Preparation method and product of modified C5 petroleum resin

Abstract

The invention belongs to the technical field of petroleum resin preparation, and relates to a preparation method of modified C5 petroleum resin, specifically, C5 petroleum resin is crushed and then subjected to vacuum plasma gas treatment modification, the plasma gas atmosphere is mixing of O2 and other gases, the modification method is simple and easy to implement, new modification substances do not need to be introduced, no by-product is generated, and the method is suitable for industrial production. Polar groups such as hydroxyl and carboxyl are introduced into original oil-soluble C5 petroleum resin molecules, so that the modified C5 petroleum resin has polarity and strong adhesive force, the softening point of the modified C5 petroleum resin is 105-112 DEG C, and the hue of the modified C5 petroleum resin is 4-6. The high-softening-point resin has the advantages of good high-temperature resistance, good oil resistance, good water resistance and the like, and can be widely applied to high-end and high-requirement technical fields.

Description

Technical Field

[0001] The invention belongs to the technical field of petroleum resin preparation, and relates to a preparation method of a modified C5 petroleum resin and a modified C5 petroleum resin product. Background Art

[0002] With the rapid development of modern economy, people's quality of life is constantly improving, and the requirements for daily necessities are also constantly increasing. In addition to the requirements for product performance, the concepts of safety and environmental protection have also been deeply rooted in people's hearts. C5 petroleum resin is the C5 fraction of cracked ethylene, which is formed by thermal polymerization or catalytic polymerization. The average molecular weight is generally between 1000 and 3000. As a low molecular weight, thermoplastic resin, it has excellent acid and alkali resistance, water resistance, aging resistance, as well as the performance of reducing the pour point, increasing viscosity and improving viscosity. It has been well used in road sign paint, coatings, inks and other industries.

[0003] In recent years, my country has explored the modification methods of C5 petroleum resin. The methods mainly include the following: (1) Hydrogenation modification, that is, under the action of a catalyst, hydrogen reacts with the unsaturated double bonds in the resin to hydrogenate the unsaturated components, and after cooling, hydrogenated petroleum resin is formed. For example, CN102718925A, CN111788240A, CN118344527A, etc. all improve the performance of C5 petroleum resin through hydrogenation reaction. The process of hydrogenation modification requires good control of reaction conditions, such as temperature, pressure and hydrogen flow rate, to ensure the modification effect. In addition, hydrogenation modification increases the risk factor and increases the cost of the resin because it requires additional equipment and energy input. (2) Chemical modification, that is, introducing polar groups into the original oil-soluble C5 petroleum resin molecules to make them have a certain polarity or even water-soluble polymers. CN 108641044 A discloses an acid-modified C5 petroleum resin and a method for preparing the same with controllable molecular weight. The base resin is prepared by polymerization reaction, and then grafted with maleic anhydride as a graft toughening agent to obtain the acid-modified C5 petroleum resin, and finally the molecular weight of the acid-modified petroleum resin is controlled. CN106432610A discloses a new method for preparing a modified C5 petroleum resin for road sign paint. The method directly uses the C5 component, a byproduct of petroleum cracking to produce ethylene, as a chemical reaction raw material, selects an acrylate monomer with antioxidant effect, and copolymerizes it with the olefin in C5 under the condition of effectively controlling the heat of the polymerization reaction to obtain a C5 petroleum resin copolymer with good solubility, moderate molecular weight and strong antioxidant performance; CN111303343A discloses a method for preparing a hydroxylated C5 petroleum resin. After the synthesis of the C5 petroleum resin, it is mixed with a sodium hydroxide aqueous solution, heated, electrolyzed, filtered, desolventized and dried to obtain a hydroxylated C5 petroleum resin with increased hydrophilicity and biocompatibility. CN 104231186 A discloses a method for modifying C5 petroleum resin by radiation grafting acrylic acid monomer. The method uses commercial grade C5 petroleum resin as raw material and acrylic acid as grafting monomer. After irradiation reaction, the non-reacted monomer is removed by vacuum distillation to obtain modified C5 petroleum resin. However, this chemical modification usually uses organic substances such as toluene or xylene as solvent. The use of a large amount of solvent requires the use of a suitable flocculant to precipitate the grafted product during post-treatment. The process is complicated and the solvent is toxic, so the energy consumption is high and the environmental pollution is serious. In addition, chemical modification may introduce some by-products, which affect the quality and performance of the resin. Summary of the invention

[0004] In view of this, the object of the present invention is to provide a method for preparing a C5 petroleum resin based on plasma surface modification, and also to provide a modified C5 petroleum resin with a high softening point, good adhesion, and lower chroma.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] 1. A method for preparing a modified C5 petroleum resin, comprising crushing the C5 petroleum resin and subjecting it to vacuum plasma gas treatment.

[0007] In the preparation method of the modified C5 petroleum resin further described, the atmosphere of the vacuum plasma gas treatment is a mixture of O2 and other gases, and the other gases are selected from CO2, Ar, N2 or air.

[0008] The size of C5 petroleum resin after crushing is 20-40μm.

[0009] In the preparation method of the modified C5 petroleum resin, the O2 flow rate is 20-40 cm 3 / s.

[0010] In the preparation method of the modified C5 petroleum resin further described, when the atmosphere is a mixture of O2 and CO2 or a mixture of O2 and N2, the gas flow rate ratio is 5:4 to 5:5; when the atmosphere is a mixture of O2 and Ar or a mixture of O2 and air, the gas flow rate ratio is 5:1 to 5:2.

[0011] In the preparation method of the modified C5 petroleum resin further described, when the atmosphere is a mixture of O2 and CO2 or a mixture of O2 and N2, the gas flow rate ratio is 5:4 or 5:5; when the atmosphere is a mixture of O2 and Ar or a mixture of O2 and air, the gas flow rate ratio is 5:1 or 5:2.

[0012] In the preparation method of the modified C5 petroleum resin, the vacuum degree during the vacuum plasma gas treatment is 800-1000 Pa. The higher the vacuum degree, the better the modification effect.

[0013] In the preparation method of the modified C5 petroleum resin, the power of the vacuum plasma gas treatment is 600W to 800W, and the time is 3 minutes to 5 minutes.

[0014] In the preparation method of the modified C5 petroleum resin, the C5 raw material contains no more than 34wt% of olefins.

[0015] The preferred C5 raw material composition includes: the C5 raw material composition used is 1.0-3.0wt% of isopentene, 3.0-5.0wt% of cyclopentene, 3.0-6.0wt% of n-pentene, 3.0-6.0wt% of isoprene, 3.0-8.0wt% of cyclopentadiene, 3.0-6.0wt% of isopentadiene, and the rest are saturated C5~C6 alkanes.

[0016] 2. The modified C5 petroleum resin obtained by any of the above preparation methods is also within the protection scope of the present invention.

[0017] The modified C5 petroleum resin provided by the present invention has a high oxygen functional group content, a softening point of 105°C to 112°C, and a hue of 4 to 6. High softening point resin refers to a resin with a higher softening point, usually a resin with a softening point above 100°C.

[0018] The beneficial effects of the present invention are as follows: the present invention provides a preparation method of C5 petroleum resin based on plasma surface modification, the modification method is simple and easy, no new modification substances need to be introduced, no by-products are produced, and polar groups such as hydroxyl and carboxyl are introduced into the C5 petroleum resin molecules which are originally oil-soluble after modification, so that the C5 petroleum resin molecules become polymers with certain polarity or even water-soluble. This method saves energy and reduces emissions, is beneficial to environmental protection, and has the characteristics of high catalytic activity of the product and short reaction time, and can be operated industrially on a large scale; secondly, the modification method of the present invention has little damage to the C5 petroleum resin material, and the C5 petroleum resin can be effectively reduced or oxidized by changing the plasma atmosphere, which not only removes harmful groups on the surface of the C5 petroleum resin, but also introduces beneficial chemical groups on the surface, and the selection of atmosphere and the ratio of atmosphere introduction are diverse, which is helpful to select according to actual conditions, so that the modified C5 petroleum resin has polarity and is better applied to industries such as adhesives and additives for coatings. Furthermore, the modified C5 petroleum resin obtained by the modification method of the present invention has a high softening point, adhesion, and low chroma. The higher the softening point of the C5 petroleum resin, the stronger its cohesive strength, the higher the holding strength of the adhesive, and the wider its application range. The molecular structure of the high softening point resin has better water resistance and can effectively resist the damage of the resin molecules caused by water evaporation, and can be widely used in products that need to be exposed to a humid or water environment for a long time. The lower chroma makes the final product have the ability to resist thermal yellowing and high aging resistance. DETAILED DESCRIPTION

[0019] The preferred embodiment of the present invention is described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention. The experimental methods without specific conditions in the embodiments are usually carried out under conventional conditions or according to the conditions recommended by the manufacturer.

[0020] In addition, for the numerical range in the present invention, it is understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0021] Plasma equipment: The drum-type vacuum plasma equipment produced by Shenzhen Chengfeng Intelligent Manufacturing Co., Ltd. is the operating platform. This equipment uses ENI RF power supply and Avac CRB60 dry vacuum pump.

[0022] When an O2 / CO2 mixed atmosphere is used, the gas flow rate ratio of O2 and CO2 introduced simultaneously is 5:4 to 1:1, and the preferred gas flow rate ratio of O2 and CO2 introduced simultaneously is 5:4 or 1:1, wherein the O2 flow rate is 20-40cm3 / s.

[0023] When an O2 / Ar mixed atmosphere is used, the flow rate ratio of the O2 and Ar gases introduced simultaneously is 5:1 to 5:2, and preferably the flow rate ratio of the O2 and Ar gases introduced simultaneously is 5:1 or 5:2, wherein the O2 flow rate is 20-40 cm3 / s.

[0024] When an O2 / N2 mixed atmosphere is used, the ratio of the gas flow rates of O2 and N2 introduced simultaneously is 5:4 to 1:1, and preferably the ratio of the gas flow rates of O2 and N2 introduced simultaneously is 5:4 or 1:1, wherein the O2 flow rate is 20-40 cm3 / s.

[0025] When an O2 / pure air mixed atmosphere is used, the ratio of the flow rates of the O2 and air gases introduced simultaneously is 5:1 to 5:2, and preferably the ratio of the flow rates of the O2 and air gases introduced simultaneously is 5:1 or 5:2, wherein the O2 flow rate is 20-40 cm3 / s.

[0026] Examples 1-4 show the effects of different treatment atmospheres on the modification results of C5 petroleum resin. The C5 raw material composition used is 1.0-3.0wt% of isopentene, 3.0-5.0wt% of cyclopentene, 3.0-6.0wt% of n-pentene, 3.0-6.0wt% of isoprene, 3.0-8.0wt% of cyclopentadiene, 3.0-6.0wt% of isoprene, and the rest are saturated C5-C6 alkanes such as isopentane, n-pentane, and cyclopentane.

[0027] Example 1

[0028] Powder C5 petroleum resin to 20-40μm, start the plasma equipment and preheat it to 40℃-55℃ for 30min, then put the treated C5 petroleum resin powder into it, connect the O2 gas cylinder and CO2 gas cylinder to the low-temperature plasma treatment system, first evacuate the gas, and after reaching the set value of vacuum degree 800Pa, introduce the O2 / CO2 mixed atmosphere with a flow ratio of 5:4 or 1:1 to normal pressure, evacuate the gas again and keep the internal pressure at 800~1000Pa, where the O2 flow rate is 20-40cm 3 / s, turn on the radio frequency for plasma modification treatment with a power of 600w-800w for 3min-5min to obtain modified C5 petroleum resin 1.

[0029] Example 2

[0030] Powder C5 petroleum resin to 20-40μm, start the plasma equipment and preheat it to 40℃-55℃ for 30min, then put the treated C5 petroleum resin powder into it, connect the O2 gas cylinder and Ar gas cylinder to the low-temperature plasma treatment system, first evacuate the gas, and after reaching the set value of vacuum degree 800Pa, introduce the O2 / Ar mixed atmosphere with a flow rate ratio of 5:1 or 5:2 to normal pressure, evacuate the gas again and keep the internal pressure at 800~1000Pa, where the O2 flow rate is 20-40cm 3 / s, turn on the radio frequency for plasma modification treatment with a power of 600w-800w for 3min-5min to obtain modified C5 petroleum resin 2.

[0031] Example 3

[0032] Powder C5 petroleum resin to 20-40μm, start the plasma equipment and preheat it to 40℃-55℃ for 30min, then put the treated C5 petroleum resin powder into it, connect the O2 gas cylinder and N2 gas cylinder to the low-temperature plasma treatment system, first evacuate the gas, and after reaching the set value of vacuum degree 800Pa, introduce the O2 / N2 mixed atmosphere with a flow rate ratio of 5:4 or 1:1 to normal pressure, evacuate the gas again and keep the internal pressure at 800~1000Pa, where the O2 flow rate is 20-40cm 3 / s, turn on the radio frequency for plasma modification treatment with a power of 600w-800w for 3min-5min to obtain modified C5 petroleum resin 3.

[0033] Example 4

[0034] Powder C5 petroleum resin to 20-40μm, start the plasma equipment and preheat it to 40℃-55℃ for 30min, then put the treated C5 petroleum resin powder into it, connect the O2 gas cylinder, pure air and low-temperature plasma treatment system, first evacuate the air, and after reaching the set value of vacuum degree 800Pa, introduce the O2 / pure air mixed atmosphere with a flow rate ratio of 5:1 or 5:2 to normal pressure, evacuate the air again and keep the internal pressure at 800~1000Pa, where the O2 flow rate is 20-40cm 3 / s, turn on the radio frequency for plasma modification treatment with a power of 600w-800w for 3min-5min to obtain modified C5 petroleum resin 4.

[0035] The relative percentage contents (atomic concentrations) of carbon, oxygen and nitrogen of the modified C5 petroleum resins prepared by Examples 1-4 of the present invention and the unmodified C5 petroleum resins obtained by XPS analysis are shown in Table 1 below:

[0036] Table 1 Atomic concentration of modified and unmodified C5 petroleum resin

[0037]

[0038] By analyzing the chemical shift of carbon element in C5 petroleum resin, the valence state of carbon element is inferred, and then the type of oxygen-containing functional group of C5 petroleum resin is analyzed and the content of various oxygen-containing functional groups is inferred semi-quantitatively to a certain extent, as shown in Table 2. It can be seen from Table 2 that after plasma modification, the content of -C=C- is significantly reduced, and the content of oxygen-containing functional groups is significantly increased.

[0039] Table 2 Functional group content of modified and unmodified C5 petroleum resin

[0040]

[0041] The hue, softening point and static contact angle of the modified C5 petroleum resin prepared by Examples 1-4 of the present invention and the unmodified C5 petroleum resin are compared as shown in Table 3 below. With the change of the functional group, the hue of the modified resin becomes significantly lighter, the softening point increases, and the static contact angle decreases. As an important chemical raw material, C5 petroleum resin can be widely used in technical fields such as adhesives, inks, plastics, coatings, rubber, asphalt, etc. Its technical indicators are an important basis for evaluating the quality of petroleum resins, and are of great significance for ensuring product quality and developing new petroleum resins.

[0042] Table 3 Technical indicators of modified and unmodified C5 petroleum resin

[0043]

[0044]

[0045] Example 5-Example 7

[0046] The influence of different C5 raw material compositions on the modification results of petroleum resin in O2 / CO2 mixed atmosphere.

[0047] The petroleum resins with different C5 raw material olefin compositions are shown in Table 4. The petroleum resins with different C5 raw material compositions are powdered to 20-40 μm. The plasma equipment is turned on and preheated to 40℃-55℃ for 30 minutes, and then the treated C5 petroleum resin powder is put in. The O2 gas cylinder and the CO2 gas cylinder are connected to the low-temperature plasma treatment system. First, the gas is evacuated to reach the set value of 800Pa of vacuum degree, and then the O2 / CO2 mixed atmosphere with a flow rate ratio of 5:4 or 1:1 is introduced to normal pressure, and the gas is evacuated again and the internal pressure is maintained at 800-1000Pa, wherein the O2 flow rate is 20-40cm 3 / s, and carried out plasma modification treatment at a power of 600 W for 3 min to obtain modified C5 petroleum resin 5-modified C5 petroleum resin 7.

[0048] Table 4 Composition of C5 raw materials of Examples 5-7

[0049] C5 raw material composition, wt% Example 5 Example 6 Example 7 Isoprene 3 1 2 Cyclopentene 5 3 5 n-pentene 6 4 6 Isoprene 3 6 3 Cyclopentadiene 3 8 5 Piperylene 3 6 3

[0050] The relative percentage contents (atomic concentrations) of carbon, oxygen and nitrogen of the modified C5 petroleum resins prepared by Examples 5-7 of the present invention and the unmodified C5 petroleum resins obtained by XPS analysis are shown in Table 5 below:

[0051] Table 5 Atomic concentration of modified and unmodified C5 petroleum resin

[0052]

[0053]

[0054] By analyzing the chemical shift of carbon element in C5 petroleum resin, the valence state of carbon element is inferred, and then the type of oxygen-containing functional groups in C5 petroleum resin is analyzed and the contents of various oxygen-containing functional groups are semi-quantitatively inferred to a certain extent. The comparison is shown in Table 6 below.

[0055] Table 6 Functional group content of modified and unmodified C5 petroleum resin

[0056]

[0057] The hue, softening point and static contact angle of the modified C5 petroleum resins prepared in Examples 5 to 7 of the present invention and the unmodified C5 petroleum resin are compared as shown in Table 7 below:

[0058] Table 7 Technical indicators of modified and unmodified C5 petroleum resin

[0059]

[0060]

[0061] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made in form and details without departing from the scope defined by the claims of the present invention.

Claims

1. A method for preparing a modified C5 petroleum resin, characterized in that: The C5 petroleum resin was crushed and then modified by vacuum plasma gas treatment.

2. The method for preparing the modified C5 petroleum resin according to claim 1, characterized in that: The atmosphere of the vacuum plasma gas treatment is a mixture of O 2 and other gases, wherein the other gases are selected from CO 2 , Ar, N 2 or air.

3. The method for preparing the modified C5 petroleum resin according to claim 2, characterized in that: O2 flow rate is 20-40cm 3 / s.

4. The method for preparing the modified C5 petroleum resin according to claim 2 or 3, characterized in that: When the atmosphere is a mixture of O2 and CO2 or a mixture of O2 and N2, the gas flow rate ratio is 5:4 to 5:5; when the atmosphere is a mixture of O2 and Ar or a mixture of O2 and air, the gas flow rate ratio is 5:1 to 5:

2.

5. The method for preparing the modified C5 petroleum resin according to claim 4, characterized in that: When the atmosphere is a mixture of O2 and CO2 or a mixture of O2 and N2, the gas flow rate ratio is 5:4 or 5:5; when the atmosphere is a mixture of O2 and Ar or a mixture of O2 and air, the gas flow rate ratio is 5:1 or 5:

2.

6. The method for preparing the modified C5 petroleum resin according to claim 1, characterized in that: The vacuum degree during vacuum plasma gas treatment is 800-1000Pa.

7. The method for preparing the modified C5 petroleum resin according to claim 1, characterized in that: During vacuum plasma gas treatment, the radio frequency power is 600W to 800W, and the time is 3 to 5 minutes.

8. The method for preparing the modified C5 petroleum resin according to claim 1, characterized in that: The C5 feedstock contains no more than 34 wt% olefins.

9. The method for preparing the modified C5 petroleum resin according to claim 8, characterized in that: The C5 raw material composition includes: the C5 raw material composition used is 1.0-3.0wt% of isopentene, 3.0-5.0wt% of cyclopentene, 3.0-6.0wt% of n-pentene, 3.0-6.0wt% of isoprene, 3.0-8.0wt% of cyclopentadiene, 3.0-6.0wt% of isopentadiene, and the rest are saturated C5~C6 alkanes.

10. The modified C5 petroleum resin obtained by the preparation method according to any one of claims 1 to 9.

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