Preparation method of 1, 5-cyclooctadiene modified petroleum resin

Abstract

The invention belongs to the technical field of resin synthesis, and particularly relates to a preparation method of 1, 5-cyclooctadiene modified petroleum resin. The preparation method of the 1, 5-cyclooctadiene modified petroleum resin provided by the invention comprises the following steps: performing rectification treatment on styrene, cyclodiolefin and ethylene cracking byproducts to obtain raw materials, mixing the raw materials, performing Friedel-Crafts reaction under the action of a heat stabilizer and a Lewis acid catalyst to obtain a polymerization product, and performing alkali washing, decoloration and gas stripping on the reaction product to obtain a final product. The invention provides the preparation method of the 1, 5-cyclooctadiene modified petroleum resin, the operation is simple, and the prepared petroleum resin has proper softening point and molecular weight, low viscosity, good compatibility, light color number and excellent actual use effect.

Description

Technical Field

[0001] The invention belongs to the technical field of resin synthesis, and particularly relates to a preparation method of 1,5-cyclooctadiene modified petroleum resin. Background Art

[0002] Petroleum resins have a wide range of applications, including plastic products, coatings and paints, adhesives, filling media, packaging media, electronic components, beauty products and medical devices. In terms of plastic products, petroleum resins have excellent plasticizing ability and plasticity due to their unique polymer structure, and are particularly suitable for the preparation of plastic bags, plastic bottles, plastic containers and other products. Through hot pressing, blow molding technology and extrusion processes, petroleum resins can produce products of various specifications and forms, precisely meeting market demand. As a key raw material component of coatings and paints, petroleum resins give coatings and paints excellent adhesion, weather resistance and chemical stability. Aromatic monomers such as indene, methyl indene, methyl styrene, naphthalene and methyl naphthalene obtained by cracking and fraction extraction of ethylene by-product C10 fractions all contain large conjugated electron cloud structures, which are easy to copolymerize with electrophilic monomers. However, how to effectively reduce viscosity and improve compatibility while maintaining a suitable softening point is a major industry technical problem that the resin industry needs to solve urgently.

[0003] Chinese patents CN 109535304A and CN 109553714A propose a method for preparing α-methylstyrene oligomers and their modified products. The reaction is completed at a low temperature not exceeding 5°C, and the resulting product has the physical and chemical properties of low molecular weight distribution, low viscosity and moderate softening point. Patent TWT 228500B discloses a technical solution for preparing an organic polymer material with a moderate softening point under Lewis acid catalysis, further enriching the selection range of resin materials. In the field of polyvinyl chloride processing, organic tin heat stabilizers have become one of the most widely used and most effective heat stabilizers with their high efficiency and environmental protection characteristics. This stabilizer not only has excellent thermal stability and weather resistance, but also can achieve good compatibility and transparency, providing a solid guarantee for improving the quality of polyvinyl chloride products.

[0004] Therefore, there is an urgent need for a petroleum resin with moderate viscosity and softening point, excellent stability and compatibility, and low color number, which has become one of the research hotspots in the current chemical industry. Summary of the invention

[0005] The present invention aims to solve the problem of excessively high viscosity of petroleum resins due to high softening point and high molecular weight. For this purpose, a modified petroleum resin based on 1,5-cyclooctadiene is innovatively provided, which successfully solves the problem of excessively high viscosity due to high molecular weight of the polymer, and the prepared product has the performance advantages of low viscosity, excellent compatibility, light color, etc. In addition, its raw material sources are wide, the production process is simple and efficient, and it is easy to achieve large-scale production, and it has extremely broad market application potential and commercial value.

[0006] The present invention provides a method for preparing a 1,5-cyclooctadiene modified petroleum resin, comprising:

[0007] S1, purifying the ethylene cracking by-product by using a distillation tower to obtain raw material A;

[0008] S2, mixing the cyclodiolefin and the styrene derivative, adding a molecular sieve, and drying to obtain a raw material B;

[0009] S3, according to the mass parts, 20-35 parts of raw material A, 5-20 parts of raw material B, 0.05-0.1 parts of heat stabilizer, 50-60 parts of solvent are mixed, added to the reaction kettle, 0.3-0.9 parts of Lewis acid catalyst are added at a temperature of -10--5°C, and then the stirring speed is set to 200-400rpm, the reaction temperature is -5-0°C, and the reaction is carried out for 2-3h to obtain a polymerization solution C;

[0010] S4, adding alkali solution to polymerization solution C, stirring at a speed of 150-300 rpm for 5-10 min, standing to separate layers, taking the organic layer, and recording it as polymerization solution D;

[0011] S5. Remove the solvent and unreacted raw materials by gas stripping the polymer solution D at 200-260° C. under negative pressure to obtain the product.

[0012] As an implementable case, the raw material A includes: indene, methylindene, naphthalene, and methylnaphthalene.

[0013] As an implementable case, the cycloalkadiene includes one or more of cyclooctadiene, 1,5-cyclooctadiene, 3-methyl-1,5-cyclooctadiene, and 1,7-cyclohexadiene.

[0014] Furthermore, the cycloalkadiene is 1,5-cyclooctadiene.

[0015] As an implementable example, the styrene derivatives include: one or more of styrene, methyl styrene, p-tert-butyl styrene, α-methyl styrene, vinyl toluene, and polystyrene.

[0016] Furthermore, the styrene derivative is styrene.

[0017] Furthermore, the mass ratio of the cycloalkadiene to the styrene derivative is (50-100):(10-25).

[0018] Furthermore, the mass ratio of the cyclodiolefin and the styrene derivative is 80:20.

[0019] As an implementable case, the molecular sieve includes: one or more of 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, and 13X molecular sieve.

[0020] Furthermore, the molecular sieve is a 4A grade molecular sieve.

[0021] As an implementable example, the thermal stabilizer includes an organic tin compound.

[0022] Furthermore, the organic tin compound includes one or more of dibutyltin oxide, dibutyltin dilaurate, dimethyltin mercaptan, dibutyltin dichloride, dibutyltin maleate, dibutyltin maleate laurate, and octyltin mercaptan.

[0023] Furthermore, the thermal stabilizer is dimethyl tin mercaptan.

[0024] As an implementable example, the solvent includes: one or more of hydrogenated white oil, cyclohexane, n-hexane, n-heptane, toluene, xylene, and acetone.

[0025] Furthermore, the solvent is xylene.

[0026] As an illustrative example, the Lewis acid catalyst includes one or more of aluminum chloride, zinc chloride, boron trifluoride etherate, and trichloromethanesulfonic acid.

[0027] Furthermore, the Lewis acid catalyst is one of boron trifluoride etherate and aluminum trichloride.

[0028] As an implementable case, the alkaline solution includes: one of ammonia water, potassium hydroxide ethanol solution, potassium hydroxide aqueous solution, sodium hydroxide ethanol solution, and sodium hydroxide aqueous solution.

[0029] Furthermore, the alkali solution is a sodium hydroxide aqueous solution.

[0030] Furthermore, the mass concentration of the sodium hydroxide aqueous solution is 15-30wt%.

[0031] Furthermore, the mass ratio of the alkali solution to the polymer solution C is 1:1.

[0032] The present invention solves the problem of excessively high viscosity of traditional petroleum resins due to high softening point and large molecular weight. The present invention mainly introduces cyclic dienes, specifically cyclic diene 1,5-cyclooctadiene, into the raw materials for preparation, and successfully optimizes and adjusts the molecular spatial structure of the petroleum resin, which not only enhances the flexibility of the petroleum resin polymer molecules, but also can accurately control the composition and structure of the copolymer based on the steric hindrance effect of the molecular groups, thereby having a positive impact on the overall performance of the synthetic resin, including viscosity, softening point, etc., significantly improving its compatibility and effectively reducing the viscosity of the product. The product petroleum resin achieves a significant reduction in viscosity and a significant improvement in compatibility while maintaining a suitable softening point and molecular weight level. In addition, in the present invention, the macromolecular long-chain polyene sequence can form specific carbonium ions with hydrofluoric acid (HF) ionized by Lewis acid catalyst boron trifluoride etherate, which can significantly increase the reaction rate of the raw materials, but the carbonium ions will cause the color of the polymer to slightly deepen. The invention can effectively remove free F ions by adding a heat stabilizer organic tin compound into the reaction system, further reducing the chromaticity of the petroleum resin and improving the application range of the product.

[0033] Beneficial Effects

[0034] (i) The present invention utilizes cyclodiolefins to finely adjust the molecular spatial structure of petroleum resins, which not only enhances the flexibility of polymer molecules, but also precisely controls the composition and structure of copolymers through steric hindrance effects, effectively improves the compatibility of synthetic petroleum resins, and significantly reduces their viscosity, making the modified petroleum resins have broader application prospects in multiple fields such as plastic products, coatings and paints, adhesives, and rubber tires.

[0035] (ii) During the reaction, the present invention preferably uses boron trifluoride etherate as a Lewis catalyst, which can form a specific carbonium ion structure with a trace amount of hydrofluoric acid through a macromolecular long-chain polyene sequence. Although this will cause a slight deepening of the color of the polymer, the organic tin compound, as a thermal stabilizer, can effectively remove free F ions in the reaction system, thereby significantly reducing the effect of the deepening of the color. The color of the petroleum resin finally prepared is lighter, and the product quality is significantly improved.

[0036] (III) The present invention also makes full use of ethylene cracking by-products as raw materials for preparation, and realizes the effective integration and reuse of waste resources through innovative technologies, thereby solving the problem of resource waste, improving the atomic economy of raw materials, and embodying the concept of green chemistry.

[0037] (IV) The preparation method of 1,5-cyclooctadiene modified petroleum resin provided by the present invention solves the problem of high viscosity caused by high softening point and high molecular weight of traditional petroleum resin; it not only improves the performance quality of petroleum resin, but also greatly broadens its market application prospects.

[0038] (V) The preparation method provided by the present invention does not require complex and expensive large-scale process equipment, the preparation steps are relatively simple, and the source of raw materials is relatively wide, the cost is relatively low, and the product 1,5-cyclooctadiene modified petroleum resin can be industrially mass-produced and can generate considerable economic benefits. DETAILED DESCRIPTION

[0039] In the following Examples 1-9 and Comparative Examples 1-2:

[0040] 4A grade molecular sieve was purchased from Jiangsu Xintao Technology Co., Ltd.

[0041] Dimethyltin mercaptan was purchased from Shandong Xinyihong Chemical Technology Co., Ltd. with the brand name YT181.

[0042] Example 1

[0043] The present invention provides a method for preparing a 1,5-cyclooctadiene modified petroleum resin, comprising:

[0044] S1. Purify the ethylene cracking byproduct by using a distillation tower to obtain raw material A; the chromatographic analysis results of raw material A show that the components are indene, methylindene, naphthalene and methylnaphthalene; in terms of mass ratio, indene:methylindene:naphthalene:methylnaphthalene=75:20:3.5:1.5;

[0045] S2, 80 parts of 1,5-cyclodiolefin and 20 parts of styrene were mixed, and then 20 parts of 4A grade molecular sieves were added, and dried for 30 hours to obtain raw material B;

[0046] S3. According to the mass fractions, 35 parts of raw material A, 5 parts of raw material B, 0.1 parts of dimethyl tin mercaptide, and 59.3 parts of xylene were mixed and added to a reactor. The mixture was replaced with nitrogen three times. Finally, the reactor was stabilized at 0.2 MPa. 0.6 parts of a xylene solution of 1 wt% boron trifluoride ether was added at a temperature of -5°C. The stirring speed was set to 300 rpm, the reaction temperature was -5°C, and the reaction was kept warm for 3 hours to obtain a polymer solution C.

[0047] S4, adding an equal amount of 20 wt% sodium hydroxide aqueous solution to the polymerization solution C, stirring at 200 rpm for 5 min at 25° C., standing to separate the layers, and taking the organic layer, which is recorded as polymerization solution D;

[0048] S5. The polymer solution D is subjected to reduced pressure distillation at 230° C. and -0.1 MPa negative pressure, and the solvent and unreacted raw materials are removed by gas stripping to obtain a 1,5-cyclooctadiene modified petroleum resin.

[0049] The softening point of the product in this example was measured to be 88.7°C, the Gardner color number was 5.9, the viscosity at 200°C was 89 mPa·s, the compatibility test conditions were EVA: petroleum resin = 5g:5g, and the measured compatibility result was 54°C.

[0050] Example 2

[0051] The present invention provides a method for preparing a 1,5-cyclooctadiene modified petroleum resin, comprising:

[0052] S1. Purify the ethylene cracking byproduct by using a distillation tower to obtain raw material A; the chromatographic analysis results of raw material A show that the components are indene, methylindene, naphthalene and methylnaphthalene; in terms of mass ratio, indene:methylindene:naphthalene:methylnaphthalene=75:20:3.5:1.5;

[0053] S2, 80 parts of 1,5-cyclodiolefin and 20 parts of styrene were mixed, and then 20 parts of 4A grade molecular sieves were added, and dried for 30 hours to obtain raw material B;

[0054] S3, according to the mass parts, 30 parts of raw material A, 10 parts of raw material B, 0.1 parts of dimethyl tin mercaptide, and 59.3 parts of xylene were mixed and added to the reactor, and nitrogen was replaced 3 times. Finally, the reactor was stabilized at 0.2MPa, and 0.6 parts of a xylene solution of 1wt% boron trifluoride ether was added at a temperature of -5°C, and then the stirring speed was set to 300rpm, the reaction temperature was -5°C, and the reaction was kept warm for 3h to obtain a polymer solution C;

[0055] S4, adding an equal amount of 20 wt% sodium hydroxide aqueous solution to the polymerization solution C, stirring at 200 rpm for 5 min at 25° C., standing to separate the layers, and taking the organic layer, which is recorded as polymerization solution D;

[0056] S5. The polymer solution D is subjected to reduced pressure distillation at 230° C. and -0.1 MPa negative pressure, and the solvent and unreacted raw materials are removed by gas stripping to obtain a 1,5-cyclooctadiene modified petroleum resin.

[0057] The softening point of the product in this example was measured to be 94.4°C, the Gardner color number was 5.7, the viscosity at 200°C was 102 mPa·s, the compatibility test conditions were EVA: petroleum resin = 5g:5g, and the measured compatibility result was 63°C.

[0058] Example 3

[0059] The present invention provides a method for preparing a 1,5-cyclooctadiene modified petroleum resin, comprising:

[0060] S1. Purify the ethylene cracking byproduct by using a distillation tower to obtain raw material A; the chromatographic analysis results of raw material A show that the components are indene, methylindene, naphthalene and methylnaphthalene; in terms of mass ratio, indene:methylindene:naphthalene:methylnaphthalene=75:20:3.5:1.5;

[0061] S2, 80 parts of 1,5-cyclodiolefin and 20 parts of styrene were mixed, and then 20 parts of 4A grade molecular sieves were added, and dried for 30 hours to obtain raw material B;

[0062] S3. According to the mass fractions, 25 parts of raw material A, 15 parts of raw material B, 0.1 parts of dimethyl tin mercaptide, and 59.3 parts of xylene were mixed and added to a reactor. The mixture was replaced with nitrogen three times. Finally, the reactor was stabilized at 0.2 MPa. 0.6 parts of a xylene solution of 1 wt% boron trifluoride ether was added at a temperature of -5°C. The stirring speed was set to 300 rpm, the reaction temperature was -5°C, and the reaction was kept warm for 3 hours to obtain a polymer solution C.

[0063] S4, adding an equal amount of 20 wt% sodium hydroxide aqueous solution to the polymerization solution C, stirring at 200 rpm for 5 min at 25° C., standing to separate the layers, and taking the organic layer, which is recorded as polymerization solution D;

[0064] S5. The polymer solution D is subjected to reduced pressure distillation at 230° C. and -0.1 MPa negative pressure, and the solvent and unreacted raw materials are removed by gas stripping to obtain a 1,5-cyclooctadiene modified petroleum resin.

[0065] The softening point of the product in this example was measured to be 100.4°C, the Gardner color number was 5.8, the viscosity at 200°C was 147 mPa·s, the compatibility test conditions were EVA: petroleum resin = 5g:5g, and the measured compatibility result was 68°C.

[0066] Example 4

[0067] The present invention provides a method for preparing a 1,5-cyclooctadiene modified petroleum resin, comprising:

[0068] S1. Purify the ethylene cracking byproduct by using a distillation tower to obtain raw material A; the chromatographic analysis results of raw material A show that the components are indene, methylindene, naphthalene and methylnaphthalene; in terms of mass ratio, indene:methylindene:naphthalene:methylnaphthalene=75:20:3.5:1.5;

[0069] S2, 80 parts of 1,5-cyclodiolefin and 20 parts of styrene were mixed, and then 20 parts of 4A grade molecular sieves were added, and dried for 30 hours to obtain raw material B;

[0070] S3. According to the mass fractions, 20 parts of raw material A, 20 parts of raw material B, 0.1 parts of dimethyl tin mercaptide, and 59.3 parts of xylene were mixed and added to a reactor. The mixture was replaced with nitrogen three times. Finally, the reactor was stabilized at 0.2 MPa. 0.6 parts of a xylene solution of 1 wt% boron trifluoride ether was added at a temperature of -5°C. The stirring speed was set to 300 rpm, the reaction temperature was -5°C, and the reaction was kept warm for 3 hours to obtain a polymer solution C.

[0071] S4, adding an equal amount of 20 wt% sodium hydroxide aqueous solution to the polymerization solution C, stirring at 200 rpm for 5 min at 25° C., standing to separate the layers, and taking the organic layer, which is recorded as polymerization solution D;

[0072] S5. The polymer solution D is subjected to reduced pressure distillation at 230° C. and -0.1 MPa negative pressure, and the solvent and unreacted raw materials are removed by gas stripping to obtain a 1,5-cyclooctadiene modified petroleum resin.

[0073] The softening point of the product in this example was measured to be 98°C, the Gardner color number was 6.3, the viscosity at 200°C was 264mPa·s, the compatibility test conditions were EVA: petroleum resin = 5g:5g, and the measured compatibility result was 97°C.

[0074] Example 5

[0075] The present invention provides a method for preparing a 1,5-cyclooctadiene modified petroleum resin, comprising:

[0076] S1. Purify the ethylene cracking byproduct by using a distillation tower to obtain raw material A; the chromatographic analysis results of raw material A show that the components are indene, methylindene, naphthalene and methylnaphthalene; in terms of mass ratio, indene:methylindene:naphthalene:methylnaphthalene=75:20:3.5:1.5;

[0077] S2, 80 parts of 1,5-cyclodiolefin and 20 parts of styrene were mixed, and then 20 parts of 4A grade molecular sieves were added, and dried for 30 hours to obtain raw material B;

[0078] S3. According to the mass fractions, 10 parts of raw material A, 30 parts of raw material B, 0.1 parts of dimethyl tin mercaptide and 59 parts of xylene were mixed and added to a reactor. The mixture was replaced with nitrogen three times. Finally, the reactor was stabilized at 0.2 MPa. 0.9 parts of a xylene solution of 1 wt% boron trifluoride ether was added at a temperature of -5°C. The stirring speed was set to 300 rpm, the reaction temperature was -5°C, and the reaction was kept warm for 3 hours to obtain a polymer solution C.

[0079] S4, adding an equal amount of 20 wt% sodium hydroxide aqueous solution to the polymerization solution C, stirring at 200 rpm for 5 min at 25° C., standing to separate the layers, and taking the organic layer, which is recorded as polymerization solution D;

[0080] S5. The polymer solution D is subjected to reduced pressure distillation at 230° C. and -0.1 MPa negative pressure, and the solvent and unreacted raw materials are removed by gas stripping to obtain a 1,5-cyclooctadiene modified petroleum resin.

[0081] The softening point of the product in this example was measured to be 91.2°C, the Gardner color number was 4.2, the viscosity at 200°C was 133 mPa·s, the compatibility test conditions were EVA: petroleum resin = 5g:5g, and the measured compatibility result was 164°C.

[0082] Example 6

[0083] The present invention provides a method for preparing a 1,5-cyclooctadiene modified petroleum resin, comprising:

[0084] S1. Purify the ethylene cracking byproduct by using a distillation tower to obtain raw material A; the chromatographic analysis results of raw material A show that the components are indene, methylindene, naphthalene and methylnaphthalene; in terms of mass ratio, indene:methylindene:naphthalene:methylnaphthalene=75:20:3.5:1.5;

[0085] S2, 80 parts of 1,5-cyclodiolefin and 20 parts of styrene were mixed, and then 20 parts of 4A grade molecular sieves were added, and dried for 30 hours to obtain raw material B;

[0086] S3. According to the mass fraction, 25 parts of raw material A, 15 parts of raw material B, 0.1 parts of dimethyl tin mercaptide, and 59.3 parts of xylene were mixed and added to the reactor. The nitrogen was replaced 3 times. Finally, the reactor was stabilized at 0.2MPa. 0.6 parts of aluminum trichloride-dichloroethane-xylene complex were added at a temperature of -5°C. The preparation method of the complex was to add 10g of aluminum trichloride to 3g of dichloroethane and 15g of xylene mixed solvent and shake for 2h. Then set the stirring speed to 300rpm, the reaction temperature to -5°C, and keep the reaction warm for 3h to obtain polymer solution C;

[0087] S4, adding an equal amount of 20 wt% sodium hydroxide aqueous solution to the polymerization solution C, stirring at 200 rpm for 5 min at 25° C., standing to separate the layers, and taking the organic layer, which is recorded as polymerization solution D;

[0088] S5. The polymer solution D is subjected to reduced pressure distillation at 230° C. and -0.1 MPa negative pressure, and the solvent and unreacted raw materials are removed by gas stripping to obtain a 1,5-cyclooctadiene modified petroleum resin.

[0089] The softening point of the product in this example was measured to be 101.7°C, the Gardner color number was 7.4, the viscosity at 200°C was 257 mPa·s, the compatibility test conditions were EVA: petroleum resin = 5g:5g, and the measured compatibility result was 208°C.

[0090] Example 7

[0091] The present invention provides a method for preparing a 1,5-cyclooctadiene modified petroleum resin, comprising:

[0092] S1. Purify the ethylene cracking byproduct by using a distillation tower to obtain raw material A; the chromatographic analysis results of raw material A show that the components are indene, methylindene, naphthalene and methylnaphthalene; in terms of mass ratio, indene:methylindene:naphthalene:methylnaphthalene=75:20:3.5:1.5;

[0093] S2, 80 parts of 1,5-cyclodiolefin and 20 parts of styrene were mixed, and then 20 parts of 4A grade molecular sieves were added, and dried for 30 hours to obtain raw material B;

[0094] S3. According to the mass fraction, 25 parts of raw material A, 15 parts of raw material B, 0.1 parts of dimethyl tin mercaptide, and 59.6 parts of xylene were mixed and added to the reactor. The nitrogen was replaced 3 times. Finally, the reactor was stabilized at 0.2MPa. 0.3 parts of aluminum trichloride-dichloroethane-xylene complex were added at a temperature of -5°C. The preparation method of the complex was to add 10g of aluminum trichloride to 3g of dichloroethane and 15g of xylene mixed solvent and shake for 2h. Then the stirring speed was set to 300rpm, the reaction temperature was -5°C, and the reaction was kept warm for 3h to obtain polymer solution C;

[0095] S4, adding an equal amount of 20 wt% sodium hydroxide aqueous solution to the polymerization solution C, stirring at 200 rpm for 5 min at 25° C., standing to separate the layers, and taking the organic layer, which is recorded as polymerization solution D;

[0096] S5. The polymer solution D is subjected to reduced pressure distillation at 230° C. and -0.1 MPa negative pressure, and the solvent and unreacted raw materials are removed by gas stripping to obtain a 1,5-cyclooctadiene modified petroleum resin.

[0097] The softening point of the product in this example was measured to be 98.2°C, the Gardner color number was 7.1, the viscosity at 200°C was 211 mPa·s, the compatibility test conditions were EVA: petroleum resin = 5g:5g, and the measured compatibility result was 204°C.

[0098] Example 8

[0099] The present invention provides a method for preparing a 1,5-cyclooctadiene modified petroleum resin, comprising:

[0100] S1. Purify the ethylene cracking byproduct by using a distillation tower to obtain raw material A; the chromatographic analysis results of raw material A show that the components are indene, methylindene, naphthalene and methylnaphthalene; in terms of mass ratio, indene:methylindene:naphthalene:methylnaphthalene=75:20:3.5:1.5;

[0101] S2, 80 parts of 1,5-cyclodiolefin and 20 parts of styrene were mixed, and then 20 parts of 4A grade molecular sieves were added, and dried for 30 hours to obtain raw material B;

[0102] S3. According to the mass fractions, 25 parts of raw material A, 15 parts of raw material B, 0.1 parts of dimethyl tin mercaptide, and 59.3 parts of anhydrous ethanol were mixed and added to a reactor. The mixture was replaced with nitrogen three times. Finally, the reactor was stabilized at 0.2 MPa. 0.6 parts of a xylene solution of 1 wt% boron trifluoride ether was added at a temperature of -5°C. The stirring speed was set to 300 rpm, the reaction temperature was -5°C, and the reaction was kept warm for 3 hours to obtain a polymer solution C.

[0103] S4, adding an equal amount of 20 wt% sodium hydroxide aqueous solution to the polymerization solution C, stirring at 200 rpm for 5 min at 25° C., standing to separate the layers, and taking the organic layer, which is recorded as polymerization solution D;

[0104] S5. The polymer solution D is subjected to reduced pressure distillation at 230° C. and -0.1 MPa negative pressure, and the solvent and unreacted raw materials are removed by gas stripping to obtain a 1,5-cyclooctadiene modified petroleum resin.

[0105] The softening point of the product in this example was measured to be 80.2°C, the Gardner color number was 10.1, the viscosity at 200°C was 124mPa·s, the compatibility test conditions were EVA: petroleum resin = 5g:5g, and the measured compatibility result was 168°C.

[0106] Example 9

[0107] The present invention provides a method for preparing a 1,5-cyclooctadiene modified petroleum resin, comprising:

[0108] S1. Purify the ethylene cracking byproduct by using a distillation tower to obtain raw material A; the chromatographic analysis results of raw material A show that the components are indene, methylindene, naphthalene and methylnaphthalene; in terms of mass ratio, indene:methylindene:naphthalene:methylnaphthalene=75:20:3.5:1.5;

[0109] S2, 80 parts of 1,5-cyclodiolefin and 20 parts of styrene were mixed, and then 20 parts of 4A grade molecular sieves were added, and dried for 30 hours to obtain raw material B;

[0110] S3. According to the mass fractions, 25 parts of raw material A, 15 parts of raw material B, 0.1 parts of dimethyl tin mercaptide, and 59.3 parts of acetone were mixed and added to a reactor. The mixture was replaced with nitrogen three times. Finally, the reactor was stabilized at 0.2 MPa. 0.6 parts of a xylene solution of 1 wt% boron trifluoride ether was added at a temperature of -5°C. The stirring speed was set to 300 rpm, the reaction temperature was -5°C, and the reaction was kept warm for 3 hours to obtain a polymer solution C.

[0111] S4, adding an equal amount of 20 wt% sodium hydroxide aqueous solution to the polymerization solution C, stirring at 200 rpm for 5 min at 25° C., standing to separate the layers, and taking the organic layer, which is recorded as polymerization solution D;

[0112] S5. The polymer solution D is subjected to reduced pressure distillation at 230° C. and -0.1 MPa negative pressure, and the solvent and unreacted raw materials are removed by gas stripping to obtain a 1,5-cyclooctadiene modified petroleum resin.

[0113] The softening point of the product in this example was measured to be 80.2°C, the Gardner color number was 10.1, the viscosity at 200°C was 124mPa·s, the compatibility test conditions were EVA: petroleum resin = 5g:5g, and the measured compatibility result was 168°C.

[0114] Comparative Example 1

[0115] The present invention provides a method for preparing 1,7-isooctadiene modified petroleum resin, comprising:

[0116] S1. Purify the ethylene cracking byproduct by using a distillation tower to obtain raw material A; the chromatographic analysis results of raw material A show that the components are indene, methylindene, naphthalene and methylnaphthalene; in terms of mass ratio, indene:methylindene:naphthalene:methylnaphthalene=75:20:3.5:1.5;

[0117] S2, 80 parts of 1.7-isooctadiene and 20 parts of styrene were mixed, and then 20 parts of 4A grade molecular sieves were added, and dried for 30 hours to obtain raw material B;

[0118] S3. According to the mass fractions, 25 parts of raw material A, 15 parts of raw material B, 0.1 parts of dimethyl tin mercaptide, and 59.3 parts of xylene were mixed and added to a reactor. The mixture was replaced with nitrogen three times. Finally, the reactor was stabilized at 0.2 MPa. 0.6 parts of a xylene solution of 1 wt% boron trifluoride ether was added at a temperature of -5°C. The stirring speed was set to 300 rpm, the reaction temperature was -5°C, and the reaction was kept warm for 3 hours to obtain a polymer solution C.

[0119] S4, adding an equal amount of 20 wt% sodium hydroxide aqueous solution to the polymerization solution C, stirring at 200 rpm for 5 min at 25° C., standing to separate the layers, and taking the organic layer, which is recorded as polymerization solution D;

[0120] S5. The polymer solution D is subjected to reduced pressure distillation at 230° C. and -0.1 MPa negative pressure, and the solvent and unreacted raw materials are removed by gas stripping to obtain a 1,7-isooctadiene modified petroleum resin.

[0121] The softening point of the product in this example was measured to be 99.6°C, the Gardner color number was 8.3, the viscosity at 200°C was 168mPa·s, the compatibility test conditions were EVA: petroleum resin = 5g:5g, and the measured compatibility result was 94°C.

[0122] Comparative Example 2

[0123] The present invention provides a method for preparing 1,7-cyclohexadiene modified petroleum resin, comprising:

[0124] S1. Purify the ethylene cracking byproduct by using a distillation tower to obtain raw material A; the chromatographic analysis results of raw material A show that the components are indene, methylindene, naphthalene and methylnaphthalene; in terms of mass ratio, indene:methylindene:naphthalene:methylnaphthalene=75:20:3.5:1.5;

[0125] S2, 80 parts of 1.7-cyclohexadiene and 20 parts of styrene were mixed, and then 20 parts of 4A grade molecular sieves were added, and dried for 30 hours to obtain raw material B;

[0126] S3. According to the mass fractions, 25 parts of raw material A, 15 parts of raw material B, 0.1 parts of dimethyl tin mercaptide, and 59.3 parts of xylene were mixed and added to a reactor. The mixture was replaced with nitrogen three times. Finally, the reactor was stabilized at 0.2 MPa. 0.6 parts of a xylene solution of 1 wt% boron trifluoride ether was added at a temperature of -5°C. The stirring speed was set to 300 rpm, the reaction temperature was -5°C, and the reaction was kept warm for 3 hours to obtain a polymer solution C.

[0127] S4, adding an equal amount of 20 wt% sodium hydroxide aqueous solution to the polymerization solution C, stirring at 200 rpm for 5 min at 25° C., standing to separate the layers, and taking the organic layer, which is recorded as polymerization solution D;

[0128] S5. The polymer solution D is subjected to reduced pressure distillation at 230° C. and -0.1 MPa negative pressure, and the solvent and unreacted raw materials are removed by gas stripping to obtain a 1,7-cyclohexadiene modified petroleum resin.

[0129] The softening point of the product in this example was measured to be 97.5°C, the Gardner color number was 7.7, the viscosity at 200°C was 133 mPa·s, the compatibility test conditions were EVA: petroleum resin = 5g:5g, and the measured compatibility result was 88°C.

[0130] Performance Evaluation

[0131] The modified petroleum resin prepared in Examples 1-9 and Comparative Examples 1-2 was used to prepare a rubber composition. The raw materials for preparing the rubber composition, in parts by mass, include: 100 parts of base rubber, 30 parts of auxiliary rubber, 20 parts of modified particles, 35 parts of filler, 20 parts of modified petroleum resin, 30 parts of additives, 4 parts of initiator, 8 parts of vulcanizer, and 260 parts of liquid polyisobutylene rubber; the manufacturer brand information of the raw material components is detailed in Table 1.

[0132] Table 1

[0133]

[0134]

[0135] The preparation method of the rubber composition is specifically as follows:

[0136] Step 1: Mix the base auxiliary rubber, modified particles, fillers, 1,5-cyclooctadiene modified petroleum resin and additives for the first time in an internal mixer for 5 minutes, and gradually heat up to 160°C;

[0137] Step 2: Add initiator and vulcanizer, mix the rubber for the second time in the internal mixer for 3 minutes, and gradually raise the temperature to 120℃;

[0138] Step 3: Mix the product obtained in step 2 with liquid polyisobutylene rubber and remove impurities from the particles. After completion, the product is obtained.

[0139] Performance Testing

[0140] 1. Flow properties: The rubber compositions prepared in Examples 1-9 and Comparative Examples 1-2 were tested for complex viscosity using a high-speed rotational rheometer (test conditions: oscillation mode, strain 0.05%, frequency 1 Hz, stress 1 N ± 0.2 N for scanning, initial temperature 30°C, heating rate 5°C / min). The test temperatures were 140°C and 160°C, respectively. The test results are detailed in Table 2.

[0141] Table 2 Flow performance test

[0142]

[0143]

[0144] 2. Low-temperature penetration: The force generated by the equipment sensor after piercing the self-sealing test examples 1-9 and comparative examples 1-2 rubber composition samples 10 mm is used to characterize the hardness of the rubber after being placed at a low temperature of -35°C for 20 minutes. The force value is guaranteed to be within the range of 1400g±500g to meet the low-temperature self-sealing performance of the rubber. The test results are detailed in Table 3.

[0145] Table 3 Low temperature penetration test

[0146] Low temperature penetration test (g) Low temperature penetration test (g) Example 1 1446 Example 2 1471 Example 3 1518 Example 4 1524 Example 5 1458 Example 6 1487 Example 7 1439 Example 8 1402 Example 9 1237 Comparative Example 1 1482 Comparative Example 2 1471

[0147] 3. Thermodynamic balance: The rubber composition of self-sealing Examples 1-9 and Comparative Examples 1-2 with fixed size and thickness of 4-5 mm was tested at 120°C for 2h, and the thermodynamic balance of the rubber was tested on the test plate. The falling distance of the rubber on the test plate was tested to verify the flow resistance of the rubber after high-speed driving in the high-temperature environment of the self-sealing tire. The test results are detailed in Table 4.

[0148] Table 4 Thermal balance test

[0149]

[0150]

[0151] Result analysis:

[0152] Example 3 and Comparative Examples 1 and 2 have obvious performance advantages over other examples in terms of flow performance, plugging performance, and thermal dynamic balance.

[0153] Compared with Comparative Examples 1 and 2, Example 3 is better in terms of performance evaluation in low-temperature penetration and thermal dynamic balance tests.

[0154] Through the above embodiments and application performance tests, it is concluded that when the catalyst is a xylene solution of boron trifluoride etherate, the mass fraction of the catalyst is 0.6 parts, the solvent is a non-polar solvent xylene, the cyclodiene is 1,5-cyclooctadiene, and the ingredient ratio is raw material A: raw material B: solvent: heat stabilizer: catalyst = 25:15:59.3:0.1:0.6, the produced 1,5-cyclooctadiene modified petroleum resin has a wider application range in the field of rubber tires and a better market development prospect.

Claims

1. A method for preparing 1,5-cyclooctadiene modified petroleum resin, characterized in that: include: S1, purifying the ethylene cracking by-product by using a distillation tower to obtain raw material A; S2, mixing the cyclodiolefin and the styrene derivative, adding a molecular sieve, and drying to obtain a raw material B; S3, according to the mass parts, 20-35 parts of raw material A, 5-20 parts of raw material B, 0.05-0.1 parts of heat stabilizer, 50-60 parts of solvent are mixed, added to the reaction kettle, 0.3-0.9 parts of Lewis acid catalyst are added at a temperature of -10--5°C, and then the stirring speed is set to 200-400rpm, the reaction temperature is -5-0°C, and the reaction is carried out for 2-3h to obtain a polymerization solution C; S4, adding alkali solution to polymerization solution C, stirring at a speed of 150-300 rpm for 5-10 min, standing to separate layers, taking the organic layer, and recording it as polymerization solution D; S5. Remove the solvent and unreacted raw materials from the polymerization solution D at 200-260° C. and -0.1 MPa negative pressure to obtain the product.

2. The method for preparing 1,5-cyclooctadiene modified petroleum resin according to claim 1, characterized in that: The raw material A includes: indene, methylindene, naphthalene and methylnaphthalene.

3. The method for preparing 1,5-cyclooctadiene modified petroleum resin according to any one of claims 1 to 2, characterized in that: The cycloalkadiene includes one or more of cyclooctadiene, 1,5-cyclooctadiene, 3-methyl-1,5-cyclooctadiene and 1,7-cyclohexadiene.

4. The method for preparing 1,5-cyclooctadiene modified petroleum resin according to claim 1, characterized in that: The styrene derivatives include: one or more of styrene, methyl styrene, p-tert-butyl styrene, α-methyl styrene, vinyl toluene and polystyrene.

5. The method for preparing 1,5-cyclooctadiene modified petroleum resin according to claim 1, characterized in that: The mass ratio of the cyclodiolefin and the styrene derivative is (50-100):(10-25).

6. The method for preparing 1,5-cyclooctadiene modified petroleum resin according to claim 1, characterized in that: The molecular sieves include: one or more of 3A molecular sieves, 4A molecular sieves, 5A molecular sieves, and 13X molecular sieves.

7. The method for preparing 1,5-cyclooctadiene modified petroleum resin according to claim 1, characterized in that: The heat stabilizer includes an organic tin compound.

8. The method for preparing 1,5-cyclooctadiene modified petroleum resin according to claim 7, characterized in that: The organic tin compound comprises one or more of dibutyltin oxide, dibutyltin dilaurate, dimethyltin mercaptan, dibutyltin dichloride, dibutyltin maleate, dibutyltin maleate laurate, and octyltin mercaptan.

9. The method for preparing 1,5-cyclooctadiene modified petroleum resin according to claim 1, characterized in that: The solvent includes: one or more of hydrogenated white oil, cyclohexane, n-hexane, n-heptane, toluene, xylene and acetone.

10. The method for preparing 1,5-cyclooctadiene modified petroleum resin according to claim 1, characterized in that: The Lewis acid catalyst includes one or more of aluminum chloride, zinc chloride, boron trifluoride etherate and trichloromethane sulfonic acid.

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