Hydrocarbon resins and their manufacturing processes

Abstract

To provide a hydrocarbon resin whose color is bright as much as possible, and a production method of the same.SOLUTION: There is provided a hydrocarbon resin which is obtained by thermal polymerization of a cyclic diolefin component containing a cyclic diolefin compound, and an aromatic component containing indene and / or C1-4- alkylindene, and has a polydispersion index (PDI) of 1 to less than 2.3. There is provided a production process of a hydrocarbon resin which polymerizes a monomer mixture containing an aromatic component containing indene and / or C1-4- alkylindene and a cyclic diolefin component containing a cyclic diolefin compound by heating it to a polymerization temperature of at least 180°C, obtains a product material stream containing a hydrocarbon resin, separates an oligomer including a unit derived from the cyclic diolefin compound and / or a unit derived from the aromatic component from the product material stream, and returns the product material stream to a monomer mixture.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a hydrocarbon resin and a cyclic diolefin component containing a cyclic diolefin compound. and indene and / or C 1-4 - It is prepared from aromatic components containing alkyl indenes The present invention relates to a method for producing hydrogenated hydrocarbon resins, their hydrogenation, and hydrogenated hydrocarbon resins. [Background technology]

[0002] Hydrocarbon resins are often used as tackifiers in hot melt adhesives. The adhesive is typically called a tackifier. The base polymer of hot melt adhesives basically determines the adhesive properties. Examples include styrene block copolymers (SBC), polyamides, polyurethanes, and In addition to polyester, metallocene polyolefin (mPO), amorphous polyalphaolefin Polyvinyl acetate (APAO), or ethylene-vinyl acetate copolymer (EVAC) are often used. will be done.

[0003] There is particular interest in hot melt adhesives that are as light in color as possible and have good processing properties. The good processing properties of hot melt adhesives depend on the tackifier and base polymer. The tackifiers typically used are mPO, A Good compatibility with only one base polymer class, such as PAO or EVAC Therefore, if good compatibility is desired, separate time series should be used for each base polymer class. However, the tackifier must be as thick as possible. It would be advantageous if the components of a hot melt adhesive were compatible with the marker class. , can be assessed, for example, by determining the cloud point.

[0004] In order to produce hot melt adhesives that are as bright in color as possible and easy to process, At least partially hydrogenated hydrocarbon resins, which are commonly used, do not produce undesirable by-products. It is important to avoid the use of hydrocarbons as much as possible. These can cause the hydrocarbon resin to turn black and This may lead to incompatibility with other components of the hot melt adhesive. Donner color, yellowness index, or Hazen color are often used.

[0005] Methods for the preparation of (hydrogenated) hydrocarbon resins are known. Cycloalkenes with two conjugated double bonds, such as pentadiene, and ethylenes, such as styrene. The resulting hydrocarbon resin is copolymerized with a carboxylic unsaturated aromatic component and further processed to produce a hydrocarbon resin with at least The hydrocarbon resin thus obtained can be used alone or in combination with other hydrocarbons. It can be used as a tackifier for hot melt adhesives together with the additives .

[0006] Such a method is described in U.S. Pat. No. 5,502,140, ​​which in particular Inexpensive dicyclopentadiene-containing starting materials are used. However, U.S. Patent No. 55021 In the specification of No. 40, instead of indene, styrene or α-methylstyrene etc. are used in the reaction. Vinyl aromatics are used.

[0007] In European Patent No. 2251364, the content of aromatic compounds is 5 to 25% by weight. A method for producing hydrocarbon resins of the first mentioned type is described. In the specification of Patent No. 2251364, pure styrene or the like is used as the ethylenically unsaturated aromatic component. Only by using vinyl aromatics are qualitatively high grade resins achieved.

[0008] In European Patent No. 0936229, a copolymer of an olefin, an aromatic monomer, and a (di)silyl group is used. Aromatic modification is achieved by subjecting a polymerization feed containing olefins to Friedel-Crafts polymerization. However, European Patent No. 093 A drawback of the process of the '6229 patent is that it uses a halogen-containing catalyst to produce the hydrocarbon resin. To do this.

[0009] In the production of hydrocarbon resins, by-products can be formed at different times for a variety of reasons. For example, in addition to the desired hydrocarbon resin, low molecular weight waxy or polymeric A large amount of thermosetting by-products may be formed during polymerization, which may affect the quality of the final product. This can damage the adhesive and contribute to incompatibility in hot melt adhesives.

[0010] Harmful by-products may occur during the purification and / or isolation of intermediate products or during the isolation of the final product. For example, both polymerization and hydrogenation are usually carried out in the presence of various inert solvents. Since the polymerization is carried out in the presence of The solvent must be removed. Solvents often have high boiling points, which usually require high temperatures to remove. Heating is required, which can result in secondary reaction by-products.

[0011] To avoid by-products, various solutions have been proposed. The specification of Unexamined Patent Publication No. 3124503 describes a method for producing a hydrocarbon resin, To improve compatibility at an acceptable cost increase, dicyclopentadiene was converted to vinyl Reaction with aromatic compounds to form phenylnorbornene derivatives, which are then used in subsequent polymerization reactions. The hydrocarbon resin thus obtained acts as a starter for the reaction. The drawback of the method is that the pre-reaction must be carried out at a high temperature to obtain the phenylnorbornene derivative with high selectivity. The problem is that the degree must be kept within a narrow window. Summary of the Invention [Problem to be solved by the invention]

[0012] Therefore, the present invention is based on the objective of providing a hydrocarbon resin with the lightest possible color. A further object of the present invention is to provide a base polymer, in particular a metallocene polyolefin ( mPO), amorphous polyalphaolefin (APAO), and / or ethylene acetate It has good compatibility with vinyl copolymers (EVAC), making it particularly suitable for hot melt bonding. Adhesives include metallocene polyolefin (mPO) and amorphous polyalphaolefin (APAO) ), and ethylene-vinyl acetate copolymer (EVAC), and therefore The present invention also provides a hydrocarbon that functions as a tackifier. The object of the present invention is to provide a method for producing a hydrocarbon resin having the above compatibility. do. [Means for solving the problem]

[0013] The object is to provide a method for producing a cyclic diolefin component containing a cyclic diolefin compound, and a method for producing a cyclic diolefin component containing indene and / or C 1-4 It is obtained by thermal polymerization of aromatic components containing alkylindenes, and is This is achieved by hydrocarbon resins having a dispersibility index (PDI) of 1 to less than 2.3.

[0014] The subject of the present invention is furthermore indene and / or C 1-4 -Contains alkyl indenes A monomer mixture comprising an aromatic component and a cyclic diolefin component comprising a cyclic diolefin compound. The mixture is polymerized by heating to a polymerization temperature of at least 180°C to form a mixture containing a hydrocarbon resin. A product stream is obtained, and units derived from cyclic diolefin compounds and / or aromatic compounds are extracted. Oligomers containing units derived from the monomer mixture are separated from the product stream. 2. A method for producing a hydrocarbon resin according to the present invention, wherein the hydrocarbon resin is recycled to the process for producing the hydrocarbon resin according to the present invention.

[0015] The subject of the present invention is also a hydrocarbon resin obtained by hydrogenating the hydrocarbon resin according to the invention, and and / or hydrogenated hydrocarbon resins obtainable by the production process according to the invention.

[0016] The subject of the present invention is also a hydrocarbon resin according to the invention or a hydrogenated hydrocarbon resin according to the invention, Adhesive base polymers, e.g. metallocene polyolefins, ethylene vinyl acetate copolymer, amorphous polyalphaolefin, or styrene block copolymer. Well, it is a composition.

[0017] The subject of the present invention is also hot melt adhesives, in particular metallocene polyolefins, ethylene olefin-vinyl acetate copolymer, amorphous polyalphaolefin, or styrene block copolymer in copolymer-based hot melt adhesives and / or solvent-containing adhesives , in particular in solvent-containing styrene block copolymer adhesives, hydrocarbon resins according to the invention or as a tackifier or tackifier for the hydrogenated hydrocarbon resins of the present invention. It is used.

[0018] The subject of the present invention is further to provide a method for the preparation of rubber articles, in particular for the preparation of rubber articles with mechanical and dynamic properties. In bitumen, especially in asphalt, as a modifier for improving the properties of As an additive and / or hydrophobizing agent for sphalt or as a modifier in printing inks The use of the hydrocarbon resins according to the invention as modifiers and / or hydrophobizing agents.

[0019] Finally, the subject of the present invention is the use of hydroxybenzoates as additives in paints; in plastic materials; As a modifier, especially in plastic materials; in rubber; in bitumen; As a hydrophobizing agent, especially in bitumen, e.g. for roofing felt; In polypropylene films, especially in polypropylene films, especially in BOPP films as a modifier and / or hydrophobizing agent; in cosmetics; or in adhesive compositions as a tackifier, especially for applications in the hygiene products industry and for use in food packaging The use of the hydrogenated hydrocarbon resin according to the present invention.

[0020] Surprisingly, the cyclic diolefin component and the indene and / or C 1-4 -Arki Hydrocarbons with a PDI of 1 to less than 2.3 obtained by thermal polymerization with components containing phenylindene The resin has excellent properties, in particular good hydrogenation ability and / or only slight discoloration. Furthermore, by hydrogenating this resin, the color index was found to be very low. low, with mPO and APAO, or preferably with mPO, APAO, and EVAC It is possible to obtain a hydrogenated resin having good compatibility with [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 is a schematic diagram of the method according to the invention. DETAILED DESCRIPTION OF THE INVENTION

[0022] The process according to the invention for producing hydrocarbon resins and the possible subsequent hydrogenation , which will be explained first below.

[0023] In the process according to the invention, the monomer mixture is heated to a polymerization temperature of at least 180°C. During polymerization, the mixture is preferably a substantially single-phase liquid. This allows for good mixing, This results in short reaction times and good heat transfer within the mixture.

[0024] The cyclic diolefin component contains a cyclic diolefin compound. is 25% by weight or more, preferably 30% by weight or more, based on the total mass of the cyclic diolefin component. Preferably 35% by weight or more, more preferably 50% by weight or more, and even more preferably 60% by weight or more More preferably, the content of the cyclic diolefin compound is 70% by weight or more. It's nice.

[0025] The cyclic diolefin component can also consist of a cyclic diolefin compound.

[0026] The cyclic diolefin compound preferably has at least two cyclic groups, which can be particularly conjugated. It includes cycloalkenes having a carbon-carbon double bond. More preferably, it is a cyclic diolefin. The compound is particularly one having at least two carbon-carbon double bonds capable of conjugation. Or it consists of multiple cycloalkenes.

[0027] Cycloalkenes having at least two carbon-carbon double bonds are suitable for use in the present invention. It is called cyclodiakenes. Cyclodialkenes, which have two conjugated carbon-carbon double bonds, are In accordance with the present invention, they are referred to as conjugated cyclodialkenes.

[0028] The cyclodialkenes, particularly conjugated cyclodialkenes, are preferably 5 to 11 carbon atoms as monomers. Examples of conjugated cyclodialkene include cyclopentadienes, cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene Dienes and cyclopentadiene derivatives such as ethyltetramethylcyclopentadiene is.

[0029] Cyclodialkenes, especially conjugated cyclodialkenes, can dimerize. Conjugated cyclodialkenes can be produced as monomers, dimers, or as a mixture of monomers and dimers. The dimerization is preferably reversible. For example, cyclopentadiene may be present as a mixture of cyclopentadiene and cyclopentadiene. Cyclopentadiene and cyclopentadiene derivatives tend to dimerize spontaneously at room temperature. When heated, the reverse reaction occurs to form the monomer again. When containing a mixture of cyclodialkene, especially conjugated cyclodialkene, monomer, dimer and Codimers and / or codimers may exist.

[0030] Therefore, the conjugated cyclodialkenes mentioned above can be converted into dimers as monomers depending on the temperature. It can exist as a dimer or as a mixture of monomers and dimers. Codimers as well as dimers may be present in mixtures of different conjugated cyclodialkenes. For example, two monomers, cyclopentadiene-cyclopentadiene dimer and methylsilyl Cyclopentadiene-methylcyclopentadiene dimer, and cyclopentadiene-methyl Methylcyclopentadiene codimer is a dimer of cyclopentadiene and methylcyclopentadiene. The ene may be present in a mixture.

[0031] According to one embodiment, the cyclic diolefin compound is cyclopentadiene, methylcyclopentadiene, Pentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetra Cyclopentadiene derivatives such as tetramethylcyclopentadiene, and mixtures thereof is selected from the group consisting of:

[0032] According to a further embodiment, the cyclic diolefin compound is cyclopentadiene and methyl ... Contains methylcyclopentadiene.

[0033] According to a further embodiment, the cyclic diolefin component comprises a cyclic diolefin compound. The cyclic diolefin compounds are cyclopentadiene, methylcyclopentadiene, ethyl cyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene cyclopentadiene derivatives such as pentazinone, and mixtures thereof. can be.

[0034] According to a further embodiment, the cyclic diolefin component comprises a cyclic diolefin compound. The cyclic diolefin compounds are cyclopentadiene, methylcyclopentadiene, ethyl cyclopentadiene, pentamethylcyclopentadiene and ethyltetramethylcyclopentadiene The compound comprises a conjugated cyclodialkene selected from the group consisting of: pentadienes;

[0035] According to one embodiment, at least 25% by weight, in particular 3% by weight, based on the mass of the hydrocarbon mixture. Containing 0 to 60% by weight of conjugated cyclodialkenes as cyclic diolefin compounds. Hydrocarbon mixtures, such as petroleum fractions, can be used as the cyclic diolefin component in the process according to the invention. The hydrocarbon mixture may also contain aromatic compounds such as indene, C 1-4 -Alkyl indene, and / or each independently of the other, 8 to 15, preferably 8 to 13 ethylenically unsaturated aromatic compounds having carbon atoms in an amount of 1 The hydrocarbon mixture may contain 0 to 20% by weight of the hydrocarbon mixture. It may contain 20 to 40% by weight of non-reactive components based on the mass.

[0036] The monomer mixture may also contain indene and / or C 1-4 -Aromatic containing alkylindenes Contains aromatic components. C 1-4 The -alkylindenes are preferably mono- or poly-, in particular Mono- or di-, C 1-4 -alkyl-substituted indene. 1-4 -Arki Examples of indene are methylindene, dimethylindene, and ethylindene. C 1-4 An important example of an -alkylindene is methylindene. , all isomers of methylindene are included. An example of an isomer of methylindene is 1-methylindene. In addition, different methylindene and 3-methylindene are present in the aromatic moiety. The isomers may also exist simultaneously.

[0037] The aromatic components are indene and / or C 1-4 -alkylindenes. The aromatic components are also indene and / or C 1-4 -alkylindenes and each other at least one alkyl group having 8 to 15, preferably 8 to 13, carbon atoms, and at least two ethylenically unsaturated aromatic compounds.

[0038] According to a preferred embodiment, the aromatic component is selected from the total mass of petroleum fractions or from tar treatment. at least 25% by weight, based on the total mass of the fractions, of indene and / or C 1-4 - Petroleum fractions or tars containing alkylindenes and various ethylenically unsaturated aromatic compounds Constituents from the process are used.

[0039] In particular, mono- or poly-C1-C4-arylsulfonic acid having carbon-carbon double bonds outside the aromatic rings The alkyl-substituted benzene compound is an alkyl-substituted benzene compound having 8 to 15, preferably 8 to 13, carbon atoms. Suitable ethylenically unsaturated aromatic compounds include: Examples of such compounds are styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, and / or p-vinyltoluene. Ethylenically unsaturated aromatic compounds are often It is called vinyl aromatic.

[0040] According to one embodiment, the aromatic mixture comprises indene and / or methylindene and sulfonyl indene. ethylene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, and p-vinyltoluene and at least two vinyl aromatic compounds selected from the group consisting of: Includes.

[0041] According to one embodiment, up to 50% by weight of styrene, α-methyl, based on the total mass of the mixture vinylstyrene, o-vinyltoluene, m-vinyltoluene, and p-vinyltoluene vinyl aromatics, not more than 30% by weight of indene, and not more than 15% by weight of C 1-4 -Alkyl A mixture of indenes is used as the aromatic mixture.

[0042] According to a further embodiment, the mixture contains up to 60% by weight of indene and and / or C 1-4 - A mixture containing alkylindenes is used as the aromatic mixture.

[0043] Cyclic diolefin compounds and indene and / or C 1-4 -Alkyl indene Preferably, the aromatic mixture is a monomer of the monomer mixture, or It is preferred to provide a marker.

[0044] The cyclic diolefin component and the aromatic component are present in different ratios in the monomer mixture. However, the ratio of the cyclic diolefin component to the aromatic component can be adjusted to olefin compounds and indene and / or C 1-4 -Alkyl indenes and ethylenically unsaturated It has been found that better results can be obtained by setting the ratio of aromatic compounds to mono- and di-aromatic compounds. It was found that:

[0045] Advantageously, the cyclic diolefin compound and the aromatic component are as defined above, The monomer mixture may comprise cyclic diolefin compounds, indene and / or C 1-4 -Arki 50 to 95% by weight based on the total mass of phenylindene and ethylenically unsaturated aromatic compounds %, preferably 60 to 95% by weight, or 65 to 90% by weight, or 65 to 85% by weight, Alternatively, it contains 65 to 80% by weight of a cyclic diolefin compound.

[0046] According to a preferred embodiment, the cyclic diolefin compound is cyclopentadiene, methyl Cyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethylene cyclopentadiene derivatives such as methyltetramethylcyclopentadiene, and and the aromatic component is selected from the group consisting of an aromatic mixture, indene and / or C 1-4 -alkyl and each independently 8 to 15, preferably 8 to 13 carbon atoms At least one, especially at least two, ethylenically unsaturated aromatic compounds containing hydrogen atoms. The monomer mixture is a cyclic diolefin compound, indene and / or C 1- 50 based on the total mass of 4-alkylindene and ethylenically unsaturated aromatic compounds to 95% by weight, preferably 60 to 95% by weight, or 65 to 90% by weight, or 65 to 80% by weight It contains 5% by weight, or 65 to 80% by weight, of a cyclic diolefin compound.

[0047] According to a further preferred embodiment, the cyclic diolefin compound is cyclopentadiene. , methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene cyclopentadiene derivatives such as cyclopentadiene, ethyltetramethylcyclopentadiene, and the aromatic component is an aromatic mixture, The mixture contains 50% by weight or less of styrene, α-methylstyrene, o-methylstyrene, α ... vinyl aromatics such as -vinyltoluene, m-vinyltoluene, and p-vinyltoluene and 25 wt. % or less of indene and 10 wt. % or less of C. 1-4-Alkyl indene or a mixture containing not more than 60% by weight of indene and / or Or C 1-4 -alkylindenes; the monomer mixture is a mixture containing cyclic di- olefin compounds, indene and / or C 1-4 -Alkyl indene, and ethylene 50 to 95% by weight, preferably 60 to 95% by weight, based on the total mass of the aromatic unsaturated aromatic compounds. % by weight, or 65 to 90% by weight, or 65 to 85% by weight, or 65 to 80% by weight It contains a diolefin compound.

[0048] The cyclic diolefin compound and the aromatic component are advantageously as defined above and The diolefin mixture is composed of cyclic diolefin compounds, indene and / or C 1-4 -Alkyl 5 to 40% by weight based on the total mass of indene and ethylenically unsaturated aromatic compounds, Preferably, the content of the ink is 10 to 35% by weight, or 15 to 35% by weight, or 25 to 35% by weight. Den and / or C 1-4 -Alkylindenes and ethylenically unsaturated aromatic compounds Contains:

[0049] According to one embodiment, the cyclic diolefin compound is cyclopentadiene, methylcyclopentadiene, Pentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetra Cyclopentadiene derivatives such as tetramethylcyclopentadiene, and mixtures thereof the aromatic moiety is selected from the group consisting of indene and / or C 1-4 -Alkyluy and phenylene, each independently having 8 to 15, preferably 8 to 13, carbon atoms. and at least one, especially at least two, ethylenically unsaturated aromatic compounds The monomer mixture is an aromatic mixture; the monomer mixture is a mixture of cyclic diolefin compounds, indene and / or or C 1-4 - alkylindenes and ethylenically unsaturated aromatic compounds 5 to 40% by weight, preferably 10 to 35% by weight, or 15 to 35% by weight, or It contains 25 to 35% by weight of an ethylenically unsaturated aromatic compound.

[0050] According to a further embodiment, the cyclic diolefin compound is cyclopentadiene, methyl Cyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethylene cyclopentadiene derivatives such as methyltetramethylcyclopentadiene dimer, and the aromatic component is an aromatic mixture, The mixture contains 50% by weight or less of styrene, α-methylstyrene, o-methylstyrene, α ... vinyl aromatics such as -vinyltoluene, m-vinyltoluene, and p-vinyltoluene and 30 wt. % or less of indene and 15 wt. % or less of C. 1-4 -Alkyl indene or a mixture containing not more than 60% by weight of indene and and / or C 1-4 - alkylindene-containing mixture; the monomer mixture is Cyclic diolefin compounds, indene and / or C 1-4 -Alkyl indenes, and 5 to 40% by weight, preferably 10 to 40% by weight, based on the total mass of the ethylenically unsaturated aromatic compounds. 35% by weight, or 15-35% by weight, or 25-35% by weight of indene and / or is C 1-4-Contains alkyl indenes and ethylenically unsaturated aromatic compounds.

[0051] As the cyclic diolefin component, a mixture with a low content of cyclic diolefin compounds, e.g. For example, when petroleum fractions are used, one or more conjugated silyl groups may be added to set the above monomer ratio. Cyclodialkenes, such as cyclopentadiene, methylcyclopentadiene, pentamethyl Cyclopentadiene, ethylcyclopentadiene and ethyltetramethylcyclopentadiene It is also possible to add cyclic diolefin compounds consisting of dienes. Den and / or C 1-4 -alkylindenes and 8 to 15, preferably 8 to 1 The same is true for ethylenically unsaturated aromatic compounds having 3 carbon atoms.

[0052] The monomer mixture may contain a non-polymerizable solvent. Suitable solvents include aromatic and and naphthenic solvents or their hydrogenation products. Thus, suitable solvents are, for example: Benzene, toluene, xylene, ethylbenzene, cyclohexane, dimethylcyclohexane The solvent is preferably mono-, ethylcyclohexane, or a mixture thereof. or poly-, especially mono- or di-, alkyl-substituted aromatic hydrocarbons having 7 to 10 carbon atoms; Aromatic compounds, such as o-xylene, m-xylene, p-xylene, and / or ethyl These preferably have a boiling point above 100°C, especially above 130°C. When xylene is used as a solvent, it can be used either as a pure compound or as an isomer. It may exist as a mixture of two or more of -xylene, m-xylene, and p-xylene.

[0053] According to a preferred embodiment, a C8-isomer mixture can be used as the solvent. The C8-isomer mixture is preferably o-xylene, m-xylene, p-xylene and Contains a mixture of ethylbenzene.

[0054] Constituents from petroleum fractions and tar distillates contain non-polymerizable constituents, such as xylene. Therefore, the cyclic diolefin component may already contain non-polymerizable aromatics. and / or petroleum fractions from petroleum fractions or tar distillation as aromatic components. If the constituent material is used, it is possible to omit the addition of a solvent.

[0055] The monomer mixture may contain non-polymerizable constituents in an amount of 0 to 40% by weight. The synthetic solvent is contained in the monomer mixture in an amount of 0 to 40% by weight based on the mass of the monomer mixture. The monomer mixture may contain 5 to 100% by weight of the monomer mixture. % by weight, particularly preferably 5 to 30% by weight, for example about 30% by weight, of a non-polymerizable solvent. It is preferable to have

[0056] The monomer mixture is preferably 0 to 40% by weight, based on the mass of the monomer mixture. non-polymerizable in an amount of 5 to 35% by weight, more preferably 5 to 30% by weight, for example about 30% by weight It is conceivable that the monomer mixture contains both solvent and non-polymerizable constituents. 0 to 40% by weight, preferably 5 to 35% by weight, more preferably 10 to 40% by weight, based on the mass of the monomer mixture. Preferably, the non-polymeric constituents are present in an amount of 5 to 30% by weight, for example about 30% by weight. It is possible.

[0057] According to one embodiment, the method is carried out with the substantial exclusion of oxygen. In particular, the formation of acid groups and ester groups in the product can be reduced. This helps to optimally achieve a colorless hydrogenated hydrocarbon resin. Cyclic diolefin components and / or aromatic components or aromatic mixtures, especially storage thereof The container is preferably inerted with a protective gas such as nitrogen. Storage containers for hydrogenated hydrocarbon resins, especially hydrocarbon resins and / or hydrogenated hydrocarbon resins, are also available. , advantageously inerted with a protective gas such as nitrogen.

[0058] The process according to the invention allows the monomer mixture to be heated rapidly to the polymerization temperature. The monomer mixture is heated at a rate of 20°C / min to 200°C / min, preferably 30°C / min to 200°C / min, More preferably, 35°C / min to 200°C / min, and even more preferably, 35°C / min to 140°C / min Particularly preferably, the heating rate is 35°C / min to 80°C / min or 35°C / min to 70°C / min. In particular, it is preferable to heat the mixture up to a temperature at which the polymerization reaction starts, particularly up to a maximum of 180°C to 235°C. The aforementioned heating rates are used to heat the monomer mixture to a temperature of Once the temperature of the material reaches 180°C or higher, the temperature thereafter can be set at a heating rate other than that mentioned above. The heating rate according to the present invention results in a low amount of by-products and a given softening point. It has been found that low Mz values ​​can be achieved in

[0059] The polymerization is already initiated at a temperature of 180° C., but in the process according to the invention the polymerization is initiated at a temperature of 180° C. It is also possible to carry out the polymerization at elevated temperatures. In the process according to the invention, the polymerization is carried out at temperatures above 180° C. For example, 200°C to 300°C, 230°C to 300°C, or 240°C The polymerization can be carried out at a polymerization temperature of 250 to 270°C.

[0060] The temperature can be varied during the polymerization. For example, the temperature can be increased during the polymerization to a final temperature. Temperature changes can be organized in various ways. For example, According to one embodiment, the temperature is the final temperature, which is reached at the end of the polymerization process. According to one embodiment, The temperature is kept substantially constant during the polymerization.

[0061] If the polymerization is carried out entirely at low temperatures, especially below 240°C, the softening point of the product will be low and the wax will be It is known that this can sometimes occur.

[0062] The polymerization can be carried out at a pressure of 10 bar or more. For example, the pressure can be 10 to 25 bar. , in particular 10 bar to 20 bar or 13 bar to 18 bar. If the pressure is less than 10 bar, the quality of the final product will be poor and the yield will be low. Furthermore, the pressures mentioned above allow the presence of a gas phase to be largely avoided. Allows for better control and better heat transfer.

[0063] The polymerization may be carried out continuously or discontinuously. The polymerization is preferably carried out continuously. The continuous mode of operation provides better heat transfer than the discontinuous method. Furthermore, the continuous nature of the process reduces operating costs, making the method more It can be done reliably.

[0064] The polymerization can be carried out in a variety of reaction vessels. The polymerization is preferably carried out in a continuous tubular reactor. This procedure has proven particularly advantageous when considering continuous polymerization. In a tubular reactor, the polymerization is carried out for 30 to 180 minutes, in particular for 40 to 120 minutes or for 50 to 90 minutes. This can be done especially for a holding time of 1 minute.

[0065] When modifying the properties of the hydrocarbon resin obtained according to the present invention, Part or all of the product can be recycled to the tubular reactor. This procedure is useful, for example, for the production of hydrocarbons. This is effective in achieving a high molecular weight of the base resin. The removal for recycle is preferably carried out at the reactor outlet. downstream and upstream separation of oligomers from the product stream. In the method, 0 to 90 wt. % of the product stream based on the mass of the resulting product stream, Preferably, 25 to 75 wt. % is recycled into the inlet monomer mixture. Such recycling can be achieved particularly easily in tubular reactors.

[0066] In the process according to the invention, units derived from cyclic diolefin compounds and / or aromatic Oligomers containing units derived from the component are separated from the product stream and then mixed with the monomer. After polymerization, a portion, preferably all, of the oligomer and any non-polymerizable solvent are added to the mixture. It is advantageously removed from the product stream by evaporation, either batchwise or preferably continuously. Advantageously, after evaporation, some or preferably all of the oligomers are removed by batch or, preferably, is continuously condensed completely or preferably partially to remove any non-polymerizable solvent. Advantageously, after condensation, the oligomers are separated from the solvent in a batchwise manner for further polymerization. Or preferably returned to the monomer mixture in a continuous manner.

[0067] The oligomers are preferably prepared at an absolute pressure of less than 100 mbar, in particular less than 50 mbar. The pressure is 30 mbar, and the temperature is 80°C or higher, preferably 80°C to 120°C, more preferably 90°C to 120°C. The oligomer can boil at 0°C to 120°C, more preferably at 100°C to 120°C. Counter pressure is 50 mbar or less, preferably 30 mbar, and the temperature is 90 to 120°C, in particular 1 It is particularly preferred that the oligomer boils at a temperature between 00°C and 120°C. This can be achieved by operating a partial condenser under conditions Thus, the oligomers are separated from the lower boiling constituents.

[0068] Furthermore, the oligomer preferably has a molecular weight of 100 to 600 g / mol, more preferably has a molecular weight of 130 to 600 g / mol, particularly preferably 150 to 600 g / mol. obtain.

[0069] Separating the oligomers from the product stream and then feeding the oligomers into the monomer mixture. It was found that high-quality hydrocarbon resins can be obtained by using PDI. It is possible to obtain a hydrocarbon resin having a molecular weight of 1 to less than 2.3. By using these resins, it is possible to obtain hydrocarbon resins having a PDI of 1 to less than 2.3. After hydrogenation, the fats are converted into mPO and APAO, especially mPO, APAO and EVAC. It exhibits good compatibility.

[0070] Furthermore, the process according to the invention comprises separating oligomers from the resulting product stream; It can then be added to the monomer mixture to form a homogeneous mixture without forming any sparingly soluble products. It is also possible to carry out polymerization at a constant temperature. Furthermore, this results in a hydrocarbon resin that is less likely to discolor. Finally, the yield can be increased by recycling the oligomer. can be done.

[0071] The recycled oligomer may also contain non-polymerizable constituents and / or solvent.

[0072] The unreacted monomer is thermally separated from the solvent and added to the feed stream raw material mixture. This allows for further recycle, which also increases the yield of resin.

[0073] The process according to the invention involves the production of oligomers boiling in the aforementioned ranges or oligomers having the aforementioned molecular weights. This can be effectively achieved by selectively separating the ligomers. The method can be carried out in steady state operation with good yields by selectively separating oligomers. In addition, there is no need to adjust the feedstock amount. Dilute feedstocks such as distillates from processing can also be used.

[0074] The polymerization of the monomer mixture to form the hydrocarbon resin is preferably carried out by Diels-A. The combination of Diels-Alder reaction and radical coupling of these poly-Diels-Alder products This is done accordingly.

[0075] The hydrocarbon resin according to the present invention can be obtained by the method described above.

[0076] The hydrocarbon resin according to the present invention preferably comprises a repeating unit derived from a cyclic diolefin compound. units and indene units and / or C 1-4 - alkylindene units, in particular The hydrocarbon resin may also contain additional units derived from aromatic moieties. Hydrogenated resins include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene It may also contain units derived from methyl methyl acrylate, ...

[0077] The above description of the process according to the invention is based on the cyclic georeflection of the hydrocarbon resin according to the invention. It is also suitable for use with olefinic compounds, cyclic diolefinic compounds, and aromatic compounds.

[0078] The hydrocarbon resin according to the present invention preferably has at least a portion of the general structural formula (I): death, [ka] In the formula, each R 1 and each R 2 are, independently of each other, -H, -CH3, -C2H5, -n- C3H7, -CH(CH3)2, -n-C4H9, -CH2CH(CH3)2, -CH( -C(CH3)(C2H5) and -C(CH3)3; Each R 3 are, independently of each other, -H, -CH3, or -C2H5, p, q, r, s, t, and u are, independently of one another, integers from 0 to 8; Each n, each m, and each o independently represents an integer of 0 to 6, preferably an integer of 0 to 4. , more preferably an integer of 0 to 2, Each a, each b, each c, and each d is independently an integer of 1 to 4, preferably 1 to 2. is an integer, However, the hydrocarbon resin has a density of 200 to 600 g / mol, preferably 220 to 500 g / m ol, more preferably 250 to 400 g / mol, and Rank and / or C1-4 - Provided that it contains alkylindene units.

[0079] Therefore, the resin preferably contains a cyclic diolefin component and an aromatic component. or the deal of constituents of the cyclic diolefin component and / or aromatic component Copolyesters in which different units, which are the products of the Schoen-Alder reaction, are linked together by radical bonds. The unit represented by the variable p in structural formula (I) is a single unit of a cyclic diolefin compound. or the result of multiple Diels-Alder reactions. The variables q and r in structural formula (I) The unit represented by is a compound consisting of a cyclic diolefin compound and an ethylenically unsaturated aromatic compound or an indo- the result of a Diels-Alder reaction with an indene or C1-C4 alkylindene, Additional cyclic diolefin compounds are optionally incorporated via a Diels-Alder reaction. The unit represented by the variable s in structural formula (I) has not undergone the Diels-Alder reaction. The structural formula (I) is a cyclic diolefin compound in which the cyclic diolefin is incorporated by a radical bond. The unit represented by the variable t undergoes a Diels-Alder reaction with a cyclic diolefin compound. Indene units or C incorporated by radical bonds not 1-4 -Alkyl indole The unit represented by the variable u in structural formula (I) is incorporated by a radical bond. It is derived from ethylenically unsaturated aromatic compounds and is a diolefin with cyclic diolefin compounds. This is a unit that has not undergone the Alder reaction.

[0080] In structural formula (I), the order of units, especially those having the variables p, q, r, s, t, and u, The presence and number of copolymer molecules in the hydrocarbon resin may vary statistically. The variables n, m, and o represent, in their respective units, one or more annular geometries. Indicates whether the fin compounds are bonded to each other by the Diels-Alder reaction. In particular, for units represented by the variable p in structural formula (I), when p is greater than 1, each n is , each independently may be an integer of 0 to 6, preferably 0 to 4, more preferably 0 to 2. The same applies to the units represented by the variables q and r in structural formula (I). do.

[0081] The sum of the variables p, q, r, s, t, and u is preferably at least 1, more preferably It is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 2 to 6.

[0082] As shown in structural formula (I), the different units may be substituted. In particular, the aromatic units The positions can be polysubstituted.

[0083] The hydrocarbon resin according to the present invention has a PDI of 1 to less than 2.3. The multiplicity is preferably 1 to 2.1, more preferably 1.5 to 2.0, and even more preferably 1.5 to 1.95. Hydrocarbon resins with the above PDI are suitable for hot melt bonding. Very good compatibility with adhesive base polymers, especially mPO, APAO, and EVAC I know I have it.

[0084] The hydrocarbon resin according to the present invention preferably has a molar ratio of 1 to 20 based on the total mass of the hydrocarbon resin. %, preferably 4 to 20% by weight, more preferably 4 to 16% by weight, and even more preferably 5 up to 15% by weight, particularly preferably 7 to 13% by weight, of indene units and / or C 1-4 - Contains alkylindene units.1-4 -a Hydrocarbon resins having alkylindene units are used as base polymers for hot melt adhesives, particularly It has been found to have very good compatibility with mPO, APAO, and EVAC. .

[0085] The indene content in hydrocarbon resins can be determined, for example, using a flame ionization detector (FID). This can be determined by pyrolysis gas chromatography. The content of residual units in the hydrocarbon resin can also be determined.

[0086] The hydrocarbon resin is preferably 40 to 85% by weight, more preferably 40 to 85% by weight, based on the total weight of the hydrocarbon resin. Preferably 45 to 70% by weight, more preferably 45 to 65% by weight of cyclic diolefination It contains units derived from a compound.

[0087] Indene and / or C 1-4 -alkylindene and, each independently of the other, 8 at least one, in particular at least two, having from 1 to 15, preferably from 8 to 13 carbon atoms; When a mixture containing an ethylenically unsaturated aromatic compound is used as the aromatic component, carbonization Hydrogen resins contain indene units and / or C 1-4 In addition to the -alkylindene units, It may also preferably have further units derived from ethylenically unsaturated aromatic compounds. The hydrocarbon resin is preferably 5 to 25% by weight, more preferably 5 to 25% by weight, based on the total weight of the hydrocarbon resin. or 10 to 25% by weight, more preferably 15 to 25% by weight of indene units and / or is C 1-4 -Alkyl indene units and mono-alkyl indene units derived from ethylenically unsaturated aromatic compounds Contains the position.

[0088] The hydrocarbon resin has a molecular weight of 800 to 2450 g / mol, preferably 800 to 1800 g / mol l, more preferably 800 to 1750 g / mol, and even more preferably 800 to 1700 g It is preferred that the polymer has an Mz of 1 / mol.

[0089] Various molecular weights are known to those skilled in the art. Therefore, one may refer to the number average molecular weight Mn, the weight average molecular weight Mn, The average molecular weight Mw and the centrifugal average molecular weight Mz are known. In this example, the centrifugal average molecular weight Mz is also called molecular weight Mz for short. The ratio Mw / Mn of number average molecular weight Mn to weight average molecular weight Mw is This is called polydispersity PDI.

[0090] Methods for determining molecular weights Mn, Mw, and Mz are known to those skilled in the art. The authors preferably identify the nucleotide sequence with the aid of gel permeation chromatography or by means of mass spectrometry. Preferably, the molecular weights Mn, Mw, and Mz are determined by gel permeation chromatography. In the measurement by gel permeation chromatography, THF is preferred as the eluent. Preferably, polystyrene is used as a calibration standard. Gel permeation Chromatographic measurements are advantageously performed using a linear column with a porosity of 1,000 Å. Preferably, refractive index and UV detectors are used. In addition to the molar mass, U It is also possible to display the hydrogenation degree of the molar mass using a V detector.

[0091] Furthermore, the hydrocarbon resin has a molecular weight of 200 to 600 g / mol, more preferably 220 to 500 g / mol. g / mol, and particularly preferably 250 to 400 g / mol of Mn. The hydrocarbon resin according to the invention advantageously has a molecular weight of 300 to 800 g / mol, preferably 400 It has a Mw of 500 to 800 g / mol, particularly preferably 500 to 800 g / mol.

[0092] As will be apparent to those skilled in the art, the molecular weights given for the oligomers are not intended to be limiting unless otherwise specified. Direct comparison with the preferred number-average or weight-average molecular weights given for hydrogen peroxide resins. This is especially true for oligomers, where the molecular weight is an absolute molecular weight. The preferred molecular weights given for the hydrocarbon resins according to the invention are those having the aforementioned molecular weights. This is due to the fact that the molecular weight is relative to a styrene standard.

[0093] Hydrocarbon resins are determined by the ring and ball method according to ASTM D3461 standard. The softening point is 80°C to 140°C, preferably 90°C to 130°C, and more preferably 100°C. Preferably, the temperature is 120°C or less.

[0094] The hydrocarbon resin according to the present invention may also have a slight color. and a Gardner color scale of 14 or less, preferably 12 or less, and more preferably 11 or less. The hydrocarbon resin according to the present invention can be used to produce, for example, hot melt adhesives. It has good hydrogenation ability in rubber products, bitumen, and printing inks, and is also effective in other components. It has good compatibility with

[0095] The Gardner color scale is preferably based on ISO 4630, especially ISO 4630:2015. It is therefore determined.

[0096] The hydrocarbon resins according to the invention are preferably not hydrogenated. Hydrocarbon resins are 1 The content of aromatic protons in the H-NMR spectrum is 1 H-NMR 1% to 30%, especially 2% to 25%, or 3% of the total amount of protons in the spectrum In particular, the hydrocarbon resin according to the present invention may have a 1 H-NMR The content of olefinic protons in the spectrum is 1 Protons in H-NMR spectra It can be 1% to 20%, especially 1% to 10% or 3% to 10% of the total amount. be. 1 H-NMR spectra are preferably measured in CDCl3. Aromatic protons in CDCl3 1 In the H-NMR spectrum, preferably 6.01 ppm to 8. Olefinic protons appear in the 00 ppm range in CDCl3. 1 H-NMR spectrum In the spectrum, it preferably appears in the range of 5.00 ppm to 6.00 ppm.

[0097] Furthermore, the hydrocarbon resins of the present invention can be effectively hydrogenated. The hydrocarbon resins described by Arai are mixtures of saturated hydrocarbons, particularly those containing no aromatics, that are liquid at room temperature. Such mixtures are soluble in D40, e.g., Exxsol It is commercially available under the name D40 or Shellsol D40.

[0098] Furthermore, the hydrocarbon resin according to the present invention is simmered for 0.5 to 5 hours, preferably 0.5 to 3 hours. Particularly preferably, the yellowness index is 5 or less, preferably 3 or less, within 0.75 to 1.5 hours. Preferably, hydrogenation can be carried out so that the yellowness index is 1 or less. According to TM D1209-05(2011) or ISO 6271:2015 standards Hydrocarbon resins that can be effectively hydrogenated are technically simpler and more cost-effective. The resulting hydrogenated hydrocarbon resin can be used in, for example, hot melt In adhesives, it has good compatibility with other components. It also has little discoloration, making it suitable for a wide range of applications. It can be used for a wide range of purposes.

[0099] During hydrogenation, a high degree of hydrogenation can be achieved. For example, the hydrocarbon derivatives according to the present invention can be The fat is hydrogenated to a residual aromatic content of less than 0.2%, preferably less than 0.15%, particularly preferably Preferably it can be less than 0.09%. A low residual aromatic content is better in terms of discoloration. This results in a more stable hydrocarbon resin.

[0100] According to one embodiment, the hydrocarbon resin according to the invention is prepared by the process according to the invention, in particular by the process described above. It can be obtained by the method described above.

[0101] The hydrocarbon resins according to the present invention can be used directly in the applications mentioned herein, especially in adhesive applications. It is possible.

[0102] The hydrocarbon resin according to the invention is particularly effective in separating solvents, unreacted monomers, and oligomers. In particular, the hydrocarbon resins according to the present invention can be functionalized and further processed. and / or hydrogenated.

[0103] For this reason, in the process according to the invention, hydrogenation can be carried out after polymerization. By hydrogenating the resin, a hydrogenated hydrocarbon resin is obtained. The oil is preferably partially hydrogenated in a subsequent hydrogenation step to obtain a hydrogenated hydrocarbon resin. Partially or completely hydrogenated.

[0104] The hydrocarbon resins may in particular be partially or fully hydrogenated. Hydrogenation is preferred. The reaction is preferably carried out in the presence of a catalyst, and various catalysts can be used. For example, nickel-based, palladium-based, cobalt-based, platinum-based, and rhodium-based catalysts are used in water. Nickel is advantageously used as the catalyst. is made up of clay minerals such as aluminum oxide, silicon dioxide, zeolite, and montmorillonite, and silicon carbide. Hydrogenation of hydrocarbon resins is preferred. According to a further preferred embodiment, the reaction is carried out in the presence of a nickel catalyst. The catalyst is used on an aluminum oxide / silicon oxide substrate. Nickel catalysts can in particular be present in heterogeneous form. As a result, hydrogenation After this is complete, it can be easily removed by filtration.

[0105] The term "partially hydrogenated" refers to hydrogenation of primarily olefinic double bonds or carbon. This is understood to mean that some of the aromatic units of the hydrocarbon resin are also hydrogenated. The fat is preferably fully hydrogenated in the hydrogenation. At least 70%, preferably at least 90%, more preferably at least Advantageously, at least 95%, particularly preferably at least 99%, of aromatic double bonds. At most 70%, preferably at least 90%, more preferably at least 95%, and particularly preferably In partial hydrogenation, the olefinic double bonds are hydrogenated to a minimum of 99%. at least 70%, more preferably at least 90%, and even more preferably at least 95%, Particularly preferably at least 99% and advantageously not more than 50% of the aromatic double bonds, preferably Not more than 30%, more preferably not more than 10% is hydrogenated.

[0106] Complete hydrogenation reduces the discoloration of hydrocarbon resins due to the small amount of by-products formed in post-reactions. The advantage is that it can be avoided whenever possible.

[0107] Whether a hydrocarbon resin is partially or fully hydrogenated can be determined by NMR spectroscopy, especially , 1 Determine the content of aromatic and / or olefinic double bonds by H-NMR spectroscopy The residual aromatic content can be determined by: 1 H-NMR The content of aromatic protons relative to the total amount of protons in the spectrum is shown.

[0108] The hydrogenation can be carried out in the presence of a solvent, especially an aliphatic solvent. A mixture of hydrocarbons, preferably 155°C to 170°C, more preferably 160°C to 165°C Suitable solvents include those having a boiling point of 0.1 to 1.0. Such mixtures include D40, e.g. Exxsol D40 or Sh It is commercially available under the name ellsol D40. By adding a solvent, It can reduce the viscosity of hydrocarbon resins. In addition, aliphatic solvents such as D40 can be used. This allows for hydrogen savings compared to the use of aromatic solvents.

[0109] Preferably, the amount is 80% by weight or more, particularly 90% by weight or more, based on the mass of the hydrocarbon resin. In some cases, 100% by weight or more of the solvent can be added to the hydrocarbon resin. Preferably, a hydrogenation mixture containing water is used. The hydrogenation mixture is advantageously a solution. The resin mixture preferably contains 50% hydrocarbon resin.

[0110] The hydrogenation may be carried out discontinuously or continuously. Preferably, the hydrogenation is Continuous or discontinuous hydrogenation can be carried out to form non-hydrogenated hydrocarbon resins. Therefore, the polymerization is carried out continuously and the hydrogenation is carried out discontinuously. Furthermore, polymerization and hydrogenation can be carried out consecutively. Finally, it is also possible to carry out the polymerization and hydrogenation discontinuously.

[0111] The hydrogenation can be advantageously carried out in a loop reactor. The hydrogenation mixture can be During the reaction, the gas is expediently circulated. The loop reactor advantageously has a gas-liquid ejector. Hydrocarbons to be hydrogenated by using a loop reactor in combination with a liquid ejector The resin is particularly well mixed with hydrogen and the optional catalyst, so that the hydrogenation time is can be shortened.

[0112] The hydrogenation is preferably carried out at a pressure above 60 bar, in particular from 65 bar to 105 bar, or 65 bar This is done at a pressure of r~100 bar or 70 bar~95 bar. The hydrogenation of the hydrocarbon resin can be set to any desired degree.

[0113] The hydrogenation is carried out at a temperature of 240°C or higher, particularly 240°C to 300°C, or 250°C to 280°C. At a hydrogenation temperature of less than 240°C, the hydrogenation proceeds slowly. It was found that above 0°C more and more by-products can be formed.

[0114] In a loop reactor commonly used on an industrial scale, the reaction time is 50 to 160 minutes, preferably 60 to 1 The hydrogenation can be carried out for 50 minutes, particularly preferably 80 to 150 minutes. The desired degree of hydrogenation and brightness of the hydrogenated hydrocarbon resin can be set.

[0115] According to a particularly preferred embodiment of the present invention, a foaming step is provided both after polymerization and after hydrogenation. The first foaming stage after polymerization removes highly volatile components, especially solvents and / or unreacted monomers. It serves to remove mers and / or oligomers from the product stream. The product stream is flashed by utilizing the pressure differential across the stages, resulting in The more volatile components are removed. The product stream containing the hydrocarbon resin is preferably The temperature is preferably 200 to 300°C, more preferably 220 to 260°C or 230 to 260°C. It can be introduced into the first expansion stage at a temperature of 250°C.

[0116] After the first foaming stage, the hydrocarbon resin contains 0.01% by weight of the solvent and 0.01% by weight of the hydrocarbon resin. and / or unreacted monomer is 3% by weight or less, preferably 1% by weight or less, more preferably 0 It is preferred that it contains no more than 0.5% by weight.

[0117] In the first expansion stage, the absolute pressure is less than 1 bar, preferably less than 0.1 bar, in particular Preferably, the pressure can be reduced to 0.03 bar or less. The reduction in pressure is effective for thin film evaporation. This means that complicated agitation systems such as a water separator or water removal device can be omitted. means that the method can be carried out in a more cost-effective and less error-prone manner However, thin film evaporators may be used in the present process after the polymerization and subsequent first foaming stage. As a result, the content of solvent in the hydrocarbon resin after polymerization can be reduced. .

[0118] A second expansion stage can be provided, preferably after hydrogenation. At least a portion of the volatile constituents, particularly the solvent, is converted into a large amount of by-products by additional thermal stress. It can be removed from hydrogenated hydrocarbon resins without producing any products and without impairing the color index of the resin. After the second foaming step, the hydrogenated hydrocarbon resins are respectively The amount of the additive is 2% by weight or less, preferably 0.5% by weight or less, or 0.03% by weight or less, based on the mass of the base resin. It is preferred that the solvent has no more than 100% by volume.

[0119] The decompression in the second expansion stage can be carried out in two expansion steps. In this case, the absolute pressure is set to 0.5 bar or less, preferably 0.2 bar or less, and preferably 0.05 bar or less. The pressure can be reduced to 0.01 bar or less, particularly preferably 0.01 bar or less. Preferably, the catalyst is first removed. The catalyst can be removed, for example, by filtration. The hydrogenated mixture is heated at a temperature of 190°C to 270°C, more preferably 200°C to 260°C, and even more preferably 300°C to 400°C. Preferably, the temperature is 210°C to 250°C, more preferably 220°C to 240°C, and even more preferably 250°C to 260°C. It is preferably introduced into the first foaming step at a temperature of 230°C. After this step, the hydrogenated mixture is heated to 190°C to 270°C, preferably 200°C to 260°C, especially The second foaming step is preferably carried out at a temperature of 210°C to 250°C or 220°C to 240°C. In the second foaming step, the absolute pressure is preferably 0.1 bar. or less, preferably 0.05 bar or less, more preferably 0.03 bar or less, and even more preferably or can be reduced to 0.01 bar or less.

[0120] Furthermore, the hydrogenation mixture from which the previously optionally added catalyst has been removed is then heated immediately before the second foaming stage. The hydrogenation mixture can be introduced into the pre-expansion stage at a temperature of 240°C to 300°C, preferably The temperature is preferably 250°C to 290°C, and more preferably 260°C to 280°C. In the pre-expansion stage, the overpressure is not more than 3 bar, preferably not more than 2 bar, more preferably not more than 1 bar. It is preferable that the pressure can be reduced to 1.5 bar or less, and more preferably to 1 bar or less.

[0121] If a pre-expansion stage is provided, the mixture removed from the pre-expansion stage is preferably It is often introduced into the second foaming stage.

[0122] By providing one or more expansion stages, the hydrocarbon resin and / or hydrogenated carbon This reduces the time that the hydrogen peroxide resin is kept at high temperature, which also helps reduce by-products. Obtainable.

[0123] According to one embodiment, hydrogenation is followed by two flash evaporation steps. These two flash evaporation steps preferably form a second expansion stage. For this purpose, the catalyst is preferably removed first. The catalyst can be removed, for example, by filtration. Subsequently, in the first flash evaporation step, a catalyst-containing The unreacted hydrogenation mixture is introduced into a first pressure vessel. The pressure in the first pressure vessel is The pressure of the hydrogenation mixture in the first pressure vessel is preferably lower than the pressure of the mixture. preferably 2 bar or less, more preferably 1.5 bar or less, and even more preferably 1 bar or less In this way, hydrogen is removed from the hydrogenation mixture. It is possible.

[0124] In the second flash evaporation step, the resulting mixture is directed to a second pressurized vessel. The pressure in the second pressurized vessel is lower than the pressure of the resulting mixture. The force is less than or equal to 0.1 bar, preferably less than or equal to 0.05 bar, particularly preferably less than or equal to 0.03 bar. It is preferable to reduce the temperature to below r. In particular, the solvent can be removed in this way. After the second flash evaporation step, the pressure is advantageously below 0.01 bar, preferably below 0.0 A thin film evaporator is provided which operates at or below 0.05 bar, more preferably at or below 0.003 bar. In this way, the solvent can be largely removed from the hydrogenated hydrocarbon resin.

[0125] The hydrogenated mixture is heated at a temperature of 190°C to 270°C, more preferably 200°C to 260°C, and even more preferably Preferably, the temperature is 210°C to 250°C, more preferably 220°C to 240°C, and even more preferably It is preferably introduced into the first flash evaporation step at a temperature of 230°C. After the flash evaporation step, the hydrogenation mixture is heated to 190°C to 270°C, preferably 20 Temperature of 0°C to 260°C, particularly preferably 210°C to 250°C or 220°C to 240°C The second flash evaporation step can be carried out by The hydrogenated mixture is then heated to 180°C to 260°C, preferably 190°C to 250°C, particularly preferably The temperature of the thin film evaporator is usually between 200°C and 240°C, or between 210°C and 230°C. can be done.

[0126] The hydrogenated hydrocarbon resin according to the present invention can be produced by hydrogenating the hydrocarbon resin according to the present invention, and and / or obtainable by the methods described herein.

[0127] The olefinic double bonds are at least 70%, preferably at least 90% or less. In a form that is at least 95% or at least 99% hydrogenated, present in a hydrogenated hydrocarbon resin It is preferred that hydrogen is present in the olefinic double bond by partial or complete hydrogenation. Alternatively or additionally, the occurrence of discoloration in hydroxylated hydrocarbon resins can be reduced. The aromatic double bonds are at least 70%, preferably at least 90% or at least 9 It can be in a form that is 5% or at least 99% hydrogenated. Partial or complete hydrogenation of the resin reduces the occurrence of discoloration in hydrogenated hydrocarbon resins. A more stable resin can be obtained.

[0128] The hydrogenated hydrocarbon resin is advantageously present in an amount of less than 0.1%, preferably less than 0.05%, particularly preferably less than 0.05%. Preferably, the residual content of olefinic double bonds is less than 0.01%, and less than 0.2%, preferably Preferably it has a residual aromatic content of less than 0.15%, particularly preferably less than 0.09%. The double bond content is 1 It can be determined by H-NMR spectroscopy.

[0129] The hydrogenated hydrocarbon resin has a molecular weight of 800 to 2500 g / mol, preferably 800 to 1800 g / mol. / mol, more preferably 800 to 1600 g / mol, and particularly preferably 800 to 140 Preferably, the hydrogenated hydrocarbon resin has an Mz of 0 g / mol. , 200 to 600 g / mol, preferably 220 to 500 g / mol, particularly preferably 2 The hydrogenated hydrocarbon resin has an Mn of 20 to 400 g / mol. Mw of ol, more preferably 250 to 700 g / mol, particularly preferably 300 to 600 It is preferred that the polymer has a Mw of 0.1 g / mol.

[0130] The hydrogenated hydrocarbon resin has a molecular weight of 1 to less than 2.3, preferably 1.5 to 2.2, and particularly preferably It preferably has a polydispersity index of 1.5 to 2.1.

[0131] Hydrogenated hydrocarbon resins by the ring and ball method according to ASTM D3461 standard The softening point of the acrylic resin is 80°C to 140°C, preferably 90°C to 130°C, or 90°C to 125°C. It is preferable that:

[0132] Furthermore, the hydrogenated hydrocarbon resin has a Hazen color number of 40 or less, particularly 25 or less. The Hazen color scale is based on the DIN EN ISO 6271:2016-05 standard. The Hazen color scale can also be called the platinum-cobalt color scale.

[0133] The hydrogenated hydrocarbon resin advantageously has a yellowness index of 3 or less, preferably 1 or less. The yellowness index is determined according to the ASTM D1209-05(2011) standard.

[0134] The aforementioned advantages of hydrocarbon resins, especially good compatibility, low color, versatility, and good stability The properties also apply appropriately to hydrogenated hydrocarbon resins.

[0135] The subject of the present invention is also a hydrocarbon resin according to the invention or a hydrogenated hydrocarbon resin according to the invention, adhesive base polymers, such as metallocene polyolefins or ethylene acetate vinyl copolymer, or amorphous polyalphaolefin, or styrene block copolymer and a polymer.

[0136] A further subject of the present invention is hot melt adhesives, in particular metallocene polyolefins, ethylene ethylene-vinyl acetate copolymer, amorphous polyalphaolefin, or styrene block copolymer in hot melt adhesives based on copolymers and / or solvent-containing adhesives, in particular Tackifier or tackifier in solvent-containing styrene block copolymer adhesives Use of the hydrocarbon resin according to the invention or the hydrogenated hydrocarbon resin according to the invention as a fire It is useful.

[0137] The subject of the present invention is also the improvement of the mechanical and dynamic properties of rubber products, in particular of rubber products. In bitumen, especially asphalt, as a modifier for improving As an additive and / or hydrophobizing agent for polyesters or as a modification in printing inks The use of hydrocarbon resins as hydrophobizing agents and / or hydrophobizing agents.

[0138] Furthermore, the subject of the invention is the use of hydroxybenzoates as additives in paints; in plastic materials; As a modifier, especially in plastic materials; in rubber; in bitumen; As a hydrophobizing agent, especially in bitumen, e.g. for roofing felt; In polypropylene films, especially in polypropylene films, especially in BOPP films as a modifier and / or hydrophobizing agent; in cosmetics; or in adhesive compositions as a tackifier, especially for applications in the hygiene products industry and for use in food packaging The main purpose is the use of hydrogenated hydrocarbon resins. [Example]

[0139] Exemplary, non-limiting examples of the preparation of hydrocarbon resins and subsequent hydrogenation of hydrocarbons according to the present invention are given below. Hydrogenation to produce resins is discussed in more detail below. The pressures specified are absolute. It is counter pressure.

[0140] In the continuous polymerization process shown in Figure 1, dicyclopentadiene, methylcyclopentadiene, Diene dimer, and cyclopentadiene-methylcyclopentadiene dimer (hereinafter Petroleum fractions (B from Dow Chemical Company) rich in cyclic diolefin compounds (also known as cyclic diolefin compounds) BN-200 (available as BN-200, hereinafter referred to as BN-200) is placed in the supply tank 11. BN-200 contains approximately 50% by weight of a cyclic diolefin compound based on the total mass of BN-200. , about 2.5 wt% indene and C 1-4 -Alkyl indene and about 6% by weight of ethylene The composition contains approximately 41.5% by weight of unreactive components and approximately 41.5% by weight of unreactive unsaturated aromatic compounds. The supply tank 12 contains styrene, vinyltoluene, indene, and methylindene (hereinafter referred to as Further petroleum fractions rich in ethylenically unsaturated aromatics (hereinafter referred to as C9 fractions) The C9 fraction is an aromatic mixture. The C9 fraction contains about 27% by weight of indene and An alkyl indene derivative, 1% by weight of styrene, and 12.5% ​​by weight of styrene. The supply tank 13 contains at least 100% by weight of the hydroxyl derivative and about 59.5% by weight of the non-reactive components. The supply tank 14 contains dicyclopentadiene having a purity of 95%. It contains xylene as a solvent.

[0141] General conduct of the experiment In receiver 15, a monomer mixture is delivered from supply tanks 11, 12, 13, and 14. Once it is introduced into the receiver 15, the monomer mixture is mixed with the static mixer The receiver 15 may also be provided with an agitator for mixing. The monomer mixture is a mixture of cyclic diolefin compounds and ethylenically unsaturated fatty acids. The ratio of cyclic diolefin compounds to ethylenically unsaturated aromatic compounds is approximately 2:1. ~Containing the constituent materials BN-200, C9 fraction, and pure dicyclohexane in a ratio of approximately 4:1 Pentadiene and xylene are taken from supply tanks 11, 12, 13 and 14. This ratio is set by adding pure dicyclopentadiene from feed tank 13. The monomer mixture can be determined as follows. Contains inactive ingredients.

[0142] This mixture is first fed to Heater 1 with a 10 kg / h feed stream from Receiver 15. The monomer mixture is brought to a temperature of 195°C in heater 16 and then introduced into tube 6. The temperature of the monomer mixture is maintained at about 68° C. / The monomer mixture is heated to 195°C at a heating rate of 1 minute. The monomer mixture is then directly transferred to the tubular reactor 20. The total residence time in the -16 is approximately 2.5 minutes. Due to the short residence time of less than 20 seconds, In particular, at reaction-related temperatures of 180°C or higher, product formation reactions may occur to a significant extent within the heater 16. In the tubular reactor 20, the temperature of the monomer mixture is heated at a heating rate of about 20°C / min. The temperature is raised to 265°C, and the monomer mixture is polymerized to form cyclic diolefin compounds. The reaction product with the ethylenically unsaturated aromatic compound is formed. The pressure in the tubular reactor 20 is 13b The residence time in the tubular reactor 20 is 60 minutes. The polymer mixture is essentially a single-phase liquid.

[0143] 10 kg / h is removed from the effluent stream at the outlet of the tubular reactor 20 is added back to the monomer mixture through line 23 at the inlet of 5 kg / h of oligomers are separated from the hydrocarbon resin and inert solvent in the process. Thus, the tubular reactor 20 contains recycled reactor product. A monomer mixture of product stream and recycled oligomers was continuously fed at 25 kg / h. will be done.

[0144] After removing 10 kg / h of reactor product stream, hydrocarbon resin, solvent, residual mono A product stream of 15 kg / h of dimers and oligomers is obtained from the tubular reactor 20; The stream is introduced into a flash evaporator 21. The stream is heated to a temperature of 265°C and 13 bar. The stream enters the flash evaporator 21 at a pressure of r. The pressure is reduced to 30 mbar, which removes the solvent and unreacted monomers in the hydrocarbon resin. The content of oligomers is reduced to 0.5% by weight or less. The bottom product from the flash evaporator 21 is a bottom product stream of 7 kg / h. The solvent and unreacted monomers are then supplied to the intermediate storage tank 22. A vapor stream of 8 kg / h containing monomers and oligomers is discharged upward. To further purify the bottom product from the flash evaporator 21, a thin film evaporator is used after the flash evaporator 21. The hydrocarbon resin that has not yet been hydrogenated is passed through line 22'. can be removed from the intermediate storage tank 22 through

[0145] The vapor stream from flash evaporator 21 is directed to partial condenser 24, where oligomers are The olefin is separated as a liquid phase, and the solvent and unreacted monomer are separated as a vapor phase. The oligomer is fed to the inlet of the tubular reactor 20 through the line 24' at a rate of 5 kg / h. The solvent and unreacted monomer are fed to the monomer mixture as a stream. The partial condenser was operated at a pressure of 30 mbar and a temperature of 110°C. As a result, oligomers are selectively recycled to the monomer mixture, while non-reactive materials are Despite the use of petroleum fractions, the method adjusts the feedstock supply. It can be operated stably without any problems.

[0146] Hydrocarbon Resin Properties The various monomer mixtures and resulting hydrocarbon resins are shown in Table 1 below. [Table 1] Description of Table 1: Cyclic diolefin compounds, indene or indene derivatives, and ethylene The ratio of the mass of cyclic diolefin compounds in the CD-monomer mixture to the mass of unsaturated aromatic hydrocarbons Content in wt.%: VA - cyclic diolefin compounds, indene or indene derivatives, and the mass of the ethylenically unsaturated aromatic in the monomer mixture relative to the mass of the ethylenically unsaturated aromatic. Aromatic content: Indene - Indene content in the resin in % by weight based on the total mass of the resin Mn - number average molecular weight in g / mol; Mw - weight average molecular weight in g / mol; PD I - Polydispersity index; Mz - Centrifugation average molecular weight in g / mol; EP - ASTM D346 Softening point in °C according to 1; Gardner color scale according to Gardner - ISO 4630 * -Oligomers are not added back into the monomer mixture, pure BN-200 is used, and C9 is used **-Comparative examples in which the oligomer was not added back into the monomer mixture.

[0147] The molecular weights Mn, Mw, and Mz were determined by gel permeation chromatography. THF was used; the operating characteristics were isocratic with an oven temperature of 40°C. In addition to the cross-linked polystyrene precolumn, linear cross-linked polystyrene precolumns with porosity of 1000 Å were used. Three polystyrene columns were used. A refractive index detector and a UV detector were used as detectors. For calibration, polystyrene standards ranging from 266 g / mol to 66,000 g / mol and a mass of 16 Polystyrene kit with 2 g / mol standards (PSS Ready Cal Kit) t) was used.

[0148] The indene content was determined by pyrolysis gas chromatography with a flame ionization detector. Each hydrocarbon resin was applied to a platinum filament and placed in a pyrolysis chamber, e.g. The pyrolysis chamber was a 60m A capillary column (e.g., Macherey-Nagel, 0.25 μm film thickness) Gas chromatograph equipped with a gas chromatograph (e.g., Thermo Trac Optima 1MS) e GC Ultra, the outlet of which was coupled to a flame ionization detector. The solution was achieved by rapidly heating the platinum filament to 600°C. The pyrolyzed fraction was directly attached to a helium carrier gas stream and the pyrolyzed fraction was transferred to a gas chromatograph. They were transported to the facility and separated.

[0149] Hydrogenation of hydrocarbon resins Hydrocarbon resins 1 to 5 were each collected from the intermediate storage tank 22 in an amount of 250 g, and five different water Remove from the oven and dissolve in 250 g of Shellsol D40 while stirring. 500 g of the obtained solution was placed in an autoclave (Parr Instruments). The nickel on silica is then introduced into a 1 L autoclave (4530 series reactor). Add the catalyst with stirring (0.75 wt. % nickel catalyst based on the total mass of the resin solution). The reactor is then closed and tested for leak-tightness with nitrogen at 50°C and 40 bar pressure. After the gas-tightness is confirmed, the nitrogen is replaced with hydrogen and the reactor outlet is closed.

[0150] To initiate the reaction, the hydrogen pressure is increased to 40 bar. Using a heat exchanger operated with hot oil, the reaction temperature can be increased to 265-270°C within 45-50 minutes. After the reaction temperature is reached, the hydrogen pressure is slowly adjusted to 85 bar. To achieve this, the reaction mixture was heated at 265°C and 85 bar for another 3-5 hours under continuous hydrogen. When the hydrogen consumption rate in the reactor becomes less than 0.5 L / h, hydrogen is added. The conversion is considered complete.

[0151] After the reaction is complete, the hydrogen supply stream and the heating oil are switched off and the reactor is refilled with nitrogen. The resin is then cooled to about 70°C within about an hour. The fat solution is filtered and charged into a three-neck flask.

[0152] The resin solution obtained after hydrogenation is distilled by steam distillation. The resin solution is heated to 180°C in the oven, and steam at 360°C is passed through the resin solution using a dip tube. In addition, the flask is connected to a vacuum pump via a cold trap, so approximately A gentle distillation can be carried out at a pressure of 10 mbar.

[0153] Usually, after about 2 hours of distillation, the solvent is almost completely separated. The liquid hydrogenated resin is bottled at high temperature. Before the hydrogenation, 0.5% by weight of an antioxidant, e.g., Irganox, based on the mass of the hydrogenated resin, is added. Add 1010 and homogenize.

[0154] In this way, from hydrocarbon resins 1, 2, 3, 4, 5, and 6, hydrogenated hydrocarbon resins were obtained. Fat 1-H, 2-H, 3-H, 4-H, 5-H, and 6-H can be obtained.

[0155] The polymerization can be carried out discontinuously. The hydrogenation can be carried out continuously. It can also be operated as.

[0156] The methods described in the previous examples can also be carried out with the substantial exclusion of oxygen.

[0157] Properties of hydrogenated hydrocarbon resins Hydrogenated hydrocarbon resins 1-H to 6-H are completely hydrogenated. The double bond content is less than 0.01% and the residual aromatic content is less than 0.1%. Hydrogenated resins 1-H to 6-H each have a VOC content of less than 300 ppm. The hydrogenated hydrocarbon resins 1-H to 6-H have the following properties shown in Tables 2 and 3.

[0158] The compatibility of the resins was determined by determining the cloud point according to the method described below. For each of H to 6-H, a mixture of 3 g of base polymer and 3 g of the relevant resin was prepared. Next, this mixture was placed in a test tube with an inner diameter of 16 mm and immersed in an oil bath to form a clear solution. The test tube was heated until the maximum temperature reached 260°C. After heating, the test tube was removed from the oil bath. The mixture was then cooled in the test tube, and the outside was wiped clean. The mixture was carefully stirred using a thermometer with a 3 mm diameter red liquid ball at the tip. The liquid ball was stirred while in contact with the bottom of the test tube. In the cylindrical region of the test tube, the red liquid ball is pressed against the wall of the test tube, and the red liquid ball is mixed along the diameter of the test tube. The red liquid ball was then placed on the test object to check whether it could be seen through the object and read the temperature of the mixture. The cloud point is the temperature at which the mixture cannot be seen through the diameter of the test tube.

[0159] To determine the cloud point more accurately, the temperature range in which the cloud point occurs was determined in a first run. The cloud point was then calculated as the average of three measurements.

[0160] The cloud point of a highly compatible resin is up to 65°C. The cloud point of resins with poor compatibility is 101°C to 150°C. The cloud point of resins with low compatibility is 150°C to 200°C. The cloud point of resins with no compatibility is 200°C. Resins with cloud points below 30°C are highly compatible.

[0161] Typically used for hot melt adhesives as the base polymer of the mixture to determine the cloud point. The base polymer used was the same as that typically used in hot melt adhesives. metallocene polyolefins, which are typically used in hot melt adhesives, or ethylene Polyethylene-vinyl acetate copolymer, or amorphous polyethylene, typically used in hot melt adhesives. Tri-alpha olefin was used.

[0162] Typically used metallocene polyolefins are available from, for example, Dow Chemical Company's Affinity GA 1900 and Affinity G A 1950. Typically used ethylene-vinyl acetate copolymers are, for example: Arkema Evatane 18-500, Evatane 28-420, and and Evatane 33-400. For polymers, the first two digits represent the average vinyl acetate content in weight percent, and the last Three digits are based on ISO1133 or ASTM D1238 at 190°C and 2.16 kg The melt flow index of the amorphous polyalphaolefins typically used is For example, Vestoplast 608 manufactured by Evonik Industries, These resins are Vestoplast 703 and Vestoplast 750. are used with their latest properties. If one of the resins is no longer available, It is instead a different resin typically used in hot melt adhesives (the corresponding mPO, EVAC, APAO).

[0163] [Table 2] Description of Table 2: Yellow color - measured according to ASTM D1209-05(2011) standard Yellowness index; Mn - number average molecular weight in g / mol; Mw - weight average molecular weight in g / mol Molecular weight; Mz - centrifugal average molecular weight in g / mol; PDI - Polydispersity Index; EP - ASTM Softening point in °C according to D3461; * and ** - for comparative hydrogenated resins, Table 1 See also the explanation.

[0164] [Table 3] Notes to Table 3: The cloud points shown were determined as above; * and ** - comparative examples See also the discussion of hydrogenated resins, Table 1.

[0165] As can be seen from the above data, in the process according to the present invention, the cyclic diolefin compound and , indene or C 1-4 -By thermally polymerizing aromatic components containing alkylindenes This makes it possible to obtain a hydrocarbon resin with a PDI of 2.27 and a Gardner color number of 14.1 or less. It is possible to obtain a hydrocarbon with a PDI of 1.91 and a Gardner color number of 11.1. It was even possible to obtain a resin. This fully hydrogenated hydrocarbon resin is suitable for hot melt adhesives. Metallocene polyolefins and amorphous polyalphaolefins typically used in In particular, the fully hydrogenated hydrocarbon resin of the present invention has good compatibility with hot melt adhesives. It even exhibits good compatibility with ethylene-vinyl acetate copolymers typically used in adhesives. are.

[0166] Reference symbol list 11 BN-200 supply tank 12 C9 fraction supply tank 13 Pure dicyclopentadiene supply tank 14 Xylene supply tank 15 Receiver 16 Heater 20 Tubular reactor 21 Flash evaporator 22 Intermediate storage tank 22' Removal 23 Product recirculation 24 Partial condenser 24' Oligomer Recycle 24" Discharge of solvent and unreacted monomer

Claims

1. a cyclic diolefin component containing a cyclic diolefin compound and indene and / or C １－４ 1. A hydrocarbon resin that is the product of the thermal polymerization of an aromatic component containing alkylindenes, the hydrocarbon resin having a polydispersity index (PDI) of 1 to less than 2.3 and a Gardner color number of 14.1 or less; The hydrocarbon resin contains a repeating unit derived from the cyclic diolefin compound and a repeating unit derived from indene and / or C １－４ - alkylindene units, optionally containing further units derived from said aromatic moiety; The hydrocarbon resin contains 4 to 20% by weight of indene units and / or C １－４ - containing alkylindene units, The Mw of the hydrocarbon resin is 500 to 800 g / mol; The hydrocarbon resin has a Mz of 1550 to 2450 g / mol.

2. 10. The hydrocarbon resin of claim 1, wherein the hydrocarbon resin has a polydispersity index (PDI) of 1 to 2.

1.

3. The hydrocarbon resin contains 4 to 16% by weight of indene units and / or C １－４ 3. The hydrocarbon resin according to claim 1, which comprises alkylindene units.

4. 4. The hydrocarbon resin according to claim 1, wherein the hydrocarbon resin has a softening point, determined according to the ring and ball method in accordance with ASTM D3461 standard, of 80°C to 140°C and / or a Gardner color number of 12 or less.

5. The hydrocarbon resin according to any one of claims 1 to 4, wherein the cyclic diolefin component contains 30 wt% or more of the cyclic diolefin compound, based on the total mass of the cyclic diolefin component.

6. 6. The hydrocarbon resin of claim 1, wherein the cyclic diolefin compound comprises a conjugated cyclodiakenes and / or is selected from the group consisting of cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene, and mixtures thereof.

7. 7. The hydrocarbon resin according to claim 1, wherein the hydrocarbon resin comprises 40 to 85% by weight of units derived from the cyclic diolefin compound, based on the total weight of the hydrocarbon resin.

8. The aromatic moiety is indene and / or C １－４ A hydrocarbon resin according to any one of claims 1 to 7, which is an aromatic mixture comprising alkylindenes and at least one ethylenically unsaturated aromatic compound having from 8 to 15 carbon atoms.

9. The aromatic mixture comprises, based on the total weight of the mixture, 50% by weight or less of vinyl aromatics such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, and p-vinyltoluene, 30% by weight or less of indene, and 15% by weight or less of C １－４ - alkylindenes or a mixture containing up to 60% by weight of indene and / or C, based on the total weight of the mixture １－４ 9. The hydrocarbon resin of claim 8, which is a mixture containing alkylindenes.

10. The hydrocarbon resin contains 5 to 25% by weight of indene units and / or C １－４ 10. A hydrocarbon resin according to claim 8 or 9, which comprises alkylindene units and units derived from ethylenically unsaturated aromatic compounds.

11. A hydrogenated hydrocarbon resin which is the hydrogenation product of the hydrocarbon resin of any one of claims 1 to 10.

12. 12. The hydrogenated hydrocarbon resin according to claim 11, wherein the olefinic double bonds are present in the hydrogenated hydrocarbon resin in a form in which they are at least 70% hydrogenated, and / or the aromatic double bonds are present in the hydrogenated hydrocarbon resin in a form in which they are at least 70% hydrogenated.

13. 13. The hydrogenated hydrocarbon resin according to claim 11 or 12, wherein the hydrogenated hydrocarbon resin has an Mz of 800 to 1600 g / mol; and / or a softening point determined according to the ring and ball method in accordance with ASTM D3461 standard of 80°C to 140°C; and / or a Hazen color index of 40 or less; and / or a yellowness index of 3 or less.

14. A hydrocarbon resin according to any one of claims 1 to 10 or a hydrogenated hydrocarbon resin according to any one of claims 11 to 13; an adhesive polymer; A composition comprising:

15. (i) and (ii) below: (i) a hot melt adhesive, and (ii) Solvent-containing adhesives 14. Use of a hydrocarbon resin according to any one of claims 1 to 10 or a hydrogenated hydrocarbon resin according to any one of claims 11 to 13 as a tackifier or tackifier in at least one of the following:

16. Use of the hydrocarbon resin according to any one of claims 1 to 10 as a modifier in natural rubber products.

17. Use of the hydrocarbon resin according to any one of claims 1 to 10 as a modifier in bitumen.

18. Use of a hydrocarbon resin according to any one of claims 1 to 10 as a modifier and / or hydrophobizing agent in printing inks.

19. Use of the hydrogenated hydrocarbon resin according to any one of claims 11 to 13 as an additive in paints.

20. Use of the hydrogenated hydrocarbon resin according to any one of claims 11 to 13 as an additive in a plastic material.

21. Use of the hydrogenated hydrocarbon resin according to any one of claims 11 to 13 as an additive in rubber.

22. Use of the hydrogenated hydrocarbon resin according to any one of claims 11 to 13 as an additive in bitumen.

23. Use of the hydrogenated hydrocarbon resin according to any one of claims 11 to 13 as an additive in a polypropylene film.

24. Use of the hydrogenated hydrocarbon resin according to any one of claims 11 to 13 as an additive in cosmetics.

25. Use of the hydrogenated hydrocarbon resin according to any one of claims 11 to 13 as a tackifier in an adhesive composition.

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