Method and application of introducing Si-O bond compounds into petroleum resin to improve processing rheological properties

Abstract

This invention, applicable to the field of polymer synthesis, provides a method and application for introducing Si-O bond compounds into petroleum resins to improve processing rheological properties. The method comprises a base resin based on petroleum resin, a modifier containing Si-O bond polysiloxane in an amount of 1% to 50%, and an initiator containing an organic peroxide in an amount of 0.1% to 12% by weight of the total weight of the raw materials. Free radical graft polymerization is performed using hot-melt bulk polymerization or solution polymerization to prepare the Si-O bond polysiloxane-modified petroleum resin. This method aims to address the technical problem of poor rheological properties of existing petroleum resins and various modified products during compounding, processing, and application.

Description

Technical Field

[0001] The invention belongs to the field of polymer synthesis, and in particular relates to a method for introducing Si-O bond compounds into petroleum resin to improve processing rheological properties and application thereof. Background Art

[0002] Petroleum resin is a low-molecular-weight thermoplastic hydrocarbon resin material, typically produced through thermal polymerization or cationic polymerization. Petroleum resin can be a viscous liquid or solid, with a relative molecular mass generally ranging from 300 to 3000. Depending on the monomers used and the reaction conditions, the resulting petroleum resin can range in color from colorless and transparent to light yellow or even dark brown. Without hydrogenation, resins prepared from pure monomers tend to be colorless and transparent, while those produced from C5 components tend to be light yellow, and those produced from C9 components tend to be darker.

[0003] Resins prepared from petroleum cracking components C5 and C9, or cyclopentadiene therein, and their combination with styrene, methyl styrene, and other raw materials primarily include: aliphatic petroleum resins prepared from the C5 component as the primary raw material. These petroleum resins are generally pale yellow to yellow, translucent, or transparent solids with a bromine value of 20-50 gBr / 100g. Also known as C5 petroleum resins, they are non-polar polymers with excellent solubility. Aromatic petroleum resins, formed by the polymerization of the C9 component, are similar to coumarone resins. The C9 fraction has a very complex composition, with two main active components: monofunctional styrene and methyl styrene, and difunctional dicyclopentadiene and methyl dicyclopentadiene. Aromatic petroleum resins generally have a bromine value of 20-50 gBr / 100g, exhibit high melt temperatures, high peel strength, good quick tack, and stable adhesive properties. Resins made from dicyclopentadiene, also known as dicyclopentadiene petroleum resins, typically have high softening points and good viscosity-increasing properties. However, these resins are highly unsaturated and thermally reactive, but their stability is poor, making them unsuitable for direct use. They are often modified through chemical grafting to produce other high-end resins. In addition to the three types of resins mentioned above, there are also C5 / C9 copolymer petroleum resins, which combine the excellent properties of both C5 and C9 petroleum resins, offering better overall performance. They have a higher bromine number than C9 petroleum resin and exhibit excellent solubility in both polar and non-polar polymers.

[0004] Petroleum resins have low surface energy, resistance to water and other polar chemicals, excellent chemical and thermal stability, and good miscibility with polyolefin materials. Petroleum resins are generally not used alone, but are often used as a viscosity regulator or modifier, often in combination with other resins. They are widely used in hot melt adhesives, pressure-sensitive adhesives, coatings, paints, and rubber tire industries.

[0005] In view of the low surface polarity of the structure of petroleum resin, people have carried out relevant work on modified petroleum resin. For example, patents CN202210895331.0, CN201811244441.0 and CN00129199.8 respectively use epoxy-modified petroleum resin, water-based alkyd-modified petroleum resin and alkylphenol-modified petroleum resin to prepare oil-based epoxy asphalt colored pavement anti-skid coating, water-dispersion modified resin with better stability and ink binder resin; patents CN202010624685.2, CN101891863A and CN2016112429873 respectively use hydroxyl-modified petroleum resin, styrene-modified C5 petroleum resin and rosin-modified C9 petroleum resin to prepare modified petroleum resin materials used in ship coatings, etc.

[0006] Patent CN96192384.9 uses a small-molecule silane-modified petroleum resin to prepare a hot-melt adhesive composition suitable for road markings. This composition improves the adhesion of glass beads to the road surface and prolongs their service life. Patent CN201810721752.5 uses a mixture of various dienes, monoolefins, and alkanes with a very low cyclopentadiene content, obtained by removing cyclopentadiene and dicyclopentadiene, as a raw material. Using one or more aromatic vinyl monomers as polymerization modifiers, the resulting modified petroleum resin exhibits stable quality, excellent performance, a moderate molecular weight, a light color, and a low softening point.

[0007] Petroleum resins are widely used in various adhesive materials due to their high peel strength and stable adhesive properties. However, when compounding with polyolefin materials to create hot-melt adhesives or pressure-sensitive adhesives, petroleum resins and their modified products suffer from poor processing fluidity and insufficient wettability at the material interface. Summary of the Invention

[0008] The purpose of the present invention is to provide a method and application of introducing Si-O bond compounds into petroleum resin to improve processing rheological properties, aiming to solve the technical problem of poor rheological properties of existing petroleum resins and various modified products during compounding, processing and application.

[0009] The present invention is achieved by introducing a Si-O bond compound into a petroleum resin to improve processing rheological properties. The method comprises: using a base resin based on the petroleum resin, a modifier containing Si-O bond polysiloxane in an amount of 1% to 50%, and an initiator containing an organic peroxide in an amount of 0.1% to 12% by weight of the total weight of the raw materials; and performing free radical graft polymerization by hot melt bulk polymerization or solution polymerization to prepare a petroleum resin modified with Si-O bond polysiloxane.

[0010] A further technical solution of the present invention is that the method further comprises adding 0.5%-10% of an acrylic acid ester compound having a functional tackifying monomer, and performing free radical graft polymerization by hot melt bulk polymerization or solution polymerization to prepare Si-O bond-containing polysiloxane and acrylic acid ester-modified petroleum resin.

[0011] A further technical solution of the present invention is that the petroleum resin is C5 petroleum resin or C9 petroleum resin or C5 / C9 copolymerized petroleum resin or a copolymerized resin of styrene or methylstyrene with C5 component or C9 component or a mixed resin of two or more thereof.

[0012] A further technical solution of the present invention is that the polysiloxane containing Si-O bonds is dimethyl polysiloxane or vinyl polysiloxane, and the amount of the polysiloxane containing Si-O bonds is 1%-20%.

[0013] A further technical solution of the present invention is that the amount of the polysiloxane containing Si-O bonds is 1%-15%.

[0014] A further technical solution of the present invention is that the organic peroxide is an acyl peroxide or a di-tert-alkyl peroxide, including dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, and di-tert-butyl peroxide.

[0015] A further technical solution of the present invention is that the acrylic acid ester compound includes ethyl acrylate, isopropyl acrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate; and the amount of the acrylic acid ester compound is 0.5%-5%.

[0016] A further technical solution of the present invention is that the hot melt bulk polymerization method is to blend the petroleum resin, the modifier and the initiator, and then slowly heat the mixture to melt the petroleum resin under the condition of inert gas isolation, and then initiate free radical graft polymerization under the action of the initiator; when the initiator is dibenzoyl peroxide or dilauroyl peroxide, the polymerization reaction temperature is controlled at 70-100°C, and the polymerization reaction time is 1-5 hours; when the initiator is dicumyl peroxide or di-tert-butyl peroxide, the polymerization reaction temperature is controlled at 90-140°C, and the polymerization reaction time is 1-5 hours. After the reaction, low-boiling substances are further removed under vacuum conditions to prepare a polysiloxane-modified petroleum resin containing Si-O bonds. The solution polymerization method is to add an appropriate amount of solvent to the petroleum resin, the modifier and the initiator to mix them, and in an inert gas-isolated atmosphere, the mixed solution undergoes a free radical graft polymerization reaction, and after the reaction, low-boiling substances are further removed under vacuum conditions to prepare a polysiloxane-modified petroleum resin containing Si-O bonds. The solvent is an aliphatic hydrocarbon, petroleum ether, a halogenated hydrocarbon, toluene or xylene, and the amount of the solvent is 20%-100% by weight of the total weight of the reaction raw materials.

[0017] A further technical solution of the present invention is that the hot melt bulk polymerization method is to blend the petroleum resin, the modifier, the initiator and the acrylate compound, and then slowly heat the mixture to melt the petroleum resin under the condition of isolating the air with an inert gas, and then initiate free radical graft polymerization under the action of the initiator; when the initiator is dibenzoyl peroxide or dilauroyl peroxide, the polymerization reaction temperature is controlled at 70-100°C and the polymerization reaction time is 1-5 hours; when the initiator is dicumyl peroxide or di-tert-butyl peroxide, the polymerization reaction temperature is controlled at 90-140°C and the polymerization reaction time is 1-5 hours, and the reaction is then carried out under vacuum conditions after the reaction is completed. Low-boiling substances are removed in one step to prepare Si-O bond-containing polysiloxane-modified petroleum resin; the solution polymerization method is to add an appropriate amount of solvent to the petroleum resin, a modifier, an initiator and an acrylate compound to mix and dissolve them, and in an inert gas-isolated atmosphere, the mixed solution is subjected to a free radical graft polymerization reaction, and after the reaction is completed, the low-boiling substances are further removed under vacuum conditions to prepare Si-O bond-containing polysiloxane and acrylate-modified petroleum resin, and the solvent is recycled during the solution polymerization. The solvent is an aliphatic hydrocarbon, petroleum ether, a halogenated hydrocarbon, toluene or xylene, and the amount of the solvent used is 20%-100% of the total weight of the reaction raw materials.

[0018] Another object of the present invention is to provide an application of a polymer prepared by a method of introducing Si-O bond compounds into a petroleum resin to improve processing rheological properties. The prepared Si-O bond-containing polysiloxane-modified petroleum resin or Si-O bond-containing polysiloxane and acrylate-modified petroleum resin can be used to prepare hot melt adhesives or pressure-sensitive adhesives with polyolefin thermoplastic elastomers.

[0019] The beneficial effects of the present invention are as follows: when the method prepares Si-O bond-containing polysiloxane-modified petroleum resin or Si-O bond-containing polysiloxane and acrylate-modified petroleum resin by hot-melt bulk polymerization, the reaction is solvent-free, the process route is environmentally friendly, safe, and does not produce any three wastes; when the method prepares Si-O bond-containing polysiloxane-modified petroleum resin or Si-O bond-containing polysiloxane and acrylate-modified petroleum resin by solution polymerization, the amount of solvent used is small, and the solvent can be recovered and recycled, without any three wastes being discharged; and the prepared polymer has a lower melting temperature, is easier to hot-melt process, and has good fluidity. By changing the amount of Si-O bond-containing polysiloxane introduced, the melt index and melt flow rate of the resin can be adjusted and improved, and it is suitable for the processing and application of products in different application scenarios; in addition, the prepared polymer also has the characteristics of good thermal oxidation stability, is not prone to color change, has good adhesive wettability, and stable adhesive performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 1 is a rheological curve diagram of the C5 petroleum resin provided in the embodiment of the present invention and the samples of Examples 1 to 5;

[0021] Figure 2 1 is a rheological curve diagram of the C9 petroleum resin provided in the embodiment of the present invention and samples of Examples 6 to 10;

[0022] Figure 3 1. The shear tensile test curves of the SBS-based hot melt adhesive reference example and the bonding samples of Examples 11 to 13 provided in the embodiments of the present invention are shown;

[0023] Figure 4 This is a shear tensile test curve of the EVA-based hot melt adhesive reference example and the bonding sample of Example 14 provided in the embodiments of the present invention. DETAILED DESCRIPTION

[0024] The present invention provides a method for improving processing rheological properties by introducing Si-O bond compounds into petroleum resin. The method comprises the following steps: using a base resin based on petroleum resin, a modifier containing Si-O bond polysiloxane in an amount of 1% to 50%, and an initiator containing an organic peroxide in an amount of 0.1% to 12% by weight of the total weight of the raw materials; and performing free radical graft polymerization by hot melt bulk polymerization or solution polymerization to prepare a petroleum resin modified with Si-O bond polysiloxane. While the properties and performance of the petroleum resin are basically unchanged, the modified petroleum resin exhibits significant changes in rheological properties as the amount of Si-O bond polysiloxane introduced into the petroleum resin increases, which is mainly manifested in an increase in melt flow rate (MFR) and melt index (MFI) under a certain stress. In addition, the petroleum resin melts at a lower temperature when the Si-O bond polysiloxane is introduced into the petroleum resin, making it easier to hot melt process.

[0025] The method further comprises adding 0.5% to 10% of an acrylic acid ester compound having a functional tackifying monomer, and performing free radical graft polymerization by a hot melt bulk polymerization method or a solution polymerization method to prepare a Si-O bond-containing polysiloxane and an acrylic acid ester-modified petroleum resin. When an appropriate amount of Si-O bond polysiloxane is introduced into the petroleum resin, and in particular, a small amount of acrylic acid ester is introduced, the water contact angle of the modified petroleum resin is reduced, the hydrophilicity of the material interface is enhanced, and the adhesion of the modified material is not adversely affected.

[0026] Si-O bond-containing polysiloxane compounds, such as silicone oil, contain both the "organic group" Si-R and the "inorganic structure" Si-O bonds. This unique composition and molecular structure combine the properties of organic compounds with the functions of inorganic compounds. Compared with general organic resins, in addition to excellent heat resistance, electrical insulation, and weather resistance, they also have a low viscosity-temperature coefficient, excellent thermal and oxygen stability, excellent low-temperature fluidity, low volatility, and are flame retardant, non-toxic, and non-corrosive. Therefore, by introducing a certain amount of Si-O bond-containing silicone oil into the structure of petroleum resin, Si-O bond-containing polysiloxane-modified petroleum resin is prepared. This effectively improves the rheological properties of the modified resin and facilitates the processing flowability of petroleum resin compound products. By adjusting the amount of Si-O bond-containing polysiloxane introduced into the petroleum resin structure, the rheological properties of the modified resin can be effectively controlled. Introducing a small amount of acrylate compound into the petroleum resin structure while introducing the Si-O bond-containing polysiloxane further improves the adhesion of the modified petroleum resin. In addition, the introduction of polysiloxane containing Si-O bonds into the structure of petroleum resin can also significantly improve the thermal and oxygen stability of petroleum resin.

[0027] The petroleum resin is one or more of C5 petroleum resin, C9 petroleum resin, C5 / C9 copolymerized petroleum resin, or copolymerized resins of styrene or methylstyrene and C5 component or C9 component.

[0028] The Si-O bond-containing polysiloxane is dimethyl polysiloxane (methyl silicone oil) or vinyl-containing polysiloxane (including vinyl-terminated polysiloxane and polysiloxane containing vinyl groups in non-vinyl-terminated segments). The amount of the Si-O bond-containing polysiloxane is 1%-20%. The amount of the Si-O bond-containing polysiloxane is 1%-15%. The Si-O bond-containing polysiloxane is a modified silicone oil, and its suitable amount is 1%-20%, with an optimal amount being 1%-15%.

[0029] The organic peroxide is an acyl peroxide or a di-tert-alkyl peroxide, including dibenzoyl peroxide (BPO), dilauroyl peroxide (LPO), dicumyl peroxide (DCP), and di-tert-butyl peroxide (DTBP). The suitable initiation temperature for BPO is 70-100°C, with a half-life of 10 minutes to several hours; the suitable initiation temperature for DCP is 90-150°C, with a half-life of 10 minutes to several hours. The free radicals generated by both have strong hydrogen abstraction capabilities, making it easy to regulate the polymerization reaction. Therefore, BPO or DCP is the more suitable initiator for the reaction system.

[0030] The acrylic acid ester compounds include ethyl acrylate, isopropyl acrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate; the acrylic acid ester compounds are used in an amount of 0.5% to 5%. To improve the decreased adhesive properties caused by the introduction of Si-O bond-containing polysiloxane into the petroleum resin, a functional tackifying monomer is introduced into the reaction system for adjustment. The functional tackifying monomer is an acrylic acid ester compound, including butyl acrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate, with hydroxyethyl acrylate and hydroxypropyl acrylate being preferred.

[0031] During the preparation process, the free graft polymerization reaction between the petroleum resin and the modifier, or between the modifier and the acrylate compound, can adopt the hot melt bulk polymerization method or the solution polymerization method. When the hot melt bulk polymerization process is adopted, the reaction materials are the petroleum resin, the modifier or the modifier and the acrylate compound and the initiator, and the free radical graft polymerization is carried out under hot melt conditions; when the solution polymerization process is adopted, in addition to the above-mentioned hot melt bulk polymerization raw materials, some solvents are added. The solvents used include: aliphatic hydrocarbons, petroleum ether, halogenated hydrocarbons, toluene, xylene, etc. Petroleum ether or toluene is used as the solvent. The chain transfer constant of the two is small and it is more economical; the amount of solvent used is 20%-100% of the total weight of the reaction raw materials. As the amount of solvent used increases, the efficiency of the free radical graft reaction decreases. The appropriate amount of solvent used is 20%-50% of the total weight of the reaction raw materials.

[0032] The hot melt bulk polymerization method is to mix the petroleum resin, the modifier and the initiator, and then slowly heat the mixture to melt the petroleum resin under the condition of inert gas isolation, and then initiate free radical graft polymerization under the action of the initiator; when the initiator is dibenzoyl peroxide or dilauroyl peroxide, the polymerization reaction temperature is controlled at 70-100°C and the polymerization reaction time is 1-5 hours; when the initiator is dicumyl peroxide or di-tert-butyl peroxide, the polymerization reaction temperature is controlled at 90-140°C and the polymerization reaction time is 1-5 hours, and the reaction is completed in a vacuum oven. The low-boiling-point substance is further removed under the conditions to prepare the Si-O bond-containing polysiloxane-modified petroleum resin; the solution polymerization method is to add an appropriate amount of solvent to the petroleum resin, the modifier and the initiator to mix and dissolve, and in the presence of an inert gas to isolate the air, the mixed solution undergoes a free radical graft polymerization reaction, and after the reaction is completed, the low-boiling-point substance is further removed under vacuum conditions to prepare the Si-O bond-containing polysiloxane-modified petroleum resin, the solvent is aliphatic hydrocarbons or petroleum ether or halogenated hydrocarbons or toluene or xylene, and the amount of the solvent is 20%-100% by weight of the total weight of the reaction raw materials.

[0033] The hot melt bulk polymerization method comprises the following steps: blending petroleum resin, a modifier, an initiator and an acrylate compound, slowly heating the mixture to melt the petroleum resin under an inert gas-isolated atmosphere, and then initiating free radical graft polymerization under the action of the initiator; when the initiator is dibenzoyl peroxide or dilauroyl peroxide, the polymerization reaction temperature is controlled at 70 to 100° C. and the polymerization reaction time is 1 to 5 hours; when the initiator is dicumyl peroxide or di-tert-butyl peroxide, the polymerization reaction temperature is controlled at 90 to 140° C. and the polymerization reaction time is 1 to 5 hours; and after the reaction is completed, low-boiling substances are further removed under vacuum conditions. , preparing a Si-O bond-containing polysiloxane-modified petroleum resin; the solution polymerization method is to add a proper amount of solvent to the petroleum resin, a modifier, an initiator and an acrylate compound and dissolve them in it, and in an inert gas-isolated atmosphere, the mixed solution undergoes a free radical graft polymerization reaction, and after the reaction is completed, low-boiling substances are further removed under vacuum conditions to prepare a Si-O bond-containing polysiloxane and an acrylate-modified petroleum resin, and the solvent is recycled during the solution polymerization, wherein the solvent is an aliphatic hydrocarbon, petroleum ether, a halogenated hydrocarbon, toluene or xylene, and the amount of the solvent used is 20%-100% of the total weight of the reaction raw materials.

[0034] Inert gas is used to isolate the air during the polymerization reaction. On the one hand, it improves the reaction efficiency, and on the other hand, it prevents the petroleum resin from thermal oxidation and discoloration during the reaction. Ordinary nitrogen or high-purity nitrogen can be introduced into the reaction system for protection.

[0035] A method for improving processing rheological properties by introducing Si-O bond compounds into petroleum resins is disclosed. The prepared Si-O bond-modified polysiloxane-containing petroleum resin or Si-O bond-polysiloxane and acrylate-modified petroleum resin can be used to prepare hot melt adhesives or pressure-sensitive adhesives with polyolefin thermoplastic elastomers. The prepared Si-O bond-modified polysiloxane-containing petroleum resin or Si-O bond-polysiloxane and acrylate-modified petroleum resin can be used as a viscosity-enhancing component in the preparation of hot melt adhesives or pressure-sensitive adhesives, significantly improving the fluidity during the preparation process and the application process. Specifically, the hot melt adhesive is prepared using thermoplastic elastomers SBS or EVA as the base polymer for the hot melt adhesive, resulting in excellent fluidity.

[0036] When the method prepares Si-O bond-containing polysiloxane-modified petroleum resin or Si-O bond-containing polysiloxane and acrylate-modified petroleum resin by hot-melt bulk polymerization, the reaction is solvent-free, the process route is environmentally friendly, safe, and does not produce any three wastes; when the Si-O bond-containing polysiloxane-modified petroleum resin or Si-O bond-containing polysiloxane and acrylate-modified petroleum resin is prepared by solution polymerization, the amount of solvent used is small, and the solvent can be recovered and recycled, without any three wastes being discharged; and the prepared polymer has a lower melting temperature, is easier to hot-melt process, and has good fluidity. By changing the introduction amount of Si-O bond-containing polysiloxane, the melt index and melt flow rate of the resin can be adjusted and improved, and is suitable for the processing and application of products in different application scenarios; in addition, the prepared polymer also has the characteristics of good thermal oxidation stability, is not prone to color change, has good adhesive wettability, and stable adhesive performance.

[0037] The invention will be described with reference to specific embodiments.

[0038] Example 1 to Example 5.

[0039] Examples 1 to 5 are implemented using a solution polymerization process, and the formulation compositions of each example are shown in Table 1 below.

[0040] The specific preparation process is as follows:

[0041] In a reactor equipped with a stirring device, a reflux condenser, a nitrogen protection device and a thermometer, a certain amount of a certain enterprise's C5 petroleum resin, methyl silicone oil, acrylate and petroleum ether were weighed and placed in the reactor. After nitrogen replacement for 10 minutes, the mixture was stirred and slowly heated to about 50°C. After the resin was completely dissolved, the mixture was gradually heated to 70°C and stirred for 4 hours. After that, the reaction temperature was further increased to 100°C, and the stirring reaction was continued for 1 hour. The reaction was then completed.

[0042] Afterwards, the reflux condenser was replaced with a vacuum distillation device, the pressure was reduced to -0.095 MPa, and the temperature was gradually raised to 150°C to remove the solvent and low-molecular compounds to obtain Si-O bond-containing polysiloxane-modified petroleum resin, with the product yield being above 98%.

[0043] The relevant performance test results of the obtained modified petroleum resin product are shown in Table 1 below.

[0044] Table 1. Formula composition and performance test results of each embodiment

[0045]

[0046] Note: In Examples 1 to 3, dimethyl silicone oil is used, and the acrylate is hydroxyethyl acrylate; in Examples 4 and 5, low vinyl methyl silicone oil is used, and the acrylate is hydroxypropyl acrylate.

[0047] The performance test results of the modified petroleum resins of Examples 1 to 5 (see Table 1 and Figure 1 ) showed that: with the increase of the amount of Si-O bond-containing polysiloxane introduced, the melt index and melt flow rate of the silicone petroleum resin increased significantly; with the increase of acrylate introduced, the water contact angle decreased significantly.

[0048] Example 6 to Example 10.

[0049] Examples 6 to 10 are implementation methods using a hot melt bulk polymerization process, and the formulation compositions of each example are shown in Table 2 below.

[0050] The specific preparation process is as follows:

[0051] In a reactor equipped with a stirring device, a reflux condenser, a nitrogen protection device and a thermometer, a certain amount of a certain enterprise's C9 petroleum resin, methyl silicone oil and acrylate were weighed and placed in the reactor. After nitrogen replacement for 10 minutes, the mixture was stirred and slowly heated to about 80°C. After the resin was completely melted, the mixture was gradually heated to 90°C and stirred for reaction for 2 hours. After that, the reaction temperature was further increased to 120°C and the stirring reaction was continued for 1 hour. The reaction temperature was further increased to 140°C and the stirring reaction was continued for 1 hour, and the reaction was completed.

[0052] The reflux condenser was replaced with a vacuum distillation device, the pressure was reduced to -0.095 MPa, and the temperature was gradually raised to 150°C to remove the solvent and low molecular weight compounds to obtain Si-O bond-containing polysiloxane modified petroleum resin, with a product yield of more than 99%.

[0053] The relevant performance test results of the obtained modified petroleum resin product are shown in Table 2 below.

[0054] Table 2. Formula composition and performance test results of each embodiment

[0055]

[0056] Note: In Examples 6 to 10, dimethyl silicone oil is used, and the acrylate is hydroxyethyl acrylate; in Examples 4 to 5, low vinyl methyl silicone oil is used, and the acrylate is hydroxypropyl acrylate.

[0057] The performance test results of the modified petroleum resins of Examples 6 to 10 (see Table 2 and Table 3) Figure 2 ) showed that: with the increase of the amount of Si-O bond-containing polysiloxane introduced, the melt index and melt flow rate of the silicone-modified petroleum resin increased significantly; with the increase of acrylate introduced, the water contact angle decreased significantly.

[0058] The prepared Si-O bond-containing polysiloxane-modified petroleum resin, or Si-O bond-containing polysiloxane and acrylate-modified petroleum resin, can be used to prepare hot melt adhesives. Specifically, the Si-O bond-containing polysiloxane-modified petroleum resin and a thermoplastic elastomer are hot-melt blended according to the formula in the table below to prepare the hot melt adhesive, and the performance of the hot melt adhesive is tested.

[0059] Example 11 to Example 13.

[0060] Baling Petrochemical's styrene-butadiene-styrene ternary block polymer SBS YH792 (i.e., SBS1401) was used as the hot melt adhesive base polymer. Four hot melt adhesives compounded with a Si-O bond-containing polysiloxane-modified C5 petroleum resin series were prepared according to the basic formula in Table 3.

[0061] The specific preparation process is as follows:

[0062] In a mixing kettle equipped with a stirring device and a temperature control device, a certain amount of styrene-butadiene-styrene ternary block polymer, petroleum resin or silicon-modified resin, cyclohexane oil and antioxidant are weighed and placed in the mixing kettle. Under stirring conditions, they are gradually heated until the materials are completely melted. After they are completely mixed, hot melt adhesive is obtained and the materials are discharged.

[0063] Polypropylene strapping tape with a specification of 100mm*10mm*0.5mm was used as the bonding specimens. Every five pairs of bonding specimens formed an experimental group. The specimens were bonded at room temperature and then subjected to a pressure of 5.0MPa for 4 hours before being tested.

[0064] Table 3. Preparation formula of SBS-based hot melt adhesive

[0065]

[0066] The bonded polypropylene PP binding tape strips were tested in accordance with GB / T 1040.1-2018 Determination of tensile properties of plastics Part 3 Test conditions for film and sheeting. The tensile shear strength-tensile deformation rate test curve is shown in Figure 3 .

[0067] The tensile shear strength-tensile deformation rate test results of the SBS-based hot melt adhesive preparation formulas of Example 11 to Example 13 (see Figure 3) shows that: compared with the hot melt adhesive prepared with SBS base and C5 petroleum resin of a certain enterprise (reference example), the hot melt adhesive prepared with SBS base and the modified petroleum resin of Example 3 and Example 5 (corresponding to Example 11 and Example 12), the appropriate introduction of modified silicone oil and acrylate can greatly improve the processing performance of the hot melt adhesive while still maintaining good bonding performance. When the modified petroleum resin introduces a high content of silicone oil, it is easy to cause the bonding strength of the hot melt adhesive to decrease. In Example 13, the modified petroleum resin prepared with C9 petroleum resin of Example 6 is used. Since the bonding performance of C9 petroleum resin itself is better than that of C5 petroleum resin, the hot melt adhesive prepared with an appropriate amount of silicone oil modified C9 petroleum resin still maintains good bonding performance.

[0068] Example 14.

[0069] Ethylene-vinyl acetate copolymer EVA310 from Mitsui of Japan was used as the base polymer for hot melt adhesive, and a hot melt adhesive containing Si-O bonded polysiloxane-modified C9 petroleum resin series was prepared according to the basic formula in Table 4.

[0070] The specific preparation process is as follows:

[0071] In a mixing kettle equipped with a stirring device and a temperature control device, a certain amount of ethylene-vinyl acetate copolymer, petroleum resin or silicon-modified resin, cyclohexane oil and antioxidant are weighed and placed in the mixing kettle. Under stirring conditions, they are gradually heated until the materials are completely melted. After they are completely mixed, hot melt adhesive is obtained and the materials are discharged.

[0072] Polypropylene strapping tape with a specification of 100mm*10mm*0.5mm was used as the bonding specimens. Every five pairs of bonding specimens formed an experimental group. The specimens were bonded at room temperature and then subjected to a pressure of 5.0MPa for 4 hours before being tested.

[0073] Table 4. EVA-based hot melt adhesive preparation formula

[0074]

[0075] The bonded polypropylene PP binding tape strips were tested in accordance with GB / T 1040.1-2018 Plastics - Determination of tensile properties - Part 3 - Test conditions for film and sheeting. The tensile shear strength-tensile deformation rate test curve is shown in Figure 3 .

[0076] The tensile shear strength-tensile deformation rate test results of the EVA-based hot melt adhesive preparation formula of Example 14 (see Figure 4) shows that: compared with the hot melt adhesive prepared by using EVA as the base and C9 petroleum resin of a certain enterprise (reference example), the hot melt adhesive prepared by using EVA as the base and the modified petroleum resin of Example 8 (corresponding to Example 13), the introduction of appropriate amounts of modified silicone oil and acrylate can greatly improve the processing performance of the hot melt adhesive while still maintaining good bonding performance.

[0077] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for improving processing rheological properties of petroleum resin by introducing Si-O bond compounds, characterized in that: The method comprises the following steps: preparing a base resin based on petroleum resin, a modifier containing Si-O bond polysiloxane in an amount of 1% to 50%, and an initiator containing an organic peroxide in an amount of 0.1% to 12% of the total weight of the raw materials; and preparing a Si-O bond polysiloxane-modified petroleum resin through a free radical graft polymerization reaction by adopting a hot melt bulk polymerization method or a solution polymerization method. The modified petroleum resin has an improved melt index, an increased melt flow rate, and a reduced melting temperature.

2. The method according to claim 1, characterized in that The method further comprises adding 0.5% to 10% of an acrylic acid ester compound having a functional tackifying monomer, and performing free radical graft polymerization by hot melt bulk polymerization or solution polymerization to prepare Si-O bond-containing polysiloxane and acrylic acid ester modified petroleum resin.

3. The method according to claim 2, characterized in that The petroleum resin is one or more of C5 petroleum resin, C9 petroleum resin, C5 / C9 copolymerized petroleum resin, or copolymerized resins of styrene or methylstyrene and C5 component or C9 component.

4. The method according to claim 3, characterized in that The Si-O bond-containing polysiloxane is dimethyl polysiloxane or vinyl-containing polysiloxane, and the amount of the Si-O bond-containing polysiloxane is 1%-20%.

5. The method according to claim 4, characterized in that The amount of the Si-O bond-containing polysiloxane is 1%-15%.

6. The method according to claim 5, characterized in that The organic peroxide is an acyl peroxide or a di-tert-alkyl peroxide, including dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, and di-tert-butyl peroxide.

7. The method according to claim 6, characterized in that The acrylic acid ester compound includes ethyl acrylate, isopropyl acrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate; the amount of the acrylic acid ester compound is 0.5%-5%.

8. The method according to any one of claims 5-6, characterized in that The hot melt bulk polymerization method is to mix the petroleum resin, the modifier and the initiator, and then slowly heat the mixture to melt the petroleum resin under the condition of inert gas isolation, and then initiate free radical graft polymerization under the action of the initiator; when the initiator is dibenzoyl peroxide or dilauroyl peroxide, the polymerization reaction temperature is controlled at 70-100°C, and the polymerization reaction time is 1-5 hours; when the initiator is dicumyl peroxide or di-tert-butyl peroxide, the polymerization reaction temperature is controlled at 90-140°C, and the polymerization reaction time is 1-5 hours, and the reaction is completed in a vacuum oven. The low-boiling-point substance is further removed under the conditions to prepare a polysiloxane-modified petroleum resin containing Si-O bonds; the solution polymerization method is to add an appropriate amount of solvent to the petroleum resin, the modifier and the initiator to mix and dissolve, and in an inert gas isolating the air, the mixed solution is subjected to a free radical graft polymerization reaction, and the low-boiling-point substance is further removed under vacuum conditions after the reaction is completed to prepare a polysiloxane-modified petroleum resin containing Si-O bonds, the solvent is aliphatic hydrocarbons or petroleum ether or halogenated hydrocarbons or toluene or xylene, and the amount of the solvent is 20%-100% of the total weight of the reaction raw materials.

9. The method according to any one of claims 5 to 7, characterized in that: The hot melt bulk polymerization method comprises the following steps: blending petroleum resin, a modifier, an initiator and an acrylate compound, slowly heating the mixture to melt the petroleum resin under an inert gas-isolated atmosphere, and then initiating free radical graft polymerization under the action of an initiator; when the initiator is dibenzoyl peroxide or dilauroyl peroxide, the polymerization reaction temperature is controlled at 70-100° C. and the polymerization reaction time is 1-5 hours; when the initiator is dicumyl peroxide or di-tert-butyl peroxide, the polymerization reaction temperature is controlled at 90-140° C. and the polymerization reaction time is 1-5 hours; and after the reaction is completed, low-boiling substances are further removed under vacuum conditions. , preparing a Si-O bond-containing polysiloxane-modified petroleum resin; the solution polymerization method is to add a proper amount of solvent to the petroleum resin, the modifier, the initiator and the acrylate compound to mix and dissolve, and in an inert gas-isolated air, the mixed solution undergoes a free radical graft polymerization reaction, and after the reaction is completed, the low-boiling point is further removed under vacuum conditions to prepare a Si-O bond-containing polysiloxane and an acrylate-modified petroleum resin, and the solvent is recycled during the solution polymerization. The solvent is an aliphatic hydrocarbon, petroleum ether, a halogenated hydrocarbon, toluene or xylene, and the amount of the solvent used is 20%-100% of the total weight of the reaction raw materials.

10. Use of a polymer prepared by the method of introducing Si-O bond compounds into petroleum resin to improve processing rheological properties according to any one of claims 1 to 9, characterized in that: The prepared Si-O bond-containing polysiloxane-modified petroleum resin or Si-O bond-containing polysiloxane and acrylate-modified petroleum resin can be used to prepare hot melt adhesive or pressure-sensitive adhesive with polyolefin thermoplastic elastomer.

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