Hydrocarbon resin and method for producing same

Abstract

The present invention relates to a method for producing a hydrocarbon resin, in which indene and / or C 1-4 A monomer mixture containing an aromatic component containing alkylindene and a cyclic diolefin component containing a cyclic diolefin compound is polymerized by heating at a polymerization temperature of 180°C or higher to obtain a product stream containing a hydrocarbon resin, and oligomers containing units derived from the cyclic diolefin compound and / or units derived from the aromatic component are separated from the product stream and returned to the monomer mixture, and the hydrocarbon resin is heated at a temperature of 150°C to 300°C for 15 minutes to 240 hours in an annealing step. The present invention also relates to the hydrocarbon resin and hydrogenated hydrocarbon resin obtained by the present invention, as well as uses of the hydrocarbon resin and hydrogenated hydrocarbon resin.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a hydrocarbon resin, to the hydrocarbon resin obtained by this method, and to uses of the hydrocarbon resin. [Background technology]

[0002] Hydrocarbon resins are widely used as tackifiers in hot melt adhesives. Hot melt adhesives have a base polymer that essentially determines the properties of the hot melt adhesive. In addition to styrene block copolymers (SBC), polyamides, polyurethanes, and polyesters, metallocene polyolefins (mPO), amorphous polyalphaolefins (APAO), or ethylene-vinyl acetate copolymers (EVAC) are often used as base polymers in hot melt adhesives.

[0003] Hot melt adhesives with good processing properties and the highest possible gloss are of great interest. A certain compatibility between the tackifier and the base polymer is essential for good processing properties of hot melt adhesives. Typically, the tackifiers used are only compatible with one base polymer class, such as mPO, APAO, or EVAC, so if good compatibility is desired, a separate tackifier is required for each base polymer class. However, it would be advantageous if the tackifier was compatible with as many base polymer classes as possible. The compatibility of the components of a hot melt adhesive can be evaluated, for example, by measuring the cloud point.

[0004] In order to produce hot melt adhesives that are as glossy and easy to process as possible, it is important that the at least partially hydrogenated hydrocarbon resins used for this purpose are as free as possible from undesirable by-products, which can lead to black discoloration of the hydrocarbon resin and incompatibility with the other components of the hot melt adhesive. The Gardner color scale, the yellowness index or the Hazen color scale are often used to assess discoloration.

[0005] Several methods for producing (hydrogenated) hydrocarbon resins are known. For example, these methods involve copolymerizing a cycloalkene having two conjugated double bonds, such as cyclopentadiene, with an ethylenically unsaturated aromatic component, such as styrene, and then at least partially hydrogenating the resulting hydrocarbon resin in a further step. The hydrocarbon resin thus obtained can be used alone or together with other additives as a tackifier for hot melt adhesives.

[0006] Such a process is described in U.S. Patent No. 5,502,140, ​​which uses starting materials containing particularly inexpensive dicyclopentadiene, but in U.S. Patent No. 5,502,140 uses vinyl aromatic compounds such as styrene or α-methylstyrene in the reaction rather than indene.

[0007] EP 2251364 describes a method for producing hydrocarbon resins of the type described above, with an aromatic content of 5-25 wt %, and in EP 2251364 high quality resins are obtained by using only pure vinyl aromatic compounds, such as styrene, as the ethylenically unsaturated aromatic component.

[0008] EP 0936229 describes a process for producing aromatic-modified aliphatic hydrocarbon resins by subjecting a polymerization feedstock containing olefins, aromatic monomers, and (di)cyclodiolefins to Friedel-Crafts polymerization. However, a drawback of the process of EP 0936229 is the use of a halogen-containing catalyst to produce the hydrocarbon resin.

[0009] In the production of hydrocarbon resins, by-products may be formed at various times for various reasons. For example, in addition to the desired hydrocarbon resin, low molecular weight waxy by-products or high molecular weight thermosetting by-products may also be formed during polymerization, which may impair the quality of the final product and may cause incompatibility in hot melt adhesives.

[0010] Additionally, harmful by-products may be formed during the purification and / or isolation of intermediate products or during the isolation of the final product. For example, both polymerization and hydrogenation are typically carried out in the presence of various inert solvents, and therefore, in some cases, significant amounts of solvent must be removed after both polymerization and hydrogenation. Removal of the solvents, which often have high boiling points, typically requires heating to high temperatures, which can lead to secondary reactions that can result in by-products.

[0011] Various solutions have been proposed to avoid by-products. For example, European Patent Application Publication No. 3124503 describes a method for producing a hydrocarbon resin in which dicyclopentadiene is reacted with a vinyl aromatic compound to form a phenylnorbornene derivative, which serves as an initiator in a subsequent polymerization reaction, to improve compatibility with an acceptable cost increase. The resulting hydrocarbon resin is then hydrogenated. The disadvantage of this method is that the pre-reaction involves an additional step in which the temperature must be maintained within a narrow window to obtain the phenylnorbornene derivative with high selectivity.

[0012] Another challenge in the production of hydrocarbon resins is to obtain resins with good compatibility and high softening points in a cost-effective manner. Summary of the Invention [Problem to be solved by the invention]

[0013] Therefore, it is an object of the present invention to provide a method for producing the most glossy hydrocarbon resin possible. A further object of the present invention is to provide a method for producing hydrocarbons that are compatible with the base polymer of hot melt adhesives, in particular metallocene polyolefins (mPO), amorphous polyalphaolefins (APOA) and / or ethylene-vinyl acetate copolymers, in particular metallocene polyolefins (mPO), amorphous polyalphaolefins (APOA), and ethylene-vinyl acetate copolymers, and therefore function as tackifiers. Finally, the present invention has the object of providing a method, particularly a cost-effective method, for producing hydrocarbon resins that have a high softening point and good compatibility with the base polymer. [Means for solving the problem]

[0014] The purpose is to 1-4 This can be achieved by a method for producing a hydrocarbon resin, which comprises polymerizing a monomer mixture containing an aromatic component containing an alkylindene and a cyclic diolefin component containing a cyclic diolefin compound by heating to a polymerization temperature of 180°C or higher to obtain a product stream containing a hydrocarbon resin, separating oligomers containing units derived from the cyclic diolefin compound and / or units derived from the aromatic component from the product stream and returning them to the monomer mixture, and heating the resulting hydrocarbon resin to a temperature of 200°C to 300°C for 15 minutes to 60 hours, particularly 15 minutes to 600 minutes, in an annealing step.

[0015] Furthermore, the present invention relates to hydrocarbon resins obtainable by the process according to the invention.

[0016] The present invention also relates to hydrogenated hydrocarbon resins obtainable by hydrogenating the hydrocarbon resins according to the present invention and / or by the production process according to the present invention.

[0017] The present invention also relates to the use of a hydrocarbon resin according to the invention or a hydrogenated hydrocarbon resin according to the invention as tackifier in hot melt adhesives, in particular as tackifier in hot melt adhesives based on metallocene polyolefins, ethylene-vinyl acetate copolymers, amorphous polyalphaolefins or styrene block copolymers, and / or as tackifier in solvent-borne adhesives, in particular as tackifier in solvent-borne styrene block copolymer adhesives.

[0018] Furthermore, the present invention relates to the use of the hydrocarbon resins according to the invention as modifiers in rubber products, in particular as modifiers for improving the mechanical and dynamic properties of rubber products, as modifiers in bitumen, in particular as additives in bitumen for asphalt, and / or as water repellents, or as modifiers and / or water repellents in printing inks.

[0019] Finally, the present invention relates to the use of the hydrogenated hydrocarbon resins according to the invention as additives in paints, as additives in plastics materials, in particular as modifiers in plastics materials, as additives in rubber, as additives in bitumen, in particular as water repellents in bitumen, for example for roofing felt, as additives in polypropylene films, in particular as modifiers and / or water repellents in polypropylene films, in particular BOPP films, as additives in cosmetics or as tackifiers in adhesive compositions, in particular for applications in the hygiene products industry and for use in food packaging. [Effects of the Invention]

[0020] Surprisingly, with recycling of oligomers from the product stream to the monomer mixture and an annealing step, indene and / or C 1-4We have found that hydrocarbon resins with good properties, particularly good hydrogenation ability and / or only slight discoloration, can be obtained by polymerizing a monomer mixture having an aromatic component containing alkylindene and a cyclic diolefin component at a temperature of at least 180°C. In addition, the softening point of the hydrocarbon resin can be adjusted in a technically and economically favorable manner. Furthermore, by hydrogenating this resin, it is possible to obtain hydrogenated resins with very low color numbers, good compatibility with mPO and APAO, or more preferably with mPO, APAO, and EVAC, and high softening points. [Brief explanation of the drawings]

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

[0022] The following first describes the method for producing a hydrocarbon resin according to the present invention and the subsequent hydrogenation method carried out.

[0023] In the process according to the invention, it is preferred that the monomer mixture is substantially a single phase liquid during heating to the polymerization temperature of 180° C. or above and during polymerization, which results in good mixing, shorter reaction times and good heat transfer within the mixture.

[0024] The cyclic diolefin component contains a cyclic diolefin compound, and the cyclic diolefin component preferably contains 30 wt% or more, preferably 35 wt% or more, more preferably 50 wt% or more, even more preferably 60 wt% or more, and even more preferably 70 wt% or more of the cyclic diolefin compound based on the total mass of the cyclic diolefin component.

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

[0026] The cyclic diolefin compound preferably comprises a cycloalkene having at least two carbon-carbon double bonds, particularly conjugable carbon-carbon double bonds, and more preferably comprises one or more cycloalkenes having at least two carbon-carbon double bonds, particularly conjugable carbon-carbon double bonds.

[0027] A cycloalkene having at least two carbon-carbon double bonds is referred to herein as a cyclodialkene. A cyclodialkene in which the two carbon-carbon double bonds are conjugated is referred to herein as a conjugated cyclodialkene.

[0028] The cyclodialkene, particularly the conjugated cyclodialkene, preferably has 5 to 11 carbon atoms, particularly 5 to 7 carbon atoms, as a monomer. Examples of the conjugated cyclodialkene include cyclopentadiene and cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, and ethyltetramethylcyclopentadiene.

[0029] Cyclodialkenes, particularly conjugated cyclodialkene, may be dimers. Cyclodialkenes, particularly conjugated cyclodialkene, may exist as monomers, dimers, or mixtures of monomers and dimers. Dimerization is preferably reversible. For example, cyclopentadiene and cyclopentadiene derivatives naturally dimerize at room temperature, and when heated, tend to form the monomer again in a reverse reaction. When a cyclic diolefin compound contains a mixture of different cyclodialkenes, particularly conjugated cyclodialkenes, monomers, dimers, and / or co-dimers may be present.

[0030] The aforementioned examples of conjugated cyclodialkene can exist as a monomer, a dimer, or a mixture of monomers and dimers, depending on the temperature. In addition to monomers and dimers, co-dimers may also be present in a mixture of different conjugated cyclodialkenes. For example, two types of monomers, cyclopentadiene-cyclopentadiene dimer, methylcyclopentadiene-methylcyclopentadiene dimer, and cyclopentadiene-methylcyclopentadiene co-dimer, may be present in a mixture of cyclopentadiene and methylcyclopentadiene.

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

[0032] According to a further embodiment, the cyclic diolefin compounds include cyclopentadiene and methylcyclopentadiene.

[0033] According to a further embodiment, the cyclic diolefin component comprises a cyclic diolefin compound selected from the group consisting of cyclopentadiene and cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene, and mixtures thereof.

[0034] According to a further embodiment, the cyclic diolefin component comprises a cyclic diolefin compound, the cyclic diolefin compound comprising a conjugated cyclodialkene selected from the group consisting of cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, and ethyltetramethylcyclopentadiene.

[0035] According to one embodiment, hydrocarbon mixtures, such as petroleum fractions, having a content of conjugated cyclodialkene as cyclic diolefin compounds of 25 wt. % or more, in particular 30-60 wt. % based on the mass of the hydrocarbon mixture, are used as the cyclic diolefin component in the process according to the invention. The hydrocarbon mixtures may also contain aromatic compounds, such as indene, C 1-4 The hydrocarbon mixture may contain alkylindenes and / or ethylenically unsaturated aromatic compounds each independently having 8 to 15, preferably 8 to 13 carbon atoms, preferably in an amount of 10 to 20 wt %, based on the mass of the hydrocarbon mixture. The hydrocarbon mixture may also contain 20 to 40 wt %, based on the mass of the hydrocarbon mixture, of non-reactive components.

[0036] The monomer mixture may comprise indene and / or C 1-4 Also includes aromatic components containing alkylindenes. 1-4 The alkylindenes are preferably mono- or poly-, in particular mono- or di-C 1-4 It means alkyl-substituted indene. 1-4 Examples of alkylindenes include methylindene, dimethylindene, and ethylindene. 1-4 A prominent example of an alkylindene is methylindene. Methylindene includes all isomers of methylindene. Examples of isomers of methylindene are 1-methylindene and 3-methylindene. Different methylindene isomers may coexist in the aromatic component.

[0037] The aromatic components are indene and / or C 1-4 The aromatic component may consist of indene and / or C alkylindene. 1-4 It may also be an aromatic mixture comprising alkylindenes and at least one, in particular at least two, ethylenically unsaturated aromatic compounds, each independently having from 8 to 15, preferably from 8 to 13, carbon atoms.

[0038] According to a preferred embodiment, at least 25 wt. % of indene and / or C, based on the total mass of the petroleum fraction or the total mass of the components from the tar treatment. 1-4 Components from petroleum distillates or tar processing, which contain alkylindenes and various ethylenically unsaturated aromatic compounds, each independently having 8 to 15, preferably 8 to 13, carbon atoms, are used as aromatic components. It is particularly preferred to use components from tar processing.

[0039] In particular, mono- or poly-C1-C4 alkyl-substituted benzene compounds having a carbon-carbon double bond outside the aromatic ring are suitable as the ethylenically unsaturated aromatic compounds having 8 to 15, preferably 8 to 13, carbon atoms. Examples of such ethylenically unsaturated aromatic compounds include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, and / or p-vinyltoluene. Ethylenically unsaturated aromatic compounds are often referred to as vinyl aromatic compounds.

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

[0041] According to a preferred embodiment, the mixture contains, relative to the total mass of the mixture, up to 50 wt. % of vinyl aromatic compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene and p-vinyltoluene, up to 30 wt. % of indene, and up to 15 wt. % of C 1-4 A mixture containing alkylindenes is used as the aromatic mixture.

[0042] According to a further embodiment, up to 60 wt. % of indene and / or C, based on the total mass of the mixture. 1-4 A mixture containing alkylindenes is used as the aromatic mixture.

[0043] Cyclic diolefin compounds, and indene and / or C 1-4 Preferably, the alkylindene or aromatic mixture is or provides a monomer of the monomer mixture.

[0044] The cyclic diolefin component and the aromatic component may be present in different ratios in the monomer mixture. However, the ratio of the cyclic diolefin component to the aromatic component may be varied depending on the amount of the cyclic diolefin compound, indene and / or C 1-4 It has been found that better results are obtained when the alkylindene and the ethylenically unsaturated aromatic compound are present in specific ratios.

[0045] Advantageously, the cyclic diolefin compound and the aromatic component are as defined above, and the monomer mixture comprises a cyclic diolefin compound, indene and / or C 1-4 The cyclic diolefin compound is contained in an amount of 50 to 95 wt%, preferably 60 to 95 wt%, or 65 to 90 wt%, or 65 to 85 wt%, or 65 to 80 wt%, based on the total mass of the alkylindene and ethylenically unsaturated aromatic compound.

[0046] According to a preferred embodiment, the cyclic diolefin compound is selected from the group consisting of cyclopentadiene and cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, and ethyltetramethylcyclopentadiene, and mixtures thereof, and the aromatic component is an aromatic mixture, indene and / or C 1-4 alkylindene and at least one, in particular at least two, independently of one another, ethylenically unsaturated aromatic compounds each having 8 to 15, preferably 8 to 13 carbon atoms, and the monomer mixture is preferably a cyclic diolefin compound, indene and / or C 1-4 The cyclic diolefin compound is contained in an amount of 50 to 95 wt%, preferably 60 to 95 wt%, or 65 to 90 wt%, or 65 to 85 wt%, or 65 to 80 wt%, based on the total mass of the alkylindene and ethylenically unsaturated aromatic compound.

[0047] According to a further preferred embodiment, the cyclic diolefin compound is selected from the group consisting of cyclopentadiene and cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene, and mixtures thereof, and the aromatic component is an aromatic mixture, which aromatic mixture contains, relative to the total mass of the mixture, up to 50 wt. % of vinyl aromatic compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, and p-vinyltoluene, up to 25 wt. % of indene, and up to 10 wt. % of C 1-4 A mixture containing alkylindene or containing 60 wt% or less of indene and / or C based on the total mass of the mixture 1-4 The monomer mixture is a mixture containing alkylindene, and the monomer mixture is a cyclic diolefin compound, indene and / or C 1-4 The cyclic diolefin compound is contained in an amount of 50 to 95 wt%, preferably 60 to 95 wt%, 65 to 90 wt%, 65 to 85 wt%, or 65 to 80 wt%, based on the total mass of the alkylindene and ethylenically unsaturated aromatic compounds.

[0048] The cyclic diolefin compound and the aromatic component are advantageously as defined above, and the monomer mixture comprises a cyclic diolefin compound, indene and / or C 1-4 5 to 40 wt%, preferably 10 to 35 wt%, 15 to 35 wt%, or 25 to 35 wt% of indene and / or C based on the total mass of alkylindenes and ethylenically unsaturated aromatic compounds. 1-4 Includes alkylindenes, as well as ethylenically unsaturated aromatic compounds.

[0049] According to one embodiment, the cyclic diolefin compound is selected from the group consisting of cyclopentadiene and cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene, and mixtures thereof, and the aromatic component is indene and / or C 1-4an aromatic mixture comprising alkylindenes and at least one, in particular at least two, independently of one another, ethylenically unsaturated aromatic compounds each having 8 to 15, preferably 8 to 13, carbon atoms, wherein the monomer mixture is a cyclic diolefin compound, indene and / or C 1-4 5 to 40 wt%, preferably 10 to 35 wt%, or 15 to 35 wt%, or 25 to 35 wt% of indene and / or C based on the total mass of alkylindenes and ethylenically unsaturated aromatic compounds. 1-4 Includes alkylindenes, as well as ethylenically unsaturated aromatic compounds.

[0050] According to a further embodiment, the cyclic diolefin compound is selected from the group consisting of cyclopentadiene and cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene dimer, and mixtures thereof, and the aromatic component is an aromatic mixture, which aromatic mixture contains, based on the total mass of the mixture, up to 50 wt. % of vinyl aromatic compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, and p-vinyltoluene, up to 30 wt. % of indene, and up to 15 wt. % of C 1-4 A mixture containing alkylindene or containing 60 wt% or less of indene and / or C based on the total mass of the mixture 1-4 The monomer mixture is a mixture containing alkylindene, and the monomer mixture is a cyclic diolefin compound, indene and / or C 1-4 5 to 40 wt%, preferably 10 to 35 wt%, 15 to 35 wt%, or 25 to 35 wt% of indene and / or C based on the total mass of alkylindenes and ethylenically unsaturated aromatic compounds. 1-4 Includes alkylindenes, as well as ethylenically unsaturated aromatic compounds.

[0051] When a mixture with a low content of cyclic diolefin compounds, such as a petroleum fraction, is used as the cyclic diolefin component, one or more conjugated cyclodiakenes, such as cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, ethylcyclopentadiene, and ethyltetramethylcyclopentadiene, may be added to achieve the above-mentioned monomer ratios. The same applies to the aromatic component and indene and / or C 1-4 It applies to alkylindenes as well as ethylenically unsaturated aromatic compounds having 8 to 15, preferably 8 to 13, carbon atoms.

[0052] The monomer mixture may contain a non-polymerizable solvent. Suitable solvents are aromatic and naphthenic solvents, or their hydrogenation products. Therefore, suitable solvents are, for example, benzene, toluene, xylene, ethylbenzene, cyclohexane, dimethylcyclohexane, ethylcyclohexane, or mixtures thereof. The solvent may contain mono- or poly-, particularly mono- or di-alkyl-substituted aromatic compounds, preferably having 7 to 10 carbon atoms, such as o-xylene, m-xylene, p-xylene, and / or ethylbenzene. These preferably have a boiling point above 100°C, particularly above 130°C. When xylene is used as the solvent, it may be present as a pure compound or as a mixture of two or more of the o-xylene, m-xylene, and p-xylene isomers.

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

[0054] Components from petroleum fractions and tar distillation may already contain non-polymerizable components, for example, non-polymerizable aromatic compounds such as xylene. Therefore, when petroleum fractions are used as the cyclic diolefin component and / or when components from petroleum fractions or tar distillation are used as the aromatic component, the addition of a solvent can be omitted. Therefore, when components from petroleum fractions and / or tar distillation are used, the monomer mixture contains non-polymerizable components that function as non-polymerizable solvents.

[0055] The monomer mixture may contain a non-polymerizable component in an amount of 0 to 40 wt %. The non-polymerizable solvent may be present in the monomer mixture in an amount of 0 to 40 wt % based on the mass of the monomer mixture. In either case, the monomer mixture preferably contains 5 to 35 wt %, particularly preferably 5 to 30 wt %, for example about 30 wt %, of the non-polymerizable solvent based on the mass of the monomer mixture.

[0056] The monomer mixture may also contain both a non-polymerizable solvent and a non-polymerizable component in an amount of 0 to 40 wt%, preferably 5 to 35 wt%, more preferably 5 to 30 wt%, for example, about 30 wt%, based on the mass of the monomer mixture.Finally, the monomer mixture may also contain a non-polymerizable component in an amount of 0 to 40 wt%, preferably 5 to 35 wt%, more preferably 5 to 30 wt%, for example, about 30 wt%, based on the mass of the monomer mixture.

[0057] According to one embodiment, the process is carried out substantially with the exclusion of oxygen. This reduces the formation of by-products, in particular avoiding the formation of acidic and ester groups in the product. This helps to obtain a hydrogenated hydrocarbon resin that is as colorless as possible. The cyclic diolefin component and / or aromatic component or aromatic mixture, in particular their storage containers, are preferably inert with a protective gas such as nitrogen. The storage containers for the hydrocarbon resin and / or hydrogenated hydrocarbon resin, in particular the hydrocarbon resin and / or hydrogenated hydrocarbon resin, are advantageously inert with a protective gas such as nitrogen.

[0058] In the method according to the present invention, the monomer mixture may be rapidly heated to the polymerization temperature. The monomer mixture is preferably 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, even more preferably 35°C / min to 140°C / min, and particularly preferably 35°C / min to 80°C / min or 35°C / min to 70°C / min. The above heating rates are particularly used when the monomer mixture is heated to a temperature at which the polymerization reaction begins, particularly to a temperature of 180°C to 235°C. Immediately after the monomer mixture reaches a temperature of 180°C or higher, the temperature may be adjusted at a heating rate other than the above heating rates. It has been found that the amount of by-products is small at the heating rate according to the present invention, and a low Mz value can be achieved at a predetermined softening point.

[0059] Although polymerization is initiated at a temperature of 180°C, the polymerization in the method according to the present invention may be carried out at a higher temperature. In the method according to the present invention, polymerization is carried out at a temperature of 180°C or higher. For example, polymerization may be carried out at a polymerization temperature of 200°C to 300°C, or 230°C to 300°C, or 240°C to 280°C, or 250°C to 270°C.

[0060] The temperature may be changed during the polymerization. For example, the temperature may be increased during the polymerization up to a final temperature. The temperature change may be performed in different ways. For example, the temperature change may be linear or abrupt. According to one embodiment, the temperature is the final temperature. It is reached at the end of the polymerization process. According to one embodiment, the temperature is kept substantially constant during the polymerization.

[0061] It has been found that if the polymerization is carried out completely at lower temperatures, particularly at temperatures below 240°C, the product may have a low softening point and be waxy.

[0062] The polymerization may be carried out at a pressure of 10 bar or more. For example, the pressure may be 10 to 25 bar, in particular 10 to 20 bar, or 13 to 18 bar. If the polymerization is carried out at a pressure below 10 bar, the final product will be of low quality. In addition, the yield will be lower. Furthermore, such pressures may make it easier to avoid the presence of a gas phase, which allows for better reaction control and better heat transfer.

[0063] The polymerization may be carried out continuously or discontinuously. It is preferred that the polymerization be carried out continuously. Operation in a continuous mode has the advantage of better heat transfer than discontinuous methods. Furthermore, continuous processing results in lower operating costs and makes the process more reliable.

[0064] The polymerization may be carried out in various reaction vessels. Preferably, the polymerization is carried out continuously in a tubular reactor. This procedure has been shown to be particularly advantageous for continuous polymerization. In a tubular reactor, the polymerization can be carried out with a residence time of 20 to 180 minutes, in particular 20 to 120 minutes, or 50 to 90 minutes.

[0065] When changing the properties of the hydrocarbon resin obtained by the present invention, a part or all of the obtained hydrocarbon resin may be recycled to the tubular reactor. For example, this method is useful when a hydrocarbon resin with a higher molecular weight is desired. The recycling is preferably carried out in the raw material mixture of the input stream. The recycling is preferably taken out downstream of the reactor outlet and upstream of the separation of oligomers from the product stream. In the process of the present invention, 0 to 90 wt %, preferably 25 to 75 wt %, of the product stream, based on the mass of the obtained product stream, may be recycled to the monomer mixture of the input stream. Such recycling can be carried out particularly easily in a tubular reactor.

[0066] In the process according to the invention, oligomers containing units derived from cyclic diolefin compounds and / or units derived from aromatic components are separated from the product stream and returned to the monomer mixture. After polymerization, the oligomers and a part, preferably all, of any non-polymerizable solvent are advantageously removed from the product stream by batchwise or, preferably, continuous vaporization. Advantageously, after vaporization, a part, preferably all, of the oligomers are separated from any polymerizable solvent by complete or, preferably, partial condensation, either batchwise or continuously. Regarding the non-polymerizable components, the above statements regarding the non-polymerizable solvent apply accordingly. Advantageously, after coagulation, the oligomers are returned to the monomer mixture for further polymerization, either batchwise or, preferably, continuously.

[0067] In particular, the oligomers may boil at an absolute pressure of 100 mbar or less, in particular 50 mbar or less, preferably 30 mbar or less, and at a temperature of 80° C. or more, preferably 80° C. to 120° C., more preferably 90° C. to 120° C., even more preferably 100° C. to 120° C. It is particularly preferred that the oligomers boil at an absolute pressure of 50 mbar or less, preferably 30 mbar or less, and at a temperature of 90° C. to 120° C., in particular 100° C. to 120° C. Under the above conditions, recycling of the oligomers can be achieved by operating a partial condenser in which the oligomers are separated from lower boiling components.

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

[0069] It has been found that separating the oligomers from the product stream and then feeding the oligomers back into the monomer mixture can result in high-quality hydrocarbon resins, particularly those with low PDIs, e.g., less than 3, especially less than 2.3. In particular, after hydrogenation, these resins exhibit good compatibility with mPO and APAO, especially mPO, APAO, and EVAC.

[0070] Furthermore, by separating the oligomers from the resulting product stream and subsequently feeding them to the monomer mixture, the process according to the invention allows the polymerization to be carried out at a constant temperature without forming poorly soluble products. This also results in hydrocarbon resins with reduced discoloration. Finally, the yield can be improved by recycling the oligomers.

[0071] The recycled oligomer may also contain non-polymerizable components and / or solvents, particularly 20 wt % of non-polymerizable components and / or solvents, based on the total mass of the recycled oligomer.

[0072] The unreacted monomer can be thermally separated from the solvent and recycled by adding the unreacted monomer back into the feed stream raw material mixture, again improving resin yield.

[0073] By selectively separating oligomers boiling in the above range or having the above molecular weight, the process according to the present invention can be carried out efficiently. In particular, by selectively separating oligomers, the process according to the present invention can be carried out with good yields in steady-state operation. In addition, there is no need to adjust the feedstock supply. Furthermore, dilute feedstocks such as petroleum fractions or components from tar processing can also be used.

[0074] The polymerization of the monomer mixture to form the hydrocarbon resin is preferably carried out by a combination of Diels-Alder reactions and radical chain reaction of these polyDiels-Alder products.

[0075] The method according to the present invention includes an annealing step in which the hydrocarbon resin is heated to a temperature of 150°C to 300°C for a period of 15 minutes to 240 hours. Annealing the hydrocarbon resin has been shown to increase the resin's softening point, among other things. It can also increase the molecular weight Mn, Mw, and / or Mz. Other properties of the resin, particularly the PDI and / or Gardner color number, change only slightly or not at all. Therefore, the annealing step effectively controls the product properties, particularly the softening point. Because the softening point is typically reached through a longer residence time in the reactor, the method according to the present invention also allows for increased reactor capacity without significantly impairing other resin properties. This allows for decoupling the reaction yield from other product properties.

[0076] The hydrocarbon resin may be heated for various periods of time, the heating time affecting the softening point of the resin. According to one embodiment, the hydrocarbon resin is heated for 15 to 600 minutes, preferably 15 to 500 minutes, more preferably 15 to 400 minutes, and even more preferably 20 to 300 minutes during the annealing step. According to a further embodiment, the hydrocarbon resin is heated for 24 to 240 hours, preferably 24 to 168 hours, more preferably 24 to 120 hours, and even more preferably 24 to 72 hours.

[0077] The temperature at which the hydrocarbon resin is annealed also affects the softening point of the resin. According to one embodiment, during the annealing step, the hydrocarbon resin is heated to a temperature of 200°C to 300°C, preferably 210°C to 280°C, more preferably 210°C to 270°C, and even more preferably 220°C to 255°C. According to a further embodiment, the hydrocarbon resin is heated to a temperature of 150°C to 210°C, preferably 170°C to 200°C, and more preferably 175°C to 195°C.

[0078] With regard to the above-mentioned times and temperatures in the annealing step, it is expedient to combine higher temperatures with shorter times. Likewise, it is expedient to combine lower temperatures with longer times. The combination of higher temperatures and shorter times is advantageous when the annealing step is carried out in an annealing vessel integrated into the method according to the invention in such a way that shorter residence times are advantageous, for example, in an annealing vessel integrated into a continuous process. For example, the combination of lower temperatures and longer times may be advantageous when the resin is annealed in a heated storage vessel separated from the rest of the process that produces the hydrocarbon resin. In this way, even very high softening points can be achieved without significantly changing other properties.

[0079] According to one embodiment, in the annealing step, the hydrocarbon resin is heated at a temperature of 200°C to 300°C, preferably 210°C to 280°C, more preferably 210°C to 270°C, even more preferably 220°C to 255°C, for 15 to 600 minutes, preferably 15 to 500 minutes, more preferably 15 to 400 minutes, even more preferably 20 to 300 minutes. In the annealing step, it is particularly preferred to heat the hydrocarbon resin at a temperature of 220°C to 255°C for 15 to 400 minutes, especially 20 to 300 minutes.

[0080] According to a further embodiment, in the annealing step, the hydrocarbon resin is heated at a temperature of 150°C to 210°C, preferably 170°C to 200°C, more preferably 175°C to 195°C for 24 hours to 240 hours, preferably 24 hours to 168 hours, more preferably 24 hours to 120 hours, even more preferably 24 hours to 72 hours. In the annealing step, it is particularly preferred to heat the hydrocarbon resin at a temperature of 175°C to 195°C for 24 hours to 120 hours, especially 24 hours to 72 hours.

[0081] The annealing step is preferably carried out after the removal of oligomers. The annealing step is preferably carried out after the removal of any non-polymerizable solvent. The annealing step is particularly preferably carried out after the removal of monomers, oligomers, any non-polymerizable solvents, and / or non-polymerizable components from the hydrocarbon resin. Therefore, during the annealing step, the hydrocarbon resin is preferably substantially free of solvents, oligomers, and / or monomers, and / or non-polymerizable components. Here, "substantially free" means that the hydrocarbon resin contains 5 wt% or less, preferably 3 wt% or less, and more preferably 1 wt% or less of solvents, monomers, oligomers, and / or non-polymerizable components, based on the total weight of the hydrocarbon resin. During the annealing step, the hydrocarbon resin is particularly preferably free of 1 wt% or less of solvents, monomers, oligomers, and non-polymerizable components, based on the total weight of the hydrocarbon resin.

[0082] The annealing step is preferably carried out in an annealing vessel. Various annealing vessels can be used as the annealing vessel. The annealing step is preferably carried out in an annealing vessel, in particular a tank, vessel or tube, in which the mixture can be annealed. However, the annealing step can also be carried out in the bottom of an apparatus for removing monomers, oligomers, non-polymerizable solvents and / or non-polymerizable components.

[0083] The annealing vessel may be completely separate from other equipment for producing the hydrocarbon resin, such as a storage vessel, or may be completely integrated into the bottom of other equipment for producing the hydrocarbon resin, such as an equipment for removing monomers, oligomers, non-polymerizable solvents, and / or non-polymerizable components.

[0084] The process described above makes it possible to obtain hydrocarbon resins. The present invention therefore also relates to hydrocarbon resins obtainable by the process according to the invention.

[0085] The hydrocarbon resin may contain indene units and / or C 1-4Preferably, the hydrocarbon resin contains repeating units derived from cyclic diolefin compounds, as well as indene units and / or C 1-4 More preferably, the hydrocarbon resin comprises alkylindene units. In particular, the hydrocarbon resin may comprise additional units derived from aromatic moieties. For example, the hydrocarbon resin may comprise units derived from styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, and / or p-vinyltoluene.

[0086] With regard to the cyclic diolefin component, the cyclic diolefin compound and the aromatic component of the hydrocarbon resin, what has been said above in relation to the process according to the invention applies as appropriate.

[0087] The hydrocarbon resin preferably has a polydispersity index (PDI) of 3 or less, particularly 1.6 to 3. The hydrocarbon resin preferably has a PDI of 3 or less, particularly 1.6 to 3, and contains an indene unit and / or C 1-4 More preferably, it contains alkylindene units.

[0088] At least a portion of the hydrocarbon resin has the general structural formula (1): [ka] wherein each R 1 and each R 2 are each independently selected from the group consisting of -H, -CH3, -C2H5, -n-C3H7, -CH(CH3)2, -n-C4H9, -CH2CH(CH3)2, -CH(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 each independently an integer of 0 to 8; Each n, each m, and each o independently represents an integer of 0 to 6, preferably 0 to 4, more preferably 0 to 2, Each a, each b, each c, and each d is independently an integer of 1 to 4, preferably 1 to 2; However, the hydrocarbon resin has a number average molecular weight Mn of 200 to 700 g / mol, preferably 200 to 600 g / mol, more preferably 220 to 500 g / mol, and even more preferably 250 to 400 g / mol, and contains an indene unit and / or C 1-4 Provided that it contains alkylindene units.

[0089] As a result, the resin is preferably a copolymer in which different units contained in the cyclic diolefin component and the aromatic component are linked together by radical chains, or a Diels-Alder reaction product of the cyclic diolefin component and / or the aromatic component constituents. The units provided by the variable p in structural formula (1) are the result of a Diels-Alder reaction of one or more cyclic diolefin compounds. The units provided by the variables q and r in structural formula (1) are the result of a Diels-Alder reaction of a cyclic diolefin compound with an ethylenically unsaturated aromatic compound, or an indene or C olefin, with additional cyclic diolefin compounds optionally incorporated by the Diels-Alder reaction. 1- The unit represented by the variable s in structural formula (1) is a cyclic diolefin compound incorporated by a radical chain reaction without going through a Diels-Alder reaction. The unit represented by the variable t in structural formula (1) is an indene unit or C alkyl indene unit incorporated by a radical chain reaction without going through a Diels-Alder reaction with a cyclic diolefin compound. 1-4 The unit represented by the variable u in structural formula (1) is an alkylindene unit that is incorporated via a radical chain from an ethylenically unsaturated aromatic compound without undergoing a Diels-Alder reaction with a cyclic diolefin compound.

[0090] In structural formula (1), specifically, the order, occurrence, and number of units marked with the variables p, q, r, s, t, and u may vary statistically among individual hydrocarbon resin copolymer molecules. The variables n, m, and o indicate whether one or more cyclic diolefin compounds are bonded to each other via a Diels-Alder reaction within each unit. Advantageously, the units represented by the variable p in structural formula (1) can be applied when p is greater than 1 and each n independently represents an integer between 0 and 6, preferably between 0 and 4, and more preferably between 0 and 2. The same applies to the units represented by the variables q and r in structural formula (1).

[0091] The sum of the variables p, q, r, s, t, and u is preferably 1 or more, more preferably 1 to 10, even more preferably 1 to 8, and particularly preferably 1 to 6.

[0092] As shown in structural formula (1), the aromatic units may be substituted with different units, specifically, the aromatic units may be polysubstituted.

[0093] Advantageously, the hydrocarbon resin has a PDI of less than or equal to 3. Polydispersity may be particularly related to the softening point. Therefore, a hydrocarbon resin may have a larger PDI at a higher softening point.

[0094] According to one embodiment, the hydrocarbon resin has a polydispersity index (PDI) of 1 to less than 2.3, preferably 1.6 to less than 2.3, more preferably 1.6 to 2.1, even more preferably 1.6 to 2.0, and even more preferably 1.6 to 1.95. Hydrocarbon resins with the above PDIs, in particular hydrogenated products, have been found to have very good compatibility with base polymers of hot melt adhesives, in particular mPO, APAO, and EVAC. The above PDIs preferably apply to hydrocarbon resins with a softening point of 120°C or less.

[0095] According to a further embodiment, the hydrocarbon resin has a polydispersity index (PDI) of 2.3 to 3, preferably 2.3 to 2.8. The above PDIs preferably apply to hydrocarbon resins with a softening point above 120°C.

[0096] The hydrocarbon resin contains 1 to 20 wt%, preferably 4 to 20 wt%, more preferably 4 to 16 wt%, even more preferably 5 to 15 wt%, particularly preferably 7 to 13 wt% of indene units and / or C, based on the total mass of the hydrocarbon resin. 1-4 It is preferred that the alkyl indene units are contained in the above amounts of indene units and / or C 1-4 Hydrocarbon resins containing alkylindene units, especially their hydrogenated products, have very good compatibility with the base polymers of hot melt adhesives, especially mPO, APAO and EVAC.

[0097] The indene content in hydrocarbon resins can be determined by pyrolysis gas chromatography, for example using a flame ionization detector (FID). This method can also be used to determine the content of other units in hydrocarbon resins.

[0098] The hydrocarbon resin preferably contains 40 to 85 wt % of units derived from cyclic diolefin compounds, more preferably 45 to 70 wt %, and even more preferably 45 to 65 wt %, based on the total mass of the hydrocarbon resin.

[0099] Indene and / or C 1-4 When a mixture comprising alkylindene and at least one, in particular at least two, ethylenically unsaturated aromatic compounds, each having independently from one another 8 to 15, preferably 8 to 13, carbon atoms, is used as the aromatic component, the hydrocarbon resin preferably contains indene units and / or C 1-4 In addition to alkylindene units, the hydrocarbon resin may contain further units derived from an ethylenically unsaturated aromatic compound. The hydrocarbon resin contains 5 to 25 wt%, preferably 10 to 25 wt%, more preferably 15 to 25 wt%, of indene units and / or C 1-4 It preferably contains alkylindene units as well as units derived from ethylenically unsaturated aromatic compounds.

[0100] The hydrocarbon resin preferably has an Mz of 800 to 3,000 g / mol, preferably 800 to 2,450 g / mol, more preferably 800 to 1,800 g / mol, even more preferably 800 to 1,750 g / mol, and even more preferably 800 to 1,700 g / mol.

[0101] Various molecular weights are known to those skilled in the art. Therefore, those skilled in the art know the number average molecular weight Mn, weight average molecular weight Mw, and centrifugal average molecular weight Mz. In this case, the centrifugal average molecular weight Mz is also abbreviated as molecular weight Mz. The ratio Mw / Mn of the number average molecular weight Mn and the weight average molecular weight Mw is called the polydispersity index PDI.

[0102] Methods for determining molecular weights Mn, Mw, and Mz are known to those skilled in the art. For example, those skilled in the art can determine molecular weights Mn, Mw, and Mz using gel permeation chromatography or mass spectrometry, preferably by gel permeation chromatography. For measurements by gel permeation chromatography, THF is preferably used as the eluent. Polystyrene is preferably used as the calibration standard. Measurements by gel permeation chromatography are advantageously carried out using a linear column with a porosity of 1000 Å. Refractive index and UV detectors are preferably used. In addition to the molar mass, the hydrogenation degree of the molar mass portion can also be shown using a UV detector.

[0103] Furthermore, the hydrocarbon resin preferably has an Mn of 200 to 700 g / mol, more preferably 200 to 600 g / mol, even more preferably 220 to 500 g / mol, and particularly preferably 250 to 400 g / mol.The hydrocarbon resin advantageously has an Mw of 300 to 1,000 g / mol, preferably 300 to 800 g / mol, more preferably 400 to 800 g / mol, and particularly preferably 500 to 800 g / mol.

[0104] As will be apparent to those skilled in the art, the molecular weights obtained from oligomers are not directly comparable to the preferred number average or weight average molecular weights obtained from hydrocarbon resins, since the molecular weights of oligomers are absolute molecular weights, whereas the preferred molecular weights obtained from hydrocarbon resins are relative molecular weights of polystyrene standards having the molecular weights stated above.

[0105] The hydrocarbon resin preferably has a softening point of 80°C to 160°C, preferably 80°C to 140°C, more preferably 90°C to 130°C, and even more preferably 100°C to 120°C, as determined by the ring and ball method in accordance with ASTM D3461.

[0106] The hydrocarbon resin may have a slight color. The hydrocarbon resin preferably has a Gardner color number of 14 or less, preferably 12 or less, and more preferably 11 or less. As a result, the hydrocarbon resin has good hydrogenation ability and good compatibility with other components, such as those in hot melt adhesives, rubber products, bitumen, and printing inks.

[0107] The Gardner color scale is preferably determined in accordance with ISO 4630, in particular ISO 4630:2015.

[0108] The hydrocarbon resin according to the invention is preferably not hydrogenated. In particular, the hydrocarbon resin according to the invention is 1 The content of aromatic protons in the H-NMR spectrum is 1 It may be 1% to 30%, particularly 2% to 25%, or 3% to 20% of the total amount of protons in the H-NMR spectrum. 1 The content of olefinic protons in the H-NMR spectrum is 1 It may be 1% to 20%, particularly 1% to 10%, or 3% to 10% of the total amount of protons in the H-NMR spectrum. 1The H-NMR spectrum is preferably measured in CDCl3. Aromatic protons preferably appear in the range of 6.01 ppm to 8.00 ppm in the NMR spectrum in CDCl3. Olefinic protons preferably appear in the range of 5.00 ppm to 6.00 ppm in the NMR spectrum in CDCl3.

[0109] Furthermore, hydrocarbon resins can be efficiently hydrogenated. In particular, hydrocarbon resins can be dissolved at room temperature in mixtures of saturated hydrocarbons that are liquid at room temperature, in particular in refined gasoline that does not contain aromatic compounds. Such mixtures are commercially available under the name D40, for example Exxsol® D40 or Shellsol® D40.

[0110] Furthermore, hydrocarbon resins can be hydrogenated to a yellowing index of 5 or less, preferably 3 or less, and particularly preferably 1 or less, within a time period of 0.5 to 5 hours, preferably 0.5 to 3 hours, and particularly preferably 0.75 to 1.5 hours. The yellowing index is determined in accordance with ASTM D1209-05 (2011) or ISO 6271:2015. Hydrocarbon resins that can be efficiently hydrogenated can be hydrogenated technically more simply and inexpensively. The resulting hydrogenated hydrocarbon resins have good compatibility with other components, such as those in hot melt adhesives. They also exhibit little discoloration, making them suitable for a wide range of applications.

[0111] During hydrogenation, a high degree of hydrogenation can be achieved. For example, the hydrocarbon resin can be hydrogenated to a residual aromatic content of 0.2% or less, preferably 0.15% or less, and particularly preferably 0.09% or less. A low residual aromatic content leads to a hydrocarbon resin that is more stable with respect to discoloration.

[0112] The hydrocarbon resins can be used directly in the applications mentioned herein, especially adhesive applications.

[0113] The hydrocarbon resin may be further processed, especially after separation of the solvent, unreacted monomers and oligomers, and in particular may be functionalized and / or hydrogenated.

[0114] For this purpose, the polymerization in the process according to the invention may be followed by hydrogenation. Hydrocarbon resins are hydrogenated to obtain hydrogenated hydrocarbon resins. Thus, in one embodiment, the hydrocarbon resin is partially or completely hydrogenated in a subsequent hydrogenation step to obtain the hydrogenated hydrocarbon resin.

[0115] In particular, hydrocarbon resins may be partially or completely hydrogenated. Preferably, hydrogenation is carried out in the presence of a catalyst. Various catalysts can be used. For example, nickel-based, palladium-based, cobalt-based, platinum-based, and rhodium-based catalysts can be used for hydrogenation. Nickel is advantageously used as the catalyst. The catalyst may be attached to a support such as aluminum oxide, silicon dioxide, zeolites, clay minerals such as montmorillonite, and silicon carbide. Preferably, hydrogenation of hydrocarbon resins is carried out in the presence of a nickel catalyst. According to a further preferred embodiment, a nickel catalyst is used on an aluminum oxide / silicon oxide support. These catalysts are commercially available. The nickel catalyst may be present in a particularly heterogeneous state. As a result, it can be easily removed by filtration after the hydrogenation is complete.

[0116] The term "partially hydrogenated" is understood to mean that most of the olefinic double bonds are hydrogenated, or that some of the aromatic units of the hydrocarbon resin are also hydrogenated. Preferably, the hydrocarbon resin is completely hydrogenated by hydrogenation. In complete hydrogenation, advantageously, 70% or more, preferably 90% or more, more preferably 95% or more, and particularly preferably 99% or more of the olefinic double bonds are hydrogenated, advantageously, 70% or more, preferably 90% or more, more preferably 95% or more, and particularly preferably 99% or more of the aromatic double bonds are hydrogenated. In partial hydrogenation, advantageously, 70% or more, more preferably 90% or more, even more preferably 95% or more, and particularly preferably 99% or more of the olefinic double bonds are hydrogenated, advantageously, 50% or less, preferably 30% or less, and more preferably 10% or less of the aromatic double bonds are hydrogenated.

[0117] Complete hydrogenation has the advantage that fewer by-products are formed by post-reactions, thereby avoiding discoloration of the hydrocarbon resin as much as possible.

[0118] Whether a hydrocarbon resin is partially or fully hydrogenated can be determined by NMR spectroscopy, in particular 1 The residual aromatic content can be determined by measuring the aromatic and / or olefinic double bond content by H-NMR spectroscopy. 1 It is preferred to indicate the content of aromatic protons relative to the total amount of protons in the H-NMR spectrum.

[0119] The hydrogenation may be carried out in the presence of a solvent, particularly an aliphatic solvent. A mixture of saturated hydrocarbons, preferably having a boiling point of 155°C to 170°C, more preferably 160°C to 165°C, and liquid at room temperature, may be used as the solvent. A suitable solvent is, for example, refined gasoline. Such mixtures are commercially available under the name D40, e.g., Exxsol® D40 or Shellsol® D40. The addition of a solvent can reduce the viscosity of the hydrocarbon resin. Furthermore, the use of an aliphatic solvent such as D40 can save hydrogen compared to the use of aromatic solvents.

[0120] Preferably, 80 wt% or more, particularly 90 wt% or more, or 100 wt% or more of a solvent may be added to the hydrocarbon resin, based on the weight of the hydrocarbon resin. Preferably, a hydrogenation mixture containing a hydrocarbon resin and a solvent is used. Advantageously, the hydrogenation mixture is a solution. Preferably, the hydrogenation mixture contains 50 wt% of the hydrocarbon resin.

[0121] The hydrogenation may be carried out discontinuously or continuously. Preferably, the hydrogenation is carried out continuously. Continuous or discontinuous hydrogenation is independent of the polymerization that forms the non-hydrogenated hydrocarbon resin. Therefore, the polymerization can be carried out continuously and the hydrogenation can be carried out discontinuously, or vice versa. Furthermore, the polymerization and hydrogenation can be carried out continuously. Ultimately, the polymerization and hydrogenation can be carried out discontinuously.

[0122] Advantageously, the hydrogenation can be carried out in a loop reactor. Conveniently, the hydrogenation mixture is circulated during the hydrogenation. Advantageously, the loop reactor has a gas-liquid atomizer. The use of a loop reactor in combination with a gas-liquid atomizer allows the hydrocarbon resin to be hydrogenated to be particularly well mixed with hydrogen and the optional catalyst, thereby shortening the hydrogenation time.

[0123] It is preferred to carry out the hydrogenation at a pressure of more than 60 bar, in particular 65 bar to 105 bar, or 65 bar to 100 bar, or 70 bar to 95 bar, in this way the hydrocarbon resin can be hydrogenated to the desired degree of hydrogenation.

[0124] It is also preferable to carry out the hydrogenation at a temperature of 240° C. or higher, particularly 240° C. to 300° C., or 250° C. to 280° C. It has been found that hydrogenation proceeds slowly at temperatures below 240° C., while temperatures above 300° C. may result in the production of increasingly large amounts of by-products.

[0125] In a loop reactor commonly used on an industrial scale, hydrogenation can be carried out for 50 to 160 minutes, preferably 60 to 150 minutes, and particularly preferably 80 to 150 minutes, thereby adjusting the desired degree of hydrogenation and brightness of the hydrogenated hydrocarbon resin.

[0126] According to a particularly preferred embodiment of the present invention, expansion stages are provided both after polymerization and after hydrogenation. The first expansion stage after polymerization serves to remove highly volatile components, in particular solvent and / or unreacted monomers and / or oligomers, from the product stream. A pressure difference is used in the first expansion stage to flash the product stream, resulting in the removal of more volatile components. The product stream containing the hydrocarbon resin can be introduced into the first expansion stage preferably at a temperature of 200°C to 300°C, particularly preferably at a temperature of 220°C to 260°C or 230°C to 250°C. After the first expansion stage, the hydrocarbon resin preferably contains no more than 3 wt. %, preferably no more than 1 wt. %, more preferably no more than 0.5 wt. % of solvent and / or unreacted monomer, in each case based on the mass of the hydrocarbon resin.

[0127] In the first expansion stage, the absolute pressure can be reduced to 1 bar or less, preferably 0.1 bar or less, and particularly preferably 0.03 bar or less. The reduced pressure allows for the omission of complex stirring systems such as thin-film evaporators or water strippers. This makes the process more cost-effective and error-free. However, a thin-film evaporator can also be used in the process after the polymerization and subsequent first expansion stage. As a result, the solvent content in the hydrocarbon resin after polymerization can be reduced. Preferably, a second expansion stage can be performed after hydrogenation. In the second expansion stage, at least a portion of the volatile components, particularly the solvent, can be removed from the hydrogenated hydrocarbon resin without generating significant amounts of by-products due to additional thermal stress and without impairing the color number of the resin. After the second expansion stage, the hydrogenated hydrocarbon resin preferably contains 2 wt. % or less of solvent, preferably 0.5 wt. % or less, or 0.03 wt. % or less, in each case based on the mass of the hydrogenated hydrocarbon resin.

[0128] The pressure reduction in the second expansion stage may be carried out in the second expansion step. In the first expansion step, the absolute temperature may be reduced to 0.5 bar or less, preferably 0.2 bar or less, preferably 0.05 bar or less, or particularly preferably 0.01 bar or less. After hydrogenation, it is preferable to first remove the catalyst. The catalyst may be removed, for example, by filtration. The hydrogenated mixture is preferably introduced into the first expansion step at a temperature of 190°C to 270°C, more preferably 200°C to 260°C, even more preferably 210°C to 250°C, even more preferably 220°C to 240°C, and even more preferably 230°C. After the first expansion step, it is preferable to introduce the hydrogenated mixture into the second expansion step at a temperature of 190°C to 270°C, preferably 200°C to 260°C, particularly preferably 210°C to 250°C, or 220°C to 240°C. In the second expansion step, the absolute pressure is preferably reduced to below 0.1 bar, preferably below 0.05 bar, more preferably below 0.03 bar, even more preferably below 0.01 bar.

[0129] Furthermore, the hydrogenation mixture, from which any optionally added catalyst has previously been removed, may be introduced into a pre-expansion stage immediately before the second expansion stage. The hydrogenation mixture may be at a temperature of 240° C. to 300° C., preferably 250° C. to 290° C., and particularly preferably 260° C. to 280° C. In the pre-expansion stage, the excess pressure is preferably reduced to 3 bar or less, preferably 2 bar or less, more preferably 1.5 bar or less, and even more preferably 1 bar or less.

[0130] If a pre-expansion stage is provided, it is preferred that the mixture removed from the pre-expansion stage is introduced into a second expansion stage.

[0131] By performing one or more expansion stages, the time that the hydrocarbon resin and / or hydrogenated hydrocarbon resin is held at elevated temperatures can be reduced, which can also help reduce by-products.

[0132] According to one embodiment, hydrogenation is followed by two flash distillation steps. These two flash distillation steps preferably form a second expansion stage. For this purpose, it is preferable to first remove the catalyst, which may be removed, for example, by filtration. Then, in a first flash distillation step, the hydrogenation mixture, preferably free of catalyst, is introduced into a first pressure vessel. The pressure in the first pressure vessel is lower than the pressure of the hydrogenation mixture. The pressure of the hydrogenation mixture in the first pressure vessel is preferably reduced to an absolute pressure of 3 bar or less, preferably 2 bar or less, more preferably 1.5 bar or less, and even more preferably 1 bar or less. In this way, in particular hydrogen can be removed from the hydrogenation mixture.

[0133] In the second flash distillation step, the resulting mixture is introduced into a second pressure vessel. The pressure in the second pressure vessel is lower than the pressure of the resulting mixture. The pressure of the resulting mixture in the second pressure vessel is preferably reduced to 0.1 bar or less, preferably 0.05 bar or less, particularly preferably 0.03 bar or less. In this way, the solvent can be removed in particular. After the second flash distillation step, it is advantageous to provide a thin-film evaporator, which is operated at 0.01 bar or less, preferably 0.005 bar or less, more preferably 0.003 bar or less. In this way, most of the solvent can be removed from the hydrogenated hydrocarbon resin.

[0134] The hydrogenated mixture is preferably introduced into the first flash distillation step at a temperature of 190°C to 270°C, more preferably 200°C to 260°C, even more preferably 210°C to 250°C, even more preferably 220°C to 240°C, and even more preferably 230°C. After the first flash distillation step, the hydrogenated mixture may be introduced into the second flash distillation step at a temperature of 190°C to 270°C, preferably 200°C to 260°C, particularly preferably 210°C to 250°C or 220°C to 240°C. After the second flash distillation step, the hydrogenated mixture may be introduced into a thin-film evaporator at a temperature of 180°C to 260°C, preferably 190°C to 250°C, particularly preferably 200°C to 240°C or 210°C to 230°C.

[0135] Hydrogenated hydrocarbon resins can be obtained by hydrogenating hydrocarbon resins and / or by the methods described herein.

[0136] The olefinic double bonds are preferably present in the hydrogenated hydrocarbon resin in a hydrogenated state of 70% or more, preferably 90% or more, or 95% or more, or 99% or more. Partial or complete hydrogenation of the olefinic double bonds can reduce the occurrence of discoloration in the hydrogenated hydrocarbon resin. Alternatively or in addition, the aromatic double bonds may be hydrogenated in a state of 70% or more, preferably 90% or more, or 95% or more, or 99% or more. Partial or complete hydrogenation of the aromatic double bonds can reduce the occurrence of discoloration in the hydrogenated hydrocarbon resin. A more stable resin can be obtained.

[0137] Advantageously, the hydrogenated hydrocarbon resin has a residual content of olefinic double bonds of less than 0.1%, preferably less than 0.05%, particularly preferably less than 0.01%, and a residual aromatic content of less than 0.2%, preferably less than 0.15%, particularly preferably less than 0.09%. 1 It can be determined by H-NMR spectroscopy.

[0138] The hydrogenated hydrocarbon resin preferably has an Mz of 800 to 3,000, preferably 800 to 2,500 g / mol, more preferably 800 to 1,800 g / mol, even more preferably 800 to 1,600 g / mol, and particularly preferably 800 to 1,400 g / mol. Furthermore, the hydrogenated hydrocarbon resin advantageously has an Mn of 200 to 700 g / mol, preferably 200 to 600 g / mol, more preferably 220 to 500 g / mol, and particularly preferably 220 to 400 g / mol. The hydrogenated hydrocarbon resin preferably has an Mw of 300 to 1,000 g / mol, more preferably 300 to 800 g / mol, even more preferably 250 to 700 g / mol, and particularly preferably 300 to 600 g / mol.

[0139] The hydrogenated hydrocarbon resin preferably has a polydispersity of 3 or less. The polydispersity may be particularly related to the softening point. Therefore, the hydrogenated hydrocarbon resin may have a higher PDI at a higher softening point.

[0140] According to one embodiment, the hydrogenated hydrocarbon resin has a polydispersity index of 1 or more and less than 2.3, preferably 1.6 or more and less than 2.3, more preferably 1.6 to 2.2, and particularly preferably 1.6 to 2.1. The above PDI preferably applies to hydrogenated hydrocarbon resins having a softening point of 120°C or less.

[0141] According to a further embodiment, the hydrogenated hydrocarbon resin has a polydispersity index (PDI) of 2.3 to 3, preferably 2.3 to 2.8. The above PDI preferably applies to hydrogenated hydrocarbon resins having a softening point above 120°C.

[0142] The softening point of the hydrogenated hydrocarbon resin according to the ring and ball method in accordance with ASTM D3461 standard is preferably 80°C to 160°C, more preferably 80°C to 140°C, even more preferably 90°C to 130°C, and even more preferably 90°C to 125°C.

[0143] Furthermore, the hydrogenated hydrocarbon resin may have a Hazen color scale of not more than 40, in particular not more than 25. The Hazen color scale is determined in accordance with the DIN EN ISO 6271:2016-05 standard. The Hazen color scale may also be referred to as the platinum-cobalt color scale.

[0144] Advantageously, the hydrogenated hydrocarbon resin has a yellowness index of less than or equal to 3, preferably less than or equal to 1. The yellowness index is determined in accordance with the ASTM D1209-05(2011) standard.

[0145] The advantages of hydrocarbon resins mentioned above, particularly good compatibility, low coloration, versatile applicability, and good stability, apply accordingly to hydrogenated hydrocarbon resins.

[0146] The present invention also relates to the use of a hydrocarbon resin according to the invention or a hydrogenated hydrocarbon resin according to the invention as tackifier in hot melt adhesives, in particular as tackifier in hot melt adhesives based on metallocene polyolefins, ethylene-vinyl acetate copolymers, amorphous polyalphaolefins, or styrene block copolymers, and / or as tackifier in solvent-borne adhesives, in particular as tackifier in solvent-borne styrene block copolymer adhesives.

[0147] Furthermore, the present invention relates to the use of the hydrocarbon resins according to the invention as modifiers in rubber products, in particular as modifiers for improving the mechanical and dynamic properties of rubber products, as modifiers in bitumen, in particular as additives in bitumen for asphalt, and / or as water repellents, or as modifiers and / or water repellents in printing inks.

[0148] The invention also relates to the use of hydrogenated hydrocarbon resins as additives in paints, as additives in plastic materials, in particular as modifiers in plastic materials, as additives in rubber, as additives in bitumen, in particular as water repellents in bitumen, for example for roofing felt, as additives in polypropylene films, in particular as modifiers and / or water repellents in polypropylene films, in particular BOPP films, as additives in cosmetics or as tackifiers in adhesive compositions, in particular for applications in the hygiene industry and for use in food packaging. [Example]

[0149] The invention will now be described in more detail with reference to the following non-limiting example of the production of a hydrocarbon resin, involving hydrogenation to produce a hydrogenated hydrocarbon resin, where the pressures stated are absolute pressures.

[0150] In the continuous polymerization process shown diagrammatically in Figure 1, a petroleum fraction (BN-200 manufactured by Dow Chemical Company can be used, hereinafter referred to as BN-200) rich in dicyclopentadiene, methylcyclopentadiene dimer, and cyclopentadiene-methylcyclopentadiene dimer (hereinafter referred to as cyclic diolefin compounds) is present in a feed tank 11. BN-200 contains about 50 wt% of cyclic diolefin compounds, about 2.5 wt% of indene and C, in each case based on the total mass of BN-200. 1-4The feed tank 13 contains dicyclopentadiene with a purity of 95% or more. The feed tank 14 contains xylene as an inert solvent.

[0151] General implementation of this experiment A monomer mixture is produced in receiver 15 from supply tanks 11, 12, 13, and 14. When introduced into receiver 15, the monomer mixture is mixed using a static mixer. Receiver 15 may have an agitator for mixing. Components BN-200, C9 fraction, pure dicyclopentadiene, and xylene are withdrawn from supply tanks 11, 12, 13, and 14 in amounts such that the monomer mixture contains the cyclic diolefin compound and the ethylenically unsaturated aromatic compound in a ratio of about 2:1 to about 4:1 relative to the mass of the cyclic diolefin compound, the ethylenically unsaturated aromatic compound, and the indene or alkylindene derivative in the monomer mixture.

[0152] Specifically, the ratio can be adjusted by adding pure dicyclopentadiene from supply tank 13. In this example, it was adjusted to a constant ratio of about 3:1 (23% ethylenically unsaturated aromatic compound and indene or alkylindene derivative, based on the weight of the cyclic diolefin compound, ethylenically unsaturated aromatic compound, and indene or alkylindene derivative in the monomer mixture) and remained constant during the test shown. However, the full range of the specified concentration ratios can be applied to improve processing. The monomer mixture also contains up to 40%, preferably up to 30%, of inert components, based on the weight of the monomer mixture.

[0153] Unless otherwise specified, the mixture was first introduced from receiver 15 to heater 16 at a feed rate of 10 kg / h (for Resin 3, the feed rate was 6.6 kg / h). In heater 16, the monomer mixture was heated to a temperature of 195°C and then polymerized in tubular reactor 20. In heater 16, the temperature of the monomer mixture was increased to 195°C at a heating rate of approximately 68°C / min. The monomer mixture remained in heater 16 only during heating and was then transferred directly to tubular reactor 20. As a result, the total residence time of the monomer mixture in heater 16 was approximately 2.5 minutes. Due to the short residence time of less than 20 seconds, almost no product-forming reaction occurred in heater 16, especially at reaction-related temperatures of 180°C or higher. In tubular reactor 20, the temperature of the monomer mixture was increased to 265°C at a heating rate of approximately 20°C / min, whereby a reaction product of a cyclic diolefin compound and an ethylenically unsaturated aromatic compound was produced by polymerization of the monomer mixture. The pressure in the tubular reactor 20 is 13 bar. Unless otherwise stated, the residence time in the tubular reactor 20 is 60 minutes (Residence time for Resin 3: 90 minutes). To demonstrate the benefits of the additional process steps, the residence time is kept the same in all examples herein except for Resin 3. However, the residence time can be varied as desired, particularly in the range of 20 to 120 minutes. During heating and polymerization, the monomer mixture is a substantially single-phase liquid.

[0154] Unless otherwise specified, 10 kg / h of resin is withdrawn from the discharge stream as the reactor product stream at the outlet of the tubular reactor 20 and added back to the monomer mixture at the inlet of the tubular reactor 20 via line 23 (Resin 3: 7 kg / h). Furthermore, depending on the example given (Resins 1a and 1b: 6.0 kg / h in each case, Resin 2: 4.4 kg / h, Resin 3: 2.2 kg / h), 2.2 to 6 kg / h of oligomers are added back to the monomer mixture, which is then separated from the hydrocarbon resin and inert solvent during processing. Thus, depending on the example given, 15.8 to 26 kg / h of the monomer mixture, including the recycled reactor product stream and the recycled oligomers, is fed to the tubular reactor 20 (Resin 1a: 26 kg / h, Resin 1b: 26 kg / h, Resin 2: 24.4 kg / h, Resin 3: 15.8 kg / h).

[0155] After removal of 10 kg / h of reactor product stream (Resin 3: 7 kg / h), a product stream of 8.8 to 16 kg / h of hydrocarbon resin, solvent, residual monomers and oligomers is obtained from tubular reactor 20 and introduced into flash evaporator 21, depending on the example specified (Resin 1a: 16 kg / h, Resin 1b: 16 kg, Resin 2: 14.4 kg / h, Resin 3: 8.8 kg / h). The stream enters flash evaporator 21 at a temperature of 265°C and a pressure of 13 bar. In flash evaporator 21, the pressure of the stream is reduced to 30 mbar. The content of solvent and unreacted monomers and oligomers in the hydrocarbon resin is reduced to less than about 0.5 wt%. The bottom product from flash evaporator 21, which constitutes the majority of the hydrocarbon resins, is annealed in non-agitated heated vessel 25 at a rate of 4.7 to 7.2 kg / h, depending on the example specified (Resin 1a: 7.0 kg / h, Resin 1b: 6.7 kg / h, Resin 2: 7.2 kg / h, Resin 3: 4.7 kg / h). After annealing, the mixture is fed to intermediate storage tank 22.

[0156] Depending on the example given (Resin 1a: 9 kg / h, Resin 1b: 9.3 kg / h, Resin 2: 7.2 kg / h, Resin 3: 4.1 kg / h), a vapor stream of 4.1 to 9.3 kg / h comprising solvent, unreacted monomers and oligomers is removed overhead from flash evaporator 21. To further purify the bottom product from flash evaporator 21, a thin-film evaporator can be used after flash evaporator 21 before feeding the product to unstirred heated vessel 25. Alternatively, a thin-film evaporator can be connected downstream of vessel 25. The hydrocarbon resin that has not yet been hydrogenated can be removed from intermediate storage tank 22 via line 22'.

[0157] The vapor stream from the flash evaporator 21 enters the partial condenser 24, which separates the oligomers as a liquid phase, while the solvent and unreacted monomers are separated as a gas phase. The oligomers are fed via line 24' to the preheated monomer mixture as an oligomer stream of 2.2 to 6 kg / h, depending on the example. The solvent and unreacted monomers are removed via line 24". The partial condenser is operated at a pressure of 30 mbar and a temperature of 110°C. As a result, the oligomers are selectively recycled to the monomer mixture, while the majority of the non-reactive materials are removed. Despite the use of petroleum fractions, the process can be carried out in a stable manner without adjusting the feedstock.

[0158] The following individual Examples 1 and 2 demonstrate a significant increase in the softening point of the hydrocarbon resin at longer residence times (Table 1, Example 1: Resins 1a and 1b) or longer residence temperatures (Table 2, Example 2: Resins 1b and 2) in the reaction mixture in the annealing vessel (vessel 25). The residence time can be adjusted as needed; in this case, it is 100 minutes unless otherwise specified. Example 3 compares the residence times of two different reactors and demonstrates the increased capacity of the tubular reactor in producing comparable hydrocarbon resins. Unless otherwise specified, the hydrocarbon resins of Examples 1-3 were obtained by the present manufacturing method described above.

[0159] Molecular weights Mn, Mw, and Mz were determined by gel permeation chromatography. THF was used as the eluent, and the oven temperature was 40°C with isocratic operating characteristics. In addition to a linear cross-linked polystyrene precolumn, three additional linear cross-linked polystyrene columns, each with a porosity of 1000 Å, were used. Refractive index and UV detectors were used. A polystyrene kit (Ready Cal Kit, PSS) with polystyrene standards from 266 g / mol to 66,000 g / mol and a standard with a mass of 162 g / mol were used for calibration.

[0160] [Table 1] Legend to Table 1: Color number is Gardner color number according to ISO 4630, VOC - volatile organic compounds by weight of the total weight of the hydrocarbon resin in wt%, SP - softening point according to ASTM D3461.

[0161] Both resins in Example 1 (Resin 1a and Resin 1b) were prepared in the tubular reactor described above using essentially the same setup. The two resin examples differ in the annealing time in the annealing vessel (Vessel 25): 35 minutes for Resin 1a and 100 minutes for Resin 1b.

[0162] Without wishing to be bound by scientific theory, increasing the residence time in the annealing vessel (vessel 25) even after separation of the monomers in flash evaporator 21 leads to a further increase in resin structure, as both SP and molecular weight distribution (Mn, Mw, Mz) continue to increase. Resin 1b can be converted by hydrogenation into a hydrogenated resin with a softening point of about 100°C and very good compatibility. In this regard, see Tables 5 and 6 for the properties of the hydrogenated and stripping resins and their compatibility.

[0163] The effect of annealing temperature on resin properties is shown in Table 2 below, Example 2.

[0164] [Table 2] Legend to Table 2: Color number is Gardner color number according to ISO 4630, VOC - volatile organic compounds by weight of the total weight of the hydrocarbon resin in wt%, SP - softening point according to ASTM D3461.

[0165] Both resins in Table 2 (Resin 2 and Resin 1b) were produced in a tubular reactor as described above using substantially identical settings and have substantially identical properties. The two resin examples differ in the temperature settings in the annealing vessel (vessel 25): 220°C for Resin 2 and 240°C for Resin 1b. These settings allow the desired properties of the hydrocarbon and hydrogenated resins to be achieved through downstream annealing alone.

[0166] The subsequent increase in softening point and molecular weight allows the production of hydrocarbon resins with properties that could otherwise only be obtained with longer residence times in the reactor (and correspondingly lower throughput), despite shorter residence times in the reactor (and correspondingly lower throughput), as shown in Table 3, i.e., Example 3.

[0167] [Table 3] Legend to Table 3: Color number is Gardner color number according to ISO 4630, VOC - volatile organic compounds by weight of the total weight of the hydrocarbon resin in wt%, and SP - softening point according to ASTM D3461.

[0168] In Example 3, as can be seen from Table 3, the positive effect of increasing the annealing temperature in combination with increasing the annealing residence time on the capacity of the tubular reactor is demonstrated. Both resins in Table 3 (Resin 3 and Resin 1b) were produced in tubular reactors with essentially identical settings, except for the feed rate, as described above. The feed rate of the tubular reactor was set to two different throughputs and therefore two different residence times (Resin 1b: 10 kg / h, corresponding to a 60-minute residence time in the tubular reactor; Resin 3: 6.6 kg / h, corresponding to a 90-minute residence time in the tubular reactor). By annealing the resins at different temperatures and residence times in the annealing vessel (vessel 25), hydrocarbon resins with comparable properties were obtained. For Resin 1b, the softening point and molecular weight distribution (Mn, Mw, Mz) were ultimately determined in the annealing vessel, whereas for Resin 3, the softening point and molecular weight distribution (Mn, Mw, Mz) were primarily determined in the tubular reactor. In the case of Resin 1b, 6.7 kg / h of resin was produced, whereas only 4.7 kg / h was obtained in the case of Resin 3. Thus, the annealing step can increase the capacity of the tubular reactor by 43% when producing the same resin.

[0169] Example 4 below shows how the softening point of a hydrocarbon resin can increase significantly with extended storage. The annealing vessel in Example 4 was a 100 mL Schlenk flask that was completely isolated from the other equipment used to prepare the hydrocarbon resin.

[0170] [Table 4] Legend to Table 4: Color number is the Gardner color number according to ISO 4630; VOC - volatile organic compounds relative to the total weight of the hydrocarbon resin in wt%; Use - annealing - properties of the hydrocarbon resin used before storage; SP - softening point according to ASTM D3461.

[0171] It is clear from Table 4 that storage at elevated temperatures, for example for 48 hours (annealing storage), significantly increases the softening point and shifts the molecular weight distribution towards higher molecular weights. In this way, resins are obtained with softening points that could otherwise only be produced using tubular reactors, with considerable capacity losses.

[0172] In this way, softening points above 140°C can be achieved. As can be seen in Table 1, the broadening of the distribution can be seen to be related to the molecular structure and may be related to the losses associated with high compatibility in some hot melt systems. However, the method according to the invention can produce hydrogenated hydrocarbon resins with good compatibility while having improved hydrocarbon resin performance.

[0173] Hydrogenation of hydrocarbon resins In four different hydrogenations, 250 g of each hydrocarbon resin 1a, 1b, 2, and 3 is dissolved in 250 g of Shellsol® D40 while stirring. 500 g of the resulting solution is introduced into an autoclave (1 L autoclave, 4530 series reactor, manufactured by Parr Instruments). Then, silica-supported nickel catalyst is added while stirring (0.75 wt.% of 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 a pressure of 40 bar. After checking the leak-tightness, the nitrogen is replaced with hydrogen and the reactor outlet is closed.

[0174] To initiate the reaction, the hydrogen pressure is increased to 40 bar. The reaction mixture is then heated to a reaction temperature of 265-270°C in 45-50 minutes using a heat exchanger powered by kerosene. After the reaction temperature is reached, the hydrogen pressure is slowly adjusted to 85 bar. For hydrogenation, the reaction mixture is maintained at 265°C and 85 bar for another 3-5 hours while continuously dosing additional hydrogen. The hydrogenation is considered complete when the hydrogen consumption in the reactor is below 0.5 L / h.

[0175] After the reaction is complete, the hydrogen feed and kerosene are turned off. The reactor is refilled with nitrogen and cooled to about 70° C. within about an hour. The resin solution containing the hydrogenated hydrocarbon is then filtered and placed in a three-neck flask.

[0176] The resin solution obtained after hydrogenation is distilled by steam distillation. For this purpose, the resin solution is heated to 180 ° C in a three-neck flask, and steam at a temperature of 360 ° C is passed through the resin solution through a dip tube. The flask is then connected to a vacuum pump via a cold trap so that the distillation can be carried out gently at a pressure of about 10 mbar.

[0177] Usually, after about 2 hours of distillation, most of the solvent is separated. Before the hot, liquid hydrogenated resin is placed in a container, 0.5 wt % of an antioxidant, such as Irganox® 1010, based on the mass of the hydrogenated resin is added and homogenized.

[0178] In this way, hydrogenated hydrocarbon resins 1a-H, 1b-H, 2-H, and 3-H are obtained from hydrocarbon resins 1a, 1b, 2, and 3.

[0179] Hydrogenated hydrocarbon resins 1a-H, 1b-H, 2-H, and 3-H are fully hydrogenated. They have a residual olefinic double bond content of less than 0.01% and a residual aromatic content of less than 0.1%. Furthermore, hydrogenated hydrocarbon resins 1a-H to 3-H have the following properties, as specified in Tables 5 and 6:

[0180] [Table 5] Legend to Table 5: Color number (YI) is the yellowness index according to ASTM D1209-05(2011) standard, VOC - volatile organic compounds relative to the total mass of the hydrocarbon resin in wt%, and SP - softening point according to ASTM D3461.

[0181] However, hydrogenated hydrocarbon resins exhibit good compatibility. Resin compatibility was determined by measuring cloud points using the method described below. For each of Resins 1b-H and 3-H, a mixture of 3 g of base polymer and 3 g of the corresponding resin was prepared. The mixture was then heated in a 16 mm internal diameter test tube in an oil bath at a maximum temperature of 260 °C until a clear solution was obtained. After heating, the test tube was removed from the oil bath and wiped clean. The mixture was then cooled in the test tube and carefully stirred using a thermometer with a 3 mm diameter red liquid bead at the end. The red liquid bead was allowed to contact the bottom of the test tube during stirring. Stirring was interrupted briefly at regular intervals, and the red liquid bead was pressed against the test tube wall with the cylindrical area of ​​the test tube. The temperature of the mixture was then read by checking the visibility of the red liquid bead through the mixture along the diameter of the test tube. The cloud point was determined as the temperature at which the red liquid bead disappeared through the mixture along the diameter of the test tube. To determine the cloud point more accurately, the temperature range in which the cloud point occurs was determined in an initial test. The cloud point was determined as the average of three measurements.

[0182] Highly compatible resins have a cloud point of up to 65°C. Compatible resins have a cloud point between 66°C and 100°C. Lowly compatible resins have a cloud point between 101°C and 150°C. Poorly compatible resins have a cloud point between 150°C and 200°C. Poorly compatible resins have a cloud point above 200°C. Resins with a cloud point below 30°C have very good compatibility.

[0183] The base polymers commonly used in hot melt adhesives were used as the base polymers of the mixtures for measuring the cloud point. Therefore, metallocene polyolefins commonly used in hot melt adhesives, or ethylene-vinyl acetate copolymers commonly used in hot melt adhesives, or amorphous polyalphaolefins commonly used in hot melt adhesives were used.

[0184] Commonly used metallocene polyolefins include, for example, Affinity® GA 1900 and Affinity® GA 1950 manufactured by Dow Chemical Company. Commonly used ethylene-vinyl acetate copolymers include, for example, Evatane® 18-500, Evatane® 28-420, and Evatane® 33-400 manufactured by Arkema. In the Evatane® ethylene-vinyl acetate copolymers, the first two digits represent the average vinyl acetate content in mass%, and the last three digits represent the average melt flow index at 190°C and 2.16 kg according to ISO 1133 or ASTM D1238. Commonly used amorphous polyalphaolefins include, for example, Vestoplast® 608, Vestoplast® 703, and Vestoplast® 750 manufactured by Evonik Industries. Resins are used according to their current properties. If one of the resins is unavailable, it is replaced with a different resin that is typically used in hot melt adhesives (corresponding to mPO, EVAC, and APAO, respectively).

[0185] [Table 6]

[0186] As can be seen from Table 6, the method according to the invention makes it possible to significantly increase the softening point while maintaining good compatibility in a technically and economically simple manner.

[0187] The polymerization described above can also be carried out discontinuously. The hydrogenation described above can also be operated continuously. The process described in the previous examples can be carried out in the substantial absence of oxygen. [Explanation of symbols]

[0188] 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 recycle 24 Condenser Recycling of 24' oligomers 24" Removal of solvent and unreacted monomer 25 Non-stirring heating vessel

Claims

1. Indene and / or C １－４ a monomer mixture containing an aromatic component containing an alkylindene and a cyclic diolefin component containing a cyclic diolefin compound is polymerized by heating to a polymerization temperature of 180°C or higher to obtain a product stream containing a hydrocarbon resin; separating oligomers comprising units derived from the cyclic diolefin compound and / or units derived from the aromatic component from the product stream and returning them to the monomer mixture; The hydrocarbon resin is heated in an annealing step at a temperature of 150°C to 300°C for 15 minutes to 240 hours; A method for producing a hydrocarbon resin, wherein said annealing step is carried out after removal of oligomers and any non-polymerizable solvent.

2. the monomer mixture is a substantially single-phase liquid during heating to the polymerization temperature and during polymerization; and / or the polymerization temperature is between 200°C and 300°C, and / or The polymerization is carried out at a pressure of 10 bar to 25 bar, and / or 2. The process of claim 1, wherein the polymerization is carried out continuously in a tubular reactor.

3. the cyclic diolefin component contains the cyclic diolefin compound in an amount of 30 wt % or more based on the total mass of the cyclic diolefin component; and / or the cyclic diolefin compound comprises a conjugated cyclodiakenes and / or is selected from the group consisting of cyclopentadiene and cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene, and mixtures thereof; and / or The aromatic component is indene and / or C １－４ 3. The method according to claim 1, wherein the aromatic mixture comprises alkylindenes and at least one ethylenically unsaturated aromatic compound, each independently having from 8 to 15 carbon atoms.

4. The cyclic diolefin compound is defined by claim 3, The aromatic component is defined by claim 3, The monomer mixture contains the cyclic diolefin compound, indene and / or C １－４ 4. The method according to claim 3, wherein the cyclic diolefin compound is present in an amount of 50 to 95 wt % based on the total mass of the alkylindene and the ethylenically unsaturated aromatic compound.

5. The cyclic diolefin compound is defined by claim 3, The aromatic component is defined by claim 3, The monomer mixture contains the cyclic diolefin compound, indene and / or C １－４ 5 to 40 wt % of indene and / or C based on the total mass of alkylindene and ethylenically unsaturated aromatic compounds １－４ 5. The method according to claim 3 or 4, characterized in that it comprises an alkylindene and an ethylenically unsaturated aromatic compound.

6. The method according to any one of claims 1 to 5, wherein the monomer mixture is a non-polymerizable solvent.

7. 7. The method according to claim 1, wherein the oligomer boils at a pressure below 100 mbar absolute and at a temperature above 80° C. and / or has a molecular weight between 100 and 600 g / mol.

8. After polymerization, the oligomers and any non-polymerizable solvent are partially or completely removed from the product stream by batch or continuous vaporization; and / or 8. The process according to claim 1, wherein the oligomers are separated after vaporization, partially or completely, by complete or partial condensation, batchwise or continuously, and / or are returned after condensation to the monomer mixture for further polymerization, batchwise or continuously.

9. 9. The method according to claim 1, wherein the hydrocarbon resin is heated in the annealing step for a period of 15 minutes to 600 minutes, or alternatively for a period of 24 hours to 240 hours.

10. 10. The method according to any one of claims 1 to 9, characterized in that the hydrocarbon resin is heated to a temperature of 200°C to 300°C, or to a temperature of 150°C to 210°C in the annealing step.

11. The method according to any one of claims 1 to 10, characterized in that the annealing step is carried out in an annealing vessel capable of annealing the mixture.

12. 12. The method according to any one of claims 1 to 11, characterized in that the hydrocarbon resin is partially or completely hydrogenated in a subsequent hydrogenation step to obtain a hydrogenated hydrocarbon resin.

Images