Preparation method and application of a modified dicyclopentadiene petroleum resin

Abstract

The present invention discloses a preparation method of a modified dicyclopentadiene petroleum resin, which comprises the following steps: S1 Add a certain amount of dicyclopentadiene, monocyclic olefin, and acrylate into a thermal polymerization kettle, add an inert solvent, stir evenly, then introduce an inert gas, extrude the air in the thermal polymerization kettle, maintain the pressure in the thermal polymerization kettle, and raise the temperature for stirring reaction; S2 After the thermal polymerization kettle is cooled and depressurized, transfer the materials in the thermal polymerization kettle to a distillation kettle for heating, and distill off the unreacted materials to obtain the modified dicyclopentadiene petroleum resin. The preparation method of the present invention can achieve good modification of the dicyclopentadiene petroleum resin without using a catalyst, the conversion rate of the introduced acrylate is high, and the color of the resin is relatively light. The prepared modified dicyclopentadiene petroleum resin has a low bromine value, good thermal stability, and a high acid value; when applied to coatings, it can effectively improve the adhesion of the coatings, has fewer residual double bonds, and more stable performance.

Description

Technical Field

[0001] The present invention relates to a preparation method and application of a modified dicyclopentadiene petroleum resin, relates to C08G, and specifically relates to a high molecular compound obtained by a reaction other than a carbon-carbon unsaturated bond. Background Art

[0002] Dicyclopentadiene petroleum resin is obtained by thermal polymerization of dicyclopentadiene under high temperature and high pressure. Dicyclopentadiene petroleum resin has the characteristics of high softening point, good tackifying effect and strong stability, and can be used as a tackifier in coatings. However, the dicyclopentadiene petroleum resin molecule does not contain polar functional groups such as hydroxyl groups and carboxyl groups, so its application in waterborne coatings is greatly limited, resulting in poor adhesion of the coatings. In traditional methods, a catalyst needs to be introduced to modify the dicyclopentadiene petroleum resin, but after the preparation is completed, the catalyst needs to be separated, and at the same time, the residual metal catalyst will inevitably be caused, affecting the purity of the modified dicyclopentadiene petroleum resin and reducing the modification effect.

[0003] Chinese invention patent CN102076734B discloses a modified resin composition, a manufacturing method thereof, and a curable resin composition containing the modified resin composition, a modified resin composition obtained by reacting an epoxy resin with a specific alkoxysilane compound at a specific ratio, adjusting the amount of residual alkoxysilane in the resin composition, achieving good transparency, and having excellent heat resistance and heat discoloration resistance at the same time. However, a catalyst needs to be introduced to achieve the modification effect. Chinese invention patent CN202210814194.3 discloses a high-content dicyclopentadiene styrene-free unsaturated polyester resin and a preparation method thereof. Through the conjugated double bonds and cyclic structures contained in the molecular chain of the dicyclopentadiene-based unsaturated polyester, the crystallinity of the dicyclopentadiene-based unsaturated polyester in the crosslinking agent can be reduced, so that it has good compatibility. However, the prepared modified resin is not suitable for application in waterborne coatings. Summary of the Invention

[0004] In order to modify the dicyclopentadiene petroleum resin so that it can be widely used in waterborne coatings and improve the adhesion of waterborne coatings, the first aspect of the present invention provides a preparation method of a modified dicyclopentadiene petroleum resin, including the following steps:

[0005] S1 Add a certain amount of dicyclopentadiene, monocyclic olefin, and acrylate to a thermal polymerization kettle, add an inert solvent, stir evenly, then introduce an inert gas, extrude the air in the thermal polymerization kettle, maintain the pressure in the thermal polymerization kettle, and raise the temperature for stirring reaction;

[0006] S2 After the thermal polymerization kettle is cooled and depressurized, transfer the materials in the thermal polymerization kettle to a distillation kettle for heating, and distill off the unreacted materials to obtain the modified dicyclopentadiene petroleum resin.

[0007] As a preferred embodiment, the weight ratio of dicyclopentadiene, monocyclic benzene olefin, and acrylate is (60 - 80):(5 - 25):(5 - 20).

[0008] As a preferred embodiment, the weight ratio of dicyclopentadiene, monocyclic benzene olefin, and acrylate is (60 - 80):(5 - 20):(10 - 20).

[0009] As a preferred embodiment, the weight ratio of dicyclopentadiene, monocyclic benzene olefin, and acrylate is 65:20:15.

[0010] As a preferred embodiment, the monocyclic benzene olefin is styrene.

[0011] As a preferred embodiment, the acrylate is selected from one or a combination of several of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and butyl methacrylate.

[0012] As a preferred embodiment, the acrylate is butyl acrylate.

[0013] As a preferred embodiment, the inert solvent is selected from one or a combination of several of toluene, xylene, trimethylbenzene, n - hexane, and cyclohexane.

[0014] As a preferred embodiment, the inert solvent is toluene.

[0015] As a preferred embodiment, the mass ratio of the inert solvent to dicyclopentadiene is (50 - 200):(60 - 80).

[0016] As a preferred embodiment, the mass ratio of the inert solvent to dicyclopentadiene is 100:65.

[0017] As a preferred embodiment, the inert gas is selected from one or a combination of several of nitrogen, argon, helium, neon, krypton, xenon, and radon.

[0018] As a preferred embodiment, the inert gas is nitrogen.

[0019] As a preferred embodiment, the heating temperature in step S1 is 160°C - 240°C.

[0020] As a preferred embodiment, the heating temperature in step S1 is 180°C - 220°C.

[0021] During the experiment, the applicant found that when dicyclopentadiene reacts with acrylate at 180 - 220 °C without using a catalyst, good modification of dicyclopentadiene petroleum resin can be achieved, with a high conversion rate of the introduced acrylate and a lighter color of the resin. It is speculated that the possible reason is that when introducing a catalyst during the modification of dicyclopentadiene petroleum resin with acrylate, the catalyst still needs to be separated. The introduction of the catalyst will affect the purity of the modified dicyclopentadiene petroleum resin, resulting in the residue of catalyst metal and affecting the subsequent use of the coating.

[0022] As a preferred embodiment, the pressure inside the thermal polymerization kettle in step S1 is 0.8 MPa - 2.0 MPa, the reaction time is 3 h - 8 h, and the stirring speed is 80 r / min - 120 r / min.

[0023] As a preferred embodiment, the pressure inside the thermal polymerization kettle in step S1 is 1.0 MPa - 1.6 MPa, the reaction time is 4 h - 6 h, and the stirring speed is 90 r / min - 100 r / min.

[0024] The applicant further found during the experiment that when using a reaction temperature of 180 - 220 °C and a reaction pressure of 1 - 1.6 MPa, the reaction efficiency is high, the residual double bonds are few, and the conversion rate of acrylate is high. Below the preferred reaction temperature, the conversion rate of acrylate is insufficient, resulting in a low acid value, a high bromine value, and a decrease in thermal stability of the modified dicyclopentadiene petroleum resin. Exceeding the preferred temperature range, the modified dicyclopentadiene petroleum resin will undergo a certain degree of oxidation, causing the color of the resin to deepen and affecting the wide application of the resin in coatings.

[0025] As a preferred embodiment, the distillation temperature in step S2 is 160 °C - 200 °C.

[0026] The second aspect of the present invention provides an application of the preparation method of the modified dicyclopentadiene petroleum resin, that is, the application of the modified dicyclopentadiene petroleum resin prepared by the preparation method of the present application in coatings.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) For the preparation method of the modified dicyclopentadiene petroleum resin of the present invention, when dicyclopentadiene reacts with acrylate without using a catalyst, good modification of dicyclopentadiene petroleum resin can be achieved, with a high conversion rate of the introduced acrylate and a lighter color of the resin.

[0029] (2) The preparation method of the modified dicyclopentadiene petroleum resin of the present invention uses a reaction temperature of 180 - 220 °C and a reaction pressure of 1 - 1.6 MPa, with a relatively high reaction efficiency, few residual double bonds, and a high conversion rate of acrylate.

[0030] (3) The modified dicyclopentadiene petroleum resin prepared by the preparation method of the present invention has a low bromine value, good thermal stability, and a high acid value; when applied to coatings, it can effectively improve the adhesion of the coatings, has few residual double bonds, and more stable performance. Detailed implementation manners

[0031] Example 1

[0032] A preparation method of a modified dicyclopentadiene petroleum resin, comprising the following steps:

[0033] S1 Add a certain amount of dicyclopentadiene, monocyclic aromatic olefin, acrylate to a thermal polymerization kettle, add an inert solvent, stir evenly, then introduce an inert gas, expel the air in the thermal polymerization kettle, maintain the pressure in the thermal polymerization kettle, and raise the temperature for stirring reaction;

[0034] S2 After the thermal polymerization kettle is cooled and depressurized, transfer the materials in the thermal polymerization kettle to a distillation kettle for heating, and distill off the unreacted materials to obtain the modified dicyclopentadiene petroleum resin.

[0035] The monocyclic aromatic olefin is styrene. The acrylate is methyl acrylate. The inert solvent is xylene. The inert gas is nitrogen.

[0036] The weight parts of the dicyclopentadiene, styrene, methyl acrylate, and xylene are 75 parts, 15 parts, 10 parts, and 50 parts respectively.

[0037] The temperature increase in step S1 is 200 °C, the pressure in the thermal polymerization kettle in step S1 is 0.8 MPa, the reaction time is 5 h, and the stirring speed is 100 r / min.

[0038] The distillation temperature in step S2 is 180 °C.

[0039] Example 2

[0040] A preparation method of a modified dicyclopentadiene petroleum resin, comprising the following steps:

[0041] S1 Add a certain amount of dicyclopentadiene, monocyclic aromatic olefin, acrylate to a thermal polymerization kettle, add an inert solvent, stir evenly, then introduce an inert gas, expel the air in the thermal polymerization kettle, maintain the pressure in the thermal polymerization kettle, and raise the temperature for stirring reaction;

[0042] S2 After the thermal polymerization kettle is cooled and depressurized, transfer the materials in the thermal polymerization kettle to a distillation kettle for heating, and distill off the unreacted materials to obtain the modified dicyclopentadiene petroleum resin.

[0043] The monocyclic olefin is styrene. The acrylate is butyl acrylate. The inert solvent is toluene. The inert gas is nitrogen.

[0044] The weight parts of dicyclopentadiene, styrene, butyl acrylate, and toluene are 65 parts, 20 parts, 15 parts, and 100 parts respectively.

[0045] The temperature increase in step S1 is 220 °C, the pressure inside the thermal polymerization kettle in step S1 is 1.4 MPa, the reaction time is 6 h, and the stirring speed is 100 r / min.

[0046] The distillation temperature in step S2 is 170 °C.

[0047] Example 3

[0048] A preparation method of a modified dicyclopentadiene petroleum resin, comprising the following steps:

[0049] S1 Add a certain amount of dicyclopentadiene, monocyclic olefin, acrylate into the thermal polymerization kettle, add an inert solvent, stir evenly, then introduce an inert gas, extrude the air in the thermal polymerization kettle, maintain the pressure inside the thermal polymerization kettle, and increase the temperature for stirring reaction;

[0050] S2 After the thermal polymerization kettle is cooled and depressurized, transfer the materials in the thermal polymerization kettle to the distillation kettle for heating, distill off the unreacted materials, and obtain the modified dicyclopentadiene petroleum resin.

[0051] The monocyclic olefin is styrene. The acrylate is methyl methacrylate. The inert solvent is mesitylene. The inert gas is nitrogen.

[0052] The weight parts of dicyclopentadiene, styrene, methyl methacrylate, and mesitylene are 80 parts, 5 parts, 15 parts, and 150 parts respectively.

[0053] The temperature increase in step S1 is 180 °C, the pressure inside the thermal polymerization kettle in step S1 is 1.6 MPa, the reaction time is 4 h, and the stirring speed is 100 r / min.

[0054] The distillation temperature in step S2 is 160 °C.

[0055] Example 4

[0056] A preparation method of a modified dicyclopentadiene petroleum resin, comprising the following steps:

[0057] S1 Add a certain amount of dicyclopentadiene, monocyclic olefin, acrylate into the thermal polymerization kettle, add an inert solvent, stir evenly, then introduce an inert gas, extrude the air in the thermal polymerization kettle, maintain the pressure inside the thermal polymerization kettle, and increase the temperature for stirring reaction;

[0058] After the S2 hot polymerization kettle is cooled and depressurized, the materials in the hot polymerization kettle are transferred to a distillation kettle for heating, and the unreacted materials are distilled off to obtain the modified dicyclopentadiene petroleum resin.

[0059] The monocyclic olefin is styrene. The acrylate is butyl methacrylate. The inert solvent is n-hexane. The inert gas is nitrogen.

[0060] The weight parts of the dicyclopentadiene, styrene, butyl methacrylate, and n-hexane are 60 parts, 20 parts, 20 parts, and 100 parts respectively.

[0061] The temperature increase in step S1 is 180 °C, the pressure in the hot polymerization kettle in step S1 is 2.0 MPa, the reaction time is 8 h, and the stirring speed is 100 r / min.

[0062] The distillation temperature in step S2 is 180 °C.

[0063] Comparative Example 1

[0064] A preparation method of a dicyclopentadiene petroleum resin includes the following steps:

[0065] S1 Add a certain amount of dicyclopentadiene to the hot polymerization kettle, add an inert solvent, stir evenly, then introduce an inert gas, expel the air in the hot polymerization kettle, maintain the pressure in the hot polymerization kettle, and raise the temperature for stirring reaction;

[0066] S2 After the hot polymerization kettle is cooled and depressurized, the materials in the hot polymerization kettle are transferred to a distillation kettle for heating, and the unreacted materials are distilled off to obtain the modified dicyclopentadiene petroleum resin.

[0067] The inert solvent is toluene. The inert gas is nitrogen.

[0068] The weight parts of the dicyclopentadiene and toluene are 100 parts and 100 parts respectively.

[0069] The temperature increase in step S1 is 200 °C, the pressure in the hot polymerization kettle in step S1 is 0.8 MPa, the reaction time is 5 h, and the stirring speed is 100 r / min.

[0070] The distillation temperature in step S2 is 180 °C.

[0071] Comparative Example 2

[0072] A preparation method of a modified dicyclopentadiene petroleum resin includes the following steps:

[0073] S1 Add a certain amount of dicyclopentadiene and acrylate to the hot polymerization kettle, add an inert solvent, stir evenly, then introduce an inert gas, expel the air in the hot polymerization kettle, maintain the pressure in the hot polymerization kettle, and raise the temperature for stirring reaction;

[0074] After the S2 hot polymerization kettle is cooled and depressurized, the materials in the hot polymerization kettle are transferred to a distillation kettle for heating, and the unreacted materials are distilled off to obtain a modified dicyclopentadiene petroleum resin.

[0075] The acrylate is methyl acrylate. The inert solvent is xylene. The inert gas is nitrogen.

[0076] The weight parts of the dicyclopentadiene, methyl acrylate, and xylene are 85 parts, 15 parts, and 100 parts respectively.

[0077] The temperature increase in step S1 is 200 °C, the pressure inside the hot polymerization kettle in step S1 is 0.8 MPa, the reaction time is 5 h, and the stirring speed is 100 r / min.

[0078] The distillation temperature in step S2 is 180 °C.

[0079] Performance Test

[0080] 1. Acrylate conversion rate: The acrylate conversion rate is obtained by multiplying the proportion of acrylate in the light components after vacuum distillation analyzed by gas chromatography by the total mass of the vacuum-distilled substances to obtain the mass of unreacted acrylate, and then subtracting the percentage of unreacted acrylate in the total input acrylate mass from 100%, that is, the acrylate conversion rate.

[0081] 2. Resin acid value: The resin acid values of the examples and comparative examples are determined by the method of ASTM D1639.

[0082] 3. Resin thermal stability: It is analyzed by the thermal stability test method described in Appendix B of GB / T24138-2022, and the color phase determination instrument is a PFXI195 model colorimeter produced by LOVIBOND in the UK.

[0083] 4. Resin bromine value: The resin bromine values of the examples and comparative examples are determined by the method of ASTM D1159.

[0084] 5. Coating adhesion determination method: It is determined by the cross-cut method of GB / T9286-2021. The determination results are divided into 0-5 levels. The larger the number, the larger the peeling area and the worse the adhesion.

[0085] The test results of the acrylate conversion rate, resin acid value, resin thermal stability, and resin bromine value are shown in Table 1.

[0086] Table 1

[0087]

[0088] The modified dicyclopentadiene petroleum resins prepared in the examples and comparative examples were applied to the coating according to the formulation in Table 2. After stirring and mixing, the coating was obtained. The coating was applied to the substrate ABS plastic sheet with a coating thickness of 200 μm and dried in a constant temperature drying oven at 60 °C for 1 h for curing, and then tested. The performance test results of the coating are shown in Table 3.

[0089] Table 2

[0090]

[0091] Table 3

[0092]

[0093]

Claims

1. A preparation method of a modified dicyclopentadiene petroleum resin, characterized in that It includes the following steps: S1 Add a certain amount of dicyclopentadiene, monocyclic benzene olefin, and acrylate into a thermal polymerization kettle, add an inert solvent, stir evenly, then introduce an inert gas to expel the air in the thermal polymerization kettle, maintain the pressure in the thermal polymerization kettle, and raise the temperature for stirring reaction; S2 After the thermal polymerization kettle is cooled and depressurized, transfer the materials in the thermal polymerization kettle to a distillation kettle for heating, distill off the unreacted materials to obtain a modified dicyclopentadiene petroleum resin; The weight ratio of the dicyclopentadiene, monocyclic benzene olefin, and acrylate is (60 - 80):(5 - 25):(5 - 20); The mass ratio of the inert solvent to the dicyclopentadiene is (50 - 200):(60 - 80); The pressure in the thermal polymerization kettle in step S1 is 0.8 MPa - 2.0 MPa, the reaction time is 3 h - 8 h, and the stirring speed is 80 r / min - 120 r / min.

2. The preparation method of the modified dicyclopentadiene petroleum resin according to claim 1, wherein, The acrylate is selected from one or a combination of several of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and butyl methacrylate.

3. The preparation method of the modified dicyclopentadiene petroleum resin according to claim 1, characterized in that, The inert solvent is selected from one or a combination of several of toluene, xylene, trimethylbenzene, n-hexane, and cyclohexane.

4. The preparation method of the modified dicyclopentadiene petroleum resin according to claim 1, characterized in that, The inert gas is selected from one or a combination of several of nitrogen, argon, helium, neon, krypton, xenon, and radon.

5. The preparation method of the modified dicyclopentadiene petroleum resin according to claim 1, characterized in that, The temperature increase in step S1 is 160°C - 240°C.

6. The preparation method of the modified dicyclopentadiene petroleum resin according to claim 1, characterized in that, The distillation temperature in step S2 is 160°C - 200°C.

7. Application of a modified dicyclopentadiene petroleum resin, characterized in that, Application of the modified dicyclopentadiene petroleum resin prepared by the preparation method according to any one of claims 1 - 6 in coatings.

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