Petroleum resin softening point regulator as well as preparation method and application thereof

Abstract

The invention discloses a petroleum resin softening point regulator as well as a preparation method and application thereof, and belongs to the technical field of petroleum resin materials. The preparation method of the petroleum resin softening point regulator comprises the following steps: carrying out polymerization reaction on pentadiene and a solvent in the presence of a solid acid catalyst to obtain an intermediate material; carrying out hydrogenation reaction on the intermediate material and hydrogen in the presence of a hydrogenation catalyst to obtain a hydrogenated material; and carrying out solvent removal treatment on the hydrogenated material to obtain the petroleum resin softening point regulator. The preparation method is simple in process and suitable for large-scale production, the prepared petroleum resin softening point regulator can effectively control and regulate the softening point of petroleum resin, the polymerization production cost in the aspect of batching conditions can be reduced, the raw material conversion rate sacrificed for controlling the softening point can be reduced, the VOC content of the resin can be reduced, and the service life of the petroleum resin is prolonged. The problem of caking of petroleum resin is solved.

Description

Technical Field

[0001] The invention relates to the technical field of petroleum resin materials, and in particular to a petroleum resin softening point regulator and a preparation method and application thereof. Background Art

[0002] Petroleum resin is a widely used tackifier in the adhesive industry, which plays a role in improving the initial viscosity, sustained viscosity, elasticity and colloid wettability of adhesives. Softening point is a key performance indicator of petroleum resin, which affects the adhesion, hardness, melt viscosity, heat resistance and cold resistance of adhesives. Therefore, how to control the softening point of petroleum resin is a key control point in the production process of petroleum resin.

[0003] The control of conventional resin softening point is mainly divided into the following methods:

[0004] The first method: Controlling the softening point by adjusting the ingredients and polymerization conditions. This method requires precise proportioning of high-cost raw materials for adjusting mono- and dienes, which leads to high production costs and reduced raw material yields.

[0005] The second method is to control the amount of solvent removed in the stripping unit to control the remaining solvent and oligomers in the resin to achieve the adjustment of the softening point. This method causes the resin product to have agglomeration problems during storage and transportation due to the large amount of residual solvent and oligomers. At the same time, the VOC content of the product is high and the odor is strong.

[0006] In view of this, the present invention is proposed. Summary of the invention

[0007] The object of the present invention is to provide a petroleum resin softening point regulator and a preparation method and application thereof, so as to solve or improve the above technical problems.

[0008] The present invention can be implemented like this:

[0009] In a first aspect, the present invention provides a method for preparing a petroleum resin softening point regulator, which comprises the following steps: subjecting isopentadiene and a solvent to a polymerization reaction in the presence of a solid acid catalyst to obtain an intermediate material; subjecting the intermediate material to a hydrogenation reaction with hydrogen in the presence of a hydrogenation catalyst to obtain a hydrogenated material; and subjecting the hydrogenated material to a solvent removal treatment to obtain a petroleum resin softening point regulator.

[0010] In an optional embodiment, the polymerization reaction includes at least one of the following characteristics:

[0011] Feature 1: The mass ratio of piperylene to solvent is 1:3 to 1:10;

[0012] Feature 2: The polymerization temperature is 10°C to 60°C;

[0013] Feature 3: The polymerization reaction pressure is 0.4 MPa to 1.0 MPa in gauge pressure.

[0014] Feature 4: The feed space velocity of isobutylene is 3h -1 ~10h -1 ;

[0015] Feature 5: The solvent includes at least one of cyclopentane, n-pentane, isopentane, and C6-C8 alkanes;

[0016] Feature 6: The solid acid catalyst includes at least one of a cation exchange resin, a supported acid, and a metal oxide.

[0017] In an optional embodiment, the mass ratio of piperylene to solvent is 1:5 to 1:8.

[0018] In an optional embodiment, the polymerization reaction temperature is 40°C to 50°C.

[0019] In an optional embodiment, the polymerization reaction pressure is 0.6 MPa to 0.8 MPa in gauge pressure.

[0020] In an optional embodiment, the feed space velocity of piperylene is 4h -1 ~6h -1 .

[0021] In an alternative embodiment, the solvent comprises at least one of cyclopentane, n-pentane and isopentane.

[0022] In an alternative embodiment, the solid acid catalyst comprises at least one of divinylbenzene copolymer, perfluorosulfonic acid resin, ZnO, H2SO4-SiO2 and H3PO4-SiO2.

[0023] In an optional embodiment, the polymerization reaction is carried out using a fixed tubular heat exchange synthesis reactor;

[0024] The fixed tube heat exchange synthesis reactor comprises a tube layer and a shell layer, the solid acid catalyst is loaded in the tube layer, and a heat exchange medium flows in the shell layer.

[0025] In an optional embodiment, the hydrogenation reaction includes at least one of the following features:

[0026] Feature 7: The temperature of the hydrogenation reaction is 100°C to 200°C;

[0027] Feature 8: The pressure of the hydrogenation reaction is 2MPa to 6MPa in gauge pressure;

[0028] Feature 9: The feed space velocity of the intermediate material is 0.5h-1 ~3h -1 ;

[0029] Feature 10: The volume ratio of hydrogen to the intermediate material is 100:1 to 400:1;

[0030] Feature 11: The hydrogenation catalyst comprises a carrier and an active component; wherein the carrier comprises alumina, silicon oxide or carbon, and the active component comprises at least one of Pd, Ni, Pt, Rh, Wu and Mo;

[0031] Feature 12: The reactor used for the hydrogenation reaction includes a fixed bed reactor, an ebullating bed hydrogenation reactor or a loop hydrogenation reactor.

[0032] In an optional embodiment, the temperature of the hydrogenation reaction is 120°C to 160°C.

[0033] In an optional embodiment, the pressure of the hydrogenation reaction is 4 MPa to 5 MPa in gauge pressure.

[0034] In an optional embodiment, the feed space velocity of the intermediate material is 1h -1 ~2h -1 .

[0035] In an optional embodiment, the volume ratio of hydrogen to the intermediate material is 200:1 to 300:1.

[0036] In an optional embodiment, the carrier in the hydrogenation catalyst is alumina, and the active component includes at least one of Pd, Ni and Pt.

[0037] In an optional embodiment, the solvent removal treatment is performed by flash evaporation.

[0038] In an optional embodiment, the operating temperature of the flash evaporation is 210° C. to 260° C.; in terms of gauge pressure, the operating pressure of the flash evaporation is 1 KPa to 50 KPa.

[0039] In an optional embodiment, the method further comprises: performing a de-weighting treatment on the removed solvent to obtain a recovered solvent; and recycling the recovered solvent to the polymerization reaction process for use.

[0040] In an optional embodiment, the operating temperature of the de-weighting treatment is 120°C to 140°C; the operating pressure of the de-weighting treatment is 1KPa to 50KPa in gauge pressure; and the reflux ratio of the de-weighting treatment is 0.5:1 to 1:1.

[0041] In a second aspect, the present invention provides a petroleum resin softening point regulator, which is prepared by the preparation method of any one of the aforementioned embodiments.

[0042] In a third aspect, the present invention provides use of the petroleum resin softening point regulator according to the aforementioned embodiment in regulating the softening point of a petroleum resin.

[0043] In an optional embodiment, the petroleum resin softening point regulator is used to adjust the softening point of the petroleum resin to 85°C to 130°C.

[0044] In a fourth aspect, the present invention provides a method for adjusting the softening point of a petroleum resin, comprising the following steps: mixing the petroleum resin softening point regulator of the aforementioned embodiment with a petroleum resin.

[0045] In an optional embodiment, the mass ratio of the petroleum resin softening point regulator to the petroleum resin is 1:100 to 5:100.

[0046] The beneficial effects of the present invention include:

[0047] The invention prepares a petroleum resin softening point regulator by polymerizing isoprene with a solvent in the presence of a solid acid catalyst, and by hydrogenation and solvent stripping. The process route is simple and reliable, has low requirements on equipment, and is suitable for large-scale production. By adding a petroleum resin softening point regulator to control the softening point after deep drawing of the petroleum resin, the polymerization production cost in terms of batching conditions can be reduced, and the raw material conversion rate sacrificed for controlling the softening point can also be reduced. In addition, the method can also reduce the VOC content of the petroleum resin and solve the problem of petroleum resin agglomeration. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0049] Figure 1 1 is a flow chart of the preparation process of the petroleum resin softening point regulator in the examples.

[0050] Icons: V1-dosing tank; V2-intermediate buffer tank; V3-flash tank; R1-synthesis reactor; R2-hydrogenation reactor; P1-first feed pump; P2-second feed pump; P3-first production pump; P4-second production pump; T1-deweight removal tower; F1-industrial isoprene; F2-fresh solvent; F3-mixed material; F4-intermediate material; F5-hydrogenation feed material; F6-hydrogen; F7-hydrogenation material; F8-tank top solvent; F9-recovery solvent; F10-oligomer; F11-petroleum resin softening point regulator. DETAILED DESCRIPTION

[0051] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0052] The petroleum resin softening point regulator provided by the present invention and its preparation method and application are specifically described below.

[0053] The present invention provides a method for preparing a petroleum resin softening point regulator, which comprises the following steps:

[0054] Step S1: performing polymerization reaction on isopentadiene and a solvent in the presence of a solid acid catalyst to obtain an intermediate material.

[0055] In this step, piperylene and the solvent may be first mixed in a batching container, and then pressurized by a pump and fed into a synthesis reactor for polymerization reaction.

[0056] In some optional embodiments, the mass ratio of piperylene to the solvent can be 1:3 to 1:10, such as 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc., or other values ​​within the range of 1:3 to 1:10. In some typical embodiments, the mass ratio of piperylene to the solvent is 1:5 to 1:8.

[0057] Wherein, piperylene can directly adopt industrial piperylene. The solvent can illustratively include at least one of cyclopentane, normal pentane, isopentane, and C6-C8 alkanes. In some typical embodiments, the solvent includes at least one of cyclopentane, normal pentane, and isopentane.

[0058] In some optional embodiments, the above polymerization reaction can be carried out in a fixed tubular heat exchange synthesis reactor. The fixed tubular heat exchange synthesis reactor includes a tube layer and a shell layer, wherein the solid acid catalyst is loaded in the tube layer, and a heat exchange medium (such as cooling water, etc.) flows in the shell layer. The heat exchange medium is used to take heat to control the reaction temperature.

[0059] The use of a fixed tubular heat exchange synthesis reactor for the synthesis of a petroleum resin softening point regulator can quickly reduce the reaction temperature to carry out a constant temperature reaction, which is beneficial for making the molecular weight distribution of the petroleum resin softening point regulator obtained by the reaction narrower.

[0060] In some optional embodiments, the solid acid catalyst may illustratively include at least one of a cation exchange resin, a supported acid, and a metal oxide. In some relatively typical embodiments, the solid acid catalyst includes at least one of a divinylbenzene copolymer, a perfluorosulfonic acid resin, ZnO, H2SO4-SiO2, and H3PO4-SiO2.

[0061] The use of solid acid catalysts in the production of petroleum resin softening point regulators is beneficial to avoiding the subsequent catalyst removal process, reducing the generation of wastewater, and the process route is safe and environmentally friendly.

[0062] In some optional embodiments, the polymerization temperature can be 10° C. to 60° C., such as 10° C., 15° C., 20° C., 25° C., 30° C., 35° C., 40° C., 45° C., 50° C., 55° C. or 60° C., or other values ​​within the range of 10° C. to 60° C. In some typical embodiments, the polymerization temperature is 40° C. to 50° C.

[0063] In some optional embodiments, the polymerization reaction pressure can be 0.4MPa to 1.0MPa, such as 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa or 1.0MPa, etc., in gauge pressure, or other values ​​within the range of 0.4MPa to 1.0MPa. In some typical embodiments, the polymerization reaction pressure is 0.6MPa to 0.8MPa in gauge pressure.

[0064] In some optional embodiments, the feed space velocity of piperylene can be 3h -1 ~10h -1 , such as 3h -1 , 4h -1 , 5h -1 , 6h -1 , 7h -1 , 8h -1 , 9h -1 or 10h -1 etc., can also be 3h -1 ~10h -1 In some typical embodiments, the feed space velocity of piperylene is 4h -1 ~6h -1 .

[0065] Step S2: hydrogenating the intermediate material with hydrogen in the presence of a hydrogenation catalyst to obtain a hydrogenated material.

[0066] In some optional embodiments, the intermediate material obtained in step S1 may be first introduced into an intermediate buffer container, then pressurized by a hydrogenation feed pump and mixed with hydrogen, and then sent to a hydrogenation reactor for hydrogenation reaction. The hydrogenation reactor may exemplarily include a fixed bed reactor, an ebullating bed hydrogenation reactor, or a loop hydrogenation reactor.

[0067] In some optional embodiments, the temperature of the hydrogenation reaction can be 100° C. to 200° C., such as 100° C., 110° C., 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., 190° C. or 200° C., etc., or other values ​​within the range of 100° C. to 200° C. In some typical embodiments, the temperature of the hydrogenation reaction is 120° C. to 160° C.

[0068] In some optional embodiments, the pressure of the hydrogenation reaction can be 2MPa to 6MPa, such as 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, 5.5MPa or 6MPa, etc., as a gauge pressure, or other values ​​within the range of 2MPa to 6MPa. In some typical embodiments, the pressure of the hydrogenation reaction is 4MPa to 5MPa as a gauge pressure.

[0069] In some optional embodiments, the feed space velocity of the intermediate material can be 0.5h -1 ~3h -1 , such as 0.5h -1 , 1h -1 , 1.5h -1 , 2h -1 , 2.5h -1 or 3h -1 etc., can also be 0.5h -1 ~3h -1 In some typical embodiments, the feed space velocity of the intermediate material is 1h -1 ~2h -1 .

[0070] In some optional embodiments, the volume ratio of hydrogen to the intermediate material can be 100: 1 to 400: 1, such as 100: 1, 150: 1, 200: 1, 250: 1, 300: 1, 350: 1 or 400: 1, etc., or other values ​​within the range of 100: 1 to 400: 1. In some typical embodiments, the volume ratio of hydrogen to the intermediate material is 200: 1 to 300: 1.

[0071] In some optional embodiments, the hydrogenation catalyst includes a carrier and an active component; wherein the carrier may include alumina, silicon oxide or carbon, and the active component may include at least one of Pd, Ni, Pt, Rh, Wu and Mo. In some typical embodiments, the carrier in the hydrogenation catalyst is alumina, and the active component includes at least one of Pd, Ni and Pt, such as Pd / Al2O3, Ni / Al2O3 or Pb-Pt / Al2O3.

[0072] Step S3: removing the solvent from the hydrogenated material to obtain a petroleum resin softening point regulator.

[0073] The solvent removal treatment can be carried out by flash evaporation, and the process can be carried out in a flash tank.

[0074] In some optional embodiments, the operating temperature of the flash evaporation can be 210°C to 260°C, such as 210°C, 220°C, 230°C, 240°C, 250°C or 260°C, or other values ​​within the range of 210°C to 260°C.

[0075] In some optional embodiments, the operating pressure of the flash evaporation can be 1 KPa to 50 KPa, such as 1 KPa, 5 KPa, 10 KPa, 15 KPa, 20 KPa, 25 KPa, 30 KPa, 35 KPa, 40 KPa, 45 KPa or 50 KPa, etc., in gauge pressure, or other values ​​within the range of 1 KPa to 50 KPa.

[0076] The product at the bottom of the flash tank can be pressurized and sent out of the flash tank and processed as needed.

[0077] Furthermore, the preparation process of the petroleum resin softening point regulator provided by the present invention may also include step S4: performing a deweighting treatment on the removed solvent to obtain a recovered solvent; and recycling the recovered solvent to the polymerization reaction process for use.

[0078] It should be noted that, during normal production, the solvent is fully circulated and applied; when the temperature of the 90% point of the solvent distillation range is greater than 260°C, de-weighting treatment is carried out.

[0079] In some optional embodiments, the solvent removed from the top of the flash tank can be passed into a deweighting tower, which can be used as a system solvent deweighting replacement tower. The oligomers obtained at the bottom of the deweighting tower are pressurized by a production pump and then produced and processed as needed.

[0080] When the recovered solvent is recycled to the polymerization process, the total amount of the recovered solvent and the fresh solvent must satisfy a mass ratio of piperylene to the solvent of 1:3 to 1:10. In other words, the insufficient amount of the recovered solvent is supplemented by newly adding fresh solvent.

[0081] In some optional embodiments, the operating temperature of the deweighting treatment can be 120°C to 140°C, such as 120°C, 125°C, 130°C, 135°C or 140°C, etc., or other values ​​within the range of 120°C to 140°C.

[0082] In some optional embodiments, the operating pressure of the deweighting treatment can be 1 KPa to 50 KPa, such as 1 KPa, 5 KPa, 10 KPa, 15 KPa, 20 KPa, 25 KPa, 30 KPa, 35 KPa, 40 KPa, 45 KPa or 50 KPa, etc., in terms of gauge pressure, or other values ​​within the range of 1 KPa to 50 KPa.

[0083] In some optional embodiments, the reflux ratio of the deweighting treatment can be 0.5:1 to 1:1, such as 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1 or 1:1, or other values ​​within the range of 0.5:1 to 1:1.

[0084] As described above, the present invention prepares a petroleum resin softening point regulator by polymerizing isopentylene with a solvent in the presence of a solid acid catalyst, and performing hydrogenation and solvent stripping. The process route is simple and reliable, has low requirements on equipment, and is suitable for large-scale production.

[0085] Correspondingly, the present invention also provides a petroleum resin softening point regulator, which is prepared by the preparation method of any one of the aforementioned implementation modes.

[0086] In addition, the present invention also provides a use of the petroleum resin softening point regulator in regulating the softening point of petroleum resin.

[0087] Exemplarily, the petroleum resin softening point regulator can be used to adjust the softening point of the petroleum resin to 85°C to 130°C.

[0088] Correspondingly, the present invention also provides a method for adjusting the softening point of petroleum resin, comprising the following steps: mixing the above petroleum resin softening point regulator with the petroleum resin.

[0089] In some optional embodiments, the mass ratio of the petroleum resin softening point regulator to the petroleum resin can be 1:100 to 5:100, such as 1:100, 1.5:100, 2:100, 2.5:100, 3:100, 3.5:100, 4:100, 4.5:100 or 5:100, or other values ​​within the range of 1:100 to 5:100.

[0090] Exemplarily, the petroleum resin softening point regulator is mixed with the petroleum resin obtained by deep drawing in a petroleum resin device, and the mixing process is carried out on a pipeline or in a stirring tank.

[0091] By adding a petroleum resin softening point regulator to control the softening point of the petroleum resin after deep drawing, a petroleum resin with a low softening point (softening point below 120°C) can be obtained. The petroleum resin with a low softening point has no odor and VOC can be reduced to below 50ppm. In addition, by using a petroleum resin softening point regulator to adjust the softening point of the petroleum resin, the problem of agglomeration of the petroleum resin during storage and transportation can also be solved.

[0092] As mentioned above, the petroleum resin softening point regulator provided by the present invention can realize the control and regulation of the softening point of the petroleum resin, can reduce the polymerization production cost in terms of ingredient conditions, and can also reduce the raw material conversion rate sacrificed in order to control the softening point. In addition, the method can also reduce the VOC content of the petroleum resin and solve the problem of petroleum resin agglomeration.

[0093] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0094] The specifications of industrial isopentadiene, industrial cyclopentane and base petroleum resin used in the following examples are shown in Tables 1 to 3 respectively.

[0095] Table 1 Specifications of Industrial Piperylene

[0096] project index Experimental methods Appearance Clear and transparent liquid, no mechanical impurities Visual inspection Piperylene ≥60wt% SH / T 1790 trans-1,3-pentadiene ≥38wt% SH / T 1790 Dicyclopentadiene + Cyclopentadiene ≤1.5wt% SH / T 1790 Moisture ≤0.025wt% SH / T0246

[0097] Table 2 Specifications of industrial petroleum-based cyclopentane

[0098] project index Appearance Colorless and transparent, no visible impurities <![CDATA[Density, ρ 20 > <![CDATA[740.0kg / m 3 ~760.0kg / m 3 ]]> Cyclopentane ≥95.0wt% Total unsaturated hydrocarbons ≤0.020wt% n-Hexane ≤10mg / kg benzene ≤1mg / kg Naphthalene ≤1mg / kg Moisture ≤0.010wt% sulfur ≤1 μg / mL

[0099] Table 3 Specifications of basic petroleum resin

[0100]

[0101] Example 1

[0102] This embodiment provides a petroleum resin softening point regulator and its application, please refer to Figure 1 The preparation of the petroleum resin softening point regulator comprises the following steps:

[0103] Step S1: industrial isopentadiene F1 and solvent (cyclopentane) are mixed in a batching tank V1 at a mass ratio of 1:6 to obtain a mixture F3; the mixture F3 is then pressurized to 0.8MPa (gauge pressure) by the first feed pump P1 and fed into the synthesis reactor R1 for polymerization reaction. The synthesis reactor R1 is a fixed tubular heat exchange synthesis reactor, which includes a tube layer and a shell layer, wherein a solid acid catalyst (perfluorosulfonic acid resin) is loaded in the tube layer, and cooling water flows in the shell layer. The feed space velocity of isopentadiene is controlled to be 6h by the feed amount. -1The polymerization reaction temperature is controlled to be 45°C by the cooling water control valve of R1 of the synthesis reactor, and the intermediate material F4 obtained after the reaction is sent to the intermediate buffer tank V2.

[0104] Step S2: The intermediate material F4 in the intermediate buffer tank V2 is pressurized to 5 MPa (gauge pressure) by the second feed pump P2, mixed with hydrogen F6 to obtain hydrogenation feed material F5 and fed into the hydrogenation reactor R2 (fixed bed reactor) for hydrogenation reaction. The temperature of the hydrogenation reaction is controlled to be 140°C, the hydrogen-oil volume ratio is 300:1, and the hydrogenation reaction space velocity is controlled to be 2h by the feed amount. -1 After hydrogenation reaction, hydrogenated material F7 is obtained. The hydrogenation catalyst used in the hydrogenation reaction is Pd / Al2O3.

[0105] Step S3: The hydrogenated material F7 is sent to the flash tank V3 for solvent removal treatment, the temperature of the flash tank V3 is controlled to be 220°C, and the flash pressure is 30KPa (in gauge pressure), and the petroleum resin softening point regulator F11 is obtained at the bottom of the flash tank. The petroleum resin softening point regulator F11 is pressurized by the first production pump P3 and sent out of the flash tank V3 and processed as needed.

[0106] Step S4: The tank top solvent F8 flashed out from the tank top of the flash tank V3 is introduced into the de-weighting tower T1, and the operating pressure of the de-weighting tower T1 is controlled to be 30KPa (in gauge pressure), the operating temperature is 130°C, and the reflux ratio is 0.8:1. The recovered solvent F9 is obtained from the top of the de-weighting tower T1 and is recycled to the polymerization reaction process of step S1 (the insufficient amount of the recovered solvent F9 is supplemented by the fresh solvent F2), and the oligomer F10 obtained from the bottom of the de-weighting tower T1 is produced after being pressurized by the second production pump P4 and processed as needed.

[0107] Application: The petroleum resin softening point regulator obtained above was added to the base petroleum resin at 110°C in an amount of 2wt%, and the changes in softening point and thermal weight loss before and after were analyzed. The final VOC content was analyzed by liquid chromatography. The results are shown in Table 4.

[0108] Example 2

[0109] This embodiment provides a petroleum resin softening point regulator and its application. The difference between the preparation method of the petroleum resin softening point regulator and that of Example 1 is that in step S1, the polymerization reaction temperature is 50°C.

[0110] Application: The petroleum resin softening point regulator obtained above was added to the base petroleum resin at 110°C in an amount of 2wt%, and the changes in softening point and thermal weight loss before and after were analyzed. The final VOC content was analyzed by liquid chromatography. The results are shown in Table 4.

[0111] Example 3

[0112] This embodiment provides a petroleum resin softening point regulator and its application. The preparation method of the petroleum resin softening point regulator is different from that of Example 1 in that: in step S1, the feed space velocity of isobutylene is 4h -1 .

[0113] Application: The petroleum resin softening point regulator obtained above was added to the base petroleum resin at 110°C in an amount of 2wt%, and the changes in softening point and thermal weight loss before and after were analyzed. The final VOC content was analyzed by liquid chromatography. The results are shown in Table 4.

[0114] Example 4

[0115] This embodiment provides a petroleum resin softening point regulator and its application. The preparation method of the petroleum resin softening point regulator is the same as that of Example 2.

[0116] Application: The obtained petroleum resin softening point regulator was added into the base petroleum resin at 110°C at an amount of 3wt%, and the changes of softening point and thermal weight loss before and after were analyzed. The final VOC content was analyzed by liquid chromatography. The results are shown in Table 4.

[0117] Example 5

[0118] This embodiment provides a petroleum resin softening point regulator and its application. The preparation method of the petroleum resin softening point regulator is the same as that of Example 1.

[0119] Application: The obtained petroleum resin softening point regulator was added into the base petroleum resin at 120°C at an amount of 2wt%. The changes of softening point and thermal weight loss before and after were analyzed. The final VOC content was analyzed by liquid chromatography. The results are shown in Table 4.

[0120] Example 6

[0121] This embodiment provides a petroleum resin softening point regulator and its application. The preparation method of the petroleum resin softening point regulator is the same as that of Example 1.

[0122] Application: The obtained petroleum resin softening point regulator was added into the base petroleum resin at 130°C at an amount of 2wt%. The changes of softening point and thermal weight loss before and after were analyzed. The final VOC content was analyzed by liquid chromatography. The results are shown in Table 4.

[0123] Example 7

[0124] This embodiment provides a petroleum resin softening point regulator and its application. The preparation method of the petroleum resin softening point regulator comprises the following steps:

[0125] Step S1: industrial isopentadiene F1 and solvent (n-pentane) are mixed in a batching tank V1 at a mass ratio of 1:5 to obtain a mixture F3; the mixture F3 is then pressurized to 0.6MPa (gauge pressure) by the first feed pump P1 and fed into the synthesis reactor R1 for polymerization reaction. The synthesis reactor R1 is a fixed tubular heat exchange synthesis reactor, which includes a tube layer and a shell layer, wherein a solid acid catalyst (perfluorosulfonic acid resin) is loaded in the tube layer, and cooling water flows in the shell layer. The feed space velocity of isopentadiene is controlled to be 4h by the feed amount. -1 The polymerization reaction temperature is controlled to be 40°C by the cooling water control valve of R1 of the synthesis reactor, and the intermediate material F4 obtained after the reaction is sent to the intermediate buffer tank V2.

[0126] Step S2: The intermediate material F4 in the intermediate buffer tank V2 is pressurized to 4 MPa (gauge pressure) by the second feed pump P2, mixed with hydrogen F6 to obtain hydrogenation feed material F5 and fed into the hydrogenation reactor R2 (ebullated bed hydrogenation reactor) for hydrogenation reaction. The temperature of the hydrogenation reaction is controlled to be 160°C, the hydrogen-oil volume ratio is 200:1, and the hydrogenation reaction space velocity is controlled to be 1h by the feed amount. -1 After hydrogenation reaction, hydrogenated material F7 is obtained. The hydrogenation catalyst used in the hydrogenation reaction is Pd / Al2O3.

[0127] Step S3: The hydrogenated material F7 is sent to the flash tank V3 for solvent removal treatment, the temperature of the flash tank V3 is controlled to be 210°C, and the flash pressure is 1 KPa (in gauge pressure), and the petroleum resin softening point regulator F11 is obtained at the bottom of the flash tank. The petroleum resin softening point regulator F11 is pressurized by the first production pump P3 and sent out of the flash tank V3 and processed as needed.

[0128] Step S4: The tank top solvent F8 flashed out from the tank top of the flash tank V3 is introduced into the de-weighting tower T1, and the operating pressure of the de-weighting tower T1 is controlled to be 1KPa (in gauge pressure), the operating temperature is 120°C, and the reflux ratio is 0.5:1. The recovered solvent F9 is obtained from the top of the de-weighting tower T1 and is recycled to the polymerization reaction process of step S1 (the insufficient amount of the recovered solvent F9 is supplemented by the fresh solvent F2), and the oligomer F10 obtained from the bottom of the de-weighting tower T1 is produced after being pressurized by the second production pump P4 and processed as needed.

[0129] Application: The petroleum resin softening point regulator obtained above was added to the base petroleum resin at 110°C in an amount of 2wt%, and the changes in softening point and thermal weight loss before and after were analyzed. The final VOC content was analyzed by liquid chromatography. The results are shown in Table 4.

[0130] Example 8

[0131] This embodiment provides a petroleum resin softening point regulator and its application. The preparation method of the petroleum resin softening point regulator comprises the following steps:

[0132] Step S1: industrial isopentane F1 is mixed with solvent (isopentane) in a batching tank V1 at a mass ratio of 1:8 to obtain a mixture F3; the mixture F3 is then pressurized to 0.7MPa (gauge pressure) by the first feed pump P1 and fed into the synthesis reactor R1 for polymerization reaction. The synthesis reactor R1 is a fixed tubular heat exchange synthesis reactor, which includes a tube layer and a shell layer, wherein a solid acid catalyst (H2SO4-SiO2) is loaded in the tube layer, and cooling water flows in the shell layer. The feed space velocity of isopentane is controlled to 5h by the feed amount. -1 The polymerization reaction temperature is controlled to be 50°C by the cooling water control valve of R1 of the synthesis reactor, and the intermediate material F4 obtained after the reaction is sent to the intermediate buffer tank V2.

[0133] Step S2: The intermediate material F4 in the intermediate buffer tank V2 is pressurized to 4.5 MPa (gauge pressure) by the second feed pump P2, mixed with hydrogen F6 to obtain hydrogenation feed material F5 and enters the hydrogenation reactor R2 (loop hydrogenation reactor) for hydrogenation reaction. The temperature of the hydrogenation reaction is controlled to be 120°C, the hydrogen-to-oil volume ratio is 250:1, and the hydrogenation reaction space velocity is controlled to be 1.5 h by the feed amount. -1 After hydrogenation reaction, hydrogenated material F7 is obtained. The hydrogenation catalyst used in the hydrogenation reaction is Ni / Al2O3.

[0134] Step S3: The hydrogenated material F7 is sent to the flash tank V3 for solvent removal treatment, the temperature of the flash tank V3 is controlled to be 260°C, and the flash pressure is 50KPa (in gauge pressure), and the petroleum resin softening point regulator F11 is obtained at the bottom of the flash tank. The petroleum resin softening point regulator F11 is pressurized by the first production pump P3 and sent out of the flash tank V3 and processed as needed.

[0135] Step S4: The tank top solvent F8 flashed out from the tank top of the flash tank V3 is introduced into the de-weighting tower T1, and the operating pressure of the de-weighting tower T1 is controlled to be 50KPa (in gauge pressure), the operating temperature is 140°C, and the reflux ratio is 1:1. The recovered solvent F9 is obtained from the top of the de-weighting tower T1 and is recycled to the polymerization reaction process of step S1 (the insufficient amount of the recovered solvent F9 is supplemented by the fresh solvent F2), and the oligomer F10 obtained from the bottom of the de-weighting tower T1 is produced after being pressurized by the second production pump P4 and processed as needed.

[0136] Application: The petroleum resin softening point regulator obtained above was added to the base petroleum resin at 110°C in an amount of 2wt%, and the changes in softening point and thermal weight loss before and after were analyzed. The final VOC content was analyzed by liquid chromatography. The results are shown in Table 4.

[0137] Example 9

[0138] This embodiment provides a petroleum resin softening point regulator and its application. The preparation method of the petroleum resin softening point regulator comprises the following steps:

[0139] Step S1: industrial isopentadiene F1 and solvent (cyclopentane) are mixed in a batching tank V1 at a mass ratio of 1:3 to obtain a mixture F3; the mixture F3 is then pressurized to 0.4MPa (gauge pressure) by the first feed pump P1 and fed into the synthesis reactor R1 for polymerization reaction. The synthesis reactor R1 is a fixed tubular heat exchange synthesis reactor, which includes a tube layer and a shell layer, wherein a solid acid catalyst (ZnO) is loaded in the tube layer, and cooling water flows in the shell layer. The feed space velocity of isopentadiene is controlled to be 3h by the feed amount. -1 The polymerization reaction temperature is controlled to be 10°C by the cooling water control valve of R1 of the synthesis reactor, and the intermediate material F4 obtained after the reaction is sent to the intermediate buffer tank V2.

[0140] Step S2: The intermediate material F4 in the intermediate buffer tank V2 is pressurized to 2 MPa (gauge pressure) by the second feed pump P2, mixed with hydrogen F6 to obtain hydrogenation feed material F5 and fed into the hydrogenation reactor R2 (ebullating bed hydrogenation reactor) for hydrogenation reaction. The temperature of the hydrogenation reaction is controlled to be 100°C, the hydrogen-oil volume ratio is 100:1, and the hydrogenation reaction space velocity is controlled to be 0.5h by the feed amount. -1 After hydrogenation reaction, hydrogenated material F7 is obtained. The hydrogenation catalyst used in the hydrogenation reaction is Pd / Al2O3.

[0141] Step S3: Same as Example 1.

[0142] Step S4: Same as Example 1.

[0143] Application: The petroleum resin softening point regulator obtained above was added to the base petroleum resin at 110°C in an amount of 2wt%, and the changes in softening point and thermal weight loss before and after were analyzed. The final VOC content was analyzed by liquid chromatography. The results are shown in Table 4.

[0144] Example 10

[0145] This embodiment provides a petroleum resin softening point regulator and its application. The preparation method of the petroleum resin softening point regulator comprises the following steps:

[0146] Step S1: industrial isopentadiene F1 and solvent (cyclopentane) are mixed in a batching tank V1 at a mass ratio of 1:10 to obtain a mixture F3; the mixture F3 is then pressurized to 1.0 MPa (gauge pressure) by the first feed pump P1 and fed into the synthesis reactor R1 for polymerization reaction. The synthesis reactor R1 is a fixed tubular heat exchange synthesis reactor, which includes a tube layer and a shell layer, wherein a solid acid catalyst (divinylbenzene copolymer) is loaded in the tube layer, and cooling water flows in the shell layer. The feed space velocity of isopentadiene is controlled to be 10h by the feed amount. -1 The polymerization reaction temperature is controlled to be 60°C by the cooling water control valve of R1 of the synthesis reactor, and the intermediate material F4 obtained after the reaction is sent to the intermediate buffer tank V2.

[0147] Step S2: The intermediate material F4 in the intermediate buffer tank V2 is pressurized to 6 MPa (gauge pressure) by the second feed pump P2, mixed with hydrogen F6 to obtain hydrogenation feed material F5 and fed into the hydrogenation reactor R2 (ebullating bed hydrogenation reactor) for hydrogenation reaction. The temperature of the hydrogenation reaction is controlled to be 200°C, the hydrogen-oil volume ratio is 400:1, and the hydrogenation reaction space velocity is controlled to be 3h by the feed amount. -1 After hydrogenation reaction, hydrogenated material F7 is obtained. The hydrogenation catalyst used in the hydrogenation reaction is Pd-Pt / Al2O3.

[0148] Step S3: Same as Example 1.

[0149] Step S4: Same as Example 1.

[0150] Application: The petroleum resin softening point regulator obtained above was added to the base petroleum resin at 110°C in an amount of 2wt%, and the changes in softening point and thermal weight loss before and after were analyzed. The final VOC content was analyzed by liquid chromatography. The results are shown in Table 4.

[0151] Test example

[0152] The petroleum resin softening point regulators obtained in the above Examples 1 to 10 were analyzed for their dropping points using a dropping point tester, their molecular weights using liquid chromatography, their color numbers using a HunterLab yellowness index meter, and their viscosities using a rotational viscometer. The results are also shown in Table 4.

[0153] Table 4 Experimental results

[0154]

[0155] It can be seen from Table 4 that the petroleum resin softening point regulator provided by the present invention can effectively adjust the softening point of the petroleum resin at a relatively low dosage, and can obtain a petroleum resin with a relatively low softening point and a small change in thermal weight loss.

[0156] In summary, the present invention prepares a petroleum resin softening point regulator by polymerizing isoprene with a solvent in the presence of a solid acid catalyst, and by hydrogenation and solvent stripping. The process route is simple and reliable, has low requirements on equipment, and is suitable for large-scale production. By adding a petroleum resin softening point regulator to control the softening point after deep drawing of the petroleum resin, the polymerization production cost in terms of batching conditions can be reduced, and the raw material conversion rate sacrificed for controlling the softening point can also be reduced. In addition, the method can also reduce the VOC content of the petroleum resin and solve the problem of petroleum resin agglomeration.

[0157] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a petroleum resin softening point regulator, characterized in that: The method comprises the following steps: subjecting isopentadiene and a solvent to a polymerization reaction in the presence of a solid acid catalyst to obtain an intermediate material; subjecting the intermediate material to a hydrogenation reaction with hydrogen in the presence of a hydrogenation catalyst to obtain a hydrogenated material; and subjecting the hydrogenated material to a solvent removal treatment to obtain the petroleum resin softening point regulator.

2. The preparation method according to claim 1, characterized in that: The polymerization reaction includes at least one of the following characteristics: Feature 1: The mass ratio of the piperylene to the solvent is 1:3 to 1:10; Feature 2: The polymerization temperature is 10°C to 60°C; Feature 3: The polymerization reaction pressure is 0.4 MPa to 1.0 MPa in gauge pressure. Feature 4: The feed space velocity of the piperylene is 3h -1 ~10h -1 ; Feature 5: The solvent includes at least one of cyclopentane, n-pentane, isopentane, and C6-C8 alkanes; Feature 6: The solid acid catalyst comprises at least one of a cation exchange resin, a supported acid and a metal oxide; Feature 7: The polymerization reaction is carried out using a fixed tubular heat exchange synthesis reactor; the fixed tubular heat exchange synthesis reactor comprises a tube layer and a shell layer, the solid acid catalyst is loaded in the tube layer, and a heat exchange medium flows in the shell layer.

3. The preparation method according to claim 2, characterized in that: The mass ratio of piperylene to the solvent is 1:5 to 1:8; and / or, the polymerization temperature is 40° C. to 50° C.; and / or, the polymerization reaction pressure is 0.6 MPa to 0.8 MPa in terms of gauge pressure; And / or, the feed space velocity of piperylene is 4h -1 ~6h -1 ; and / or, the solvent comprises at least one of cyclopentane, n-pentane and isopentane; And / or, the solid acid catalyst includes at least one of divinylbenzene copolymer, perfluorosulfonic acid resin, ZnO, H2SO4-SiO2 and H3PO4-SiO2.

4. The preparation method according to claim 1, characterized in that: The hydrogenation reaction includes at least one of the following characteristics: Feature 7: The temperature of the hydrogenation reaction is 100°C to 200°C; Feature 8: The pressure of the hydrogenation reaction is 2 MPa to 6 MPa in gauge pressure; Feature 9: The feed space velocity of the intermediate material is 0.5h -1 ~3h -1 ; feature 10: The volume ratio of the hydrogen to the intermediate material is 100:1 to 400:1; Feature 11: The hydrogenation catalyst comprises a carrier and an active component; wherein the carrier comprises alumina, silicon oxide or carbon, and the active component comprises at least one of Pd, Ni, Pt, Rh, Wu and Mo; Feature 12: The reactor used for the hydrogenation reaction includes a fixed bed reactor, an ebullating bed hydrogenation reactor or a loop hydrogenation reactor.

5. The preparation method according to claim 4, characterized in that: The temperature of the hydrogenation reaction is 120°C to 160°C; and / or, the pressure of the hydrogenation reaction is 4 MPa to 5 MPa in terms of gauge pressure; And / or, the feed space velocity of the intermediate material is 1h -1 ~2h -1 ; and / or, the volume ratio of the hydrogen to the intermediate material is 200:1 to 300:1; And / or, the carrier in the hydrogenation catalyst is alumina, and the active component includes at least one of Pd, Ni and Pt.

6. The preparation method according to claim 1, characterized in that: The solvent removal treatment is carried out by flash evaporation; Preferably, the operating temperature of the flash evaporation is 210° C. to 260° C.; in terms of gauge pressure, the operating pressure of the flash evaporation is 1 KPa to 50 KPa.

7. The preparation method according to any one of claims 1 to 6, characterized in that: Also includes: The removed solvent is subjected to a de-weighting treatment to obtain a recovered solvent; and the recovered solvent is recycled to the polymerization reaction process for use; Preferably, the operating temperature of the degravity treatment is 120° C. to 140° C.; the operating pressure of the degravity treatment is 1 KPa to 50 KPa in gauge pressure; and the reflux ratio of the degravity treatment is 0.5:1 to 1:

1.

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

9. Use of the petroleum resin softening point regulator as claimed in claim 8 in regulating the softening point of petroleum resin; Preferably, the petroleum resin softening point regulator is used to adjust the softening point of the petroleum resin to 85°C to 130°C.

10. A method for adjusting the softening point of a petroleum resin, characterized in that: The method comprises the following steps: mixing the petroleum resin softening point regulator according to claim 9 with the petroleum resin; Preferably, the mass ratio of the petroleum resin softening point regulator to the petroleum resin is 1:100 to 5:100.

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