JP2004346154A - Nonaromatic hydrocarbon resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a hydrocarbon resin which is a nonaromatic hydrocarbon resin not substantially containing an aromatic compound, does not contain a gel content and has a wide molecular weight distribution and a high softening point and to provide a method for producing the hydrocarbon resin using an inexpensive and readily available raw material. <P>SOLUTION: The hydrocarbon resin is obtained by copolymerizing a mixture comprising (a) at least one kind of vinylcyclohexene and tetrahydroindene, (b) at least one kind selected from cyclopentadiene, methylcyclopentadiene and their dimmers by Diels-Alder reaction and (c) a fraction through a process removing the component (b) from a cracked petroleum fraction having 20-100°C boiling point obtained by thermal cracking of petroleum in the ratio of 10-40 parts by mass of the total of the components (a) and (b) in the rate of 3.0 ≤parts by mass of the component (a)/parts by mass of the component (b)≤8 and 90-60 parts by mass of the component (c) (100 parts by mass of the total of the components (a), (b) and (c)) in the presence of a Friedel-Crafts catalyst. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

（２）軟化点 ＪＩＳ Ｋ−２５４３により測定した。
【００３３】
（実施例）
重合可能成分（ａ）（ｂ）（ｃ）として以下の物を用いた。
（ａ）成分：テトラヒドロインデン（実施例１、２、３および比較例１、２）およびビニルシクロヘキセン（実施例４、５）
（ｂ）成分：ジシクロペンタジエン（純度９５質量％以上）
（ｃ）成分：
常法により、蒸留により石油分解油の２０〜１００℃留分からＣＰＤ系化合物を分離した。ＣＰＤ系化合物除去後の組成は以下のとおりであった。
なお、蒸留により得られる石油分解油の２０〜１００℃留分の平均的な組成を（ ）内に示す。

本実施例においては、上記他の化合物を分離せずに溶剤として使用した。
【００３４】
［重合反応］
１０００ｍｌのオートクレーブに、（ａ）（ｂ）（ｃ）成分合計３００ｇおよびベンゼン５０ｇを投入し、触媒として三塩化アルミニウムを加えて攪拌しつつ３時間重合した。表１に、実施例、参考例および比較例における、各成分の配合割合（質量部）、（ａ）（ｂ）（ｃ）成分合計１００質量部に対する触媒の使用量（質量部）、重合温度を示す。
【００３５】
得られた炭化水素樹脂の性状を表１に示す。表から、実施例１〜５の軟化点は比較例２および参考例１よりも高く、その一方で流動性については数および重量分子量データ、分子量分布（Ｍｗ／Ｍｎ）が４以上であることから、流動性が優れていることがわかる。また、比較例１および参考例２においてゲルの生成が認められた。これは、比較例１においては、ジエン系化合物の（ａ）成分と（ｂ）成分との質量比の値が本発明の範囲外となったためで、参考例２においては、本発明に係る（ａ）成分に替えて、ジオレフィン成分として、エチリデンノルボルネンを使用したためである。
【００３６】
【表１】

【００３７】
【発明の効果】
本発明による炭化水素樹脂は、従来技術に比べ広い分子量分布（優れた流動性）および高軟化点を有し、これらのバランスに優れるものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a non-aromatic hydrocarbon resin having a specific monomer composition, particularly having an excellent effect of improving properties such as hot melt, and having an excellent balance between fluidity and softening point, and a method for producing the same.
[0002]
[Prior art]
Non-aromatic hydrocarbon resins containing substantially no aromatic compounds are used as modifiers for various materials having excellent environmental pollution resistance, such as hot melts, printing inks, vibration damping materials, rubber compositions, and traction drives. It is useful as a regulator for fluids and resin decorative sheets.
[0003]
In recent years, highly functionalized hot melts, for example, in a packaging operation such as filling a container with a high-temperature liquid and further packing these in a cardboard box or the like, the heat of the contents is transferred to the packaging box. Need to respond. Generally, in a hot-melt adhesive which exhibits an adhesive force due to solidification, the adhesive force is likely to be reduced in a high-temperature environment. Therefore, since the contents must be left until the contents are sufficiently cooled and the temperature of the packaging box becomes sufficiently low, the production speed of the packaging is reduced by the amount of time for which the packaging is left. Therefore, it is desired to improve the heat resistance of various substrates, especially paper substrates such as corrugated paper. In general, an increase in the molecular weight of the resin is considered to be effective in improving the heat resistance of hot melt adhesiveness. However, an increase in the molecular weight tends to cause a decrease in processability and adhesive properties.
[0004]
For the purpose of improving the heat resistance of the hot melt, the higher the softening point of the hydrocarbon resin, the better. In order to improve the softening point of the hydrocarbon resin, the degree of polymerization is increased to increase the molecular weight. However, when the degree of polymerization is increased by using a cyclic diene such as dicyclopentadiene and cyclopentadiene and a chain C5 diene and the like which are widely used as a raw material of the non-aromatic hydrocarbon resin, the production of the hydrocarbon resin becomes difficult. A gel is likely to be generated, and this gel has an adverse effect as a foreign substance in products such as hot melt. On the other hand, for the purpose of improving the heat fluidity of products such as hot melts, a low polymerization degree, low molecular weight hydrocarbon resin will be selected, but the softening point will be low, and products containing this hydrocarbon resin will be selected. Has a reduced heat resistance. Despite such a reciprocal relationship, demands for high fluidity and high heat resistance in recent hot-melt functionalization have increased.
The inventor of the present invention, even if the softening point is increased by increasing the molecular weight, simultaneously increases the mass average molecular weight (Mw) / number average molecular weight (Mn) (hereinafter, referred to as “molecular weight distribution”), and thereby the fluidity of the hydrocarbon resin. Thought that it is possible to improve. However, it has not been achieved to increase the molecular weight without generating a gel during polymerization and to broaden the molecular weight distribution at the same time.
[0005]
The fraction having a boiling point of 20 to 100 ° C. obtained from the cracked naphtha mainly consists of hydrocarbons having 5 carbon atoms, such as chain diolefin compounds such as isoprene, 1,3-pentadiene and 1,4-pentadiene, and cyclopentadiene. Cyclic conjugated diolefinic compounds and their Diels-Alder adducts, methylbutene, pentene chain olefinic compounds, and cyclic olefinic compounds such as cyclopentene (hereinafter, this fraction is referred to as " C5 fraction "). This C5 cut has attracted attention as meeting the recent demand for non-aromatized materials.
[0006]
It is known to polymerize a C5 cut in the presence of a Friedel-Crafts reaction type catalyst to obtain a hydrocarbon resin. The presence of the cyclopentadiene-based compound provides a hydrocarbon resin having a high softening point, but has the disadvantage of producing a gel (insoluble material) due to the high polymerization reactivity of the cyclopentadiene-based compound. In order to avoid such adverse effects of cyclopentadiene, there is a disclosure of performing a polymerization reaction after removing a cyclopentadiene-based compound (see Patent Document 1), but the specific technical contents and effects are unknown. is there.
[0007]
In addition, Patent Document 1 discloses that in polymerization of a C5 fraction from which cyclopentadiene (CPD), dicyclopentadiene (DCPD) and the like have been removed, an unreacted fraction obtained after a hydrocarbon resin is obtained by a polymerization reaction of the fraction. Although a method to be used has been proposed, a non-aromatic hydrocarbon resin having an excellent balance between fluidity and high softening point has not been obtained.
That is, even if the weight average molecular weight is 4890, its softening point is as low as 106 ° C., and it is inferior in adaptability as a property modifier of a highly functionalized hot melt in recent years.
[0008]
Attempts have also been made to adjust the properties of the hydrocarbon resin obtained by adding a specific copolymerizable compound to the C5 fraction from which the cyclopentadiene-based compound has been removed and then conducting the reaction. However, it is insufficient to produce a hydrocarbon resin excellent in balance between high fluidity and softening point while maintaining the characteristics of the non-aromatic raw material.
[0009]
JP-A-49-30489 (Patent Document 2) discloses that a fraction containing a chain or cyclic ethylenically unsaturated hydrocarbon having a boiling point range of -20 to + 100 ° C is added to a conjugated diene in the fraction. Attempts have been made to add unsaturated alicyclic hydrocarbon compounds having 6 or more carbon atoms at a ratio of 0.1 to 5 mass ratio, but in the examples, although the hue and the adhesion are improved, And their softening points are in the range of 83 to 90 ° C., which are too low to be used as modifiers for hot melts and the like.
[0010]
Further, Japanese Patent Publication No. 63-2966 (Patent Document 3) discloses a C5 olefin and a diolefin, a C6 olefin and a diolefin or a mixture of a C5 and C6 olefin and a diolefin, and a vinyl which is a non-aromatic cyclic compound. Attempts have been made to add norbornene or tetrahydroindene, and also to include the latter with cyclopentadiene (CDP) or a cotrimer of cyclopentadiene and a C5 conjugated diene. The highest softening point in the examples of Patent Document 3 is 138 ° C. (Table 3), but the problem is that the additive in that case is expensive vinyl norbornene. Since the molecular weight is 2565 in number average molecular weight, the balance between fluidity and softening point is considered to be about the same as that of a conventional non-aromatic hydrocarbon resin unless there is a special feature in the molecular weight distribution or the like.
[0011]
Further, the softening point described in Table 7 in this patent document is about 118 ° C., and the additive in that case is a copolymer of cyclopentadiene and C5 conjugated diene, which is not easily available. Since its molecular weight is 1915 in number average molecular weight, considering that the “molecular weight distribution” of a normal hydrocarbon resin is around 3, its mass average molecular weight is estimated to be about 6000, and its fluidity and softening point Is inferior in balance.
[0012]
In Japanese Patent Publication No. 7-178008 (Patent Document 4), C5 distillate (B) having a boiling point of −20 to + 100 ° C., which does not contain cyclopentadiene, and styrene and / or a styrene derivative having 9 carbon atoms of 20% by mass or more. After completely polymerizing any of the petroleum distillates (A) having a boiling point of 100 to 200 ° C. containing any of (A) and (B), the polymerization is continued by adding one of (A) and (B) to obtain a hot melt compounding agent. Although a method is disclosed, an aromatic compound such as styrene is used as an essential and main polymerization component, which is different from a non-aromatic hydrocarbon resin.
[0013]
[Patent Document 1]
JP-A-5-140238 (paragraph 0003 and description of examples)
[Patent Document 2]
JP-A-49-30489 (Description of Examples, etc.)
[Patent Document 3]
JP-B-63-2966 [Patent Document 4]
Japanese Patent Publication No. 7-178008
[Problems to be solved by the invention]
The present invention relates to a non-aromatic hydrocarbon resin containing substantially no aromatic compound, containing no gel component, and having a wide molecular weight distribution and a high softening point. It is an object of the present invention to provide a method for producing the hydrocarbon resin using
[0015]
[Means for Solving the Problems]
The first of the present invention is
(A) at least one of vinylcyclohexene or tetrahydroindene;
(B) at least one selected from cyclopentadiene, methylcyclopentadiene, and a dimer obtained by a Diels-Alder reaction thereof; and (c) a cracked oil having a boiling point in the range of 20 to 100 ° C obtained by pyrolysis of petroleum. The fraction passing through the step of removing the component (b) from the fraction is
(A) and (b) in a ratio of 3.0 parts by mass of (a) / parts by mass of (b) ≦ 8.0 and 10 to 40 parts by mass and (c) 90 to 60 parts by mass (( The present invention relates to a hydrocarbon resin obtained by copolymerizing a mixture containing (a), (b) and (c) in a proportion of 100 parts by mass in the presence of a Friedel-Crafts catalyst.
[0016]
A second aspect of the present invention relates to a hydrocarbon resin, wherein the first hydrocarbon resin of the present invention has a mass average molecular weight / number average molecular weight of 4 or more.
[0017]
A third aspect of the present invention is
(A) at least one of vinylcyclohexene or tetrahydroindene;
(B) at least one selected from cyclopentadiene, methylcyclopentadiene, and a dimer obtained by a Diels-Alder reaction thereof; and (c) a cracked oil having a boiling point in the range of 20 to 100 ° C obtained by pyrolysis of petroleum. The fraction passing through the step of removing the component (b) from the fraction is
(A) and (b) in a ratio of 3.0 parts by mass of (a) / parts by mass of (b) ≦ 8.0 and 10 to 40 parts by mass and (c) 90 to 60 parts by mass (( a) a mixture containing (a), (b), and (c) in a proportion of 100 parts by mass) in the presence of a Friedel-Crafts catalyst. .
[0018]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described more specifically.
As the component (a), 4-vinylcyclohexene (hereinafter referred to as "vinylcyclohexene"), which is an alicyclic diolefin having 8 carbon atoms, and / or tetrahydroindene, which is an alicyclic diolefin having 9 carbon atoms. (Bicyclo [4.3.0] 3,7-nonadiene, hereinafter referred to as "tetrahydroindene"). All of these are inexpensive raw materials because they can be obtained on an industrial scale as by-products when producing ethylidene norbornene from cyclopentadiene and butadiene.
[0019]
Further, from the viewpoint of the chemical structure, even if an alicyclic diolefin having 9 carbon atoms, which is the same as the component (a) tetrahydroindene, has a norbornene ring structure (for example, ethylidene norbornene), a gel is formed. Sometimes. This is presumably because the compound having a norbornene structure has higher reactivity than the component (a). Further, even in the case of an alicyclic diolefin, if the number of carbon atoms is smaller than 7, a gel is easily generated. This is presumed to be due to a high reactivity due to a reduction in steric hindrance. On the other hand, in the case of an alicyclic diolefin having more than 10 carbon atoms, on the other hand, the reactivity becomes low and a hydrocarbon resin having a high softening point cannot be obtained.
[0020]
The component (b) is cyclopentadiene, methylcyclopentadiene and a dimer obtained by a Diels-Alder reaction thereof. The dimer includes the same dimer such as dicyclopentadiene and dimethyldicyclopentadiene, as well as a co-dimer.
[0021]
In the component (c), the cracked oil fraction having a boiling point in the range of 20 to 100 ° C. obtained by the thermal cracking of petroleum refers to a non-aromatic hydrocarbon having at least one carbon-carbon double bond as an essential component. As specific components, chain diolefin compounds such as isoprene, 1,3-pentadiene, and 1,4-pentadiene; cyclic conjugated diolefin compounds such as cyclopentadiene; and Diels-Alder addition thereof. Olefinic compounds such as olefinic compounds, chain olefinic compounds such as methylbutene and pentene, and cyclopentenes. The component (c) used in the present invention is obtained by substantially removing the component corresponding to the component (b) from the above-mentioned fraction, but it is more specific as long as the effects of the present invention are not impaired. May contain up to 3% by mass or less. The method for removing the component (b) is not particularly limited, and any known method such as an extraction method can be used.
[0022]
The component (c) usually contains 20 to 30% by mass of a chain diolefin such as isoprene and piperylene, but the effect of the present invention is not impaired as long as the mass% of the compound falls within the above range. On the other hand, although the aromatic hydrocarbon may contain only benzene, its content is 2% by mass or less, usually 1% by mass or less.
[0023]
In the present invention, the mixing ratio among the components (a), (b) and (c) is important.
The present invention is a cyclopentadiene-based compound (b), which is contrary to the conventional technical knowledge that when a cracked oil fraction containing a cyclopentadiene is directly polymerized, a gel (insolubilized product) may be formed. By positively using and coexisting with the components (a) and (c), a hydrocarbon resin having a high softening point, containing no gel component, and having a wide molecular weight distribution can be obtained.
[0024]
The present inventors have pointed out that the fact that the compound of the component (a) has a milder reactivity in relation to the compound of the component (b) while having similarity and affinity in chemical structure is a factor in suppressing gel formation. It is assumed that it is working effectively.
First, in order to exhibit the relationship between the two most effectively, it is necessary that 3.0 ≦ (a) parts by mass / (b) parts by mass ≦ 8.0. If it is less than 3.0, a gel is formed, and if it is more than 8.0, the characteristics of the polymerization reaction of the component (b) compound are weakened, and it is difficult to obtain a hydrocarbon resin having a high softening point.
Even with the same molecular weight and softening point, the wider the molecular weight distribution (Mw / Mn), the better the fluidity. According to the present invention, by using a specific polymerization raw material at a specific ratio, even if the number average molecular weight is large, one having a molecular weight distribution of 4 or more can be obtained.
[0025]
Further, the ratio of the total parts by mass of the components (a) and (b) to the parts by mass of the component (c) is also important, and the total of (a) and (b) is 10 to 40 parts by mass, ) Is 60 to 90 parts by mass, and the total of (a), (b) and (c) is 100 parts by mass. If the total of (a) and (b) is less than 10 parts by mass, a high softening point cannot be obtained, and if it exceeds 40 parts by mass, a gel may be formed.
[0026]
The polymerization can be carried out by any of a batch system and a continuous system. The order of supplying the raw materials (a), (b) and (c) to the polymerization apparatus is not particularly limited, but it is preferable to mix them before the polymerization is started. The reaction solvent can be appropriately used as needed. After the reaction, unreacted components and solvent are removed and recovered by distillation or extraction to obtain a product hydrocarbon resin.
[0027]
Examples of the Friedel-Crafts catalyst used as the polymerization catalyst include aluminum halide, boron halide, and the like. One or more of these can be used. This is a complex structure using boron fluoride and an alcohol or ether as a ligament. These are usually used as particles having a mesh size of 5 to 200, but are not limited thereto, and may be used as larger particles or smaller particles. The present invention is not limited to this method, and a complex of boron fluoride (liquid) or a complex of aluminum chloride and alcohol (suspension) may be selected as necessary.
[0028]
The amount of the catalyst used is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 5.0 parts by mass, based on 100 parts by mass of the total of the components (a), (b) and (c). Used in parts proportions. If the amount used is less than 0.1 part by mass, the yield of the obtained hydrocarbon resin may be low, while if it exceeds 10.0 parts by mass, the hue of the resulting resin may be deteriorated. .
[0029]
The reaction temperature is preferably from 20 to 150C, more preferably from 40 to 100C. The reaction time depends on the reaction solvent and reaction temperature, but is preferably 5 minutes to 10 hours, more preferably 30 minutes to 5 hours. The reaction product is purified and recovered by distillation, extraction and the like.
[0030]
In the present invention, other non-aromatic olefin compounds besides (a), (b), and (c), and 3% by mass or less of aromatic olefin compounds, in addition to (a), (b), and (c) as long as the objects and effects of the present invention are not impaired. Compounds may be added. Further, carbon-carbon unsaturated bonds remaining in the hydrocarbon resin obtained in the present invention, or, in addition, when present in trace amounts, when used in applications where the presence of compound components having various unsaturated structures is not preferred, It can be used after hydrogenation.
[0031]
【Example】
Next, the present invention will be described specifically with reference to examples. In addition, the test method in an Example and a comparative example is as follows.
[0032]
(Test method)
(1) Mass average molecular weight and number average molecular weight The mass average molecular weight and the number average molecular weight of a petroleum resin are measured by GPC. The columns and analysis conditions are as follows.

(2) Softening point Measured according to JIS K-2543.
[0033]
(Example)
The following were used as the polymerizable components (a), (b) and (c).
Component (a): tetrahydroindene (Examples 1, 2, and 3 and Comparative Examples 1 and 2) and vinylcyclohexene (Examples 4 and 5)
Component (b): dicyclopentadiene (purity 95% by mass or more)
Component (c):
According to a conventional method, a CPD-based compound was separated from a petroleum cracked oil fraction at 20 to 100 ° C. by distillation. The composition after removing the CPD-based compound was as follows.
The average composition of the petroleum cracked oil obtained by distillation at a fraction of 20 to 100 ° C. is shown in parentheses.

In this example, the other compound was used as a solvent without separation.
[0034]
[Polymerization reaction]
A total of 300 g of the components (a), (b) and (c) and 50 g of benzene were put into a 1000 ml autoclave, aluminum trichloride was added as a catalyst, and polymerization was carried out for 3 hours with stirring. Table 1 shows the mixing ratio (parts by mass) of each component, the amount of the catalyst used (parts by mass) based on 100 parts by mass of the total of components (a), (b) and (c), and the polymerization temperature in Examples, Reference Examples and Comparative Examples Is shown.
[0035]
Table 1 shows the properties of the obtained hydrocarbon resin. From the table, the softening points of Examples 1 to 5 are higher than those of Comparative Example 2 and Reference Example 1, while the number and weight molecular weight data and the molecular weight distribution (Mw / Mn) of the fluidity are 4 or more. It can be seen that the fluidity is excellent. In Comparative Example 1 and Reference Example 2, formation of a gel was observed. This is because the value of the mass ratio between the component (a) and the component (b) of the diene compound was out of the range of the present invention in Comparative Example 1, and in Reference Example 2 according to the present invention ( This is because ethylidene norbornene was used as the diolefin component instead of component a).
[0036]
[Table 1]

[0037]
【The invention's effect】
The hydrocarbon resin according to the present invention has a broad molecular weight distribution (excellent flowability) and a high softening point as compared with the prior art, and is excellent in balance between these.

Claims (3)

(A) at least one of vinylcyclohexene or tetrahydroindene;
(B) at least one selected from cyclopentadiene, methylcyclopentadiene, and a dimer obtained by a Diels-Alder reaction thereof; and (c) a cracked oil having a boiling point in the range of 20 to 100 ° C obtained by pyrolysis of petroleum. The fraction passing through the step of removing the component (b) from the fraction is
(A) and (b) in a ratio of 3.0 parts by mass of (a) / parts by mass of (b) ≦ 8.0 and 10 to 40 parts by mass and (c) 90 to 60 parts by mass (( (a) A hydrocarbon resin obtained by copolymerizing a mixture containing (b) and (c) in a proportion of 100 parts by mass in the presence of a Friedel-Crafts catalyst. The hydrocarbon resin according to claim 1, wherein the weight average molecular weight / number average molecular weight is 4 or more. (A) at least one of vinylcyclohexene or tetrahydroindene;
(B) at least one selected from cyclopentadiene, methylcyclopentadiene, and a dimer obtained by a Diels-Alder reaction thereof; and (c) a cracked oil having a boiling point in the range of 20 to 100 ° C obtained by pyrolysis of petroleum. The fraction passing through the step of removing the component (b) from the fraction is
(A) and (b) in a ratio of 3.0 parts by mass of (a) / parts by mass of (b) ≦ 8.0 and 10 to 40 parts by mass and (c) 90 to 60 parts by mass (( a) a mixture containing (a), (b) and (c) in a proportion of 100 parts by mass) in the presence of a Friedel-Crafts catalyst.