Hydrogenated modified resin as well as preparation method and application thereof

Abstract

The invention discloses hydrogenated modified resin as well as a preparation method and application thereof, and belongs to the technical field of bio-based materials. The preparation method comprises the following steps: carrying out polymerization reaction on cyclopentadiene and derivatives thereof and norbornene monomers in the presence of a first solvent, and then adding modified monomers for continuous reaction; separating out the cycloolefin copolymer and reacting the cycloolefin copolymer with bio-based carboxylic acid in the presence of a second solvent to obtain a second polymerization solution; and removing unreacted monomers and residual solvents and oligomers, then carrying out a hydrogen reaction with deeply hydrogenated naphthenic oil under the action of a noble metal hydrogenation catalyst, and removing impurities, gel substances, residual solvents and oligomers to obtain the hydrogenated modified resin. The method is simple in process, easy to operate and mild in condition, the bio-based synthetic resin with medium-low molecular weight and high performance can be obtained, and the hydrogenated modified resin has excellent tackifying performance and can be applied to the fields of hot melt adhesives, automobile parts, packaging materials or medical equipment and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of bio-based materials, and in particular to a hydrogenated modified resin and a preparation method and application thereof. Background Art

[0002] In the current context of increasing global environmental awareness, biomass-based materials have received extensive attention and research due to their renewable and degradable properties. Among them, biomass-based tear-resistant resin, as an important biomass-based material, is widely used in various fields, such as automobile tires, packaging materials, electronic equipment, etc.

[0003] Existing research on bio-based synthetic resin technology is mainly centered around thermosetting bio-based resins using furandicarboxylic acid as raw materials, while research on hot-melt bio-based modified resins is relatively limited. Hot-melt bio-based modified resins are thermoplastic and can melt into liquid when heated and solidify into shape after cooling, which gives them advantages in processing and molding.

[0004] However, the current preparation process of hot-melt bio-based modified resins is complex, with low reaction efficiency, high cost, and many process by-products. The resulting products still need to be improved in terms of mechanical properties, thermal stability, processing performance, biocompatibility, and biodegradability.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] The object of the present invention is to provide a hydrogenated modified resin and a preparation method and application thereof, so as to solve or improve at least one of the above technical problems.

[0007] The present invention can be implemented like this: In a first aspect, the present invention provides a method for preparing a hydrogenated modified resin, comprising the following steps: The cyclopentadiene and its derivatives are polymerized with norbornene monomers in the presence of a first solvent, and then a modified monomer is added to continue the reaction to obtain a first polymerization solution; Separating the cyclic olefin copolymer in the first polymerization liquid, and reacting the separated cyclic olefin copolymer with a bio-based carboxylic acid in the presence of a second solvent to obtain a second polymerization liquid; removing unreacted monomers and remaining solvents and oligomers in the second polymerization liquid to obtain a modified resin; The modified resin and the deeply hydrogenated naphthenic oil are subjected to hydrogenation reaction under the action of a noble metal hydrogenation catalyst to obtain a resin liquid; Impurities, gel substances, residual solvents and oligomers in the resin liquid are removed to obtain hydrogenated modified resin.

[0008] In an optional embodiment, preparing the first polymer solution includes at least one of the following features: Feature 1: The polymerization reaction is carried out at 100°C to 250°C and 0.15MPa to 2.0MPa for 0.5h to 5.0h; Feature 2: The mass ratio of cyclopentadiene and its derivatives to norbornene monomers is 1:(0.1~2.0); Feature 3: The first solvent accounts for 15% to 50% of the total material mass, and the total material is the sum of cyclopentadiene and its derivatives, norbornene monomers and modified monomers; Feature 4: After adding the modified monomer, react for 1.0h~10h at 100℃~250℃ and 0.15MPa~2.0MPa; Feature 5: The amount of modified monomer added is 0.01% to 10% of the total material mass, and the total material is the sum of cyclopentadiene and its derivatives, norbornene monomers and modified monomers; Feature 6: Cyclopentadiene and its derivatives include at least one of cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, dicyclopentadiene, methylcyclopentadiene dimer and cyclopentadiene-methylcyclopentadiene dimer; Feature 7: The norbornene monomer includes at least one of norbornene, 2,5-norbornadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 2-allyl-5-norbornene; Feature 8: The first solvent includes decahydronaphthalene; Feature 9: The modified monomer includes styrene and its derivatives or divinyl ether monomers.

[0009] In an alternative embodiment, styrene and its derivatives include at least one of styrene, α-methylstyrene, o-vinyltoluene, p-vinyltoluene, m-vinyltoluene and divinylbenzene.

[0010] In an optional embodiment, the divinyl ether monomer includes at least one of divinyl ether, diethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether and 1,4-cyclohexanedimethanol divinyl ether.

[0011] In an alternative embodiment, separating the cyclic olefin copolymer in the first polymer solution comprises at least one of the following features: Feature 10: Separating the cycloolefin copolymer in the first polymerization solution by flash evaporation at 20 kPa to 80 kPa and 180° C. to 280° C.; Feature 11: The Gardner color number of the separated cycloolefin copolymer is ≤4.0#, the melt viscosity at 40°C is ≤5000 mPa·s, and the Z-average molecular weight is ≤3000.

[0012] In an optional embodiment, the flash evaporation is performed using a flash tower, and a light component is separated from the top of the flash tower; the light component is subjected to membrane separation, and the first solvent obtained by the membrane separation is returned to the preparation process of the first polymerization solution.

[0013] In an optional embodiment, the membrane used for membrane separation is a polyvinylidene fluoride microporous membrane.

[0014] In an optional embodiment, the temperature of membrane separation is 15° C. to 35° C., and the pressure of membrane separation is 0.1 MPa to 0.3 MPa.

[0015] In an optional embodiment, preparing the second polymer solution includes at least one of the following features: Feature 12: Cyclic olefin copolymer and bio-based carboxylic acid are reacted at 200°C to 280°C and 0.1MPa to 2.0MP for 0.25h to 5.0h; Feature 13: The mass ratios of the cyclic olefin copolymer, the bio-based carboxylic acid, and the second solvent are 1:(0.2-1.5):(0.75-10) respectively; Feature 14: The bio-based carboxylic acid includes at least one of 3-hydroxypropionic acid, 2,5-furandicarboxylic acid, abietic acid, dehydroabietic acid, dehydroabietic acid, 2,2-dimethylsuccinic anhydride, allylsuccinic anhydride, butylsuccinic anhydride, 2-octenylsuccinic anhydride, ricinoleic acid, dehydrated ricinoleic acid and hexylitaconic acid; Feature 15: The second solvent includes benzene, cyclohexane and its derivatives.

[0016] In an alternative embodiment, the second solvent comprises methylcyclohexane and benzene.

[0017] In an optional embodiment, the second solvent includes methylcyclohexane and benzene in a mass ratio of 1:(0.5~1.0).

[0018] In an alternative embodiment, the cyclic olefin copolymer is firstly freed of impurities in a packed tower before reacting with the bio-based carboxylic acid.

[0019] In an alternative embodiment, the packing in the packed column comprises α-alumina and diatomaceous earth.

[0020] In an optional embodiment, the packing in the packed tower includes α-alumina and diatomaceous earth in a volume ratio of 1: (0.2~1.5).

[0021] In an optional embodiment, the removal of unreacted monomers in the second polymerization solution is carried out by eluting with organic alcohol.

[0022] In an alternative embodiment, the organic alcohol comprises at least one of methanol, ethanol and propanol.

[0023] In an optional embodiment, the mass ratio of the second polymerization liquid to the organic alcohol is 1:(0.05-0.50).

[0024] In an optional embodiment, the removal of the remaining solvent and oligomers in the second polymerization solution is carried out by distillation, wherein the distillation is carried out at 180° C. to 280° C. and 20 kPa to 50 kPa.

[0025] In an optional embodiment, the reaction of the modified resin with the deeply hydrogenated naphthenic oil includes at least one of the following characteristics: Feature 16: The mass ratio of the modified resin to the deeply hydrogenated naphthenic oil is 1:(1-5); Feature 17: The temperature of the hydrogenation reaction is 120℃~300℃, the pressure is 2.0MPa~15.0MPa, and the reaction space velocity is 0.2h -1 ~2.0h -1 ; Feature 18: The volume ratio of hydrogen to modified resin is (300-800):1; Feature 19: The density of deep hydrogenated naphthenic oil is 0.90 g / cm 3 ~0.98g / cm 3 , the kinematic viscosity at 100°C is 3 mm 2 / s~8mm 2 / s, aniline point is 70℃~80℃, condensed aromatic hydrocarbon content is less than 3%, bromine value is less than 1.0gBr / 100g; Feature 20: The precious metal hydrogenation catalyst comprises an active metal component and a carrier, wherein the active metal component comprises at least one of Pd, Pt, Ru and Rh, and the carrier comprises at least one of activated carbon, alumina, titanium dioxide and silicon dioxide; the active metal component accounts for 0.5wt%~8.0wt% of the precious metal hydrogenation catalyst.

[0026] Feature 21: The amount of the precious metal hydrogenation catalyst is 1wt% to 20wt% of the total hydrogenation material; Feature 22: The reaction of the modified resin and the deeply hydrogenated cyclohexane oil is carried out in a reflux reaction system, and the mass ratio of the circulation volume to the production volume is (5~40):1.

[0027] In an optional embodiment, a centrifugal separation device is used to remove impurities and gel substances in the resin liquid.

[0028] In an optional embodiment, the mesh size of the filter cloth in the centrifugal separation device is 80 mesh to 200 mesh.

[0029] In an optional embodiment, a distillation tower is used to remove the remaining solvent and oligomers in the resin solution, wherein the distillation pressure is 20 kPa to 50 kPa and the distillation temperature is 180° C. to 280° C.

[0030] In a second aspect, the present invention provides a hydrogenated modified resin, which is prepared by the preparation method of any one of the aforementioned embodiments; The hydrogenated modified resin has at least one of the following characteristics: Feature 23: The softening point of the hydrogenated modified resin is 80°C~140°C; Feature 24: The yellowness index of the hydrogenated modified resin is ≤10; Feature 25: The acid value of the hydrogenated modified resin is 3 mgKOH / g~200 mgKOH / g; Feature 26: The iodine value of the hydrogenated modified resin is ≤30gI2 / 100g.

[0031] In a third aspect, the present invention provides a composite material, wherein raw materials for preparing the composite material include a rubber material and the hydrogenated modified resin of the aforementioned embodiment.

[0032] In a fourth aspect, the present invention generally provides an application of the composite material of the aforementioned embodiment in hot melt adhesives, automotive parts, packaging materials or medical devices.

[0033] The beneficial effects of the present invention include: The present invention synthesizes cyclopentadiene and its derivatives with norbornene monomers through Diels-Alder to generate cyclic molecules, and adds modified monomers to participate in copolymerization reaction in time, which can effectively regulate the relative molecular weight and physical and chemical properties of the product, prevent excessive polymerization to form macromolecular gel, and obtain medium and low molecular weight cycloolefin copolymers. By further reacting the medium and low molecular weight cycloolefin copolymers with bio-based carboxylic acids, a new biomass-based modified resin with strong polarity and small relative molecular weight is obtained. By reacting the modified resin with deep hydrogenated cycloalkane oil under the action of a precious metal hydrogenation catalyst, a hydrogenated modified resin with excellent properties (such as low color, low iodine value, strong stability, good mechanical properties, good biocompatibility, etc.) can be obtained.

[0034] The preparation method of the hydrogenated modified resin has simple process, high reaction efficiency, low cost, less by-products, and is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0036] Figure 1 The process flow chart of the preparation method of the hydrogenated modified resin provided in the embodiment of the present invention.

[0037] Icons: R101-first high-pressure reactor; M101-membrane separator; T101-flash tower; T102-packing tower; R102-second high-pressure reactor; V101-alcohol washing kettle; T103-first distillation tower; V102-dosing tank; R103-loop reactor; V103-centrifugal separator; T104-second distillation tower. DETAILED DESCRIPTION

[0038] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0039] The hydrogenated modified resin provided by the present invention and its preparation method and application are described in detail below.

[0040] The present invention provides a method for preparing a hydrogenated modified resin, comprising the following steps: S1: polymerizing cyclopentadiene and its derivatives with norbornene monomers in the presence of a first solvent, and then adding a modified monomer to continue the reaction to obtain a first polymer solution.

[0041] In some optional embodiments, the polymerization reaction is carried out at 100° C. to 250° C. and 0.15 MPa to 2.0 MPa for 0.5 h to 5.0 h.

[0042] The polymerization reaction temperature may be illustratively 100°C, 120°C, 150°C, 180°C, 200°C, 220°C or 250°C, etc., or other values ​​within the range of 100°C to 250°C.

[0043] If the polymerization reaction temperature is lower than 100°C, it is not conducive to the growth of the polymer reaction chain and the reaction is slow; if the polymerization reaction temperature is higher than 250°C, the free radical polymerization activity of cyclopentadiene and its derivatives is too high, and a large amount of insoluble high molecular weight polymers, also known as explosive polymer "slag", are easily generated, affecting the reaction yield.

[0044] The pressure of the polymerization reaction can be illustratively 0.15 MPa, 0.5 MPa, 0.8 MPa, 1.0 MPa, 1.2 MPa, 1.5 MPa, 1.8 MPa or 2.0 MPa, etc., or other values ​​within the range of 0.15 MPa to 2.0 MPa.

[0045] The polymerization reaction time can be 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h or 5 h, etc., or other values ​​within the range of 0.5 h to 5.0 h.

[0046] If the polymerization reaction time is shorter than 0.5 h, it is not conducive to obtaining the desired polymer with a suitable relative molecular mass; if the polymerization reaction time is longer than 5.0 h, a large amount of high molecular weight polymer is easily generated, and the molecular structure of the cycloolefin polymer is affected.

[0047] In some optional embodiments, the mass ratio of cyclopentadiene and its derivatives to norbornene monomers can be 1:(0.1~2.0), such as 1:0.1, 1:0.2, 1:0.5, 1:0.8, 1:10, 1:1.2, 1:1.5, 1:1.8 or 1:2.0, etc., or other values ​​within the range of 1:0.1 to 1:2.0.

[0048] In some optional embodiments, cyclopentadiene and its derivatives may illustratively but not limitatively include at least one of cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, dicyclopentadiene, methylcyclopentadiene dimer and cyclopentadiene-methylcyclopentadiene dimer.

[0049] The norbornene-based monomer may illustratively but not limitatively include at least one of norbornene, 2,5-norbornadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, and 2-allyl-5-norbornene.

[0050] In some optional embodiments, the first solvent may be 15% to 50% of the total mass of the material, such as 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, etc., or other values ​​within the range of 15% to 50%. The above-mentioned "total material" is the sum of cyclopentadiene and its derivatives, norbornene monomers and modified monomers, the same below.

[0051] The first solvent may include decahydronaphthalene by way of example but not limitation. In some typical embodiments, the first solvent is decahydronaphthalene. By using decahydronaphthalene as the first solvent, cyclopentadiene and its derivatives and norbornene monomers can be effectively dissolved on the one hand, and the reaction can be controlled not to be too violent on the other hand.

[0052] In some optional embodiments, after the modified monomer is added, the reaction may be carried out at 100° C. to 250° C. and 0.15 MPa to 2.0 MPa for 1.0 h to 10 h.

[0053] The reaction temperature after adding the modified monomer may be illustratively 100°C, 120°C, 150°C, 180°C, 200°C, 220°C or 250°C, etc., or other values ​​within the range of 100°C to 250°C.

[0054] The reaction pressure after adding the modified monomer can be illustratively 0.15 MPa to 2.0 MPa, such as 0.15 MPa, 0.5 MPa, 0.8 MPa, 1.0 MPa, 1.2 MPa, 1.5 MPa, 1.8 MPa or 2.0 MPa, etc., or other values ​​within the range of 0.15 MPa to 2.0 MPa.

[0055] The reaction time after adding the modified monomer can be illustratively 1.0 h to 10 h, such as 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h or 10 h, etc., and can also be other values ​​within the range of 0.5 h to 10.0 h.

[0056] In some optional embodiments, the amount of modified monomer added can be 0.01% to 10% of the total material mass, such as 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc., or other values ​​within the range of 0.01% to 10%.

[0057] In some optional embodiments, the modifying monomer may include styrene and its derivatives or divinyl ether monomers.

[0058] Styrene and its derivatives may illustratively but not limitatively include at least one of styrene, α-methylstyrene, o-vinyltoluene, p-vinyltoluene, m-vinyltoluene and divinylbenzene.

[0059] The divinyl ether monomer may illustratively but not limitatively include at least one of divinyl ether, diethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether and 1,4-cyclohexanedimethanol divinyl ether.

[0060] As mentioned above, cyclopentadiene and its derivatives are synthesized with norbornene monomers through Diels-Alder to generate cyclic molecules, and modified monomers are added in time to participate in the copolymerization reaction, which can effectively regulate the relative molecular weight and physical and chemical properties of the products, prevent excessive polymerization to form macromolecular gels, and obtain medium and low molecular weight cycloolefin copolymers.

[0061] S2: separating the cyclic olefin copolymer in the first polymerization liquid, and reacting the separated cyclic olefin copolymer with a bio-based carboxylic acid in the presence of a second solvent to obtain a second polymerization liquid.

[0062] In some optional embodiments, the cycloolefin copolymer in the first polymerization liquid can be separated by flash evaporation, and the process can be carried out in a flash tower. Exemplarily, the pressure of the flash evaporation can be 20kPa~80kPa, such as 20kPa, 25kPa, 30kPa, 35kPa, 40kPa, 45kPa, 50kPa, 55kPa, 60kPa, 65kPa, 70kPa, 75kPa or 80kPa, etc., or other values ​​within the range of 20kPa~80kPa. The temperature of the flash evaporation can be 180℃~280℃, such as 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃ or 280℃, etc., or other values ​​within the range of 180℃~280℃.

[0063] Flash evaporation is carried out under the above conditions, light components are separated from the top of the flash tower, and cycloolefin copolymer is obtained in the bottom of the tower, thereby effectively separating the light components from the cycloolefin copolymer.

[0064] In some optional embodiments, the isolated cyclic olefin copolymer has a Gardner color number of ≤4.0#.

[0065] In some optional embodiments, the melt viscosity of the separated cyclic olefin copolymer at 40° C. is ≤5000 mPa·s.

[0066] In some optional embodiments, the Z average molecular weight (Mz) of the isolated cyclic olefin copolymer is ≤3000.

[0067] In some preferred embodiments, the light component separated from the top of the flash tower can be subjected to membrane separation, and the first solvent obtained by membrane separation can be recycled back to the preparation process of the first polymerization solution.

[0068] Illustratively, the membrane used in the above membrane separation may be a polyvinylidene fluoride microporous membrane.

[0069] In some optional embodiments, the temperature of membrane separation can be 15°C to 35°C, such as 15°C, 20°C, 25°C, 30°C or 35°C, etc., or other values ​​within the range of 15°C to 35°C.

[0070] In some optional embodiments, the pressure of membrane separation can be 0.1 MPa~0.3 MPa, such as 0.1 MPa, 0.15 MPa, 0.2 MPa, 0.25 MPa or 0.3 MPa, etc., or other values ​​within the range of 0.1 MPa~0.3 MPa.

[0071] In some optional embodiments, the cyclic olefin copolymer and the bio-based carboxylic acid may be reacted at 200° C. to 280° C. and 0.1 MPa to 2.0 MPa for 0.25 h to 5.0 h.

[0072] The reaction temperature of the cycloolefin copolymer and the bio-based carboxylic acid may be 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C or 280°C, or other values ​​within the range of 200°C to 280°C.

[0073] The reaction pressure of the cycloolefin copolymer and the bio-based carboxylic acid may be 0.1 MPa, 0.5 MPa, 1 MPa, 1.5 MPa or 2 MPa, or other values ​​within the range of 0.1 MPa to 2.0 MPa.

[0074] The reaction time of the cyclic olefin copolymer and the bio-based carboxylic acid can be 0.25 h, 0.5 h, 1.0 h, 1.5 h, 2.0 h, 2.5 h, 3.0 h, 3.5 h, 4.0 h, 4.5 h or 5.0 h, etc., or other values ​​within the range of 0.25 h to 5.0 h.

[0075] In some optional embodiments, the mass ratio of the cyclic olefin copolymer to the bio-based carboxylic acid and the second solvent can be 1:(0.2-1.5):(0.75-10), such as 1:0.2:0.75, 1:0.2:1, 1:0.2:2, 1:0.2:5, 1:0.2:8, 1:0.2:10, 1:0.5:0.75, 1:0.5:1, 1:0.5:2, 1:0.5: :5, 1:0.5:8, 1:0.5:10, 1:1:0.75, 1:1:1, 1:1:2, 1:1:5, 1:1:8, 1:1:10, 1:1.5:0.75, 1:1.5:1, 1:1.5:2, 1:1.5:5, 1:1.5:8 or 1:1.5:10, etc., and can also be other values ​​within the range of 1:(0.2~1.5):(0.75~10).

[0076] In some optional embodiments, the bio-based carboxylic acid may illustratively but not limitatively include at least one of 3-hydroxypropionic acid, 2,5-furandicarboxylic acid, abietic acid, dehydroabietic acid, dehydroabietic acid, 2,2-dimethylsuccinic anhydride, allylsuccinic anhydride, butylsuccinic anhydride, 2-octenylsuccinic anhydride, ricinoleic acid, dehydrated ricinoleic acid, and hexylitaconic acid.

[0077] In some optional embodiments, the second solvent includes benzene and cyclohexane and its derivatives. In some typical embodiments, the second solvent includes methylcyclohexane and benzene, and the mass ratio of methylcyclohexane to benzene can be 1:(0.5-1.0), such as 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1:1, etc., or other values ​​within the range of 1:(0.5-1.0).

[0078] In some preferred embodiments, impurities in the cyclic olefin copolymer may be removed in a packed tower before reacting with the bio-based carboxylic acid.

[0079] The filler in the packed tower may include α-alumina and diatomaceous earth, and the volume ratio of α-alumina to diatomaceous earth may be 1:(0.2-1.5), such as 1:0.2, 1:0.5, 1:0.8, 1:1, 1:1.2 or 1:1.5.

[0080] Based on the above, the medium and low molecular weight cycloolefin copolymers are further reacted with bio-based carboxylic acids to obtain a new type of biomass-based modified resin with strong polarity and relatively small molecular weight.

[0081] S3: removing unreacted monomers and remaining solvents and oligomers in the second polymerization solution to obtain a modified resin.

[0082] The removal of unreacted monomers in the second polymerization solution may be carried out by eluting with an organic alcohol, which may include at least one of methanol, ethanol and propanol.

[0083] In some optional embodiments, the mass ratio of the second polymerization liquid to the organic alcohol can be 1:(0.05-0.50), such as 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4 or 1:0.5, or other values ​​within the range of 1:(0.05-0.50).

[0084] Removal of the remaining solvent and oligomers in the second polymerization solution may be carried out by distillation. The distillation may be carried out at 180°C to 280°C (e.g., 180°C, 200°C, 220°C, 240°C, 260°C, or 280°C) and 20kPa to 50kPa (e.g., 20kPa, 30kPa, 40kPa, or 50kPa).

[0085] S4: The modified resin and the deeply hydrogenated cyclohexane oil are subjected to hydrogenation reaction under the action of a noble metal hydrogenation catalyst to obtain a resin liquid.

[0086] Since there are more carboxylic acid groups and unsaturated double bonds in the molecular structure of bio-based carboxylic acid modified resin, the color is relatively dark, the light and heat stability is poor, there is odor at high temperature, and the application field is severely limited, so further hydrogenation modification is required.

[0087] In some optional embodiments, the mass ratio of the modified resin to the deeply hydrogenated cyclohexane oil can be 1:(1-5), such as 1:1, 1:2, 1:3, 1:4 or 1:5, etc., or other values ​​within the range of 1:(1-5).

[0088] If the mass ratio of modified resin to deeply hydrogenated cyclohexane oil is less than 1:1 (such as 1:0.5), the viscosity of the hydrogenated material is too high, and mass and heat transfer in the reaction are difficult, which may easily lead to local "temperature runaway" in the catalyst bed, resulting in degradation of product performance and reduced catalyst life; if the mass ratio of modified resin to deeply hydrogenated cyclohexane oil is greater than 1:5 (such as 1:6), a large amount of saturated cyclohexane oil will "idle" with the system, increasing energy consumption and material consumption, which is not conducive to process economy.

[0089] In some optional embodiments, the temperature of the hydrogenation reaction is 120°C to 300°C, such as 120°C, 150°C, 180°C, 200°C, 220°C, 250°C, 280°C or 300°C, etc., and may also be other values ​​within the range of 120°C to 300°C. Further optionally, the temperature of the hydrogenation reaction may be 140°C to 245°C.

[0090] If the temperature of the hydrogenation reaction is lower than 120°C, it is not conducive to the hydrogenation of the modified resin, and the product will retain a large number of unsaturated olefin groups, with a dark color and a high iodine value. If the temperature of the hydrogenation reaction is higher than 300°C, the modified resin will undergo severe hydrogenation degradation, the softening point of the product will be greatly reduced, and the carboxylic acid groups will be oversaturated.

[0091] In some optional embodiments, the pressure of the hydrogenation reaction is 2.0 MPa to 15.0 MPa, such as 2 MPa, 4 MPa, 6 MPa, 8 MPa, 10 MPa, 12 MPa or 15 MPa, etc., or other values ​​within the range of 2.0 MPa to 15.0 MPa. Further optionally, the pressure of the hydrogenation reaction can be 6.0 MPa to 12.0 MPa.

[0092] If the pressure of the hydrogenation reaction is lower than 2.0 MPa, the hydrogenation depth of the modified resin may be insufficient, and the product may be dark in color and have a high iodine value. If the pressure of the hydrogenation reaction is higher than 15.0 MPa, the modified resin may also undergo severe hydrogenation degradation, and the risk and cost of the hydrogenation process may be greatly increased, making it difficult to industrialize.

[0093] In some optional embodiments, the reaction space velocity can be 0.2h -1 ~2.0h -1 , such as 0.2h -1 、0.4h -1 , 0.6h -1 、0.8h -1 , 1.0h -1 , 1.2h -1 , 1.4h -1 , 1.6h -1 , 1.8h -1 or 2.0h -1 etc., can also be 0.2h -1 ~2.0h -1 Alternatively, the reaction space velocity may be 0.25 h -1 ~1.0h -1 .

[0094] If the reaction space velocity is less than 0.2h -1 The saturation of the hydrogenation product does not increase much, but the color may deteriorate due to long residence time at high temperature. If the reaction space velocity is greater than 2.0h -1 The hydrogenation depth of the modified resin is insufficient, the product has a high degree of unsaturation and poor performance.

[0095] In some optional embodiments, the volume ratio of hydrogen to the modified resin may be (300-800):1, such as 300:1, 400:1, 500:1, 600:1, 700:1 or 800:1, etc., or other values ​​within the range of (300-800):1. Further optionally, the volume ratio of hydrogen to the modified resin may be (500-600):1.

[0096] If the volume ratio of hydrogen to modified resin is less than 300:1 (such as 200:1), it is not conducive to the hydrogenation reaction of the modified resin, the reaction heat transfer is difficult, it is difficult to stably control the temperature rise of the catalyst bed, and it is easy to cause local coking of the high-viscosity resin system, affecting the life of the catalyst; if the volume ratio of hydrogen to modified resin is higher than 800:1 (such as 1000:1), the energy consumption of hydrogenation catalysis will increase significantly, and the process economy will deteriorate.

[0097] In some optional embodiments, the density of the deep hydrogenated naphthenic oil is 0.90 g / cm 3 ~0.98g / cm 3 , the kinematic viscosity at 100°C is 3 mm 2 / s~8mm 2 / s, aniline point is 70℃~80℃, condensed aromatic hydrocarbon content is <3%, and bromine value is <1.0gBr / 100g.

[0098] In some optional embodiments, the noble metal hydrogenation catalyst comprises an active metal component and a carrier, wherein the active metal component comprises at least one of Pd, Pt, Ru and Rh, and the carrier comprises at least one of activated carbon, alumina, titanium dioxide and silicon dioxide.

[0099] It should be noted that in existing studies, common non-precious metal hydrogenation catalysts such as Raney Ni are very easy to be "poisoned" and fail in the hydrogenation reaction of high acid value resins, with an average "lifespan" of less than 72 hours, and their acid resistance is weak; while nickel-molybdenum (Ni-Mo) catalysts have certain toxicity resistance in such hydrogenation reactions, but their hydrogenation selectivity is poor, and they are prone to excessive hydrogenation of carboxylic acid groups and reduce the polarity of the resin. Therefore, the present invention uses more suitable palladium-based, ruthenium-based and other precious metal catalysts and their compositions as hydrogenation catalysts for modified resins, which have the advantages of high catalytic activity, good hydrogenation selectivity and stability, and are conducive to industrial production.

[0100] In addition, the carrier used for the noble metal hydrogenation catalyst in the present invention has a large specific surface area, good pore structure, high temperature resistance, acid and alkali resistance and good support type, which is conducive to the preparation of highly dispersed catalysts, and can change the conduction band of the grains at the nanoscale, thereby helping to enhance the effective activity of the noble metal catalyst. In addition, some carriers can also adjust the acid sites, which can cause the noble metal to form electron vacancies, weaken its interaction with sulfur, and improve the anti-sulfur and anti-poison properties of the catalyst.

[0101] In some typical embodiments, the active metal component is Pd and the carrier is titanium dioxide. Pd / TiO2 using titanium dioxide as a carrier has better hydrogenation activity and selectivity, because the acid sites on the surface of TiO2 carriers have a stronger promoting effect on the reaction activity by adsorbing cyclic groups through d-π compared to activated carbon; secondly, the weakly acidic TiO2 carrier can make the precious metal Pd form electron vacancies, weaken the interaction of impurities, and is beneficial to the "anti-toxicity" of the precious metal; thirdly, Pd / TiO2 has a more stable pore structure, the palladium atoms are firmly attached to the carrier, and the catalyst stability is better.

[0102] In some optional embodiments, the active metal component may account for 0.5wt%~8.0wt% of the precious metal hydrogenation catalyst, such as 0.5wt%, 1wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 5wt%, 6wt%, 7wt% or 8wt%, etc., or it can be other values ​​within the range of 0.5wt%~8.0wt%.

[0103] In some optional embodiments, the particle size of the carrier can be 300-400 mesh, and the specific surface area can be 800m 2 / g~1000m2 / g.

[0104] In some optional embodiments, taking activated carbon as a carrier, the noble metal hydrogenation catalyst can be prepared by referring to the following method: impregnating activated carbon (can be assisted by ultrasound) with excess dilute nitric acid (concentration of 5% to 30%) at a volume ratio of 1:1.5 to 1:10 for 0.5h to 1h at room temperature, separating the solid and liquid to obtain fresh activated carbon; adding the fresh activated carbon to deionized water at a volume ratio of 1:1 to 1:5, slowly heating to 85°C, and then adding the acidic palladium chloride solution (obtained after palladium chloride is dissolved in hydrochloric acid) and hydrochloric acid solution to the above solution according to the preset active metal component ratio, and then adding 35wt% formaldehyde solution equal to the hydrochloric acid solution, and then modulating weak alkalinity (pH 7.1 to 9.0) with 30wt% sodium hydroxide solution, stirring at 70°C to 90°C for 15min. Filter the catalyst, wash it with deionized water 10 times, filter it, and then continue to dry it with potassium hydroxide at room temperature for 24h to obtain the Pd / C catalyst.

[0105] It should be noted that when the active metal component and / or the carrier are changed, the preparation can also be carried out by referring to the preparation process of the above-mentioned Pd / C catalyst.

[0106] In some optional embodiments, the amount of precious metal hydrogenation catalyst can be 1wt% to 20wt% of the total hydrogenation material, such as 1wt%, 2wt%, 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt% or 20wt%, etc., or other values ​​within the range of 1wt% to 20wt%.

[0107] In some optional embodiments, the reaction of the modified resin and the deeply hydrogenated naphthenic oil is carried out in a reflux reaction system (such as a loop hydrogenation reactor). The use of a loop hydrogenation reactor is conducive to the full mixing of reactants in the multiphase hydrogenation reaction, strengthening mass transfer and heat transfer, accelerating the reaction process, and inhibiting the occurrence of side reactions, thereby effectively improving product quality.

[0108] In some optional embodiments, the mass ratio of the circulation volume to the production volume can be (5-40): 1, such as 5: 1, 10: 1, 15: 1, 20: 1, 25: 1, 30: 1, 35: 1 or 40: 1, or other values ​​within the range of (5-40): 1. Under this condition, the failure and loss of the precious metal catalyst can be effectively reduced, and the production cost can be reduced.

[0109] As mentioned above, by subjecting the modified resin to a hydrogenation reaction with deeply hydrogenated naphthenic oil under the action of a noble metal hydrogenation catalyst, a hydrogenated modified resin with low color and low iodine value can be obtained.

[0110] S5: removing impurities, gel substances, residual solvents and oligomers from the resin solution to obtain a hydrogenated modified resin.

[0111] In some optional embodiments, a centrifugal separation device may be used to remove impurities and gel substances in the resin liquid.

[0112] Among them, the mesh number of the filter cloth in the centrifugal separation device can be illustratively 80 mesh to 200 mesh, such as 80 mesh, 100 mesh, 120 mesh, 150 mesh, 180 mesh or 200 mesh, etc., or it can be other values ​​within the range of 80 mesh to 200 mesh.

[0113] In some optional embodiments, a distillation tower may be used to remove the remaining solvent and oligomers in the resin solution.

[0114] For example, the distillation pressure can be 20 kPa~50 kPa, such as 20 kPa, 25 kPa, 30 kPa, 35 kPa, 40 kPa, 45 kPa or 50 kPa, or other values ​​within the range of 20 kPa~50 kPa.

[0115] The distillation temperature may be 180°C to 280°C, such as 180°C, 200°C, 220°C, 240°C, 260°C or 280°C, or other values ​​within the range of 180°C to 280°C.

[0116] As mentioned above, the preparation method of the hydrogenated modified resin provided by the present invention, on the one hand, by using active monomers to regulate the cycloaddition reaction of cyclopentadiene and its derivatives with norbornene monomers, cycloolefin compounds with suitable molecular weight and physical and chemical properties can be obtained, explosion polymerization can be prevented, and the generation of macromolecular gel substances in the polymerization reaction can be reduced; on the other hand, by using an optimized solvent system and polymerization process, the polymerization conversion rate of cycloolefin compounds and bio-based carboxylic acids can be improved, and a biomass-based modified resin with excellent performance can be obtained; in addition, the biomass-based modified resin is selectively hydrogenated by a precious metal hydrogenation catalyst and a suitable hydrogenation reaction process, and the carboxylic acid group content of the product is regulated on the basis of saturating unsaturated bonds, reducing color number, and improving light and heat stability, so as to obtain a hydrogenated modified resin with suitable polarity, thereby improving the compatibility of the hydrogenated modified resin in various polar substrates.

[0117] Correspondingly, the present invention also provides a production system for preparing the above-mentioned biomass-based resin, which production system includes a first high-pressure reactor, a flash tower, a membrane separator, a packed tower, a second high-pressure reactor, an alcohol wash kettle, a first distillation tower, a batching tank, a loop reactor, a centrifugal separator and a second distillation tower.

[0118] The first high-pressure reactor is used for reacting cyclopentadiene and its derivatives, norbornene monomers and modified monomers; the bottom discharge port of the first high-pressure reactor is connected to the feed port of the flash tower to separate the cycloolefin copolymer in the first polymerization liquid; the light component is obtained at the top of the flash tower, and the cycloolefin copolymer is obtained in the bottom of the tower; the inlet of the membrane separator is connected to the top of the flash tower, and the outlet of the membrane separator is connected to the first high-pressure reactor, and the first solvent in the light component can be recovered through the membrane separator, and the recovered first solvent can be returned to the first high-pressure reactor for recycling; the bottom discharge port of the flash tower is connected to the bottom of the packing tower The inlet of the tower kettle is connected to remove impurities in the cycloolefin copolymer through the packed tower; the top outlet of the packed tower is connected to the inlet of the second high-pressure reactor, so that the cycloolefin copolymer with impurities removed reacts with the bio-based carboxylic acid introduced into the second high-pressure reactor; the material outlet of the second high-pressure reactor is connected to the inlet of the alcohol washing kettle, so that the unreacted monomers are eluted by the organic alcohols in the alcohol washing kettle; the bottom outlet of the alcohol washing kettle is connected to the inlet of the first distillation tower, so as to remove the second solvent and the oligomers generated by the reaction, that is, the oligomers and the second solvent are obtained at the top of the first distillation tower, and the modified resin is obtained in the bottom of the first distillation tower. The bottom outlet of the first distillation tower is connected to the inlet of the batching tank so that the modified resin is mixed with the hydrogenated cyclohexane oil introduced into the batching tank; the outlet of the batching tank is connected to the inlet of the loop reactor, and the loop reactor is provided with a noble metal hydrogenation catalyst so that the mixture of the modified resin and the hydrogenated cyclohexane oil undergoes a hydrogenation reaction under the catalytic action of the catalyst to obtain a resin liquid; the main material outlet of the loop reactor is connected to the inlet of the centrifugal separator so that impurities and gel substances in the resin liquid are removed by centrifugation; the outlet of the centrifugal separator is connected to the inlet of the second distillation tower so as to remove the residual solvent and oligomers, that is, the oligomers and the residual solvent are obtained at the top of the second distillation tower, and the hydrogenated modified resin is obtained in the bottom of the second distillation tower.

[0119] Correspondingly, the present invention also provides a hydrogenated modified resin, which is prepared by the above preparation method.

[0120] In some optional embodiments, the softening point of the hydrogenated modified resin is 80°C to 140°C, such as 88.2°C to 112°C, such as 88.2°C, 89.5°C, 95.8°C, 96.2°C, 96.3°C, 96.5°C, 98°C, 98.6°C, 99.0°C, 99.3°C, 101.5°C or 112°C, etc.

[0121] In some optional embodiments, the yellowness index of the hydrogenated modified resin is ≤10, such as 0.9-8.2, such as 0.9, 1.1, 1.2, 2.0, 3.6, 4.5, 4.7, 5.0, 5.5, 6.0, 7.0 or 8.2.

[0122] In some optional embodiments, the acid value of the hydrogenated modified resin is 3 mgKOH / g~200 mgKOH / g, such as 38 mgKOH / g~102 mgKOH / g, such as 38 mgKOH / g, 48 mgKOH / g, 55 mgKOH / g, 59 mgKOH / g, 60 mgKOH / g, 61 mgKOH / g, 66 mgKOH / g, 70 mgKOH / g, 87 mgKOH / g, 90 mgKOH / g or 102 mgKOH / g, etc.

[0123] In some optional embodiments, the iodine value of the hydrogenated modified resin is ≤30gI2 / 100g, such as 6gI2 / 100g~22gI2 / 100g, such as 6gI2 / 100g, 7gI2 / 100g, 8gI2 / 100g, 10gI2 / 100g, 12gI2 / 100g, 15gI2 / 100g, 19.5gI2 / 100g or 22gI2 / 100g, etc.

[0124] In addition, the present invention also provides a composite material, the raw materials for preparing the composite material include a rubber material and the above-mentioned hydrogenated modified resin. By using the hydrogenated modified resin in the composite material, the comprehensive properties of the composite material such as cohesive strength and heat resistance can be improved.

[0125] In some optional embodiments, the rubber compound may include at least one of natural rubber, synthetic rubber and elastomer. In some more typical embodiments, the rubber compound includes at least one of styrene-butadiene rubber (SBR), natural rubber (NR), SBC elastomer and SIS elastomer.

[0126] For example, the composite material may include, by weight, 45 parts of SIS thermoplastic elastomer, 31.5 parts of hydrogenated modified resin, 3 parts of pure styrene-based monomer resin, 20 parts of hydrogenated naphthenic oil, and 0.5 parts of antioxidant.

[0127] Furthermore, the present invention also provides the use of the above-mentioned composite material in hot melt adhesives, automotive parts (such as automotive interiors), packaging materials or medical devices. In particular, in the field of medical devices, its biocompatibility and biodegradability are significantly optimized, meeting the high standard requirements for materials in the field of medical devices.

[0128] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0129] The preparation method of the noble metal hydrogenation catalyst used in the following examples and comparative examples is as follows: Catalyst I: At room temperature, activated carbon was impregnated with excess dilute nitric acid (concentration of 20%) at a volume ratio of 1:4, and then ultrasonically treated for 0.5 h to separate the solid and liquid to obtain fresh activated carbon. The fresh activated carbon (particle size 400 mesh, specific surface area 800m 2 / g) was added into deionized water at a volume ratio of 1:2, and slowly heated to 85°C. Then, palladium chloride solution (solvent is hydrochloric acid) was added into the above solution according to the active component content in Table 1, and then a 35wt% formaldehyde solution was added in an amount equal to the hydrochloric acid solution, and then weak alkalinity was adjusted with a 30wt% sodium hydroxide solution (specific pH value is 8.0), and stirred at 85°C for 15 minutes. The catalyst was filtered, washed with deionized water 10 times, filtered, and then dried with potassium hydroxide at room temperature for 24 hours to obtain a Pd / C catalyst, which was recorded as catalyst I.

[0130] The preparation methods of catalyst II, catalyst III and catalyst IV are the same as catalyst I, except that the carrier and active metal component are replaced.

[0131] The differences in precious metal hydrogenation catalysts are shown in Table 1.

[0132] Table 1 Composition of precious metal hydrogenation catalysts

[0133] Example 1 This embodiment provides a hydrogenated modified resin, referring to Figure 1 , and its preparation method is as follows: S1: In a first high-pressure reactor R101 with stirring and nitrogen protection, decalin accounting for 40% of the total material mass is pre-added as the first solvent, cyclopentadiene (CPD) and norbornene (VN) are fully mixed in a mass ratio of 1:1 and added into the first high-pressure reactor R101, and polymerization is carried out at 175°C and 0.25MPa for 2.0h; then divinyl ether (DE) accounting for 1.5% of the total material mass is added, and the reaction is continued at 200°C and 0.25MPa for 8h to obtain a first polymerization liquid.

[0134] S2: The first polymerization liquid is transported to the flash tower T101, and the first solvent and unreacted monomers are removed at a pressure of 40 kPa and 235°C; the light component obtained at the top of the flash tower T101 is passed into the microporous membrane separator M101 (the membrane is a polyvinylidene fluoride microporous membrane), and decalin is separated under the conditions of 20°C and 0.2 MPa, and the separated decalin is recycled to the first high-pressure reactor R101; the reactor of the flash tower T101 obtains a cycloolefin copolymer with a Gardner color number of 2.0 #, a melt viscosity (@40°C) of 1250 mPa·s, and an Mz of 1320.

[0135] The cycloolefin copolymer is pre-transported into a packed tower T102 (the packing in the packed tower T102 consists of α-alumina and diatomaceous earth in a volume ratio of 1:0.3) to filter and remove impurities, and then the cycloolefin copolymer after impurity removal is reacted with dehydroabietic acid and a second solvent (methylcyclohexane:benzene=1:1) in a second high-pressure reactor R102 with stirring, wherein the mass ratio of the cycloolefin copolymer, dehydroabietic acid and the second solvent is 1:0.8:2, and the reaction is carried out at 220°C and 0.15MPa for 1.5h to obtain a second polymerization solution.

[0136] S3: The second polymerization liquid is passed into the alcohol washing kettle V101, and the unreacted monomers in the second polymerization liquid are eluted with methanol, and the amount of methanol added accounts for 20% of the mass of the second polymerization liquid; the material after the monomers are removed is then passed into the first distillation tower T103, and the second solvent and oligomers are removed at a pressure of 40 kPa and 250°C to obtain a modified resin.

[0137] S4: The modified resin and the deep hydrogenated naphthenic oil are fully mixed in the batching tank V102 at a mass ratio of 1:4, and then enter the loop reactor R103. Under the action of the precious metal hydrogenation catalyst I, the hydrogenation reaction is carried out at a temperature of 160°C and a pressure of 11.0 MPa. The reaction space velocity is 1.0 h -1 The volume ratio of hydrogen to modified resin is 500:1. The density of deep hydrogenated naphthenic oil is 0.93g / cm 3 , the kinematic viscosity at 100°C is 4 mm 2 / s, aniline point of 71℃, polycyclic aromatic hydrocarbon (PCA) content of 0.8%, bromine value of 0.2gBr / 100g. The dosage of precious metal hydrogenation catalyst I is 8wt% of the total hydrogenation material, and the mass ratio of circulation volume to production volume is 15:1.

[0138] The hydrogenated resin liquid was further filtered through a centrifugal separator V103 (filter cloth mesh number was 150 mesh) to remove impurities and gel substances, and then entered the second distillation tower T104 to remove hydrogenated cycloalkane oil and oligomers under the conditions of pressure 40 kPa and 250°C to obtain a hydrogenated modified resin with a softening point of 96.2°C, a yellow index of 5.5, an acid value of 61 mgKOH / g, and an iodine value of 12 gI2 / 100g.

[0139] Example 2 This embodiment provides a hydrogenated modified resin, and the preparation method thereof is different from that of Embodiment 1 only in that the noble metal hydrogenation catalyst used in step S4 is different. The catalyst used in this embodiment is catalyst II.

[0140] Example 3 This embodiment provides a hydrogenated modified resin, and the preparation method thereof is different from that of Embodiment 1 only in that the noble metal hydrogenation catalyst used in step S4 is different. The catalyst used in this embodiment is catalyst III.

[0141] Example 4 This embodiment provides a hydrogenated modified resin, and the preparation method thereof is different from that of Embodiment 1 only in that the noble metal hydrogenation catalyst used in step S4 is different. The catalyst used in this embodiment is catalyst IV.

[0142] The differences between the above-mentioned Examples 2 to 4 and the performance results of the hydrogenated modified resins prepared from them are shown in Table 2.

[0143] Table 2 Effects of different precious metal hydrogenation catalysts on the properties of hydrogenated modified resins

[0144] It can be seen from Table 2 that Examples 2 to 4 using Rh / C, Pd-Pt / TiO2 and Ru / TiO2 noble metal hydrogenation catalysts can all obtain low-color, low-iodine-value hydrogenated modified resins through hydrogenation reactions.

[0145] Among them, Example 3 uses Pd and Pt bimetallic catalysts as active components, and the resulting hydrogenated modified resin has a lighter color, higher acid value and iodine value, indicating that compared with the precious metal catalysts Rh / C and Ru / TiO2, Pd-Pt / TiO2 has a weaker hydrogenation effect on the cyclic olefin groups in the resin through the strong synergistic effect between the composite active catalytic components, and has a better hydrogenation selectivity for the bio-based carboxylic acid groups. The Rh / C catalyst used in Example 2 causes the resin to produce more hydrogen degradation and a higher hydrogenation depth, the softening point and iodine value of the product are lower, and there are more saturated carboxylic acid groups, and the product acid value is lower. The hydrogenation catalyst in Example 4 has a more balanced hydrogenation capacity, the product has a high softening point, less hydrogen degradation, and has a suitable acid value and iodine value.

[0146] Example 5 This embodiment provides a hydrogenated modified resin. The preparation method thereof is different from that of embodiment 1 only in that in step S4, the hydrogenation temperature is 140°C, the hydrogenation pressure is 12.0 MPa, and the reaction space velocity is 0.25 h -1 , the volume ratio of hydrogen to oil is 600:1.

[0147] Example 6 This embodiment provides a hydrogenated modified resin. The preparation method thereof is different from that of embodiment 1 only in that in step S4, the hydrogenation temperature is 180°C, the hydrogenation pressure is 6.0 MPa, and the reaction space velocity is 1.0 h -1 , the volume ratio of hydrogen to oil is 600:1.

[0148] Example 7 This embodiment provides a hydrogenated modified resin. The preparation method thereof is different from that of embodiment 1 only in that in step S4, the hydrogenation temperature is 180°C, the hydrogenation pressure is 12.0 MPa, and the reaction space velocity is 1.0 h -1 , the volume ratio of hydrogen to oil is 600:1.

[0149] Example 8 This embodiment provides a hydrogenated modified resin. The preparation method thereof is different from that of embodiment 1 only in that in step S4, the hydrogenation temperature is 245°C, the hydrogenation pressure is 12.0 MPa, and the reaction space velocity is 0.25 h -1 , the volume ratio of hydrogen to oil is 600:1.

[0150] The differences between the above-mentioned Examples 5 to 8 and the performance results of the hydrogenated modified resins prepared from them are shown in Table 3.

[0151] Table 3 Effect of different hydrogenation reaction conditions on the properties of resin

[0152] It can be seen from Table 3 that by carrying out hydrogenation reaction with Pd / C catalyst, under the conditions of high temperature, high pressure and low space velocity provided in Example 8, the degree of hydrogenation of the modified resin is deeper, and the color and iodine value of the hydrogenated product are lower, but obvious cracking occurs during the hydrogenation process, and the softening point is significantly lower than that of Example 1.

[0153] Under the same hydrogen-to-oil volume ratio, it can be seen from the comparison between Example 6 and Example 7 that increasing the hydrogenation reaction pressure is helpful to obtain a hydrogenated product with lighter color and higher degree of saturation.

[0154] Under the same hydrogen-to-oil volume ratio, it can be seen from the comparison between Example 5 and Example 7 that under the conditions of low reaction temperature and low space velocity, the carboxylic acid groups of the hydrogenated product are more retained and less degraded, but the color is higher and the saturation is low.

[0155] Therefore, the present invention can obtain a high-performance hydrogenated modified resin with differentiated properties and suitable for different application fields by regulating the hydrogenation process.

[0156] Example 9 This embodiment provides a hydrogenated modified resin, and the preparation method thereof is different from that of Example 1 only in that in step S4, the amount of the precious metal hydrogenation catalyst I is 10wt% of the total hydrogenation material, the hydrogenation reaction temperature is 180°C, and the hydrogenation reaction is carried out at a pressure of 12.0MPa, and the other process conditions are the same as those of Example 1.

[0157] Example 10 This embodiment provides a hydrogenated modified resin, and the preparation method thereof is different from that of embodiment 9 only in that the noble metal hydrogenation catalyst is a Pd / TiO2 catalyst. That is, the carrier in the Pd / C catalyst used in embodiment 9 is replaced by TiO2 from activated carbon C.

[0158] Comparative Example 1 This comparative example provides a hydrogenated modified resin, the preparation method of which is different from that of Example 9 only in that conventional Raney nickel (Ni-Al alloy, Ni content of 40 wt%) is used as a catalyst for hydrogenation reaction.

[0159] The differences among the above-mentioned Example 9, Example 10 and Comparative Example 1 and the performance results of the hydrogenated modified resins prepared from them are shown in Table 4.

[0160] Table 4 Effect of different catalyst carriers on the performance of hydrogenated modified resin

[0161] It can be seen from Table 4 that compared with the precious metal catalysts used in Examples 9 and 10 of the present invention, the high-content Raney nickel has a deeper degree of hydrogenation reaction in the hydrogenation reaction of the modified resin, that is, the color and iodine value of the hydrogenated product are relatively low, but the resin is severely degraded during the reaction, and the softening point is greatly reduced; and the carboxylic acid groups in the resin are also saturated at the same time, and the hydrogenation selectivity is poor.

[0162] From the comparison between Example 9 and Example 10, it can be seen that under the action of the same concentration of precious metal catalyst, Pd / TiO2 with titanium dioxide carrier has better hydrogenation activity and selectivity. This is because compared with activated carbon, the acid sites on the surface of TiO2 carrier are d -Π adsorbs cyclic groups, which has a stronger promoting effect on reaction activity; the weakly acidic TiO2 carrier can cause the precious metal to form electron vacancies, weaken the interaction between impurities, and is beneficial to the "anti-toxicity" of the precious metal; Pd / TiO2 has a more stable pore structure, the palladium atoms are more firmly attached to the carrier, and the catalyst stability is better.

[0163] Embodiment 11 This embodiment provides a hydrogenated modified resin, and the preparation method thereof is as follows: S1: In a first high-pressure reactor R101 with stirring and nitrogen protection, decalin accounting for 38% of the total material mass is pre-added as the first solvent, methylcyclopentadiene (MCPD) and 2-allyl-5-norbornene are fully mixed in a mass ratio of 1:1.2 and added into the first high-pressure reactor R101, and polymerization is carried out at 200°C and 0.20 MPa for 4.0 h; then styrene accounting for 3.0% of the total material mass is added, and the reaction is continued at 200°C and 0.20 MPa for 1 h to obtain a first polymerization liquid.

[0164] S2: The first polymerization liquid is transported to the flash tower T101, and the first solvent and unreacted monomers are removed at a pressure of 40 kPa and 235°C; the light component obtained at the top of the flash tower T101 is passed into the microporous membrane separator M101 (the membrane is a polyvinylidene fluoride microporous membrane), and decalin is separated under the conditions of 20°C and 0.2 MPa, and the separated decalin is recycled to the first high-pressure reactor R101; the bottom of the flash tower T101 obtains a cycloolefin copolymer with a Gardner color number of 1.3#, a melt viscosity (@40°C) of 2100 mPa·s, and an Mz of 1360.

[0165] The cycloolefin copolymer is pre-transported into a packed tower T102 (the packing in the packed tower T102 consists of α-alumina and diatomaceous earth in a volume ratio of 1:0.3) to filter and remove impurities, and then the impurity-removed cycloolefin copolymer is reacted with allyl succinic anhydride and a second solvent (methyl cyclohexane:benzene=1:1) in a second high-pressure reactor R102 with stirring, wherein the mass ratio of the cycloolefin copolymer, allyl succinic anhydride and the second solvent is 1:0.5:1.5, and the reaction is carried out at 240°C and 0.18 MPa for 2 hours to obtain a second polymerization solution.

[0166] S3: The second polymerization liquid is passed into the alcohol washing kettle V101, and the unreacted monomers in the second polymerization liquid are eluted with methanol, and the amount of methanol added accounts for 20% of the mass of the second polymerization liquid; the material after the monomers are removed is then passed into the first distillation tower T103, and the second solvent and oligomers are removed at a pressure of 40 kPa and 250°C to obtain a modified resin.

[0167] S4: The modified resin and the deep hydrogenated naphthenic oil are fully mixed in the batching tank V102 at a mass ratio of 1:4, and then enter the loop reactor R103. Under the action of the noble metal hydrogenation catalyst III, the hydrogenation reaction is carried out at a temperature of 220°C and a pressure of 10.0 MPa. The reaction space velocity is 0.5 h -1 The volume ratio of hydrogen to modified resin is 600:1. The density of deep hydrogenated naphthenic oil is 0.90g / cm 3 , the kinematic viscosity at 100°C is 3mm 2 / s, aniline point is 70℃, polycyclic aromatic hydrocarbon (PCA) content is 0.75%, and bromine value is 0.3gBr / 100g. The dosage of precious metal hydrogenation catalyst III is 10wt% of the total hydrogenation material, and the mass ratio of circulation volume to production volume is 15:1.

[0168] The hydrogenated resin liquid was further filtered through a centrifugal separator V103 (filter cloth mesh number was 150 mesh) to remove impurities and gel substances, and then entered the second distillation tower T104 to remove hydrogenated cycloalkane oil and oligomers under the conditions of pressure 40 kPa and 250°C to obtain a hydrogenated modified resin with a softening point of 99.3°C, a yellow index of 0.9, an acid value of 48 mgKOH / g, and an iodine value of 7 gI2 / 100g.

[0169] Example 12 This embodiment provides a hydrogenated modified resin, and the preparation method thereof is as follows: S1: In a first high-pressure reactor R101 with stirring and nitrogen protection, decalin accounting for 38% of the total material mass is pre-added as the first solvent, cyclopentadiene-methylcyclopentadiene (CPD-MCPD) and 2,5-norbornadiene are fully mixed in a mass ratio of 1:0.75 and added into the first high-pressure reactor R101, and polymerization is carried out at 200°C and 0.20MPa for 2.5h; then divinylbenzene accounting for 1.0% of the total material mass is added, and the reaction is continued at 200°C and 0.20MPa for 1h to obtain a first polymerization liquid.

[0170] S2: The first polymerization liquid is transported to the flash tower T101, and the first solvent and unreacted monomers are removed at a pressure of 40 kPa and 235°C; the light component obtained at the top of the flash tower T101 is passed into the microporous membrane separator M101 (the membrane is a polyvinylidene fluoride microporous membrane), and the decalin is separated under the conditions of 20°C and 0.2 MPa, and the separated decalin is recycled to the first high-pressure reactor R101; the bottom of the flash tower T101 obtains a cycloolefin copolymer with a Gardner color number of 3.0#, a melt viscosity (@40°C) of 3400 mPa·s, and an Mz of 2700.

[0171] The cycloolefin copolymer is pre-transported into a packed tower T102 (the packing in the packed tower T102 consists of α-alumina and diatomaceous earth in a volume ratio of 1:0.3) to filter and remove impurities, and then the impurity-removed cycloolefin copolymer is reacted with 2,5-furandicarboxylic acid and a second solvent (methylcyclohexane:benzene=1:1) in a second high-pressure reactor R102 with stirring, wherein the mass ratio of the cycloolefin copolymer, 2,5-furandicarboxylic acid and the second solvent is 1:0.5:1.5, and the reaction is carried out at 240°C and 0.18 MPa for 2.0 hours to obtain a second polymerization solution.

[0172] S3: The second polymerization liquid is passed into the alcohol washing kettle V101, and the unreacted monomers in the second polymerization liquid are eluted with methanol, and the amount of methanol added accounts for 20% of the mass of the second polymerization liquid; the material after the monomers are removed is then passed into the first distillation tower T103, and the second solvent and oligomers are removed at a pressure of 40 kPa and 250°C to obtain a modified resin.

[0173] S4: The modified resin and the deep hydrogenated naphthenic oil are fully mixed in the batching tank V102 at a mass ratio of 1:4, and then enter the loop reactor R103. Under the action of the noble metal hydrogenation catalyst III, the hydrogenation reaction is carried out at a temperature of 220°C and a pressure of 10.0 MPa. The reaction space velocity is 0.5 h -1 The volume ratio of hydrogen to modified resin is 600:1. The density of deep hydrogenated naphthenic oil is 0.90g / cm 3 , the kinematic viscosity at 100°C is 3mm 2 / s, aniline point is 70℃, polycyclic aromatic hydrocarbon (PCA) content is 0.75%, and bromine value is 0.3gBr / 100g. The dosage of precious metal hydrogenation catalyst III is 10wt% of the total hydrogenation material, and the mass ratio of circulation volume to production volume is 15:1.

[0174] The hydrogenated resin liquid was further filtered through a centrifugal separator V103 (filter cloth mesh number was 200 meshes) to remove impurities and gel substances, and then entered the second distillation tower T104 to remove hydrogenated cycloalkane oil and oligomers under the conditions of pressure 40 kPa and 250°C to obtain a hydrogenated modified resin with a softening point of 112.0°C, a yellow index of 1.1, an acid value of 102 mgKOH / g, and an iodine value of 15 gI2 / 100g.

[0175] Comparative Example 2 This comparative example provides a hydrogenated modified resin, the preparation method of which is different from that of Example 1 only in that no modified monomer is added in step S1: In a first high-pressure reactor R101 with stirring and nitrogen protection, decalin accounting for 40% of the total material mass is pre-added as the first solvent, cyclopentadiene (CPD) and norbornene (VN) are fully mixed in a mass ratio of 1:1 and then added into the first high-pressure reactor R101, and polymerization is carried out at 175°C and 0.25MPa for 2.0h to obtain a first polymerization liquid.

[0176] S2: The first polymerization liquid is transported to the flash tower T101, and the first solvent and unreacted monomers are removed at a pressure of 40 kPa and 235°C; the light component obtained at the top of the flash tower T101 is passed into the microporous membrane separator M101 (the membrane is a polyvinylidene fluoride microporous membrane), and decalin is separated under the conditions of 20°C and 0.2 MPa, and the separated decalin is recycled to the first high-pressure reactor R101; the reactor of the flash tower T101 obtains a cycloolefin copolymer with a Gardner color number of 1.2#, a melt viscosity (@40°C) of 780 mPa·s, and an Mz of 1020.

[0177] The cycloolefin copolymer is pre-transported into a packed tower T102 (the packing in the packed tower T102 consists of α-alumina and diatomaceous earth in a volume ratio of 1:0.3) to filter and remove impurities, and then the cycloolefin copolymer after impurity removal is reacted with dehydroabietic acid and a second solvent (methylcyclohexane:benzene=1:1) in a second high-pressure reactor R102 with stirring, wherein the mass ratio of the cycloolefin copolymer, dehydroabietic acid and the second solvent is 1:0.8:2, and the reaction is carried out at 220°C and 0.15MPa for 1.5h to obtain a second polymerization solution.

[0178] Steps S3 and S4 are the same as those in Example 1, and finally a hydrogenated modified resin having a softening point of 68.5° C., a yellow index of 3.2, an acid value of 33 mgKOH / g, and an iodine value of 7 gI2 / 100 g is obtained.

[0179] Comparative Example 3 This comparative example provides a bio-resin, the preparation method of which is different from that of Example 1 only in that dehydroabietic acid is not added for modification in step S2, and the final bio-resin obtained has a softening point of 59.0°C, a yellow index of 2.0, an acid value of 0.2 mgKOH / g, and an iodine value of 12 gI2 / 100 g.

[0180] From Example 1 and Comparative Examples 2-3, it can be seen that the polymerization effect of the cycloolefin copolymer and bio-based carboxylic acid prepared without adding the modified monomer in the present invention is poor, the acid value of the hydrogenated resin is significantly reduced, and because the relative molecular weight of the modified resin is greatly reduced, its softening point will also be significantly reduced; similarly, the product without bio-based carboxylic acid modification shows a significant reduction in softening point and acid value. The above two types of resin products cannot meet the application requirements in the field of conventional hot melt adhesives due to their physical and chemical properties.

[0181] Application Examples This application example provides 6 different hot melt adhesives. The raw materials for preparing each hot melt adhesive include, by weight: 45 parts of SIS thermoplastic elastomer, 31.5 parts of tackifying resin, 3 parts of pure styrene-based monomer resin, 20 parts of hydrogenated cyclohexane oil and 0.5 parts of compound antioxidant.

[0182] The SIS thermoplastic elastomer, pure styrene-based monomer resin hydrogenated cyclohexane oil and compounded antioxidant used in each hot melt adhesive are the same, and the tackifying resin used in each hot melt adhesive corresponds to the hydrogenated modified resin prepared in the above-mentioned Example 1, Example 7, Examples 10 to 12 and Comparative Example 1, and the bio-resin that has not been hydrogenated and modified in Comparative Example 3.

[0183] Among them, SIS elastomer uses Kraston from Kraton, USA TM D1126, styrene content 26.5%, melt mass flow rate (200℃ / 5kg) 22g / 10min; The pure styrene-based monomer resin uses the monomer resin Greentack produced by Henghe Materials Technology Co., Ltd. TM Y-85, softening point 80-90°C, yellowness index 2.0, glass transition temperature (Tg) 49°C; Hydrogenated naphthenic oil uses Karamay naphthenic oil KN4010; The composite antioxidant is selected from antioxidant AT-1010 and antioxidant AT-168 produced by SI-Group (USA), which are uniformly mixed in a mass ratio of 1:1.

[0184] The preparation process of hot melt adhesive is as follows: 45 parts of SIS thermoplastic elastomer, 20 parts of hydrogenated cyclohexane oil, and 0.3 parts of compound antioxidant are put into a vacuum kneader. The temperature of the kneader is controlled at 170°C. After the SIS thermoplastic elastomer is completely dissolved, 31.5 parts of tackifying resin and 3 parts of pure styrene-based monomer resin are added. The resin is completely dissolved and mixed evenly, and the material is discharged after the bubbles are exhausted. The adhesive is coated while hot. PET tape with a thickness of 100±5μm is selected for relevant application tests. The coating thickness is 30±3μm (to prevent cracking of the unsaturated middle rubber segment, nitrogen is filled for protection during the preparation process).

[0185] Among them, dynamic viscosity and annular initial adhesion are tested by the national standard GB / T4852 method; peel strength is tested by the national standard GB / T2792 method; holding force is tested by the national standard GB / T4851 method; SAFT is the shear adhesion failure temperature, which is tested by the American standard PSTC-17 "Test Method for Shear Failure Temperature of Pressure-Sensitive Adhesive Tapes".

[0186] The test results of various hot-melt pressure-sensitive adhesive tapes (PSA) are shown in Table 5.

[0187] Table 5 Effects of different tackifying resins on the performance of hot-melt pressure-sensitive adhesive tapes

[0188] It can be seen from Table 5 that the dynamic viscosity of the hot melt adhesive can be adjusted by tackifying resins with different softening points, and the addition of a high softening point tackifying resin can significantly increase the dynamic viscosity of the adhesive.

[0189] When the proportion of bio-based carboxylic acid groups in the tackifying resin is increased (i.e., the acid value is increased), the compatibility of the components in the PSA is improved, and its room temperature and medium temperature viscosity, such as peel strength and holding force, will be greatly improved, and the cohesion of the PSA can be further enhanced by increasing the softening point. At the same time, the bio-based carboxylic acid modified tackifying resin with a suitable softening point can improve the ring adhesion between PSA and materials such as stainless steel to a certain extent.

[0190] Shear Adhesion Failure Temperature (SAFT) is an important performance index for evaluating the cohesive strength and heat resistance of PSA, and has no significant correlation with the geometry and thickness of the PSA sample. The comparative test results in the above table show that compared with the unmodified resin in Comparative Example 3, the bio-based carboxylic acid modified tackifying resin has a very significant improvement in the SAFT performance of PSA. In practical applications, high cohesive strength PSA can maintain a good tackifying effect under the condition of appropriately thinning the adhesive coating thickness, which helps to reduce the raw material costs of downstream application customers.

[0191] In summary, the present invention synthesizes cyclopentadiene and its derivatives with norbornene monomers through Diels-Alder to generate cyclic molecules, and adds modified monomers to participate in copolymerization reaction in a timely manner, which can effectively regulate the relative molecular weight and physical and chemical properties of the product, prevent excessive polymerization to form macromolecular gel, and obtain medium and low molecular weight cycloolefin copolymers. By further reacting the medium and low molecular weight cycloolefin copolymers with bio-based carboxylic acids, a new biomass-based modified resin with strong polarity and small relative molecular weight is obtained. By reacting the modified resin with deeply hydrogenated cycloalkane oil under the action of a precious metal hydrogenation catalyst, a hydrogenated modified resin with low color, low iodine value and strong stability can be obtained; by regulating the carboxylic acid group content of the product, a hydrogenated modified resin with suitable polarity can be obtained, and the compatibility of the hydrogenated modified resin in various polar substrates can be improved.

Claims

1. A method for preparing a hydrogenated modified resin, It is characterized in that The following steps are involved: The cyclopentadiene and its derivatives are polymerized with norbornene monomers in the presence of a first solvent, and then a modified monomer is added to continue the reaction to obtain a first polymerization solution; separating the cyclic olefin copolymer in the first polymerization liquid, and reacting the separated cyclic olefin copolymer with a bio-based carboxylic acid in the presence of a second solvent to obtain a second polymerization liquid; removing unreacted monomers and remaining solvents and oligomers in the second polymerization solution to obtain a modified resin; The modified resin and deeply hydrogenated naphthenic oil are subjected to hydrogenation reaction under the action of a noble metal hydrogenation catalyst to obtain a resin liquid; Impurities, gel substances, residual solvents and oligomers in the resin liquid are removed to obtain hydrogenated modified resin.

2. The preparation method according to claim 1, It is characterized in that The preparation of the first polymer solution includes at least one of the following features: Feature 1: The polymerization reaction is carried out at 100°C to 250°C and 0.15MPa to 2.0MPa for 0.5h to 5.0h; Feature 2: The mass ratio of the cyclopentadiene and its derivatives to the norbornene monomer is 1:(0.1-2.0); Feature 3: The first solvent accounts for 15% to 50% of the total material mass, and the total material is the sum of the cyclopentadiene and its derivatives, the norbornene monomers and the modified monomers; Feature 4: After adding the modified monomer, reacting at 100° C. to 250° C. and 0.15 MPa to 2.0 MPa for 1.0 h to 10 h; Feature 5: The amount of the modified monomer added is 0.01% to 10% of the total material mass, and the total material is the sum of the cyclopentadiene and its derivatives, the norbornene monomers and the modified monomers; Feature 6: The cyclopentadiene and its derivatives include at least one of cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, dicyclopentadiene, methylcyclopentadiene dimer and cyclopentadiene-methylcyclopentadiene dimer; Feature 7: The norbornene monomer includes at least one of norbornene, 2,5-norbornadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 2-allyl-5-norbornene; Feature 8: The first solvent includes decahydronaphthalene; Feature 9: The modified monomer includes styrene and its derivatives or divinyl ether monomers.

3. The preparation method according to claim 1, It is characterized in that Separating the cyclic olefin copolymer in the first polymer solution comprises at least one of the following features: Feature 10: Separating the cycloolefin copolymer in the first polymerization solution by flash evaporation at 20 kPa to 80 kPa and 180° C. to 280° C.; Feature 11: The isolated cycloolefin copolymer has a Gardner color number of ≤4.0#, a melt viscosity at 40°C of ≤5000 mPa·s, and a Z-average molecular weight of ≤3000.

4. The preparation method according to claim 1, It is characterized in that The preparation of the second polymer solution includes at least one of the following features: Feature 12: The cyclic olefin copolymer and the bio-based carboxylic acid are reacted at 200° C. to 280° C. and 0.1 MPa to 2.0 MPa for 0.25 h to 5.0 h; Feature 13: The mass ratio of the cyclic olefin copolymer to the bio-based carboxylic acid and the second solvent is 1:(0.2-1.5):(0.75-10) respectively; Feature 14: The bio-based carboxylic acid includes at least one of 3-hydroxypropionic acid, 2,5-furandicarboxylic acid, abietic acid, dehydroabietic acid, dehydroabietic acid, 2,2-dimethylsuccinic anhydride, allylsuccinic anhydride, butylsuccinic anhydride, 2-octenylsuccinic anhydride, ricinoleic acid, dehydrated ricinoleic acid and hexylitaconic acid; Feature 15: The second solvent includes benzene, cyclohexane and its derivatives.

5. The preparation method according to any one of claims 1 to 4, It is characterized in that First, impurities in the cycloolefin copolymer are removed in a packed tower, and then the cycloolefin copolymer after the impurities are removed is reacted with the bio-based carboxylic acid; the packing in the packed tower includes α-alumina and diatomaceous earth.

6. The preparation method according to any one of claims 1 to 4, It is characterized in that Removing unreacted monomers in the second polymerization liquid by eluting with organic alcohol, and / or removing the remaining solvent and oligomers in the second polymerization liquid by distillation; The distillation is carried out at 180°C to 280°C and 20kPa to 50kPa.

7. The preparation method according to claim 1, It is characterized in that The reaction of the modified resin with the deeply hydrogenated naphthenic oil includes at least one of the following characteristics: Feature 16: The mass ratio of the modified resin to the deeply hydrogenated naphthenic oil is 1:(1-5); Feature 17: The temperature of the hydrogenation reaction is 120℃~300℃, the pressure is 2.0MPa~15.0MPa, and the reaction space velocity is 0.2h -1 ~2.0h -1 ; Feature 18: The volume ratio of hydrogen to the modified resin is (300-800):1; Feature 19: The density of the deep hydrogenated naphthenic oil is 0.90 g / cm 3 ~0.98g / cm 3 , the kinematic viscosity at 100°C is 3 mm 2 / s~8mm 2 / s, aniline point is 70℃~80℃, condensed aromatic hydrocarbon content is less than 3%, bromine value is less than 1.0gBr / 100g; Feature 20: The noble metal hydrogenation catalyst comprises an active metal component and a carrier, wherein the active metal component comprises at least one of Pd, Pt, Ru and Rh, and the carrier comprises at least one of activated carbon, alumina, titanium dioxide and silicon dioxide; the active metal component accounts for 0.5wt% to 8.0wt% of the noble metal hydrogenation catalyst; Feature 21: The amount of the precious metal hydrogenation catalyst is 1wt% to 20wt% of the total hydrogenation material; Feature 22: The reaction of the modified resin and the deeply hydrogenated cyclohexane oil is carried out in a reflux reaction system, and the mass ratio of the circulation amount to the production amount is (5~40):

1.

8. A hydrogenated modified resin, It is characterized in that The hydrogenated modified resin is prepared by the preparation method according to any one of claims 1 to 7; The hydrogenated modified resin has at least one of the following characteristics: Feature 23: The softening point of the hydrogenated modified resin is 80°C to 140°C; Feature 24: The yellowness index of the hydrogenated modified resin is ≤10; Feature 25: The acid value of the hydrogenated modified resin is 3 mgKOH / g to 200 mgKOH / g; Feature 26: The iodine value of the hydrogenated modified resin is ≤30gI 2 / 100g.

9. A composite material, It is characterized in that The raw materials for preparing the composite material include rubber and the hydrogenated modified resin according to claim 7 or 8.

10. Use of the composite material according to claim 9 in hot melt adhesives, automobile parts, packaging materials or medical devices.

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