JP2005336346A - New petroleum resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new petroleum resin suppressing the formation of gel in the petroleum resin and having high adhesive property independent of the content of cyclopentadiene and/or dicyclopentadiene in a pyrolytic oil used as a raw material for the petroleum resin and having high adhesive property. <P>SOLUTION: A pyrolytic oil obtained by the pyrolysis of a petroleum fraction and having a boiling point of ≤110°C is reacted under heating at ≥150°C for a reaction time satisfying the formula (I): H(min)≥4×10<SP>6</SP>×e<SP>-0.05T</SP>(H is the thermal reaction time and T(°C) is the thermal reaction temperature), and the obtained reaction product is polymerized in the presence of a polymerization catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel petroleum resin. More specifically, the present invention relates to a novel petroleum resin having excellent performance in hot melt adhesive applications and ink applications.

  A hydrocarbon resin obtained by polymerizing with a Friedel-Crafts-type catalyst using various fractions obtained in the cracking or refining of petroleum hydrocarbons as a raw material oil is generally called a petroleum resin. Since this petroleum resin is excellent in adhesiveness, tackiness, water resistance, chemical resistance and electrical insulation, it is widely used in various industrial fields such as adhesives, tackifiers, inks and asphalts.

  As a petroleum resin having properties for pressure-sensitive adhesives, a petroleum resin obtained by dimerizing a diene and polymerizing the dimer with a Friedel-Crafts catalyst is known. For example, from a reaction mixture obtained by heating a C5 fraction containing a diolefin having a carbon number of 5 having a boiling point in the range of 20 to 100 ° C. to a temperature in the range of 100 to 300 ° C. A method is disclosed in which a petroleum resin is obtained by polymerizing a component obtained by removing the C5 component of the reaction by distillation with a Friedel-Crafts catalyst (see, for example, Patent Document 1). However, in this method, when a large amount of cyclopentadiene or dicyclopentadiene is contained in the C5 fraction, a gel is generated in the petroleum resin during the polymerization reaction, and the pressure-sensitive adhesive using the petroleum resin is uniform. There was a problem that the adhesive could not be applied and good adhesiveness could not be exhibited.

  In addition, the piperylene content of 60% by weight or more obtained by rectifying the residue after obtaining isoprene from any fraction having a boiling point of 0 to 100 ° C. produced as a by-product during cracking or reforming of petroleum, A method of using a dimer obtained by reacting a fraction having a total content of pentadiene and dicyclopentadiene of 1% by weight or less as a raw material, and a boiling point of 0 to 100 ° C. A method using a raw material in which an arbitrary fraction is adjusted to 1% or less of cyclopentadiene and the total content of isoprene and piperylene to 35% by weight or more is disclosed (for example, see Patent Documents 2 and 3). However, in any of these methods, in order to suppress the formation of gel in the petroleum resin, cyclopentadiene and / or dicyclopentadiene in the pyrolysis product oil used as a raw material is prepared in advance to 1% by weight or less. There is a problem in terms of operational complexity and economy required for such pre-preparation.

Japanese Patent Publication No.56-17364 (first page)

JP 48-66683 A (first page) JP 48-91187 A (first page)

  The present invention has been made in view of the above problems, and suppresses the formation of gel in petroleum resin regardless of the content of cyclopentadiene and / or dicyclopentadiene in pyrolysis oil used as a raw material for petroleum resin. Another object of the present invention is to provide a novel petroleum resin having high adhesive properties.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors obtained a pyrolysis oil having a boiling point of 110 ° C. or less obtained by pyrolysis of a petroleum fraction by heating and reacting at a specific reaction temperature and reaction time. A petroleum resin obtained by polymerizing the obtained reaction product in the presence of a specific polymerization catalyst and a method for producing the same were found, and the present invention was completed.

  That is, the present invention is a method in which a pyrolysis oil having a boiling point of 110 ° C. or less obtained by pyrolysis of a petroleum fraction is subjected to a heat reaction under a condition where the reaction temperature is 150 ° C. or more and the reaction time satisfies the following formula (I). The present invention relates to a petroleum resin obtained by polymerizing the obtained reaction product in the presence of a polymerization catalyst and a method for producing the same.

Heating reaction time H (min) ≧ 4 × 10 ⁶ × e ^{−0.05 T} (I)
(However, T (° C) indicates the heating reaction temperature)
Here, the pyrolysis oil having a boiling point of 110 ° C. or less obtained by pyrolysis of a petroleum fraction refers to a pyrolysis oil having a boiling point of 110 ° C. or less (hereinafter referred to as “pyrolysis oil”). Such pyrolysis oil may be obtained by any pyrolysis method. For example, a petroleum fraction obtained from crude oil, a fraction produced as a by-product during decomposition or reforming of a petroleum fraction obtained from crude oil, and the like can be mentioned.

  The pyrolysis oil may have any component constitution as long as its boiling point is 110 ° C. or lower. For example, petroleum fractions obtained from crude oil, fractions produced by decomposition or reforming of petroleum fractions obtained from crude oil, and residual fractions using specific components from these fractions, etc. In addition, if necessary, mention may be made of these distillates obtained by adding a chain diene having 4 to 5 carbon atoms and / or a cyclic diene having 5 to 6 carbon atoms or an oil containing these dienes. Can do. Among these, pyrolysis oil obtained from pyrolysis of naphtha is preferable because it contains many components that generate petroleum resin by heating and polymerization reaction. Here, the chain diene having 4 to 5 carbon atoms is not particularly limited, and examples thereof include butadiene, isoprene, trans-1,3-pentadiene, cis-1,3-pentadiene, and mixtures thereof. It is done. Moreover, C5-C6 cyclic diene is not specifically limited, For example, cyclopentadiene, methylcyclopentadiene, and these mixtures are mentioned.

  The petroleum resin of the present invention is produced by the following steps. First, the pyrolysis oil is heated and reacted under a condition where the reaction temperature is 150 ° C. or higher and the reaction time satisfies the following formula (I) to obtain a reaction product.

Heating reaction time H (min) ≧ 4 × 10 ⁶ × e ^{−0.05 T} (I)
(However, T (° C) indicates the heating reaction temperature)
Next, the reaction product is polymerized in the presence of a polymerization catalyst.

  Here, the reaction product is an oily product produced by a heating reaction, and is an oily product having a boiling point of at least 110 ° C., preferably 120 ° C. or higher. The cyclopentadiene content is preferably 5% by weight or less, more preferably 3% by weight or less, and particularly preferably 2% by weight or less. When the content of dicyclopentadiene in the reaction product exceeds 5% by weight, gel is generated in the obtained petroleum resin and the resin is easily oxidized, which is not preferable. The petroleum resin of the present invention obtained by such a method is a novel resin having a high adhesive property in which the formation of gel in the petroleum resin is suppressed regardless of the content of cyclopentadiene and / or dicyclopentadiene in the pyrolysis oil. Petroleum resin.

  The manufacturing process of the petroleum resin of the present invention will be further described in detail.

  The heating reaction of the pyrolysis oil is not particularly limited as long as it is carried out within the range satisfying the above conditions. For example, the heating reaction temperature is preferably 150 to 300 ° C, more preferably 180 to 280 ° C, since the dicyclopentadiene content in the reaction product can be 5% by weight or less. The reaction time is not particularly limited as long as it is within the reaction time range defined by the formula (I) depending on the reaction temperature used. The reaction pressure is not particularly limited. For example, the absolute pressure is usually preferably 0.1 to 20 MPa, more preferably 0.5 to 15 MPa, and particularly preferably 1 to 10 MPa. The type of the reactor for the heating reaction may be a known type such as a continuous flow type or a batch type.

  In addition, the residue in the pyrolysis oil which did not contribute to the production | generation of the reaction product by this heating reaction is removed by well-known methods, such as distillation, prior to operation in the following superposition | polymerization process. Alternatively, the entire residue may not be removed, and a part or the whole may be left together with the reaction product and used as a solvent in the polymerization step.

  The polymerization reaction of the reaction product is not particularly limited as long as the polymerization is performed in the presence of a polymerization catalyst. For example, a method of mixing a reaction product and an organic solvent, adding a polymerization catalyst to the mixture and polymerizing the mixture, deactivating and removing the polymerization catalyst after completion of the polymerization, and then removing the organic solvent can be exemplified.

  The polymerization catalyst used here is not particularly limited. For example, Friedel-Crafts catalysts such as aluminum trichloride, aluminum tribromide, boron trifluoride or their ethyl ether complexes, phenol complexes, butyl ether complexes, butyl alcohol complexes, methyl alcohol complexes; mineral acids such as sulfuric acid and hydrochloric acid And solid acids such as silica, alumina, silica alumina, and zeolite; heteropolyacids such as phosphotungstic acid and silicotungstic acid; or acidic ion exchange resins. Of these, Friedel-Crafts type catalysts are preferably used because of high yield of petroleum resin and excellent post-treatment after completion of the reaction such as catalyst removal. More preferably, boron trifluoride and its complex are used, and boron trifluoride-phenol complex is particularly preferably used. These catalysts can be used not only alone but also in a mixture of two or more. The amount of the polymerization catalyst is not particularly limited, and is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, based on the reaction product, because the polymerization reaction can be efficiently performed. Particularly preferred is 0.1 to 2% by weight.

  The organic solvent used for the polymerization reaction is not particularly limited. For example, the residue in the pyrolysis oil that did not contribute to the formation of the reaction product by the above heating reaction; fats such as pentane, cyclopentane, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, etc. Aromatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, propylbenzene, trimethylbenzene, cumene, butylbenzene, dibutylbenzene; ethers such as 1,4-dioxane, tetrahydrofuran, furfural, butylglycidyl ether Ketones such as acetone, methyl ethyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl cellosolve, and butyl cellosolve; and kerosene. These organic solvents can be used alone or in combination of two or more.

  In the present invention, the polymerization temperature is not particularly limited. For example, it is -30-150 degreeC, Preferably it is -20-100 degreeC. The polymerization pressure is not particularly limited. For example, the absolute pressure is usually 0.1 to 1 MPa, preferably 0.1 to 0.5 MPa. Moreover, the reaction atmosphere at the time of superposition | polymerization is not specifically limited, For example, it is preferable to carry out in inert gas atmosphere, such as nitrogen and argon, Furthermore, it is preferable to carry out in nitrogen atmosphere. As the type of the reactor for the polymerization reaction, a known type such as a continuous flow type or a batch type can be adopted.

  In the present invention, after completion of the polymerization reaction, the polymerization catalyst is deactivated, and then the polymerization catalyst is removed from the polymerization solution. The compound used for the deactivation treatment of the polymerization catalyst is not particularly limited as long as the compound has an effect of deactivating the polymerization catalyst. Examples thereof include alcohols such as methanol, ethanol and propanol, alkaline aqueous solutions such as sodium hydroxide and potassium hydroxide, amines such as ethylamine and diethylamine, aqueous ammonia, and water. Of these, alkaline aqueous solutions are preferably used because no corrosive gas such as halogen is generated, and sodium hydroxide aqueous solution is more preferably used. These compounds can be used not only alone but also in a mixture of two or more.

  The removal of the polymerization catalyst from the polymerization solution of the present invention is not particularly limited, but can be performed by a usual oil-water separation method, for example, decantation.

  Furthermore, in this invention, the petroleum resin manufactured by this invention can be obtained by removing the organic solvent from the polymerization solution from which the polymerization catalyst has been removed. There is no particular limitation on the method for removing the organic solvent from the polymerization solution. For example, the method of removing an organic solvent by distillation is mentioned. Moreover, in order to improve the handling property of the polymerization solution at the time of distillation, it is also possible to distill by adding a new organic solvent prior to distillation of the organic solvent. The organic solvent newly added here is not particularly limited. For example, pentane, cyclopentane, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, benzene, toluene, xylene, ethylbenzene, propylbenzene, trimethylbenzene, cumene, butylbenzene, dibutylbenzene, 1,4 -Dioxane, tetrahydrofuran, furfural, butyl glycidyl ether, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethyl cellosolve, butyl cellosolve, kerosene, etc., as well as various petroleum hydrocarbon solvents and various lubricating oils that are mixed solvents Can be mentioned. These organic solvents can be used alone or as a mixture of two or more. Of these, tetrahydrofuran, hexane and xylene are preferably used because the amount of heat and time required for distillation can be reduced.

  The amount of the organic solvent to be newly added is not particularly limited, but it is 1 to 200 parts by weight with respect to 100 parts by weight of the obtained petroleum resin because the polymerization product tends to be uniform and the time required for distillation is shortened. Is preferable.

  The temperature during distillation of the organic solvent cannot be generally specified depending on the type of the organic solvent. For example, in the case of atmospheric distillation, 150 to 350 ° C. is preferable because the solvent hardly remains and the resin is less susceptible to thermal degradation. More preferably, it is 200-300 degreeC. In the case of vacuum distillation, the distillation temperature can be lowered according to the type of solvent and the degree of vacuum.

  The distillation time of the organic solvent depends on the type and amount of the obtained petroleum resin and the type and addition amount of the organic solvent. For example, in order to suppress residual solvent and thermal degradation of the resin, 0.05 to 10 hours Is preferable, and more preferably 0.5 to 5 hours.

  According to the present invention, a novel petroleum oil that suppresses the formation of gel in petroleum resin and has high adhesive properties regardless of the content of cyclopentadiene and / or dicyclopentadiene in pyrolysis oil used as a raw material for petroleum resin. A resin can be provided.

  Such a petroleum resin is a suitable raw material for hot melt adhesives and a suitable raw material for printing ink that does not contain an aromatic solvent.

  The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

1. Of the pyrolysis oil obtained by pyrolysis of the raw material petroleum fraction, the fraction shown in Table 1 having a boiling point in the range of 20 to 110 ° C. (hereinafter referred to as fraction A) was used.

２．分析方法
「数平均分子量測定」
高速ＧＰＣ装置（東ソー（株）製、商品名Ｈ８０２０ＧＰＣ）を用い、下記条件で測定した。即ち、石油樹脂をテトラヒドロフランに溶解し、樹脂の溶液濃度を５０ｇ／ｌに調製後、このポリマー溶液を、カラムとしてＴＳＫｇｅｌ２０００Ｈ（商品名）２本、ＴＳＫｇｅｌ３０００Ｈ（商品名）１本、及びＴＳＫｇｅｌ４０００Ｈ（商品名）１本が備わった上記ＧＰＣ装置に注入し、標準試料としてポリスチレンを用い、ポリスチレン換算値として数平均分子量を測定した。

2. Analysis method "Number average molecular weight measurement"
Using a high speed GPC device (trade name H8020GPC, manufactured by Tosoh Corporation), the measurement was performed under the following conditions. That is, after dissolving petroleum resin in tetrahydrofuran and preparing a resin solution concentration of 50 g / l, this polymer solution is used as a column with two TSKgel2000H (trade name), one TSKgel3000H (trade name), and TSKgel4000H (trade name). ) It was injected into the above GPC apparatus equipped with one, polystyrene was used as a standard sample, and the number average molecular weight was measured as a polystyrene conversion value.

"Softening point measurement"
It was measured by the ring and ball method according to JIS K-2207 (1991).

"Gel measurement"
Using a transparent container, petroleum resin and toluene are mixed at 1: 1 (weight ratio) to dissolve the petroleum resin. This solution was visually seen under white sunlight, and when insoluble components such as suspended matters and precipitates were not visually recognized in the solution, it was determined that no gel was formed.

Example 1
1 l of fraction A was placed in a 2 l autoclave, sealed, and reacted at 230 ° C. for 90 minutes (time calculated from formula (I): 41 minutes). After completion of the reaction, the autoclave was cooled, and unreacted components were removed by distillation to obtain 200 g of an oily reaction product. The proportion of dicyclopentadiene in the reaction product was 1.9% by weight.

  100 g of the above reaction product and 900 g of toluene were placed in a three-necked flask and stirred at 40 ° C. While stirring, 20 g of boron trifluoride-phenol complex was added dropwise over 1 hour, and stirring was continued for another hour. After completion of the reaction, 250 g of a 4 wt% aqueous sodium hydroxide solution and 250 g of xylene were added to deactivate the polymerization catalyst, and then the aqueous layer was separated to remove the polymerization catalyst. The oil layer was heated at 220 ° C. for 30 minutes, and unreacted components were distilled to obtain 69.7 g of a resin. The obtained resin had a number average molecular weight of 367 and a softening point of 85 ° C. In this polymerization, no gel was formed in the petroleum resin.

Example 2
The reaction was carried out under the same conditions as in Example 1 except that the fraction A was reacted at 220 ° C. for 80 minutes (time calculated from the formula (I): 67 minutes) to obtain 174 g of an oily reaction product. The proportion of dicyclopentadiene in the reaction product was 2.7% by weight.

  Polymerization was carried out under the same conditions as in Example 1 using the above mixture of cyclized products to obtain 67.7 g of a resin. The obtained resin had a number average molecular weight of 369 and a softening point of 84 ° C. In this polymerization, no gel was formed in the petroleum resin.

Example 3
The reaction was conducted under the same conditions as in Example 1 except that the fraction A was reacted at 210 ° C. for 120 minutes (time calculated from the formula (I): 110 minutes) to obtain 165 g of an oily reaction product. The proportion of dicyclopentadiene in the reaction product was 4.7% by weight.

  Polymerization was performed using the mixture of the cyclized product under the same conditions as in Example 1 to obtain 65.7 g of a resin. The obtained resin had a number average molecular weight of 373 and a softening point of 81 ° C. In this polymerization, no gel was formed in the petroleum resin.

Comparative Example 1
1 l of fraction A was placed in a 2 l autoclave, sealed, and reacted at 220 ° C. for 40 minutes (time calculated from formula (I): 67 minutes). After completion of the reaction, the autoclave was cooled, and unreacted components were removed by distillation to obtain 148 g of an oily reaction product. The proportion of dicyclopentadiene in the reaction product was 13.6% by weight.

  When polymerization was carried out under the same conditions as in Example 1 using the above mixture of cyclized products, gel formation was observed in the petroleum resin.

Comparative Example 2
1 l of fraction A was placed in a 2 l autoclave, sealed, and reacted at 210 ° C. for 50 minutes (time calculated from formula (I): 110 minutes). After completion of the reaction, the autoclave was cooled, and unreacted components were removed by distillation to obtain 135 g of an oily reaction product. The proportion of dicyclopentadiene in the reaction product was 22.0% by weight.

When polymerization was carried out under the same conditions as in Example 1 using the above mixture of cyclized products, gel formation was observed in the petroleum resin.

Claims (4)

A reaction product obtained by subjecting a pyrolysis oil having a boiling point of 110 ° C. or less obtained by pyrolysis of a petroleum fraction to a heat reaction under a condition where the reaction temperature is 150 ° C. or more and the reaction time satisfies the following formula (I) A petroleum resin obtained by polymerizing a polymer in the presence of a polymerization catalyst.
Heating reaction time H (min) ≧ 4 × 10 ⁶ × e ^{−0.05 T} (I)
(However, T (° C) indicates the heating reaction temperature) The petroleum resin according to claim 1, wherein the concentration of dicyclopentadiene in the reaction product obtained by the heating reaction is 5% by weight or less. The petroleum resin according to claim 1 or 2, wherein a chain diene having 4 to 5 carbon atoms and / or a cyclic diene having 5 to 6 carbon atoms is used as the pyrolysis oil. A reaction product obtained by subjecting a pyrolysis oil having a boiling point of 110 ° C. or less obtained by pyrolysis of a petroleum fraction to a heat reaction under a condition where the reaction temperature is 150 ° C. or more and the reaction time satisfies the following formula (I) Is produced in the presence of a polymerization catalyst.
Heating reaction time H (min) ≧ 4 × 10 ⁶ × e ^{−0.05 T} (I)
(However, T (° C) indicates the heating reaction temperature)