A kind of petroleum resin and preparation method thereof

Abstract

The present invention belongs to the field of petrochemical technology. More specifically, it relates to a petroleum resin and a preparation method thereof. The specific preparation steps of the present invention include: raw material blending: C5 petroleum resin and C9 petroleum resin are mixed uniformly at a mass ratio of 1: (0.85-0.90) to obtain a compounded petroleum resin; graded graphene oxide and compounded petroleum resin are mixed at a mass ratio of 1.5: (9.5-10.0), and ultrasonically dispersed uniformly to obtain a premix; polymerization reaction: maleic anhydride of 15-18% of the mass of the compounded petroleum resin and an initiator of 2.0-2.5% of the mass of the compounded petroleum resin are added to the premix, heated and stirred to react, mixed with an extraction solvent, heated and extracted for 8-12 hours, cooled, and the petroleum resin and the solvent are centrifuged and discharged to obtain a petroleum resin.

Description

Technical Field

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

[0002] Plastics are widely used in information technology, energy and electricity, agricultural production, transportation, aerospace, and marine life, and have become one of the four basic materials in modern society. However, most plastics also have disadvantages such as poor heat and low temperature resistance, poor dimensional stability, and easy aging, and need to be modified during use.

[0003] Petroleum resin is a low molecular weight polymer obtained by heating and catalytic polymerization after separation of C5 and C9 fractions, which are by-products of petroleum cracking. It is insoluble in water but easily soluble in organic solvents. It has excellent properties such as acid and alkali resistance and aging resistance. It is widely available and inexpensive, and can be used in the plastic modification industry.

[0004] However, ordinary petroleum resins have many unsaturated double bonds and impurities such as halides generated during the polymerization process, which makes them have disadvantages such as dark color, low thermal stability, high brittleness and poor adhesion. In the future, in emerging fields such as lightweight automobiles and smart terminal devices, high-performance petroleum resins used in plastic modification will become a potential direction for market development. Summary of the invention

[0005] The technical problem to be solved by the present invention is: for petroleum resin products, there are many unsaturated double bonds, so it is necessary to introduce a modifier to modify them, such as maleic anhydride or acrylic acid, however, due to the difference in polarity between the modifier and the petroleum resin, the reaction is not sufficient or uniform during the modification process, resulting in the problem that the performance of the plastic cannot be further improved after the product is added to the plastic. The present invention provides a petroleum resin and a preparation method thereof.

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

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

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

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

[0010] Raw material blending:

[0011] C5 petroleum resin and C9 petroleum resin are uniformly mixed in a mass ratio of 1: (0.85-0.90) to obtain a compounded petroleum resin;

[0012] The graded graphene oxide and the compounded petroleum resin are mixed in a mass ratio of 1.5:(9.5-10.0), and then ultrasonically dispersed to obtain a premix;

[0013] Polymerization reaction:

[0014] Add maleic anhydride in an amount of 15-18% by weight of the compound petroleum resin and initiator in an amount of 2.0-2.5% by weight of the compound petroleum resin into the premix, heat and stir to react, cool, and discharge to obtain the petroleum resin.

[0015] The above technical solution preferably uses a certain amount of C5 petroleum resin and C9 petroleum resin for combination, wherein C5 petroleum resin generally has a lower polarity because it is mainly based on aliphatic compounds; whereas C9 petroleum resin generally contains more aromatic hydrocarbon components, and its structure contains more polar groups, such as benzene rings, which increases its polarity; therefore, by compounding the two, the polarity of the petroleum resin can be improved to a certain extent, making it easy to mix with graphene oxide and maleic anhydride, and reducing phase separation during the reaction, so that the raw materials can be more sufficient and uniform during the reaction;

[0016] In addition, by further introducing a certain amount of graphene oxide on the basis of the above, on the one hand, the graphene oxide structure contains abundant oxygen-containing functional groups, such as carboxyl, hydroxyl and epoxy groups, which have good polarity, while its conjugated region exhibits non-polarity, so that it can interact with both petroleum resin and maleic anhydride, thereby helping to improve the binding ability between the components and improve the sufficiency of the reaction; on the other hand, it can improve the dispersion between materials, thereby making the reaction more uniform; more importantly, graphene oxide has high thermal conductivity. After being uniformly dispersed in the system, the reaction temperature can be evenly distributed in the system, and the functional groups on its surface also provide reaction active sites, so that the reaction can also occur evenly when the temperature is uniformly distributed.

[0017] Furthermore, the graded graphene oxide includes small-particle graphene oxide with a D50 of 50-55 nm and large-particle graphene oxide with a D50 of 120-130 nm; and the mass ratio of the small-particle graphene oxide to the large-particle graphene oxide is (2.2-2.6):1.

[0018] Furthermore, the sphericity of the small-particle graphene oxide is 9.2-9.4; and the sphericity of the large-particle graphene oxide is 9.2-9.4.

[0019] The inventors found that by selecting spherical graphene oxide and using the above-mentioned specific size-graded graphene oxide particles, on the one hand, the spherical structure has a balanced contact with the various components in the system at all angles; on the other hand, small-particle graphene oxide has a higher surface energy, which is easier to adsorb various components and diffuses quickly after adsorption, thereby facilitating the uniform distribution of various components, while larger-particle graphene oxide is beneficial to the stability of the system.

[0020] Furthermore, a silane coupling agent is adsorbed on the surface of the graded graphene oxide, and the silane coupling agent is selected from any one of silane coupling agent KH-540, silane coupling agent KH-550, silane coupling agent KH-560, silane coupling agent KH-570, and silane coupling agent KH-580.

[0021] Furthermore, the initiator is selected from any one of benzoyl peroxide, diisopropylbenzene peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptanenitrile, potassium persulfate, and ammonium persulfate.

[0022] Furthermore, the polymerization reaction further comprises:

[0023] After the heating and stirring reaction, the mixture is mixed with the extraction solvent, and then heated and extracted for 8-12 hours. The petroleum resin and the solvent are centrifuged and cooled to obtain the petroleum resin.

[0024] Furthermore, the extraction solvent is selected from any one of xylene, furfural, and N-methylpyrrolidone.

[0025] Further, the heating and stirring reaction comprises:

[0026] In a nitrogen atmosphere, first heat and stir the mixture at 100-110° C. and 180-200 r / min for 80-100 min, then continue heating to 175-180° C. and stir at 550-600 r / min for 60-80 min.

[0027] A petroleum resin is prepared by the above preparation method. DETAILED DESCRIPTION

[0028] 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.

[0029] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0030] Example 1

[0031] Graphene oxide and water were mixed in a mass ratio of 1:7, and ultrasonically dispersed for 20 minutes at a temperature of 60°C and an ultrasonic frequency of 60kHz. The mixture was then transported to a spray dryer through a screw pump, and spray granulated at a feed rate of 100 g / min, a main disk speed of 7800 r / min, an inlet air temperature of 140°C, and an outlet air temperature of 120°C to obtain dry spherical graphene oxide.

[0032] The dried spherical graphene oxide is sieved to obtain small-particle graphene oxide with a D50 of 50 nm and a sphericity of 9.2; and large-particle graphene oxide with a D50 of 120 nm and a sphericity of 9.2 is obtained;

[0033] The small-particle graphene oxide and the large-particle graphene oxide are added to a reactor at a mass ratio of 2.2:1, and a 50% ethanol solution with a mass fraction of 10 times the mass of the small-particle graphene oxide is added, and the pH is adjusted to 7.5, and then a silane coupling agent with a mass fraction of 8% of the small-particle graphene oxide is added dropwise, and after the dropwise addition is completed, the temperature is 70° C. and the stirring speed is 300 r / min. After heating and stirring for 2 hours, the filter cake is filtered, and the filter cake is collected, and the filter cake is washed with deionized water for 3 times, and the washed filter cake is dried in an oven to constant weight to obtain composite graphene oxide;

[0034] C5 petroleum resin and C9 petroleum resin are heated and melted at a mass ratio of 1:0.85, and then mixed evenly to obtain a compounded petroleum resin;

[0035] The graded graphene oxide and the compounded petroleum resin were mixed in a mass ratio of 1.5:9.5, heated to melt, and ultrasonically dispersed for 40 minutes at an ultrasonic frequency of 200 kHz in a molten state to obtain a premix;

[0036] Polymerization reaction:

[0037] Add maleic anhydride (15% by weight of the compound petroleum resin) and initiator (2.0% by weight of the compound petroleum resin) to the premix, and heat and stir for 80 minutes at 100° C. and 180 r / min in a nitrogen atmosphere, then continue heating to 175° C. and stir for 60 minutes at 550 r / min;

[0038] After heating and stirring for reaction, the mixture is mixed with an extraction solvent, and then heated and extracted for 8 hours. The petroleum resin and the solvent are centrifuged and cooled to obtain the petroleum resin.

[0039] The silane coupling agent is selected from silane coupling agent KH-540;

[0040] The initiator is selected from benzoyl peroxide;

[0041] The extraction solvent is selected from xylene.

[0042] Example 2

[0043] Graphene oxide and water were mixed in a mass ratio of 1:7, and ultrasonically dispersed for 20 minutes at a temperature of 60°C and an ultrasonic frequency of 60kHz. The mixture was then transported to a spray dryer through a screw pump, and spray granulated at a feed rate of 100 g / min, a main disk speed of 7800 r / min, an inlet air temperature of 140°C, and an outlet air temperature of 120°C to obtain dry spherical graphene oxide.

[0044] The dried spherical graphene oxide was sieved to obtain small-particle graphene oxide with a D50 of 52 nm and a sphericity of 9.3; and large-particle graphene oxide with a D50 of 125 nm and a sphericity of 9.3 was obtained;

[0045] The small-particle graphene oxide and the large-particle graphene oxide are added to a reactor at a mass ratio of 2.4:1, and a 50% ethanol solution with a mass fraction of 10 times the mass of the small-particle graphene oxide is added, and the pH is adjusted to 7.5, and then a silane coupling agent with a mass fraction of 9% of the small-particle graphene oxide is added dropwise. After the dropwise addition is completed, the reaction is heated and stirred at a temperature of 70° C. and a stirring speed of 300 r / min for 2 hours, and then filtered to collect the filter cake, and the filter cake is washed with deionized water for 3 times, and then the washed filter cake is dried in an oven to a constant weight to obtain a composite graphene oxide;

[0046] C5 petroleum resin and C9 petroleum resin are heated and melted at a mass ratio of 1:0.88, and then mixed evenly to obtain a compounded petroleum resin;

[0047] The graded graphene oxide and the compounded petroleum resin were mixed in a mass ratio of 1.5:9.8, heated to melt, and ultrasonically dispersed for 50 minutes at an ultrasonic frequency of 200 kHz in a molten state to obtain a premix;

[0048] Polymerization reaction:

[0049] Add maleic anhydride (16% by weight of the compound petroleum resin) and initiator (2.2% by weight of the compound petroleum resin) to the premix, and heat and stir for 90 minutes at 105° C. and 190 r / min in a nitrogen atmosphere, then continue heating to 178° C. and stir for 70 minutes at 580 r / min;

[0050] After heating and stirring for reaction, the mixture is mixed with an extraction solvent, and then heated and extracted for 10 hours, and the petroleum resin and the solvent are centrifuged and cooled to obtain the petroleum resin;

[0051] The silane coupling agent is selected from silane coupling agent KH-550;

[0052] The initiator is selected from dicumyl peroxide;

[0053] The extraction solvent is selected from xylene.

[0054] Example 3

[0055] Graphene oxide and water were mixed in a mass ratio of 1:7, and ultrasonically dispersed for 20 minutes at a temperature of 60°C and an ultrasonic frequency of 60kHz. The mixture was then transported to a spray dryer through a screw pump, and spray granulated at a feed rate of 100 g / min, a main disk speed of 7800 r / min, an inlet air temperature of 140°C, and an outlet air temperature of 120°C to obtain dry spherical graphene oxide.

[0056] The dried spherical graphene oxide was sieved to obtain small-particle graphene oxide with a D50 of 55 nm and a sphericity of 9.4; and large-particle graphene oxide with a D50 of 130 nm and a sphericity of 9.4 was obtained;

[0057] The small-particle graphene oxide and the large-particle graphene oxide are added to a reactor at a mass ratio of 2.6:1, and a 50% ethanol solution with a mass fraction of 10 times the mass of the small-particle graphene oxide is added, and the pH is adjusted to 7.5, and then a silane coupling agent with a mass fraction of 10% of the small-particle graphene oxide is added dropwise, and after the dropwise addition is completed, the reaction is heated and stirred at a temperature of 70° C. and a stirring speed of 300 r / min for 2 hours, and then filtered to collect the filter cake, and the filter cake is washed with deionized water for 3 times, and then the washed filter cake is dried in an oven to a constant weight to obtain composite graphene oxide;

[0058] C5 petroleum resin and C9 petroleum resin are heated and melted at a mass ratio of 1:0.90, and then mixed evenly to obtain a compounded petroleum resin;

[0059] The graded graphene oxide and the compounded petroleum resin were mixed in a mass ratio of 1.5:10.0, heated to melt, and ultrasonically dispersed for 60 minutes at an ultrasonic frequency of 200 kHz in a molten state to obtain a premix;

[0060] Polymerization reaction:

[0061] Add maleic anhydride (18% by weight of the compound petroleum resin) and initiator (2.5% by weight of the compound petroleum resin) to the premix, and heat and stir for 100 minutes at 110° C. and 200 r / min in a nitrogen atmosphere, then continue heating to 180° C. and stir for 80 minutes at 600 r / min;

[0062] After heating and stirring for reaction, the mixture is mixed with an extraction solvent, and then heated and extracted for 12 hours, and the petroleum resin and the solvent are centrifuged and cooled to obtain a petroleum resin;

[0063] The silane coupling agent is selected from silane coupling agent KH-560;

[0064] The initiator is selected from tert-butyl hydroperoxide;

[0065] The extraction solvent is selected from xylene.

[0066] Example 4

[0067] Compared with Example 1, this embodiment is different in that:

[0068] The sphericity of the small-particle graphene oxide is 9.0; and the sphericity of the large-particle graphene oxide is 9.0, and the other conditions remain unchanged.

[0069] Example 5

[0070] Compared with Example 1, this embodiment is different in that:

[0071] The graded graphene oxide includes small-particle graphene oxide with a D50 of 100 nm and large-particle graphene oxide with a D50 of 120 nm; and the mass ratio of the small-particle graphene oxide to the large-particle graphene oxide is 2.2:1; and the other conditions remain unchanged.

[0072] Example 6

[0073] Compared with Example 1, this embodiment is different in that:

[0074] Polymerization reaction:

[0075] Add maleic anhydride (15% by weight of the compound petroleum resin) and initiator (2.0% by weight of the compound petroleum resin) to the premix, and heat and stir to react for 60 minutes at a temperature of 175° C. and a stirring speed of 550 r / min in a nitrogen atmosphere;

[0076] The rest of the conditions remain unchanged.

[0077] Comparative Example 1

[0078] The difference between this comparative example and Example 1 is that an equal mass of C5 petroleum resin is used to replace C9 petroleum resin, and other conditions remain unchanged.

[0079] Comparative Example 2

[0080] The difference between this comparative example and Example 1 is that graded graphene oxide is not added, and other conditions remain unchanged.

[0081] The performance tests were performed on the products obtained in the above examples and comparative examples. The specific test methods and test results are as follows:

[0082] By weight, 100 parts of polypropylene plastic, 15 parts of 800-mesh talc, 15 parts of petroleum resin prepared in the above embodiment or comparative example, and 2 parts of antioxidant 1010 were taken, heated and stirred for 2 hours at a temperature of 220°C and a stirring speed of 300 r / min, and then injected into a 1 mm thick mold, allowed to stand and cool for 2 hours, and then demolded, and then the mechanical properties were tested;

[0083] The tensile properties were tested according to GB / T1040.2-2006, with a tensile rate of 10mm / min. The fracture energy test measured the fracture energy of the material using a tensile machine with a 1000N load sensor. The material was cut into a size of 10mm×10mm and clamped with two stainless steel clamps to keep the size of the measured material at 2mm×10mm. Five sets of parallel samples were taken for the relevant tests, and the average value of the corresponding properties and the difference between the maximum and minimum values ​​were obtained respectively; all mechanical property tests were carried out at room temperature.

[0084] The specific test results are shown in Table 1;

[0085] Table 1: Product performance test results

[0086]

[0087] It can be seen from the test results in Table 1 that the product obtained by the present invention is added to PP plastic, so that the plastic product can obtain excellent mechanical properties, and the overall uniformity of the product is excellent. When sampling from different parts, the deviation of the test results is small.

[0088] 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 petroleum resin, characterized in that: The specific preparation steps include: Raw material blending: C5 petroleum resin and C9 petroleum resin are uniformly mixed at a mass ratio of 1: (0.85-0.90) to obtain a compounded petroleum resin; The graded graphene oxide and the compounded petroleum resin are mixed in a mass ratio of 1.5:(9.5-10.0), and ultrasonically dispersed to obtain a premix; Polymerization reaction: Add maleic anhydride in an amount of 15-18% by weight of the compound petroleum resin and an initiator in an amount of 2.0-2.5% by weight of the compound petroleum resin to the premix, heat and stir to react, cool, and discharge to obtain petroleum resin; the graded graphene oxide comprises small-particle graphene oxide with a D50 of 50-55 nm and large-particle graphene oxide with a D50 of 120-130 nm; and the mass ratio of the small-particle graphene oxide to the large-particle graphene oxide is (2.2-2.6):1; the sphericity of the small-particle graphene oxide is 9.2-9.4; and the sphericity of the large-particle graphene oxide is 9.2-9.

4.

2. The method for preparing a petroleum resin according to claim 1, characterized in that: A silane coupling agent is adsorbed on the surface of the graded graphene oxide, and the silane coupling agent is selected from any one of silane coupling agent KH-540, silane coupling agent KH-550, silane coupling agent KH-560, silane coupling agent KH-570, and silane coupling agent KH-580.

3. The method for preparing a petroleum resin according to claim 1, characterized in that: The initiator is selected from any one of benzoyl peroxide, diisopropylbenzene peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptanenitrile, potassium persulfate and ammonium persulfate.

4. The method for preparing a petroleum resin according to claim 1, characterized in that: The polymerization reaction further comprises: After the heating and stirring reaction, the mixture is mixed with the extraction solvent, and then heated and extracted for 8-12 hours. The petroleum resin and the solvent are centrifuged and cooled to obtain the petroleum resin.

5. The method for preparing a petroleum resin according to claim 4, characterized in that: The extraction solvent is selected from any one of xylene, furfural and N-methylpyrrolidone.

6. The method for preparing a petroleum resin according to claim 1, characterized in that: The heating and stirring reaction comprises: In a nitrogen atmosphere, first heat and stir the mixture at 100-110° C. and 180-200 r / min for 80-100 min, then continue heating to 175-180° C. and stir at 550-600 r / min for 60-80 min.

7. A petroleum resin, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 6.

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