A preparation method of C5 petroleum resin

Abstract

A preparation method of C5 petroleum resin comprises the following steps: First, concentrated piperylene, a part of solvent, monoolefin, dicyclopentadiene, α-pinene, and styrene monomers are mixed evenly and placed in a raw material tank to obtain reaction materials; Second, the remaining solvent is added into a reaction kettle, the temperature is raised to 50°C - 60°C under stirring, then a catalyst is added, and then the reaction materials obtained in the first step are added at a rate of 20 g / min for reaction. During the feeding process, the reaction temperature in the reaction kettle is controlled at 50°C - 60°C; Third, after the reaction materials are added, the reaction continues for 10 min - 15 min at the reaction temperature of 50°C - 60°C, the temperature is lowered and the product is discharged to obtain a reaction solution, and the reaction solution is post-treated to obtain C5 petroleum resin. Compared with the prior art, the resin prepared by the present invention has a high softening point and can reduce insoluble matters.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer synthesis, and in particular relates to a method for preparing C5 petroleum resin. Background Art

[0002] At present, the total domestic petroleum resin production capacity is close to 1.4 million tons / year, of which the C5 petroleum resin production capacity is about 500,000 tons / year. C5 petroleum resin is mainly used in the adhesive field and road sign paint field to provide product viscosity. With the increasing production of C5 petroleum resin, the demand for new products with excellent performance in downstream application fields is becoming more and more intense.

[0003] At present, C5 petroleum resin is generally synthesized by cationic polymerization, with Lewis acid as catalyst, concentrated isoprene as raw material, and saturated hydrocarbon as solvent. The product after polymerization is washed with water to remove the catalyst (the catalyst is soluble in water), desolventized, and oligomerized to obtain the final product, isoprene petroleum resin. Cationic polymerization is a reaction with fast initiation, fast growth, easy transfer, and difficult termination. The chain transfer phenomenon is serious, and the activation energy of chain transfer is only slightly higher than the activation energy of chain growth, 8.37-12.55 kJ / mol. Due to the existence of chain transfer, the molecular weight of the obtained C5 resin is low, and the softening point is generally between 90-100°C.

[0004] Research has found that high molecular weight, high softening point C5 petroleum resin can increase the strength of hot melt adhesives for packaging, which is helpful for improving product performance and downstream applications.

[0005] In order to increase the softening point, dicyclopentadiene is added to the raw materials, such as the process disclosed in the invention patent "A method for producing isopentylene petroleum resin by free radical thermal polymerization" (authorization announcement number CN104277179B) with patent number ZL201410494202.6. This patent uses free radical thermal polymerization to produce isopentylene petroleum resin, and the softening point of the resin obtained by the raw materials doped with dicyclopentadiene is increased.

[0006] If dicyclopentadiene is doped into the raw materials of cationic polymerization, the participation of dicyclopentadiene in the reaction will increase the softening point of the obtained resin. However, cross-linking will occur between the molecular chains during the reaction, which will greatly increase the molecular weight, increase the amount of insoluble matter, and increase the viscosity of the reaction liquid, thereby increasing the difficulty of water elution of the catalyst. Summary of the invention

[0007] The technical problem to be solved by the present invention is to provide a method for preparing a C5 petroleum resin with a high softening point and capable of reducing insoluble matter in view of the current status of the prior art.

[0008] The technical solution adopted by the present invention to solve the above technical problems is: a method for preparing C5 petroleum resin, characterized by the following steps:

[0009] 1. Mix the concentrated piperylene, a part of the solvent, monoolefin, dicyclopentadiene, α-pinene, and styrene monomer in proportion and uniformly, and place them in a raw material tank to obtain a reaction material;

[0010] 2. Add the remaining solvent into the reaction kettle, heat it up to 50°C - 60°C under stirring, then add the catalyst, and then add the reaction material from the above step 1 at a rate of 18 g / min - 22 g / min for reaction. During the feeding process, control the reaction temperature in the reaction kettle at 50°C - 60°C;

[0011] 3. After the reaction material is added, continue the reaction for 10 min - 15 min at the reaction temperature of 50°C - 60°C, cool it down to 20°C - 30°C and discharge to obtain a reaction solution. The reaction solution is post-treated to obtain a C5 petroleum resin;

[0012] Among them, by weight, the amount of the concentrated piperylene used is 2.4 parts - 2.5 parts, the amount of the monoolefin used is 0.19 parts - 0.21 parts, the amount of the dicyclopentadiene used is 1 part - 1.6 parts, the amount of the α-pinene used is 1.6 parts - 1.8 parts, the amount of the styrene monomer used is 0.9 parts - 1.1 parts, the amount of the catalyst used is 0.03 parts - 0.05 parts, and the catalyst is a Lewis acid. The total amount of the solvent used is 3 parts - 3.6 parts, and the ratio of the solvent used in step 1 to the solvent used in step 2 is 2 - 6:5. The solvent is a cycloalkane or a straight-chain alkane.

[0013] Preferably, the monoolefin is isopentene.

[0014] Preferably, the styrene monomer is styrene or α-methylstyrene.

[0015] Preferably, the catalyst is aluminum trichloride or boron trifluoride.

[0016] Further, the solvent is cyclopentane or n-pentane.

[0017] In the above various solutions, preferably, the method for post-treating the reaction solution in step 3 is: adding pure water to the reaction solution to dissolve the catalyst, and then separating the water dissolved with the catalyst and the reaction solution with a separating funnel. After separation, the reaction solution is subjected to flash solvent removal and stripping to remove oligomers to obtain a C5 petroleum resin. Among them, the temperature of the above pure water is 50°C - 60°C, and the pure water accounts for 8% - 15% of the weight of the reaction solution. And the processes of the above flash solvent removal and stripping to remove oligomers are all prior arts and will not be elaborated here.

[0018] Preferably, the softening point of the C5 petroleum resin is 110°C - 120°C.

[0019] The aniline point value of the C5 petroleum resin is preferably 70°C to 75°C.

[0020] The average molecular weight of the C5 petroleum resin is preferably 10,000 to 15,000.

[0021] Preferably, the reaction temperature in the second step is lower than 60°C.

[0022] Compared with the prior art, the advantages of the present invention are as follows: The present invention uses concentrated piperylene, monoolefin, dicyclopentadiene, α-pinene, and styrene monomers as raw materials, a Lewis acid as a catalyst, and a cycloalkane or a straight-chain alkane as a solvent, and the C5 petroleum resin prepared by a specific process has a controllable molecular weight, a high softening point, and excellent properties, and can better meet the requirements of the downstream fields for the product performance. At the same time, the addition of α-pinene in the present invention can participate in the reaction, increasing the molecular weight of the product and raising the softening point, but the participation of α-pinene in the reaction will not cause cross-linking between molecular chains, so that the molecular weight of the product will not increase significantly, thus reducing the insoluble matter in the product. That is, the combination of dicyclopentadiene and α-pinene in the present invention can effectively increase the softening point of the product without significantly increasing the molecular weight. Detailed implementation manners

[0023] Example 1:

[0024] A preparation method of a C5 petroleum resin comprises the following steps:

[0025] Add 160 g of cyclopentane into a 2 L reaction kettle, start stirring, and heat up. Add 39 g of cyclopentane, 165 g of piperylene, 13 g of isopentene, 105 g of dicyclopentadiene, 66 g of styrene, and 112 g of α-pinene into the raw material tank, mix evenly and set aside. When the temperature of the reaction kettle rises to 55°C, add 2.64 g of aluminum trichloride catalyst, immediately start the feed pump, and add the reaction materials in the raw material tank into the reaction kettle for reaction. The feeding speed of the reaction materials is controlled at about 20 g / min. During the whole reaction process, control the reaction temperature at 55°C. After the reaction materials in the raw material tank are added, continue to react at 55°C for 10 min. After the reaction is completed, discharge the material to obtain a reaction solution. Add pure water at 50°C (the pure water accounts for 10% of the weight of the reaction solution) to the reaction solution to dissolve the catalyst in the reaction solution, and then separate the water dissolving the catalyst and the reaction solution with a separating funnel. After separation, the reaction solution is subjected to flash evaporation to remove the solvent and then to stripping to remove the oligomers to obtain the C5 petroleum resin product.

[0026] Tested by gel permeation chromatography, the average molecular weight (Mz) of the product is 12,000; tested by a softening point tester, the softening point of the product is 115°C; tested, the aniline point value of the product is 72.5°C.

[0027] The reaction solution obtained in this example is easy to remove the catalyst, and after the reaction is completed, only a small amount of insoluble matter remains in the reaction kettle.

[0028] Example 2:

[0029] A preparation method of a C5 petroleum resin is as follows:

[0030] Add 160 g of cyclopentane to a 2 L reaction kettle, start stirring, and heat up. Add 74 g of cyclopentane, 165 g of m-pentadiene, 13 g of isopentene, 70 g of dicyclopentadiene, 66 g of styrene, and 112 g of α-pinene to the raw material tank, mix evenly and set aside. When the temperature of the reaction kettle rises to 55 °C, add 2.64 g of aluminum trichloride catalyst, immediately start the feed pump, and add the reaction materials in the raw material tank to the reaction kettle for reaction. The feed rate of the reaction materials is controlled at about 20 g / min. During the whole reaction process, control the reaction temperature at 55 °C. After the reaction materials in the raw material tank are added, continue to react at 55 °C for 10 min. After the reaction is completed, discharge the material to obtain a reaction solution. Add pure water at 50 °C (the pure water accounts for 10% of the weight of the reaction solution) to the reaction solution to dissolve the catalyst in the reaction solution, and then use a separating funnel to separate the water and the reaction solution in which the catalyst is dissolved. After separation, the reaction solution is subjected to flash evaporation to remove the solvent and stripping to remove the oligomers to obtain a C5 petroleum resin product.

[0031] Tested by gel permeation chromatography, the average molecular weight (Mz) of the product is 10,000; tested by a softening point tester, the softening point of the product is 110 °C; tested, the aniline point value of the product is 70.9 °C.

[0032] The reaction solution obtained in this example is easy to remove the catalyst, and after the reaction is completed, only a small amount of insoluble matter remains in the reaction kettle.

[0033] Example 3:

[0034] A preparation method of a C5 petroleum resin is as follows:

[0035] Add 160 g of cyclopentane to a 2 L reactor, start stirring, and heat up. Add 74 g of cyclopentane, 158 g of pentadiene, 13.8 g of isopentene, 92 g of dicyclopentadiene, 60 g of styrene, and 105 g of α-pinene to the raw material tank. After mixing evenly, set aside. When the temperature of the reactor rises to 50 °C, add 3.3 g of aluminum trichloride catalyst, immediately start the feed pump, and add the reaction materials in the raw material tank to the reactor for reaction. The feeding rate of the reaction materials is controlled at 18 g / min. During the whole reaction process, control the reaction temperature at 50 °C. After the reaction materials in the raw material tank are added, continue to react at 50 °C for 15 min. After the reaction is completed, discharge the material to obtain the reaction liquid. Add pure water at 60 °C (the pure water accounts for 15% of the weight of the reaction liquid) to the reaction liquid to dissolve the catalyst in the reaction liquid, and then use a separating funnel to separate the water containing the dissolved catalyst and the reaction liquid. After separation, the reaction liquid is subjected to flash evaporation to remove the solvent and steam stripping to remove the oligomers to obtain the C5 petroleum resin product.

[0036] Example 4:

[0037] A preparation method of C5 petroleum resin comprises the following steps:

[0038] Add 160 g of n-pentane to a 2 L reactor, start stirring, and heat up. Add 74 g of n-pentane, 160 g of pentadiene, 13.2 g of isopentene, 90 g of dicyclopentadiene, 72 g of α-methylstyrene, and 118 g of α-pinene to the raw material tank. After mixing evenly, set aside. When the temperature of the reactor rises to 60 °C, add 2 g of boron trifluoride catalyst, immediately start the feed pump, and add the reaction materials in the raw material tank to the reactor for reaction. The feeding rate of the reaction materials is controlled at 22 g / min. During the whole reaction process, control the reaction temperature at 59 °C. After the reaction materials in the raw material tank are added, continue to react at 60 °C for 10 min. After the reaction is completed, discharge the material to obtain the reaction liquid. Add pure water at 55 °C (the pure water accounts for 8% of the weight of the reaction liquid) to the reaction liquid to dissolve the catalyst in the reaction liquid, and then use a separating funnel to separate the water containing the dissolved catalyst and the reaction liquid. After separation, the reaction liquid is subjected to flash evaporation to remove the solvent and steam stripping to remove the oligomers to obtain the C5 petroleum resin product.

[0039] Comparative Example 1:

[0040] A preparation method of C5 petroleum resin comprises the following steps:

[0041] Add 160 g of cyclopentane to a 2 L reactor, start stirring, and heat up. Add 109 g of cyclopentane, 165 g of pentadiene, 13 g of isopentene, 35 g of dicyclopentadiene, 66 g of styrene, and 112 g of α-pinene to the raw material tank. After mixing evenly, set aside. When the temperature of the reactor rises to 55 °C, add 2.64 g of aluminum trichloride catalyst, immediately start the feed pump, and add the reaction materials in the raw material tank to the reactor for reaction. The feeding rate of the reaction materials is controlled at about 20 g / min. During the whole reaction process, control the reaction temperature at 55 °C. After the reaction materials in the raw material tank are added, continue to react at 55 °C for 10 min. After the reaction is completed, discharge the material to obtain the reaction solution. Add pure water at 50 °C (the pure water accounts for 10% of the weight of the reaction solution) to the reaction solution to dissolve the catalyst in the reaction solution, and then use a separating funnel to separate the water dissolving the catalyst and the reaction solution. After separation, the reaction solution is subjected to flash solvent removal and stripping to remove oligomers to obtain a C5 petroleum resin product.

[0042] Tested by gel permeation chromatography, the average molecular weight (Mz) of the product is 0.9×10⁴; tested by a softening point tester, the softening point of the product is 106 °C; tested, the aniline point value of the product is 70.0 °C.

[0043] The reaction solution prepared in this comparative example is easy to remove the catalyst, and after the reaction is completed, only a small amount of insoluble matter remains in the reactor.

[0044] Comparative Example 2:

[0045] A preparation method of C5 petroleum resin is as follows:

[0046] Add 160 g of cyclopentane to a 2 L reactor, start stirring, and heat up. Add 180 g of cyclopentane, 234 g of pentadiene, 20 g of isopentene, and 66 g of styrene to the raw material tank. After mixing evenly, set aside. When the temperature of the reactor rises to 55 °C, add 2.64 g of aluminum trichloride catalyst, immediately start the feed pump, and add the reaction materials in the raw material tank to the reactor for reaction. The feeding rate of the reaction materials is controlled at about 20 g / min. During the whole reaction process, control the reaction temperature at 55 °C. After the reaction materials in the raw material tank are added, continue to react at 55 °C for 10 min. After the reaction is completed, discharge the material to obtain the reaction solution. Add pure water at 50 °C (the pure water accounts for 10% of the weight of the reaction solution) to the reaction solution to dissolve the catalyst in the reaction solution, and then use a separating funnel to separate the water dissolving the catalyst and the reaction solution. After separation, the reaction solution is subjected to flash solvent removal and stripping to remove oligomers to obtain a C5 petroleum resin product.

[0047] Tested by gel permeation chromatography, the average molecular weight (Mz) of the product is 0.4×10⁴; tested by a softening point tester, the softening point of the product is 93 °C; tested, the aniline point value of the product is 68.0 °C.

[0048] Comparative Example 3:

[0049] A preparation method of a C5 petroleum resin is as follows:

[0050] Add 160 g of cyclopentane into a 2 L reactor, start stirring, and heat up. Add 100 g of cyclopentane, 165 g of piperylene, 13 g of isopentene, 156 g of dicyclopentadiene, and 66 g of styrene into the raw material tank, mix evenly and set aside. When the temperature of the reactor rises to 55 °C, add 2.64 g of aluminum trichloride catalyst, immediately start the feed pump, and add the reaction materials in the raw material tank into the reactor for reaction. The feeding rate of the reaction materials is controlled at about 20 g / min. During the whole reaction process, control the reaction temperature at 55 °C. After the reaction materials in the raw material tank are added, continue to react at 55 °C for 10 min. After the reaction is completed, discharge the material to obtain a reaction liquid. Add pure water at 50 °C (the pure water accounts for 10% of the weight of the reaction liquid) to the reaction liquid to dissolve the catalyst in the reaction liquid, and then use a separating funnel to separate the water and the reaction liquid in which the catalyst is dissolved. After separation, the reaction liquid is subjected to flash evaporation to remove the solvent and steam stripping to remove the oligomers to obtain the C5 petroleum resin product.

[0051] During the experiment, it was found that it was difficult to remove the catalyst from the obtained reaction liquid, and it was necessary to increase the standing time and the number of water washing times to remove the catalyst; after opening the reactor, a large amount of insoluble substances were found remaining in the reactor.

[0052] Tested by gel permeation chromatography, the average molecular weight (Mz) of the product is 24,000; tested by a softening point tester, the softening point of the product is 114 °C; tested, the aniline point value of the product is 74.5 °C.

[0053] The products of the above Examples 1 and 2 and Comparative Examples 1 and 2 were tested for adhesive application, and the results are shown in Table 1 below.

[0054] Table 1

[0055]

[0056] As can be seen from Table 1, the softening point of the resin of the present application is increased and the molecular weight is increased, which significantly improves the peel strength, initial adhesion, and holding power of the downstream adhesive.

Claims

1. A preparation method of C5 petroleum resin, characterized in that The steps are as follows:

1. Mix concentrated piperylene, part of the solvent, monoolefin, dicyclopentadiene, α-pinene, and styrene monomer evenly in proportion and place them in a raw material tank to obtain reaction materials; 2. Add the remaining solvent into the reaction kettle, heat it up to 50°C - 60°C under stirring, then add the catalyst, and then add the reaction materials from step 1 at a rate of 18 g / min - 22 g / min for reaction. During the feeding process, control the reaction temperature in the reaction kettle at 50°C - 60°C; 3. After the reaction materials are added, continue the reaction for 10 min - 15 min at a reaction temperature of 50°C - 60°C, cool down to 20°C - 30°C and discharge to obtain the reaction liquid. Post-treat the reaction liquid to obtain the C5 petroleum resin; Among them, by weight, the dosage of the concentrated piperylene is 2.4 parts - 2.5 parts, the dosage of the monoolefin is 0.19 parts - 0.21 parts, the dosage of the dicyclopentadiene is 1 part - 1.6 parts, the dosage of the α-pinene is 1.6 parts - 1.8 parts, the dosage of the styrene monomer is 0.9 parts - 1.1 parts, the dosage of the catalyst is 0.03 parts - 0.05 parts, and the catalyst is a Lewis acid. The total dosage of the solvent is 3 parts - 3.6 parts, and the dosage ratio of the solvent in step 1 to the solvent in step 2 is 1:5 - 1:

2. The solvent is a naphthene or a straight-chain alkane.

2. The preparation method of the C5 petroleum resin according to claim 1, characterized in that: The monoolefin is isopentene.

3. The preparation method of the C5 petroleum resin according to claim 1, characterized in that: The styrene monomer is styrene or α-methylstyrene.

4. The preparation method of the C5 petroleum resin according to claim 1, characterized in that: The catalyst is aluminum trichloride or boron trifluoride.

5. The preparation method of the C5 petroleum resin according to claim 1, characterized in that: The solvent is cyclopentane or n-pentane.

6. The preparation method of the C5 petroleum resin according to any one of claims 1 to 5, characterized in that: The method for post-treating the reaction liquid in step 3 is: add pure water to the reaction liquid to dissolve the catalyst, then use a separating funnel to separate the water dissolved with the catalyst and the reaction liquid. After separation, the reaction liquid is subjected to flash evaporation to remove the solvent and steam stripping to remove the oligomers to obtain the C5 petroleum resin, where the temperature of the above pure water is 50°C - 60°C, and the pure water accounts for 8% - 15% of the weight of the reaction liquid.

7. The preparation method of the C5 petroleum resin according to claim 6, characterized in that: The softening point of the C5 petroleum resin is 110°C - 120°C.

8. The preparation method of the C5 petroleum resin according to claim 6, characterized in that: The aniline point value of the C5 petroleum resin is 70°C - 75°C.

9. The preparation method of the C5 petroleum resin according to claim 6, characterized in that: The average molecular weight of the C5 petroleum resin is 10,000 - 15,000.

10. The preparation method of the C5 petroleum resin according to claim 1, wherein: The reaction temperature in step 2 is lower than 60°C.

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