A modified petroleum resin and its preparation method

Abstract

The present invention belongs to the technical field of petrochemical industry. More specifically, it relates to a modified petroleum resin and a preparation method thereof. The preparation steps of the present invention include: selecting a C9 petroleum resin with a number average molecular weight distribution range of 500-2000 as a base resin; adding a graphene oxide-maleic anhydride blend of 14-16% of the base resin mass and a diisopropylbenzene peroxide of 2.0-2.5% of the base resin mass to the base resin, heating and stirring the reaction, cooling, discharging, and obtaining a modified petroleum resin; wherein, the preparation steps of the graphene oxide-maleic anhydride blend include: mixing 20-25 parts of graphene oxide, 8-12 parts of maleic anhydride, 0.3-0.5 parts of a surfactant, 80-120 parts of water, and 0.04-0.06 parts of dopamine by weight, adjusting the pH to 7.2-7.4, ultrasonically dispersing evenly, and then spray drying to obtain a graphene oxide-maleic anhydride blend.

Description

Technical Field

[0001] The present invention belongs to the technical field of petrochemical industry, and more specifically, relates to a modified petroleum resin and a preparation method thereof. Background Art

[0002] Petroleum resin is a low molecular weight thermoplastic polymer made from the C5-C9 fraction of petroleum cracking byproducts through polymerization and other processes. It has good water resistance and acid and alkali resistance and is widely used in coatings, rubber additives, paper additives, inks, adhesives and other fields. However, untreated petroleum resin contains complex and diverse unsaturated groups and impurities, which will directly affect the properties of the resin, such as light and heat stability, softening point, viscosity, color, etc. Therefore, in order to improve the performance and application range of petroleum resin, modification methods are usually used.

[0003] For example, a common modification method is to modify petroleum resin with maleic anhydride to improve the compatibility and dispersibility of petroleum resin with polar compounds. However, the inventors found that in the process of modifying C9 petroleum resin with maleic anhydride, polymer crosslinking or self-polymerization of maleic anhydride is likely to occur, resulting in a decrease in the modification effect and affecting product performance.

[0004] Therefore, how to improve the above-mentioned problems existing in the above-mentioned reaction process is one of the technical difficulties that technicians in this field still need to face. Summary of the invention

[0005] The technical problem to be solved by the present invention is: when C9 petroleum resin is used as the base petroleum resin and modified by maleic anhydride, the inventors found that since the raw material of C9 petroleum resin is a complex mixture containing a variety of aromatic hydrocarbon components, it contains polymerizable active components such as styrene, vinyl toluene and dicyclopentadiene. These active components are prone to produce free radicals in the polymerization reaction, triggering chain polymerization reactions and causing polymer cross-linking. In addition, maleic anhydride itself is also a highly active monomer, which contains double bonds and can react with other compounds containing double bonds to undergo diene synthesis reactions, thereby causing self-polymerization. Based on the above difficulties, the present invention provides a modified petroleum resin and a preparation method thereof.

[0006] The object of the present invention is to provide a method for preparing a modified petroleum resin.

[0007] Another object of the present invention is to provide a modified petroleum resin.

[0008] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0009] A method for preparing a modified petroleum resin, the specific preparation steps comprising:

[0010] Select C9 petroleum resin with a number average molecular weight distribution range of 500-2000 as the base resin;

[0011] Adding 14-16% of the graphene oxide-maleic anhydride blend and 2.0-2.5% of the diisopropylbenzene peroxide to the base resin, heating and stirring for reaction, cooling and discharging to obtain a modified petroleum resin;

[0012] Wherein, the preparation steps of the graphene oxide-maleic anhydride blend include:

[0013] By weight, 20-25 parts of graphene oxide, 8-12 parts of maleic anhydride, 0.3-0.5 parts of a surfactant, and 80-120 parts of water are mixed, ultrasonically dispersed evenly, and then spray-dried to obtain a graphene oxide-maleic anhydride blend.

[0014] First, the present invention selects C9 petroleum resin with a wide number average molecular weight as the base resin, so that the base resin contains mixed components with different molecular weights, especially the low molecular weight components contained therein can provide the base resin with a lower viscosity, and the presence of the low molecular weight components weakens the intermolecular force of the high molecular weight compounds of the base resin, so that in the subsequent reaction process, it will be easier for the base resin to contact with raw materials such as maleic anhydride, thereby realizing the modification process of the base resin;

[0015] Secondly, by widening the interlayer spacing of graphene oxide under the action of surfactant and ultrasonic treatment, maleic anhydride can penetrate into the interlayer, and maleic anhydride can be effectively adsorbed under the action of epoxy functional groups, hydroxyl groups or carboxyl groups between the graphene oxide layers, thereby reducing the self-polymerization reaction of maleic anhydride itself during the reaction with petroleum resin;

[0016] Finally, during the heating and stirring reaction process, under the shear force of the stirrer, the layers of graphene oxide gradually slip and gradually expose the maleic anhydride adsorbed inside, thereby achieving the gradual sustained release of maleic anhydride; more importantly, the structure of graphene oxide itself is amphiphilic, which can assist the diffusion and dispersion of maleic anhydride in the matrix resin, making the distribution of maleic anhydride in the reaction system more uniform, and graphene oxide has excellent thermal conductivity, which can assist the uniform and rapid transfer of heat in the reaction system, so that during the reaction process, side reactions such as cross-linking of the polymer and self-polymerization of maleic anhydride are suppressed to a certain extent.

[0017] Further, the heating and stirring reaction comprises:

[0018] First, under the conditions of the first temperature and the first stirring rate, heat and stir the reaction for 0.8-1.5h;

[0019] Then, heating and stirring the reaction at the second temperature and the second stirring rate for 80-120 minutes;

[0020] Wherein, the first temperature is 120-130°C; the first stirring rate is 80-100r / min;

[0021] The second temperature is 180-185° C.; the second stirring rate is 180-200 r / min.

[0022] Furthermore, the heating and stirring reaction further comprises:

[0023] First, under the conditions of the first temperature and the first stirring rate, heat and stir the reaction for 0.8-1.5h;

[0024] Then, a diluent of 10-12% of the mass of the matrix resin is added, and the heating and stirring reaction is continued at the first temperature and the first stirring rate for 20-30 minutes;

[0025] Then, the reaction was heated and stirred at the second temperature and the second stirring rate for 80-120 minutes;

[0026] The dilution solvent is selected from any one of ethyl acetate, acetone and methyl ethyl ketone.

[0027] First, stirring and mixing are carried out under relatively low temperature conditions. During this process, the resin molecular chains are not fully stretched, and the overall viscosity of the reaction system is relatively large. Under the action of the agitator, the graphene oxide sheets can slip or peel off under the action of shear force, so that the adsorbed maleic anhydride is fully and evenly dispersed; secondly, under higher temperature and stirring rate conditions, a certain amount of diluent is used to assist in the stretching of the molecular chains of compounds with larger molecular weight in the petroleum resin, thereby further achieving sufficient and uniform contact and mixing between the materials through optimization and adjustment in the process.

[0028] Further, the surfactant is selected from nonionic surfactants;

[0029] The nonionic surfactant is selected from any one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether and sorbitan ester.

[0030] By selecting a nonionic surfactant, the ionization of the surfactant in water during the preparation of the graphene oxide-maleic anhydride blend is reduced. Most importantly, it can be adsorbed together with maleic anhydride in the graphene oxide, thereby entering the subsequent reaction system. During the reaction, its presence can reduce the interfacial tension between the petroleum resin and the graphene oxide-maleic anhydride blend, thereby facilitating the mixing and reaction of the two.

[0031] Furthermore, the preparation step of the graphene oxide-maleic anhydride blend also includes:

[0032] By weight, 20-25 parts of graphene oxide, 8-12 parts of maleic anhydride, 0.3-0.5 parts of a surfactant, 80-120 parts of water, and 0.04-0.06 parts of dopamine are mixed, the pH value is adjusted to 7.2-7.4, ultrasonically dispersed uniformly, and then spray-dried to obtain a graphene oxide-maleic anhydride blend.

[0033] By further introducing an appropriate amount of dopamine into the spray-drying raw materials, and utilizing its rapid oxidative self-polymerization in a weakly alkaline environment during the spray-drying process, the spray-dried blend has a certain cohesive force. The certain cohesive force ensures that the blend is not prone to collapse during the transfer process, thereby making its properties more stable and the control of subsequent process steps can become more precise and adaptable.

[0034] Further, the spray drying comprises:

[0035] The spray drying is carried out under the conditions of an inlet air temperature of 120-125°C and an outlet air temperature of 100-105°C.

[0036] Furthermore, the spray drying further comprises:

[0037] After spray drying, the mixture is sieved to obtain a graphene oxide-maleic anhydride blend with a D50 of 20-25 μm.

[0038] A modified petroleum resin is prepared by the above preparation method. DETAILED DESCRIPTION

[0039] The present invention is further described below with reference to specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0040] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0041] Example 1

[0042] By weight, 20 parts of graphene oxide, 8 parts of maleic anhydride, 0.3 parts of a surfactant, 80 parts of water, and 0.04 parts of dopamine were mixed, the pH was adjusted to 7.2, and ultrasonic dispersion was performed for 15 minutes at an ultrasonic frequency of 140 kHz. The mixture was then transported to a spray dryer, spray-dried at a feed rate of 80 g / min, an inlet air temperature of 120° C., and an outlet air temperature of 100° C., and then sieved to obtain a graphene oxide-maleic anhydride blend having a D50 of 20 μm;

[0043] The surfactant is selected from nonionic surfactants;

[0044] The nonionic surfactant is selected from fatty alcohol polyoxyethylene ether;

[0045] Select C9 petroleum resin with a number average molecular weight distribution range of 500-2000 as the base resin;

[0046] Adding 14% of the graphene oxide-maleic anhydride blend by weight of the matrix resin and 2.0% of dicumyl peroxide by weight of the matrix resin to the matrix resin, heating and stirring the mixture under the first temperature and the first stirring rate for 0.8 h;

[0047] Then, a diluent of 10% of the mass of the matrix resin is added, and the heating and stirring reaction is continued at the first temperature and the first stirring rate for 20 minutes;

[0048] Then, the reaction was stirred and heated at the second temperature and the second stirring rate for 80 minutes;

[0049] After the reaction is completed, the solvent is removed by extraction, and then cooled and discharged to obtain modified petroleum resin;

[0050] Wherein, the first temperature is 120°C; the first stirring rate is 80r / min;

[0051] The second temperature is 180°C; the second stirring rate is 180r / min;

[0052] The diluting solvent is selected from ethyl acetate.

[0053] Example 2

[0054] By weight, 22 parts of graphene oxide, 10 parts of maleic anhydride, 0.4 parts of a surfactant, 100 parts of water, and 0.05 parts of dopamine were mixed, the pH was adjusted to 7.3, and ultrasonic dispersion was performed for 18 minutes at an ultrasonic frequency of 145 kHz. The mixture was then transported to a spray dryer, spray-dried at a feed rate of 85 g / min, an inlet air temperature of 122° C., and an outlet air temperature of 103° C., and then sieved to obtain a graphene oxide-maleic anhydride blend having a D50 of 22 μm;

[0055] The surfactant is selected from nonionic surfactants;

[0056] The nonionic surfactant is selected from alkylphenol polyoxyethylene ether;

[0057] Select C9 petroleum resin with a number average molecular weight distribution range of 500-2000 as the base resin;

[0058] Adding 15% of the graphene oxide-maleic anhydride blend by weight of the matrix resin and 2.2% of dicumyl peroxide by weight of the matrix resin to the matrix resin, heating and stirring the mixture under the first temperature and the first stirring rate conditions for 1.2 hours;

[0059] Then, a diluent solvent with a mass percentage of 11% of the matrix resin is added, and the reaction is continued under heating and stirring at the first temperature and the first stirring rate for 25 minutes;

[0060] Then, the reaction was stirred under heating at the second temperature and the second stirring rate for 100 min;

[0061] After the reaction is completed, the solvent is removed by extraction, and then cooled and discharged to obtain modified petroleum resin;

[0062] Wherein, the first temperature is 125°C; the first stirring rate is 90r / min;

[0063] The second temperature is 182°C; the second stirring rate is 190r / min;

[0064] The dilution solvent is selected from acetone.

[0065] Example 3

[0066] By weight, 25 parts of graphene oxide, 12 parts of maleic anhydride, 0.5 parts of a surfactant, 120 parts of water, and 0.06 parts of dopamine were mixed, the pH was adjusted to 7.4, and ultrasonic dispersion was performed for 20 minutes at an ultrasonic frequency of 150 kHz. The mixture was then transported to a spray dryer, spray-dried at a feed rate of 90 g / min, an inlet air temperature of 125° C., and an outlet air temperature of 105° C., and then sieved to obtain a graphene oxide-maleic anhydride blend having a D50 of 25 μm;

[0067] The surfactant is selected from nonionic surfactants;

[0068] The nonionic surfactant is selected from fatty acid polyoxyethylene ether;

[0069] Select C9 petroleum resin with a number average molecular weight distribution range of 500-2000 as the base resin;

[0070] Adding 16% of the graphene oxide-maleic anhydride blend by weight of the matrix resin and 2.5% of dicumyl peroxide by weight of the matrix resin to the matrix resin, heating and stirring the mixture under the first temperature and the first stirring rate conditions for 1.5 hours;

[0071] Then, a diluent solvent with a mass percentage of 12% of the matrix resin is added, and the reaction is continued under heating and stirring at the first temperature and the first stirring rate for 30 minutes;

[0072] Then, the reaction was heated and stirred at the second temperature and the second stirring rate for 120 minutes;

[0073] After the reaction is completed, the solvent is removed by extraction, and then cooled and discharged to obtain modified petroleum resin;

[0074] Wherein, the first temperature is 130°C; the first stirring rate is 100r / min;

[0075] The second temperature is 185°C; the second stirring rate is 200r / min;

[0076] The dilution solvent is selected from methyl ethyl ketone.

[0077] Example 4

[0078] Compared with Example 1, this example is different in that no diluent solvent is added and other conditions remain unchanged.

[0079] Example 5

[0080] By weight, 20 parts of graphene oxide, 8 parts of maleic anhydride, 0.3 parts of a surfactant, 80 parts of water, and 0.04 parts of dopamine were mixed, the pH was adjusted to 7.2, and ultrasonic dispersion was performed for 15 minutes at an ultrasonic frequency of 140 kHz. The mixture was then transported to a spray dryer, spray-dried at a feed rate of 80 g / min, an inlet air temperature of 120° C., and an outlet air temperature of 100° C., and then sieved to obtain a graphene oxide-maleic anhydride blend having a D50 of 20 μm;

[0081] The surfactant is selected from nonionic surfactants;

[0082] The nonionic surfactant is selected from fatty alcohol polyoxyethylene ether;

[0083] Select C9 petroleum resin with a number average molecular weight distribution range of 500-2000 as the base resin;

[0084] Adding 14% of the graphene oxide-maleic anhydride blend and 2.0% of dicumyl peroxide by weight of the matrix resin to the matrix resin, heating and stirring the mixture at a temperature of 180° C. and a stirring rate of 180 r / min for 0.8 h;

[0085] Then, a diluent of 10% of the mass of the matrix resin was added, and the mixture was heated and stirred for 100 minutes at a temperature of 180° C. and a stirring rate of 180 r / min.

[0086] After the reaction is completed, the solvent is removed by extraction, and then cooled and discharged to obtain modified petroleum resin;

[0087] Wherein, the first temperature is 120°C; the first stirring rate is 80r / min;

[0088] The second temperature is 180°C; the second stirring rate is 180r / min;

[0089] The diluting solvent is selected from ethyl acetate.

[0090] Example 6

[0091] The difference between this embodiment and embodiment 1 is that dopamine is not added, and other conditions remain unchanged.

[0092] Comparative Example 1

[0093] By weight, 20 parts of graphene oxide, 8 parts of maleic anhydride, 0.3 parts of a surfactant, and 0.04 parts of dopamine were stirred and mixed with a stirrer at a speed of 60 r / min for 15 minutes to obtain a graphene oxide-maleic anhydride blend;

[0094] The surfactant is selected from nonionic surfactants;

[0095] The nonionic surfactant is selected from fatty alcohol polyoxyethylene ether;

[0096] Select C9 petroleum resin with a number average molecular weight distribution range of 500-2000 as the base resin;

[0097] Adding 14% of the graphene oxide-maleic anhydride blend by weight of the matrix resin and 2.0% of dicumyl peroxide by weight of the matrix resin to the matrix resin, heating and stirring the mixture under the first temperature and the first stirring rate for 0.8 h;

[0098] Then, a diluent of 10% of the mass of the matrix resin is added, and the heating and stirring reaction is continued at the first temperature and the first stirring rate for 20 minutes;

[0099] Then, the reaction was stirred and heated at the second temperature and the second stirring rate for 80 minutes;

[0100] After the reaction is completed, the solvent is removed by extraction, and then cooled and discharged to obtain modified petroleum resin;

[0101] Wherein, the first temperature is 120°C; the first stirring rate is 80r / min;

[0102] The second temperature is 180°C; the second stirring rate is 180r / min;

[0103] The diluting solvent is selected from ethyl acetate.

[0104] The performance tests were performed on the products obtained in the above embodiments and comparative examples. The specific test methods and test results are as follows:

[0105] By weight, 100 parts of ethylene-vinyl acetate copolymer (EVA resin), 20 parts of PP wax, 55 parts of the modified petroleum resin obtained in the above examples or comparative examples, and 10 parts of rosin resin were taken;

[0106] First, raise the temperature to 145°C and keep it warm for 12 minutes; after adding the EVA resin, raise the temperature; when the materials are completely melted, add the modified petroleum resin, rosin resin, and PP wax in sequence; when all the materials are completely melted, continue to stir and mix for 10 minutes; pour the EVA hot melt adhesive into a glass container coated with a anti-sticking agent, remove it after cooling, and the EVA hot melt adhesive is obtained.

[0107] Take an appropriate amount of EVA hot melt adhesive and put it into a mold of 210×210×4mm; set the temperature of the flat vulcanizer to 140℃ and keep it warm for 10 minutes to ensure that the temperature of the EVA hot melt adhesive is constant when it melts; put the mold into the flat vulcanizer and pressurize and heat it, and set the melting heating time to 30 minutes. After taking it out, cool it down by cold pressing to obtain the EVA hot melt adhesive sample;

[0108] Tensile properties test:

[0109] The test was conducted using a universal testing machine in accordance with GB / T 528-2009, with a tensile rate of 500 mm / min;

[0110] Shear strength test:

[0111] Using an electronic tensile tester, in accordance with GB / T 7124-2008, the stretching rate is 10mm / min;

[0112] The specific test results are shown in Table 1;

[0113] Table 1: Product performance test results

[0114] Tensile strength / MPa Shear strength / MPa Example 1 4.25 3.96 Example 2 4.28 4.01 Example 3 4.27 3.98 Example 4 4.13 3.88 Example 5 4.09 3.85 Example 6 4.01 3.81 Comparative Example 1 3.87 3.55

[0115] It can be seen from the test results in Table 1 that the product obtained by the present invention has a more complete and uniform reaction, and is added to the EVA resin, which has a greater advantage in improving the mechanical properties of the resin.

[0116] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing a modified petroleum resin, characterized in that: The specific preparation steps include: Select C9 petroleum resin with a number average molecular weight distribution range of 500-2000 as the base resin; Adding 14-16% of the graphene oxide-maleic anhydride blend and 2.0-2.5% of the diisopropylbenzene peroxide to the base resin, heating and stirring for reaction, cooling and discharging to obtain a modified petroleum resin; Wherein, the preparation steps of the graphene oxide-maleic anhydride blend include: By weight, 20-25 parts of graphene oxide, 8-12 parts of maleic anhydride, 0.3-0.5 parts of a surfactant, and 80-120 parts of water are mixed, ultrasonically dispersed evenly, and then spray-dried to obtain a graphene oxide-maleic anhydride blend.

2. The method for preparing a modified petroleum resin according to claim 1, characterized in that: The heating and stirring reaction comprises: First, under the conditions of the first temperature and the first stirring rate, heat and stir the reaction for 0.8-1.5h; Then, heating and stirring the reaction at the second temperature and the second stirring rate for 80-120 minutes; Wherein, the first temperature is 120-130°C; the first stirring rate is 80-100r / min; The second temperature is 180-185° C.; the second stirring rate is 180-200 r / min.

3. The method for preparing a modified petroleum resin according to claim 2, characterized in that: The heating and stirring reaction further comprises: First, under the conditions of the first temperature and the first stirring rate, heat and stir the reaction for 0.8-1.5h; Then, a diluent of 10-12% of the mass of the matrix resin is added, and the heating and stirring reaction is continued at the first temperature and the first stirring rate for 20-30 minutes; Then, the reaction was stirred under heating at the second temperature and the second stirring rate for 80-120 minutes; The dilution solvent is selected from any one of ethyl acetate, acetone and methyl ethyl ketone.

4. The method for preparing a modified petroleum resin according to claim 1, characterized in that: The surfactant is selected from nonionic surfactants; The nonionic surfactant is selected from any one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether and sorbitan ester.

5. The method for preparing a modified petroleum resin according to claim 1, characterized in that: The preparation step of the graphene oxide-maleic anhydride blend also includes: By weight, 20-25 parts of graphene oxide, 8-12 parts of maleic anhydride, 0.3-0.5 parts of a surfactant, 80-120 parts of water, and 0.04-0.06 parts of dopamine are mixed, the pH value is adjusted to 7.2-7.4, ultrasonically dispersed uniformly, and then spray-dried to obtain a graphene oxide-maleic anhydride blend.

6. The method for preparing a modified petroleum resin according to claim 5, characterized in that: The spray drying comprises: The spray drying is carried out under the conditions of an inlet air temperature of 120-125°C and an outlet air temperature of 100-105°C.

7. The method for preparing a modified petroleum resin according to claim 5, characterized in that: The spray drying further comprises: After spray drying, the mixture is sieved to obtain a graphene oxide-maleic anhydride blend with a D50 of 20-25 μm.

8. A modified petroleum resin, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 7.