex and 10.00 g of phenol (total of phenol and alcohol to boron trifluoride (molar ratio) is 10.2, phenol / alcohol (molar ratio) is equivalent to 3.7) Then, a catalyst for petroleum resin production was prepared.

  A glass autoclave having an internal volume of 2 liters was charged with 500 g of a C9 (B) fraction (see Table 1) obtained by decomposition of naphtha as a raw material oil. Next, after heating to 40 ° C. in a nitrogen atmosphere, 13.00 g of the obtained petroleum resin production catalyst (corresponding to 2.60 parts by weight with respect to 100 parts by weight of the raw oil) was added at 40 ° C. Polymerized for 3 hours. The charging conditions (ratio) are shown in Table 4.

  After the completion of the polymerization reaction, a sodium hydroxide aqueous solution was added to neutralize the solution, and then the gel was collected by filtration, dried, and the weight of the gel was measured. In addition, petroleum resin was recovered by distillation of unreacted oil in the oil layer.

  Table 5 shows the physical properties of the obtained petroleum resin. The monomer polymerization conversion was 94%, and the obtained petroleum resin did not contain gel and the hue was excellent at 7.

  A novel petroleum resin production catalyst that has excellent hue and raw material monomer conversion, and can be used for petroleum resins with a low gel content, especially raw oils containing a large amount of dicyclopentadiene, and the same The present invention provides a method for producing a petroleum resin, and its industrial value is extremely high.

Claims (5)

A catalyst for producing a petroleum resin comprising a boron trifluoride alcohol complex and phenol, the composition comprising a boron trifluoride alcohol complex and phenol, the catalyst for producing a petroleum resin comprising a total of phenol and alcohol with respect to boron trifluoride. (Molar ratio) is 2.5 to 14.0, and phenol / alcohol (molar ratio) at that time is in the range of 0.2 to 5.5. The catalyst for producing petroleum resin according to claim 1, wherein the boron trifluoride alcohol complex is a boron trifluoride butanol complex, a boron trifluoride ethanol complex or a boron trifluoride methanol complex. A petroleum resin characterized by polymerizing raw oil, which is an unsaturated hydrocarbon-containing fraction obtained by thermal cracking and / or refining of petroleum, using the petroleum resin production catalyst according to claim 1 or 2. Production method. The method for producing a petroleum resin according to claim 3, wherein the raw material oil is a raw material oil containing 10% by weight or more of dicyclopentadiene. The feedstock oil is one or more selected from the group consisting of a C5 fraction having a boiling range of 20 to 110 ° C, a C9 fraction having a boiling range of 140 to 280 ° C, and a dicyclopentadiene fraction. 4. A method for producing a petroleum resin according to 4.