Acrylated hydrocarbon resins, methods of making and use thereof

Abstract

This disclosure provides an acrylated hydrocarbon resin, its preparation method, and its applications. The acrylated hydrocarbon resin has the following characteristics: a functionality of 1 to 12 per molecular chain; a vinyl content of 15% to 75% in the main chain; a number-average molecular weight of 5000 to 15000; a molecular weight distribution of 1.1 to 3.0; a viscosity of 5000 to 100000 mPa·s at 45°C; and a main molecular chain consisting of hydrocarbon resin segments with functional groups located on the side chains, the side chains being attached to unsaturated cyclic anhydride residues, which are connected to acrylate groups via ester bonds. The preparation method involves heating an unsaturated cyclic anhydride-grafted hydrocarbon resin to a fluid state, followed by reaction with a hydroxyl acrylate in the presence of a composite catalyst and a polymerization inhibitor. This resin possesses excellent dielectric properties, interfacial adhesion, storage stability, and photocurability, and can be widely used in various fields. Its preparation method is simple, environmentally friendly, and easy to industrialize, showing broad application prospects.

Description

Technical Field

[0001] This disclosure relates to the field of polymer materials technology, specifically to acrylated hydrocarbon resins, their preparation methods, and applications. Background Technology

[0002] With the rapid development of 5G / 6G high-frequency communication and high-speed computing technologies, increasingly stringent requirements are being placed on the dielectric properties of substrates in fields such as high-performance electronic packaging materials, copper clad laminates (CCLs), and photoresists. Hydrocarbon resins (such as polybutadiene, polyethylene, and styrene-butadiene resins), due to their molecular structure containing only carbon and hydrogen atoms, exhibit extremely low dielectric constants and dielectric losses, and possess excellent water resistance and chemical corrosion resistance, making them a core candidate material in the field of high-frequency communication materials. Summary of the Invention

[0003] The inventors unexpectedly discovered that by using hydroxyl acrylates to perform ring-opening modification on hydrocarbon resins grafted from unsaturated cyclic anhydrides, the resulting acrylated hydrocarbon resin exhibits significantly improved overall performance. This acrylated hydrocarbon resin possesses excellent dielectric properties, interfacial adhesion, and storage stability. Furthermore, the acrylated hydrocarbon resin disclosed herein is suitable for multiple core fields such as copper-clad laminate bonding, UV-curable adhesives, high-end coatings, electronic packaging, and printing inks, possessing significant industrial application value and market prospects. This disclosure was obtained based on the above unexpected discovery.

[0004] In a first aspect of this disclosure, an acrylated hydrocarbon resin is provided, wherein the acrylated hydrocarbon resin may have the following characteristics:

[0005] The functionality is 1 to 12 per molecular chain, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 to 12 per molecular chain, said functionality being calculated in terms of acrylate groups;

[0006] The vinyl content of the main chain is 15% to 75%, for example 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% to 75%;

[0007] Number average molecular weight is 5,000 to 15,000, for example 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 11,000, 12,000, 13,000, 14,000 to 15,000;

[0008] The molecular weight distribution is from 1.1 to 3.0, for example, 1.1, 1.4, 1.7, 2.0, 2.3, 2.6, 2.8 to 3.0;

[0009] Viscosities at 45°C ranging from 5000 to 100000 mPa·s, for example, 5000, 6000, 7000, 8000, 10000, 12000, 14000, 16000, 18000 to 100000 mPa·s; and

[0010] The main molecular chain is a hydrocarbon resin segment, and the functional groups are located on the molecular side chain. Unsaturated cyclic anhydride residues are attached to the side chain, and the unsaturated cyclic anhydride residues are connected to acrylate groups through ester bonds.

[0011] In a second aspect of this disclosure, a method for preparing the acrylated hydrocarbon resin according to the first aspect is provided, which may include:

[0012] Pretreatment: The unsaturated cyclic anhydride-grafted hydrocarbon resin is heated to a fluid state; and

[0013] Esterification reaction: The pretreated unsaturated cyclic anhydride-grafted hydrocarbon resin is reacted with hydroxy acrylate at 70 to 115°C for 3 to 7 hours in the presence of a single catalyst or a composite catalyst and a polymerization inhibitor to obtain the crude product.

[0014] In a third aspect of this disclosure, the use of the acrylated hydrocarbon resin according to the first aspect in the preparation of copper-clad laminate interlayer adhesives, light-curing adhesives, crosslinking agents, interfacial adhesives, mixing aids, polymer coatings, or interfacial compatibilizers is provided.

[0015] In a fourth aspect of this disclosure, a copper-clad laminate interlayer adhesive is provided, comprising an acrylated hydrocarbon resin as described in the first aspect.

[0016] In a fifth aspect of this disclosure, a light-curing adhesive is provided that comprises an acrylated hydrocarbon resin as described in the first aspect.

[0017] In a sixth aspect of this disclosure, a coating comprising an acrylated hydrocarbon resin as described in the first aspect is provided.

[0018] This disclosure provides an acrylated hydrocarbon resin with clearly defined and adjustable parameters such as functionality, vinyl content of the main chain, molecular weight, and viscosity, enabling precise selection based on different application scenarios. This disclosure is the first to achieve precise control of the vinyl content from 15% to 75% within an ultra-wide range in an acrylated hydrocarbon resin system. This capability grants unprecedented design freedom for the material's performance, allowing for the acquisition of materials ranging from ultra-low dielectric flexible materials to ultra-high crosslinking density fast-curing materials using the same chemical structure and preparation method. Specifically, the acrylated hydrocarbon resin provided in this disclosure possesses at least one of the following advantages: a balance between high solids content (≥99 wt%) and low viscosity; excellent storage stability; and photocurable activity, strong substrate adhesion, and chemical resistance. Furthermore, this resin can be prepared using various unsaturated cyclic anhydride-grafted hydrocarbon resin main chains, achieving comprehensive coverage across multiple scenarios and meeting the differentiated needs of various industries such as electronics, chemicals, printing and packaging, automotive, and construction. It is widely applicable in fields such as interlayer bonding of copper-clad laminates, photocurable adhesives, coatings, crosslinking agents, and interface compatibilizers. Its preparation method is simple, environmentally friendly, and easy to industrialize. Detailed Implementation

[0019] This disclosure will be described in more detail below to aid in understanding it.

[0020] It should be understood that the terms or words used in this specification and the appended claims should not be construed as limited to their general or dictionary meanings, but rather interpreted based on their meanings and concepts corresponding to the technical aspects of this disclosure, on the basis of the principle that the inventors are allowed to define terms appropriately for the purpose of best illustration.

[0021] It should be further understood that, unless otherwise expressly stated, when used in the specification, "comprising" or "including" indicates the presence of the said element and does not exclude the presence or addition of one or more other elements.

[0022] As used herein, a range is used as a shorthand to describe the individual values ​​within the range and each value. Any value within the range can be chosen as an endpoint of the range. Thus, the ranges 1 to 5 specifically include 1, 2, 3, 4, and 5, as well as subranges such as 2 to 5, 3 to 5, 2 to 3, 2 to 4, 1 to 4, etc.

[0023] As used in this article, “selected from” means selecting one, two or more candidates.

[0024] As used in this article, "derived from" indicates that a structural segment is derived from a specific original raw material through a chemical reaction. For example, "acrylate group derived from hydroxyacrylate" means that the hydroxyacrylate is attached to the anhydride residue through an esterification reaction, while retaining its acrylate double bond activity.

[0025] As used herein, the term "acrylated hydrocarbon resin" refers to a polymer with acrylate groups in its side chains, obtained by esterification of an unsaturated cyclic anhydride-grafted liquid hydrocarbon resin with a hydroxy acrylate monomer.

[0026] As used herein, the term "unsaturated cyclic anhydride" refers to a compound whose molecular structure contains at least one carbon-carbon double bond (C=C) and an anhydride group, such as, but not limited to, maleic anhydride, itaconic anhydride, citraconic anhydride, 2-methylmaleic anhydride, and 2,3-dimethylmaleic anhydride. These anhydrides, due to their highly reactive double bonds and anhydride rings, can be effectively grafted onto the main chain.

[0027] As used herein, the term "cyclic anhydride residue" refers to the structural unit formed when an unsaturated cyclic anhydride molecule is introduced into the resin side chain through a chemical reaction (such as grafting, addition, or copolymerization).

[0028] As used herein, the term “functionality” refers to the average number of acrylate groups attached to each acrylated hydrocarbon resin molecule chain, as determined according to GB / T 32867-2016.

[0029] As used herein, the term "vinyl content of the main chain" refers to the molar percentage of unsaturated carbon-carbon double bonds (C=C) in the main chain segments of a hydrocarbon resin, as determined according to GB / T 28728-2012.

[0030] As used herein, the term "hydrocarbon resin segment" refers to a saturated or unsaturated polymer segment whose main molecular chain consists only of carbon and hydrogen atoms. It is selected from one or more of polybutadiene, styrene-butadiene resin, pentadiene-butadiene resin, polyethylene, or polypropylene.

[0031] As used herein, the term “number-average molecular weight (Mn)” refers to the statistical average molecular weight of a resin sample, which is determined according to GB / T 21863-2008.

[0032] As used in this article, the term “molecular weight distribution (Mw / Mn)” refers to the ratio of peak molecular weight to number-average molecular weight, reflecting the degree of molecular weight dispersion, which is determined according to GB / T 21863-2008.

[0033] As used herein, the term “viscosity” refers to the dynamic viscosity measured at 45°C, as determined according to GB / T 10247-2008.

[0034] As used herein, the term "semi-esterified group" refers to a combination of functional groups formed after the ring opening of an unsaturated cyclic anhydride, with one end being a free carboxyl group and the other end being an ester bond.

[0035] As used herein, the term "hydrocarbon resin backbone" refers to a polymer backbone consisting only of carbon and hydrogen atoms, which may be derived from homopolymers or copolymers of monoolefins or dienes.

[0036] As used herein, the term "composite catalyst" refers to a catalyst system consisting of two or more components used to catalyze esterification reactions.

[0037] In a first aspect of this disclosure, an acrylated hydrocarbon resin is provided, wherein the acrylated hydrocarbon resin may have the following characteristics:

[0038] The functionality is 1 to 12 per molecular chain, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 to 12 per molecular chain, said functionality being calculated in terms of acrylate groups;

[0039] The vinyl content of the main chain is 15% to 75%, for example 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% to 75%;

[0040] Number average molecular weight is 5,000 to 15,000, for example 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 11,000, 12,000, 13,000, 14,000 to 15,000;

[0041] The molecular weight distribution is from 1.1 to 3.0, for example, 1.1, 1.4, 1.7, 2.0, 2.3, 2.6, 2.8 to 3.0;

[0042] Viscosities at 45°C ranging from 5000 to 100000 mPa·s, for example, 5000, 6000, 7000, 8000, 10000, 12000, 14000, 16000, 18000 to 100000 mPa·s; and

[0043] The main molecular chain is a hydrocarbon resin segment, and the functional groups are located on the molecular side chain. Unsaturated cyclic anhydride residues are attached to the side chain, and the unsaturated cyclic anhydride residues are connected to acrylate groups through ester bonds.

[0044] In some embodiments, the side chain is connected to an unsaturated cyclic anhydride residue via carbon-carbon bonds, and the unsaturated cyclic anhydride residue forms a half-ester structure after ring opening; one end of the half-ester structure is a free carboxyl group, and the other end is connected to an acrylate group containing a carbon-carbon double bond via an ester bond.

[0045] In some embodiments, the acrylated hydrocarbon resin has the structure of formula (I):

[0046] (I)

[0047] Wherein: * indicates the extension direction of the hydrocarbon resin backbone; n indicates the average number of grafted side chain structural units per molecular chain, and n is 1 to 12; R1 is selected from H, methyl, ethyl, propyl, butyl or -CH2COOH; A represents a C1 to C10 divalent hydrocarbon group, preferably C1 to C6 straight or branched alkylene groups, such as methylene, ethylene, propylene, butylene and pentylene; R2 is selected from H or methyl or ethyl; and the hydrocarbon resin segments are derived from homopolymers or copolymers of C2 to C10 monoolefins or C4 to C10 dienes and the backbone is a saturated or unsaturated segment consisting only of carbon atoms and hydrogen atoms.

[0048] In some embodiments, the hydrocarbon resin segments are derived from homopolymers or copolymers of C2, C3, C4, C5, C6, C7, C8, C9 to C10 monoolefins or C4, C5, C6, C7, C8, C9 to C10 dienes. In some embodiments, the hydrocarbon resin segments are derived from polybutadiene, styrene-butadiene resin, pentylene-butadiene resin, polyethylene, or polypropylene. More preferably, the hydrocarbon resin segments are derived from polybutadiene and styrene-butadiene resin.

[0049] It should be understood that Formula (I) described in this disclosure is intended to illustrate a typical functionalized unit composition in acrylated hydrocarbon resins. Formula (I) represents an acrylate-containing side chain unit grafted onto the hydrocarbon resin backbone, where n represents the average number of such units per molecular chain. Those skilled in the art will understand that the repeating units identified by brackets [ ]n in Formula (I) do not limit the strict order, continuity, or spatial proportion of the units in the hydrocarbon resin backbone; the side chain residues are randomly or in a specific distribution bonded to the active sites of the hydrocarbon resin backbone through a grafting reaction.

[0050] In some embodiments, the unsaturated cyclic anhydride is a five-membered cyclic anhydride containing an alkenyl group. Examples of unsaturated cyclic anhydrides include maleic anhydride, itaconic anhydride, and citraconic anhydride. More preferably, the unsaturated cyclic anhydride is maleic anhydride.

[0051] In some embodiments, the carbon-carbon double bond-containing acrylate group is introduced by reacting a hydroxyacrylate with the anhydride group or carboxyl group of the unsaturated cyclic anhydride residue. Preferably, the hydroxyacrylate can be selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. For example, in some embodiments, the acrylated hydrocarbon resin can be prepared by esterification of an unsaturated cyclic anhydride-grafted hydrocarbon resin with a hydroxyacrylate. Unsaturated cyclic anhydride-grafted hydrocarbon resins are commercially available or synthesized by known synthetic methods. There are no particular limitations on the method for synthesizing unsaturated cyclic anhydride-grafted hydrocarbon resins, and synthetic methods known in the art can be used. Commercially available grades include, but are not limited to, MPB-L3017, MPB-L7017, and MBS-2006 from Shandong Jingbo Petrochemical Co., Ltd., and the specific technical features of each grade are as follows:

[0052] MPB-L3017: This product is maleic anhydride-grafted polybutadiene with a matrix vinyl content of 18 to 33 mol%, characterized by a high grafting rate, and is a dark brown viscous liquid. As a precursor to the acrylated products disclosed herein, its low vinyl content imparts a low initial viscosity and moderate crosslinking density to the product. MPB-L3017 has high functionality, strong adhesive properties, and high polarity, but relatively poor dielectric properties. It can be used as an intermediate for acrylated products, applicable to multiple fields, and is particularly suitable for scenarios requiring high adhesive strength and moderate dielectric properties.

[0053] MPB-L7017: This product is maleic anhydride-grafted polybutadiene with a matrix vinyl content of 65 to 75 mol%, characterized by a high grafting rate. It is a dark brown, viscous liquid. The high vinyl content imparts high viscosity and crosslinking density to the product. MPB-L7017 has high functionality, strong adhesion, and high polarity, but relatively poor dielectric properties. It exhibits excellent photocuring activity and can be used as an intermediate for acrylate esterification products in various fields, especially suitable for applications requiring high photocuring efficiency and crosslinking density.

[0054] MBS-2006: This product is a maleic anhydride-grafted styrene-butadiene resin, a dark brown viscous liquid. Its moderate functionality and low vinyl content allow the final product to achieve a balance between viscosity, crosslinking density, and adhesive properties, while exhibiting low polarity and excellent dielectric properties. Thanks to the introduction of benzene ring structures into the backbone, this grade significantly improves the product's thermal stability and compatibility with styrene-butadiene materials, making it particularly suitable for applications requiring thermal stability and adhesion to benzene-containing matrices, such as interlayer bonding and coating of copper-clad laminates.

[0055] In some embodiments of this disclosure, the hydrocarbon resin matrix is ​​preferably MPB-L3017 or MPB-L7017. These two types of matrices have optimized grafting rates and high reactivity, which can significantly improve the hydrolytic stability and overall processing rheology of the final product. Furthermore, MBS-2006 can be used as a supplementary solution to meet low cost and specific dielectric requirements, thus covering multiple application scenarios.

[0056] In this disclosure, the acrylated hydrocarbon resin has a purity ≥99 wt%. Furthermore, the acrylated hydrocarbon resin disclosed herein can be mixed and dissolved with organic solvents such as toluene and xylene to produce a finished product in solution form, and the solution concentration can be customized. In addition, the acrylated hydrocarbon resin disclosed herein exhibits excellent hydrolysis resistance; after long-term storage at 25°C and 60% relative humidity for 12 months, no surface curing layer forms, and it does not harden or become brittle, making it convenient to use.

[0057] In this disclosure, the functional groups are located on the side chains of the molecular chain. This spatial configuration gives it excellent hydrolytic stability, with no cured layer forming on the surface during long-term storage, and it possesses excellent compatibility and processability. Experimental verification unexpectedly revealed that for acrylated hydrocarbon resins, the vinyl content of the main chain is correlated with the product viscosity and the crosslinking density after curing; higher vinyl content results in higher viscosity and crosslinking density; higher functionality leads to stronger adhesion, higher product polarity, and poorer dielectric properties. Furthermore, products containing butyl-phenyl groups, due to the presence of benzene rings, can significantly improve thermal stability and adhesion strength to styrene-butadiene matrices, making them particularly suitable for applications requiring high thermal stability.

[0058] In a second aspect of this disclosure, a method for preparing an acrylated hydrocarbon resin according to the first aspect is provided, which may include: pretreatment: heating an unsaturated cyclic anhydride-grafted hydrocarbon resin to a fluid state; and esterification reaction: reacting the pretreated unsaturated cyclic anhydride-grafted hydrocarbon resin with a hydroxy acrylate at 70 to 115°C for 3 to 7 hours in the presence of a composite catalyst and a polymerization inhibitor to obtain a crude product.

[0059] Specifically, the pretreatment in the above steps can be carried out in a vacuum drying oven at 80 to 100°C and a vacuum degree of -0.08 to -0.1 MPa for 2 to 4 hours to remove moisture and volatile impurities, and then cooled to room temperature. The esterification reaction may include adding the pretreated unsaturated cyclic anhydride-grafted hydrocarbon resin to the reactor, adding hydroxyl acrylate, stirring evenly, adding a composite catalyst and a polymerization inhibitor, and purging with nitrogen for protection. During this process, the reaction temperature can be controlled at 85 to 115°C, the stirring speed at 200 to 500 r / min, and the reaction time at 3 to 7 hours to obtain the crude product.

[0060] In some embodiments, the unsaturated cyclic anhydride-grafted hydrocarbon resin and hydroxy acrylate are the same as defined in the first aspect above. In some embodiments, the mass ratio of the unsaturated cyclic anhydride-grafted hydrocarbon resin to the hydroxy acrylate can be from 1:0.2 to 0.9. This ratio can be adjusted according to the vinyl content and functionality of the matrix. The higher the vinyl content and functionality, the less acrylate can be used to ensure sufficient reaction of the unsaturated cyclic anhydride graft groups.

[0061] In some embodiments, the composite catalyst is selected from a mixture of an acidic catalyst and an organophosphorus compound, or a mixture of a molecular sieve and a heteropoly acid. In some embodiments, the composite catalyst is selected from a mixture of p-toluenesulfonic acid and triphenylphosphine, or a mixture of ZSM5 molecular sieve and a heteropoly acid. Preferably, the mass ratio of p-toluenesulfonic acid to triphenylphosphine can be 2 to 3:1. Compared with a single catalyst, the composite catalyst can significantly improve the esterification reaction efficiency, reduce side reactions, and improve the hydrolysis resistance of the product. In some embodiments, the amount of composite catalyst added can be 0.1 to 2.0% of the total mass of the unsaturated cyclic anhydride-grafted hydrocarbon resin and hydroxyacrylate. Using a composite catalyst can improve reaction efficiency, the purification process is environmentally friendly and efficient, and it is easy to realize industrial production.

[0062] In some embodiments, the polymerization inhibitor is selected from phenolic or phenolic ether polymerization inhibitors. Preferably, the polymerization inhibitor is selected from hydroquinone and p-hydroxyanisole, and the amount added can be 0.5-1.0% of the total mass of the unsaturated cyclic anhydride-grafted hydrocarbon resin and hydroxy acrylate. The polymerization inhibitor can effectively prevent the acrylate monomer from undergoing self-polymerization during the reaction, ensuring product quality.

[0063] In some embodiments, the method further includes a purification step, which may include: adding an organic solvent and activated carbon to the crude product, stirring for 1 to 2 hours, then performing solid-liquid separation to remove solid impurities, obtaining a separated liquid, and then performing vacuum distillation and precision filtration on the separated liquid to obtain an acrylated hydrocarbon resin.

[0064] In some embodiments, the method may further include a packaging step, which may include cooling the purified product to room temperature and sealing the package under nitrogen protection. Packaging may be done in 15 kg / 18L chrome-plated drums or 180 kg / 200L galvanized drums. The packaged product should be stored in a dark, cool, and well-ventilated place, away from fire and heat sources, and must be sealed with nitrogen after opening.

[0065] In some embodiments, the organic solvent is selected from cyclohexane, toluene, and xylene, and its amount can be 10% to 50% of the crude product volume. In some embodiments, the vacuum distillation temperature can be 90 to 150°C, the vacuum degree can be -0.07 to -0.1 MPa, and the time can be 1 to 3 hours. In some embodiments, the precision filtration has a filtration accuracy of 0.22 to 0.45 μm. In some embodiments, the solid-liquid separation method can be centrifugation or filtration, with a centrifugation speed of 3000 to 5000 r / min and a centrifugation time of 10 to 20 minutes. In some embodiments, the amount of activated carbon added can be 1% to 3% of the crude product mass.

[0066] In a third aspect of this disclosure, the use of the acrylated hydrocarbon resin according to the first aspect in the preparation of copper-clad laminate interlayer adhesives, light-curing adhesives, crosslinking agents, interfacial adhesives, mixing aids, polymer coatings, or interfacial compatibilizers is provided.

[0067] Specifically, the acrylated hydrocarbon resin prepared using MPB-L3017 has low viscosity, moderate crosslinking density, high functionality, strong adhesion, and excellent photocuring performance, making it suitable for multiple fields. It is particularly suitable for applications requiring high bonding strength, such as interlayer adhesives for copper-clad laminates, photocuring agents, and compatibilizers for polymer-filled inorganic fillers. The acrylated hydrocarbon resin prepared using MPB-L7017 has high viscosity, high crosslinking density, high functionality, strong adhesion, and excellent photocuring activity, making it suitable for multiple fields. It is particularly suitable for applications requiring high photocuring efficiency and crosslinking density, such as low-dielectric adhesive films, low-dielectric flexible printed circuit boards (FPCs), low-dielectric rigid printed circuit boards (PCBs), and photocurable adhesives. The acrylic esterified hydrocarbon resin prepared by MBS-2006 has moderate viscosity, moderate crosslinking density, low functionality, and moderate bonding performance. Due to its excellent thermal stability containing benzene rings and strong adhesion to benzene ring-containing matrices, it is suitable for many fields, especially for low dielectric circuit boards with requirements for thermal stability, rubber and plastic bonding with metal, polymer bonding with nylon cord / polyester cord, coating and other scenarios.

[0068] In a fourth aspect of this disclosure, an interlayer adhesive for copper-clad laminates is provided, comprising an acrylated hydrocarbon resin as described in the first aspect, preferably comprising an acrylated hydrocarbon resin prepared from MPB-L3017. This resin has high functionality and strong adhesion, significantly improving the interlayer adhesion of copper-clad laminates, meeting the needs of high-end copper-clad laminate manufacturing, and possessing excellent resistance to damp heat and dielectric properties. The formulation can be adjusted according to dielectric requirements to compensate for dielectric differences caused by high functionality.

[0069] In a fifth aspect of this disclosure, a photocurable adhesive is provided, comprising an acrylated hydrocarbon resin as described in the first aspect, preferably comprising an acrylated hydrocarbon resin prepared from MPB-L7017. This resin has a high vinyl content, high viscosity, high crosslinking density, and excellent photocuring efficiency (curing time of 3 to 10 seconds under UV light intensity of 30 mW / cm²), which can improve photocuring efficiency and is suitable for applications such as bonding low-dielectric electronic devices and rapid prototyping. The cured adhesive layer possesses excellent flexibility (elongation at break ≥80%) and resistance to damp heat, meeting the stability requirements for long-term use of electronic devices.

[0070] In a sixth aspect of this disclosure, a coating is provided comprising the acrylated hydrocarbon resin described in the first aspect, preferably comprising the acrylated hydrocarbon resin prepared from MBS-2006. This resin exhibits strong chemical resistance and excellent thermal stability. After film formation, the coating achieves an adhesion grade ≤1 (cross-cut adhesion test) and salt spray resistance ≥1000 hours. It is suitable for surface protection and decoration of various substrates such as metals, plastics, and wood, meeting the high-performance requirements of industrial equipment, automotive parts, and building components.

[0071] This disclosure provides a crosslinking agent comprising an acrylated hydrocarbon resin as described in the first aspect and an auxiliary crosslinking agent. Resins prepared from different matrices can be selected according to the application scenario; among them, MPB-L3017 and MPB-L7017 have high functionality and strong adhesion; MBS-2006 has excellent thermal stability and strong adhesion to butadiene-phenylene compounds. All can be adapted to different needs such as rubber-plastic blending and polymer modification, and can significantly improve the mechanical properties and aging resistance of the blended materials.

[0072] Furthermore, the acrylated hydrocarbon resin disclosed in this paper can also be used in applications such as interfacial adhesives, compounding aids, polymer coatings, and interfacial compatibilizers. As an interfacial adhesive, it can solve the bonding problem between polar and non-polar materials. As a compounding aid, it can improve the processing and mechanical properties of rubber and plastics. As a polymer coating, it can impart excellent weather resistance, water resistance, and adhesion to the coating. As an interfacial compatibilizer, it can improve the compatibility between polymers and inorganic fillers, as well as between different polymers, thereby enhancing the overall performance of composite materials.

[0073] One of the key technological advantages of this disclosure lies in the first-ever precise control of vinyl content from 15% to 75% within an ultra-wide range in an acrylated hydrocarbon resin system. This capability grants unprecedented freedom in the material's performance design, enabling the acquisition of materials ranging from ultra-low dielectric flexible materials to ultra-high crosslinking density rapid-curing materials using the same chemical structure and preparation method. This represents not only a breakthrough in resin synthesis technology but also provides crucial material solutions for fields such as electronic packaging, photopolymer additive manufacturing, and high-frequency communications, demonstrating significant technological innovation and industrial application value.

[0074] Example

[0075] The effects and functions of this disclosure will be described in more detail below through specific embodiments thereof. However, these embodiments are for illustrative purposes only, and the scope of the claims of this disclosure is not defined thereto.

[0076] Example 1

[0077] Using MPB-L3017 (30mol% vinyl content, high grafting rate maleic anhydride-grafted polybutadiene) from Shandong Jingbo Petrochemical Co., Ltd. as the matrix and hydroxypropyl methacrylate as the acrylate monomer, the preparation steps are as follows:

[0078] (1) Pretreatment: Take 100 g of MPB-L3017 and place it in an oven. Heat it at 75°C for 30 minutes until it is in a flowable state. Set aside for later use.

[0079] (2) Esterification reaction: The pretreated MPB-L3017 was added to the reactor, and 28 g of hydroxypropyl methacrylate (matrix to monomer mass ratio 1:0.28, molar ratio of acrylate to maleic anhydride group in MPB-L3017 was 1.1:1, i.e. 10% excess M) was added. After stirring evenly, 1.16 g of composite catalyst (0.77 g of p-toluenesulfonic acid, 0.39 g of triphenylphosphine, 0.4% of total mass) and 1.45 g of hydroquinone (0.5% of total mass) were added. Nitrogen gas was introduced for protection (flow rate 50 mL / min). The reaction temperature was controlled at 85℃, the stirring speed was 300 r / min, and the reaction was carried out for 6 hours to obtain the crude product.

[0080] (3) Purification: Add 25 mL of toluene and 1.5 g of activated carbon (1.2% of the crude product mass) to the crude product, stir for 1.5 hours, centrifuge at 4000 r / min for 15 minutes to separate the solid and liquid and remove solid impurities; vacuum distill the separated liquid at 130℃ and vacuum degree -0.09 MPa for 2.5 hours to remove unreacted hydroxypropyl methacrylate and toluene; after 0.3 μm precision filtration, acrylated hydrocarbon resin is obtained.

[0081] (4) Finished product packaging: Cool the product to room temperature, seal it under nitrogen protection (15 kg / 18L chrome-plated packaging drum), and store it in a light-proof, cool, and ventilated warehouse.

[0082] Example 2

[0083] Using MPB-L7017 (70 mol% vinyl content, high grafting rate maleic anhydride-grafted polybutadiene) from Shandong Jingbo Petrochemical Co., Ltd. as the matrix and hydroxyethyl methacrylate as the acrylate monomer, the preparation steps are as follows:

[0084] (1) Pretreatment: Take 100 g of MPB-L7017 and place it in an oven. Heat it at 85°C for 20 minutes until it is in a flowable state. Set aside for later use.

[0085] (2) Esterification reaction: The pretreated MPB-L7017 was added to the reactor, and 35 g of hydroxyethyl methacrylate (matrix to monomer mass ratio 1:0.35, acrylate slightly excess) was added. After stirring evenly, 1.35 g of composite catalyst (ZSM5 molecular sieve-heteropolyacid solid acid composite catalyst, 0.38% of total mass) and 2.33 g of p-hydroxyanisole (0.5% of total mass) were added. Nitrogen gas was introduced for protection (flow rate 60 mL / min). The reaction temperature was controlled at 95℃, the stirring speed was 400 r / min, and the reaction was carried out for 4.5 hours to obtain crude product.

[0086] (3) Purification: Add 25 mL xylene and 1.5 g activated carbon to the crude product, stir for 1 hour, and separate the solid and liquid by filtration to remove solid impurities; vacuum distill the separated liquid at 130℃ and vacuum degree -0.09 MPa for 2.5 hours to remove unreacted hydroxyethyl methacrylate and xylene; after 0.22 μm precision filtration, acrylated hydrocarbon resin is obtained;

[0087] (4) Finished product packaging: Cool the product to room temperature, seal it under nitrogen protection, and store it in a cool and ventilated warehouse.

[0088] Example 3

[0089] Using MBS-2006 (low vinyl content, low grafting rate maleic anhydride-grafted styrene-butadiene resin) from Shandong Jingbo Petrochemical Co., Ltd. as the matrix and methyl methacrylate as the acrylate monomer, the preparation steps are as follows:

[0090] (1) Pretreatment: Take 100 g of MBS-2006 and place it in an oven. Heat it at 90°C for 25 minutes until it is in a flowable state. Set aside for later use.

[0091] (2) Esterification reaction: The pretreated MBS-2006 was added to the reactor, and 42 g of hydroxymethyl methacrylate (matrix to monomer mass ratio 1:0.42, acrylate slightly excess) was added. After stirring evenly, 1.42 g of composite catalyst (0.95 g of p-toluenesulfonic acid, 0.47 g of triphenylphosphine, 0.32% of total mass) and 2.218 g of hydroquinone (0.5% of total mass) were added. Nitrogen gas was introduced for protection (flow rate 40 mL / min). The reaction temperature was controlled at 105℃, the stirring speed was 250 r / min, and the reaction was carried out for 5 hours to obtain the crude product.

[0092] (3) Purification: Add 35 mL of cyclohexane and 2.5 g of activated carbon (1.8% of the crude product mass) to the crude product, stir for 2 hours, and centrifuge at 3500 r / min for 18 minutes to separate the solid and liquid components and remove solid impurities; vacuum distill the separated liquid at 140℃ and vacuum degree -0.1 MPa for 1.5 hours to remove unreacted methyl methacrylate and cyclohexane; after 0.45 μm precision filtration, acrylated hydrocarbon resin is obtained.

[0093] (4) Finished product packaging: Cool the product to room temperature, seal it under nitrogen protection (15 kg / 18L chrome-plated packaging drum), and store it in a light-proof, cool, and ventilated warehouse.

[0094] Example 4

[0095] The preparation steps were the same as in Example 1, except that the amount of acrylate monomer added was 35 g, with MPB-L3017 and MBS-2006 mixed at a mass ratio of 1:1 as the matrix and hydroxypropyl methacrylate as the acrylate monomer.

[0096] Comparative Example 1

[0097] Using MPB-L3017 produced by Shandong Jingbo Petrochemical Co., Ltd. as a comparative example sample, without acrylate esterification treatment, the performance was tested directly according to the same test method as in Example 1.

[0098] Comparative Example 2

[0099] Using MPB-L7017 produced by Shandong Jingbo Petrochemical Co., Ltd. as a comparative sample, without acrylate esterification treatment, the performance was tested according to the same test method as in Example 2.

[0100] Comparative Example 3

[0101] MBS-2006 produced by Shandong Jingbo Petrochemical Co., Ltd. was used as a comparative sample. Without acrylate esterification treatment, its performance was tested according to the same test method as in Example 3.

[0102] Performance testing

[0103] Functionality was determined according to GB / T 32867-2016; number-average molecular weight and molecular weight distribution were determined according to GB / T 21863-2008; viscosity at 45℃ was determined according to GB / T 10247-2008; vinyl content was determined according to GB / T 28728-2012.

[0104] The acrylic esterified hydrocarbon resin prepared in Example 1 was tested and found to have the following properties: functionality 7 / molecular chain, Mn=8500, Mp / Mn=1.7, vinyl content=32% (M); purity=99.3 wt% (according to GB / T 4498-2017). The functionality was tested using quantitative 1H NMR spectroscopy at room temperature. The functional groups were found to be located on the side chains of the molecular chain; the esterification rate of the maleic anhydride functional groups was ≥98%; after 12 months of storage at 25℃ and 60% relative humidity, there was no surface curing layer, no hardening or brittleness, and excellent hydrolysis resistance; after 500 hours of toluene immersion, the performance retention rate was 94%; it is suitable for copper-clad laminate interlayer adhesive applications, with an interlayer peel strength of 0.627 P / S.

[0105] The acrylic esterified hydrocarbon resin prepared in Example 2 was tested and found to have the following properties: functionality 10 / molecular chain, Mn=12500, Mp / Mn=2.1, vinyl content=62% (M); purity=99.4 wt%; functional groups located on the side chain of the molecular chain; esterification rate of maleic anhydride functional groups ≥97.5%; excellent photocuring efficiency (curing time=5 seconds under UV light intensity of 30mW / cm²); no surface cured layer after 12 months of storage at 25℃ and 60% relative humidity; high photocuring activity, applicable to multiple fields, especially suitable for photocurable adhesives and low dielectric circuit board scenarios (dielectric performance differences need to be compensated by formula adjustments).

[0106] The acrylic esterified hydrocarbon resin prepared in Example 3 was tested and found to have the following properties: functionality 4 / molecular chain, Mn 6000, Mp / Mn 1.5, vinyl content 25% (M); purity 99.1 wt%; functional groups located on the side chain of the molecular chain. Its properties conform to the following characteristics: low vinyl content, low functionality, moderate viscosity and crosslinking density, moderate adhesion, low polarity, and relatively good dielectric properties; due to the presence of a benzene ring, it exhibits excellent thermal stability and strong adhesion to butadiene-phenylene compounds; it has good hydrolysis resistance and is applicable in multiple fields, especially suitable for rubber-plastic bonding and general coating applications. When used as an adhesive at a dosage of 10 phr, it can significantly improve the bonding strength between rubber / plastic and metal.

[0107] The acrylated hydrocarbon resin prepared in Example 4 was tested and found to have the following properties: functionality of 5 / molecular chain to 9 / molecular chain, Mn of 7000, Mp / Mn of 1.7, vinyl content of 30% (M), and purity of 99.2 wt%. Its properties combine the advantages of both matrices, with moderate viscosity and crosslinking density, moderate functionality, and good adhesion. Due to the presence of butyl phenyl groups, it exhibits good thermal stability, making it suitable for multiple applications. It combines adhesive strength and cost advantages, making it particularly suitable for mid-to-high-end general coatings and polymer-filled inorganic filler compatibilizer applications.

[0108] Comparative Examples 1 to 3, after being stored at 25°C and 60% relative humidity for 6 months, all showed a slight curing layer on their surfaces and exhibited hardening. Although they can be applied to some fields, their adaptability is limited, their application range is restricted, and their overall performance is inferior to the product disclosed herein.

[0109] Based on the comparison of Examples 1 to 4 and the comparative examples, the present invention significantly improves the product performance through acrylate modification: the unmodified maleic anhydride grafted hydrocarbon resin showed a surface curing layer and hardening after 6 months of storage and did not have photocuring activity, while the product of the examples disclosed in this invention showed no curing layer after 12 months of storage at 25°C and 60% relative humidity, with a functionality of 4 to 10 / molecular chain, and could be rapidly cured under ultraviolet light.

[0110] In other words, the acrylated hydrocarbon resin prepared in this disclosure not only completely solves the core defects of the original matrix, such as easy hydrolysis, poor storage stability, and limited functionality, but also endows the product with properties such as photocuring activity, high bonding strength, and excellent chemical resistance through performance regulation, achieving an upgrade from a basic additive to a high-performance functional material. The modified product exhibits excellent performance and a wide range of applications, significantly enhancing its overall competitiveness compared to the unmodified original matrix product. Furthermore, the preparation method disclosed in this paper is simple and easy to industrialize, possessing significant technological innovation and industrial application value.

[0111] Although several embodiments of this disclosure have been described and illustrated herein, those skilled in the art will readily contemplate a variety of other ways and / or structures for performing the functions described herein and / or obtaining the results described herein and / or one or more advantages, and each such variation and / or modification is considered to be within the scope of this disclosure.

Claims

1. An acrylated hydrocarbon resin, wherein the acrylated hydrocarbon resin has the following characteristics: The functionality is 1 to 12 per molecular chain, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 to 12 per molecular chain, said functionality being calculated in terms of acrylate groups; The vinyl content of the main chain is 15% to 75%, for example 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% to 75%; Number average molecular weight is 5,000 to 15,000, for example 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 11,000, 12,000, 13,000, 14,000 to 15,000; The molecular weight distribution is from 1.1 to 3.0, for example, 1.1, 1.4, 1.7, 2.0, 2.3, 2.6, 2.8 to 3.0; Viscosities at 45°C ranging from 5000 to 100000 mPa·s, for example, 5000, 6000, 7000, 8000, 10000, 12000, 14000, 16000, 18000 to 100000 mPa·s; and The main molecular chain is a hydrocarbon resin segment, and the functional groups are located on the molecular side chain. Unsaturated cyclic anhydride residues are attached to the side chain, and the unsaturated cyclic anhydride residues are connected to acrylate groups through ester bonds.

2. The acrylated hydrocarbon resin according to claim 1, wherein: The side chain is connected to the unsaturated cyclic anhydride residues by carbon-carbon bonds, and the unsaturated cyclic anhydride residues form a half-ester structure after ring opening; The half-ester structure has a free carboxyl group at one end and an acrylate group containing a carbon-carbon double bond connected to the other end via an ester bond.

3. The acrylated hydrocarbon resin according to claim 1 or 2, wherein the acrylated hydrocarbon resin has the structure of formula (I): (I) in: * indicates the direction of extension of the hydrocarbon resin backbone; n represents the average number of side chain structural units grafted per molecular chain, and n is between 1 and 12; R1 is selected from H, methyl, ethyl, propyl, butyl, or -CH2COOH; A represents a divalent hydrocarbon group selected from C1 to C10, preferably a straight-chain or branched alkylene group from C1 to C6, such as methylene, ethylene, propylene, butylene, and pentylene; R2 is selected from H, methyl, or ethyl; and The hydrocarbon resin segments are derived from homopolymers or copolymers of C2 to C10 monoolefins or C4 to C10 dienes, and the main chain is a saturated or unsaturated segment consisting only of carbon and hydrogen atoms; preferably, the hydrocarbon resin segments are derived from homopolymers or copolymers of C2, C3, C4, C5, C6, C7, C8, C9 to C10 monoolefins or C4, C5, C6, C7, C8, C9 to C10 dienes, such as polybutadiene, styrene-butadiene resin, pentylene-butadiene resin, polyethylene, or polypropylene; more preferably, the hydrocarbon resin segments are derived from polybutadiene and styrene-butadiene resin.

4. The acrylated hydrocarbon resin according to any one of claims 1 to 3, wherein the unsaturated cyclic anhydride is an alkenyl-containing five-membered cyclic anhydride, such as maleic anhydride, itaconic anhydride and citraconic anhydride, more preferably, the unsaturated cyclic anhydride is maleic anhydride.

5. The acrylated hydrocarbon resin according to any one of claims 1 to 4, wherein the acrylate group containing a carbon-carbon double bond is introduced by a hydroxy acrylate through a reaction with the anhydride group or carboxyl group of the unsaturated cyclic anhydride residue; wherein the hydroxy acrylate is selected from hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate.

6. A method for preparing an acrylated hydrocarbon resin according to any one of claims 1 to 5, comprising: Pretreatment: The unsaturated cyclic anhydride-grafted hydrocarbon resin is heated to a fluid state; as well as Esterification reaction: The pretreated unsaturated cyclic anhydride-grafted hydrocarbon resin is reacted with hydroxy acrylate at 70 to 115°C for 3 to 7 hours in the presence of a single catalyst or a composite catalyst and a polymerization inhibitor to obtain the crude product.

7. The method of claim 6, wherein the method further comprises a purification step, the purification step comprising: Organic solvent and activated carbon are added to the crude product, and the mixture is stirred for 1 to 2 hours. Then, solid-liquid separation is performed to remove solid impurities, and the separated liquid is obtained. The separated liquid is then vacuum distilled and then finely filtered to obtain the acrylated hydrocarbon resin.

8. The method according to claim 6 or 7, wherein it satisfies one or more of the following: The mass ratio of the unsaturated cyclic anhydride-grafted hydrocarbon resin to the hydroxyl acrylate is 1:0.2 to 0.9; The composite catalyst is selected from a mixture of acidic catalyst and organophosphorus compound, or a mixture of molecular sieve and heteropoly acid; preferably, the composite catalyst is selected from a mixture of p-toluenesulfonic acid and triphenylphosphine, or a mixture of ZSM5 molecular sieve and heteropoly acid; the addition amount is 0.1 to 2.0% of the total mass of the unsaturated cyclic anhydride-grafted hydrocarbon resin and the hydroxyacrylate; The polymerization inhibitor is selected from phenolic or phenolic ether polymerization inhibitors, preferably hydroquinone and p-hydroxyanisole, and the amount added is 0.5% to 1% of the total mass of the unsaturated cyclic anhydride-grafted hydrocarbon resin and the hydroxy acrylate; The organic solvent is selected from cyclohexane, toluene, and xylene, and is added in an amount of 10% to 50% of the volume of the crude product. The vacuum distillation is performed at a temperature of 90 to 150°C, a vacuum level of -0.07 to -0.1 MPa, and a time of 1 to 3 hours; and The precision filter has a filtration accuracy of 0.22 to 0.45 μm.

9. The use of the acrylated hydrocarbon resin according to any one of claims 1 to 5 in the preparation of copper-clad laminate interlayer adhesives, light-curing adhesives, crosslinking agents, interfacial adhesives, mixing aids, polymer coatings, or interfacial compatibilizers.

10. A copper-clad laminate interlayer adhesive comprising an acrylated hydrocarbon resin according to any one of claims 1 to 5.

11. A light-curing adhesive comprising an acrylated hydrocarbon resin according to any one of claims 1 to 5.

12. A coating comprising an acrylated hydrocarbon resin according to any one of claims 1 to 5.

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