CN110204657B - Light-color C9 heat-polymerized petroleum resin product with high softening point and preparation process thereof - Google Patents
Light-color C9 heat-polymerized petroleum resin product with high softening point and preparation process thereof Download PDFInfo
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Abstract
The invention discloses a C9 heat-polymerized petroleum resin product with light color and high softening point and a preparation process thereof, belonging to the technical field of petroleum resin preparation. The preparation method comprises the following steps: by taking a byproduct C9 aromatic hydrocarbon fraction of a cracking ethylene preparation device as a main raw material, rectifying C9 raw oil to obtain a heavy-weight-removed C9 raw material; accurately weighing the substances such as the C9 raw material, dicyclopentadiene, methyl dicyclopentadiene, indene, indan and the like which are subjected to the weight removal treatment according to a certain proportion relation, dissolving the substances in the solvent oil, adding the substances into a thermal polymerization reaction kettle, adding a reaction initiator, uniformly stirring, carrying out polymerization reaction under the protection of nitrogen atmosphere and normal pressure, and recovering the solvent oil from the polymerized reactants through a stripping device to obtain the C9 thermal polymerized petroleum resin. The C9 heat polymerized petroleum resin with light color number and high softening point and suitable for the paint industry can be prepared by blending the contents of certain components in the reaction materials and simultaneously adopting a mode of adding a reaction initiator.
Description
Technical Field
The invention belongs to the technical field of petroleum resin preparation, and particularly relates to a C9 heat-polymerized petroleum resin product with a light color number and a high softening point and a preparation process thereof.
Background
The C9 heat polymerized petroleum resin has good adhesiveness, and in the paint and coating industry, the petroleum resin can be mixed with other resins to partially or even completely replace the resin with higher cost, so that the quality is ensured, the cost is reduced, and the water resistance, stability, chemical resistance and other physical and chemical properties of the product are improved. In the printing ink industry, the petroleum resin and a plurality of components in the printing ink have good compatibility, and for the printing ink with different specifications, the petroleum resin can meet the requirements of performances such as solvent release property, water resistance, alkali resistance, drying speed, wetting speed and the like, and meanwhile, the printing ink containing the petroleum resin has quick film forming and can keep the stable dispersion state of the pigment for a long time.
World C9 petroleum resin production is basically monopolized by major companies in western europe, the united states and japan. Among them, the united states and japan are the major C9 petroleum resin consumers, accounting for 2/3 of the total world sales. The suppliers of C9 petroleum resin as raw materials are mainly Lyondell corporation, Exxon corporation, Rsm corporation in Western Europe, and Dow corporation, USA. The foreign C9 petroleum resin products mainly comprise: (1) the conventional C9 petroleum resin is prepared by polymerizing fractions at 140-210 ℃ in pyrolysis gasoline. (2) Aliphatically modified aromatic hydrocarbon resins, C9 aromatic hydrocarbon resins being alkylated with C5 fractions, such as styrene, vinyl toluene, in order to improve coordination with ethylene vinyl acetate copolymers; dicyclopentadiene and cyclopentadiene produced by decomposition thereof; indene and derivatives thereof. (3) Hydrogenated C9 petroleum resins, such as ArTkon resins from Arakawa, japan, in which C9 aromatic hydrocarbon resins are partially or fully hydrogenated to control their polarity. (4) Pure monomeric aromatic resins are unhydrogenated water-white resins, and the monomers used are mainly α -methylstyrene (available from Amoco Co., Ltd.), styrene (available from Hercules Co., Ltd.), α -methylstyrene and vinyltoluene (available from Hercules Co., Ltd.), and the like. (5) Copolymerized petroleum resins, copolymerized with certain C5 concentrates using C9 fractions, have higher iodine values than either coumarone resins or conventional C9 resins, and are very soluble, such as the Nevchem series of Neville corporation. (6) And (3) secondary polymerization resin. (7) Black tar resin, which is thermally polymerized from cracked aromatic tar in an ethylene plant.
The total number of the synthesis methods of the C9 petroleum resin is three, namely thermal polymerization, catalytic polymerization and free radical polymerization. Thermal polymerization is generally carried out by heating a C9 cut in a reactor to about 260 ℃ to first form a Diels-Alder addition intermediate from two polymerizable molecules, reacting with another polymerizable component molecule to form two radicals, and then initiating polymerization. The thermal polymerization method has the advantages of simple process, high yield and deep color of the produced resin, so that the method is mainly used for producing C9 petroleum resin in the ink industry and the paint industry at present in China. However, the research of domestic C9 heat-polymerized petroleum resin starts late, basic research and reaction mechanism research have certain gap compared with foreign countries, meanwhile, the production scale of domestic C9 heat-polymerized petroleum resin is smaller than that of foreign countries, the obtained product has deep color (the Gardner color number is mostly 11-15), the softening point is lower (100 ℃ -120 ℃), and the requirements of the ink industry and the paint industry on the quality of the petroleum resin, especially on the softening point are strict, so that the petroleum resin used in the ink industry and the paint industry in China is mostly imported from foreign countries, which seriously limits the development of domestic enterprises.
The applicant has been dedicated to the research and process improvement of domestic petroleum resin products and applied for the following name in 2018: a light color C9 heat polymerized petroleum resin product and its preparation process patent, the application uses the byproduct C9 aromatic fraction of the cracking ethylene preparation device as the main raw material, firstly, the heavy and light removing treatment is carried out to the C9 raw oil; then mixing the heavy component-removed and light component-removed C9 raw material with dicyclopentadiene, methyl dicyclopentadiene, indene and indan, and blending the components of the reaction materials, thereby preparing a light-color C9 hot polymerized petroleum resin product and solving the problem of deep chroma of the existing C9 hot polymerized petroleum resin. However, the softening point of the C9 heat polymerized petroleum resin produced by the process of the application is still relatively low, and the use requirements of fields with high requirements on the softening point, such as the ink and paint industries, are difficult to meet.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defects that the C9 heat-polymerized petroleum resin produced by the domestic existing process has deeper color number and lower softening point and is difficult to meet the use requirements of the industries such as printing ink, paint and the like, and provides a C9 heat-polymerized petroleum resin product with light color number and high softening point and a preparation process thereof. According to the invention, through regulating and controlling the components of the reaction materials and adding a certain polymerization initiator, the softening point of the obtained C9 heat polymerized petroleum resin product can be effectively improved, a product with a light color number and a high softening point can be obtained, and the use requirements of the industries such as printing ink and paint can be further met.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a preparation process of a C9 heat-polymerized petroleum resin product with light color and high softening point, which takes a byproduct C9 aromatic hydrocarbon fraction of a cracking ethylene preparation device as a main raw material, and firstly carries out rectification treatment on C9 raw oil to remove heavier components in the C9 raw oil; then mixing the C9 raw material, dicyclopentadiene, methyl dicyclopentadiene, indene and solvent oil after the weight removal treatment according to a certain proportion, placing the mixture into a thermal polymerization reaction kettle, adding a certain reaction trigger into the thermal polymerization reaction kettle for thermal polymerization reaction, and preparing the C9 thermal polymerization petroleum resin product with light color number and high softening point.
Furthermore, when the C9 raw oil is rectified, naphthalene and other polycyclic aromatic hydrocarbon substances in the C9 raw material are mainly removed, and the removal amount of heavy components accounts for about 10-15% of the total weight of the raw material, preferably 12-15%.
Furthermore, the main components of the raw material C9 after weight removal are styrene and derivatives (5-15%) thereof, methyl styrene and derivatives (10-20%) thereof, dicyclopentadiene (20-30%), indene and indan (10-20%), methyl dicyclopentadiene (5-15%) and alkane compounds (1-30%) below C9.
Furthermore, the mixing mass ratio of the heavy component removing C9 raw material, dicyclopentadiene, methyl dicyclopentadiene, indene, indan and solvent oil is (800-1200): 100-500): 50-100: (100-200): 100.
Furthermore, the reaction initiator is a reaction polymerization solution reserved for the previous thermal polymerization, and the addition amount of the reaction initiator is 10-30% of the total mass of the reaction raw materials, and is preferably 15-25%.
Furthermore, the temperature of the thermal polymerization reaction is 230-260 ℃, and the reaction time is controlled to be 5-24 h; more preferably, the polymerization temperature is 240-250 ℃, and the polymerization time is 10-18 h.
Further, the solvent oil is one or more of benzene, toluene, xylene, n-pentane, isopentane, hexane, cyclohexane, heptane, octane, nonane, decane, solvent D40 and solvent D60; the polymerization liquid obtained by the thermal polymerization is stripped to recover the solvent oil.
The invention relates to a light-color C9 heat-polymerized petroleum resin product with high softening point, which is prepared by the method.
Furthermore, the C9 heat polymerized petroleum resin has a Gardner color number of 9-13 and a softening point of 120-140 ℃.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation process of the C9 heat-polymerized petroleum resin product with the light color number and the high softening point, a byproduct C9 aromatic hydrocarbon fraction of a cracking ethylene preparation device is used as a main raw material, the composition and the proportion of a C9 reaction raw material are blended, and a certain reaction initiator is added during polymerization reaction, so that the C9 heat-polymerized petroleum resin product with the light color number and the high softening point can be prepared, and the quality requirement of the paint and graphite industry on the C9 petroleum resin can be met.
(2) According to the preparation process of the C9 heat-polymerized petroleum resin product with the light color number and the high softening point, the chromaticity and the softening point of the obtained C9 heat-polymerized petroleum resin product can be regulated and controlled by regulating the component composition of reaction raw materials and the addition amount of a reaction trigger, the Gardner color number of the obtained resin product can be controlled to be 9-13, the softening point can be controlled to be 120-140 ℃, and the regulation and control range is relatively wide.
(3) According to the preparation process of the C9 heat polymerized petroleum resin product with the light color number and the high softening point, heavy components cut off by rectifying the C9 raw material can be used for blending oil products after hydrogenation, and the method is simple, convenient, easy to operate, suitable for large-scale and automatic production, free of pollutants and high in resource utilization rate.
(4) According to the C9 heat-polymerized petroleum resin product with the light color number and the high softening point, the preparation process is optimally designed, so that the softening point of the C9 heat-polymerized petroleum resin product can be effectively improved, the chromaticity of the product is reduced, and the quality requirement of the paint and graphite industry on the C9 petroleum resin can be met.
Detailed Description
Aiming at the problems that high-quality C9 heat-polymerized petroleum resin cannot be produced due to various and complicated components of C9 raw materials in the prior art, particularly the obtained C9 heat-polymerized petroleum resin has relatively deep chroma and low softening point, and cannot meet the use requirements of the ink industry and the paint industry. Therefore, at present, most of petroleum resins used in the ink industry and the paint industry in China are imported abroad, which seriously limits the development of domestic enterprises. According to the invention, through optimally designing the production process of the C9 heat polymerized petroleum resin, on one hand, the components of the C9 reaction raw materials are blended, and on the other hand, a certain amount of heat polymerized C9 petroleum resin is added as a reaction initiator during the polymerization reaction, so that the chroma of the C9 petroleum resin can be reduced on the basis of effectively improving the softening point of the obtained C9 petroleum resin. The C9 heat polymerized petroleum resin prepared by the method has the Gardner color number controlled to be 9-13, the softening point controlled to be 120-140 ℃, and can be dissolved in non-aromatic solvent oil, thereby meeting the requirements of downstream customers in the paint and ink industry on the quality of the C9 heat polymerized resin.
For a further understanding of the present invention, the following examples are provided for illustration and are not intended to limit the scope of the present invention.
Example 1
Firstly, distilling the C9 raw material to remove 15% of heavier components in the C9 raw material (accounting for the total mass of the C9 raw material). Then 1000g of the C9 raw material after weight removal treatment, 250g of dicyclopentadiene, 50g of methyl dicyclopentadiene and 100g of indene and indan are respectively weighed and dissolved in 100g of solvent naphtha; adding 20% of reaction initiator into a reaction kettle, adding the reaction material into a thermal polymerization reaction kettle, uniformly stirring, controlling the polymerization reaction temperature to be 240 ℃ under the protection of nitrogen atmosphere and normal pressure, controlling the reaction time to be 16h, and after the reaction is finished, stripping the polymerized reaction product to recover solvent oil to obtain the C9 thermal polymerized petroleum resin. The resin was found to have a Gardner color number of 10# and a softening point of 135.2 ℃.
Example 2
Firstly, distilling the C9 raw material to remove 12 percent of heavier components in the C9 raw material (accounting for the total mass of the C9 raw material). Then respectively weighing 800g of the C9 raw material after weight removal treatment, 400g of dicyclopentadiene, 70g of methyl dicyclopentadiene and 130g of indene and indan, and dissolving the raw materials in 100g of solvent naphtha; adding 26% of reaction initiator into a reaction kettle, then adding the reaction material into a thermal polymerization reaction kettle, uniformly stirring, controlling the polymerization reaction temperature to be 245 ℃ under the protection of nitrogen atmosphere and normal pressure, controlling the reaction time to be 18h, and after the reaction is finished, carrying out steam stripping on the polymerized reaction product to recover solvent oil to obtain the C9 thermal polymerization petroleum resin. The Gardner color number of the resin was found to be 12# and the softening point was found to be 140.3 ℃.
Example 3
Firstly, distilling the C9 raw material to remove 15% of heavier components in the C9 raw material (accounting for the total mass of the C9 raw material). Then 1100g of the C9 raw material, 100g of dicyclopentadiene, 100g of methyl dicyclopentadiene and 100g of indene and indan which are subjected to weight removal treatment are respectively weighed and dissolved in 100g of solvent naphtha; adding 25% of reaction initiator into a reaction kettle, adding the reaction material into a thermal polymerization reaction kettle, uniformly stirring, controlling the polymerization reaction temperature to be 240 ℃ under the protection of nitrogen atmosphere and normal pressure, controlling the reaction time to be 12h, and after the reaction is finished, stripping the polymerized reaction product to recover solvent oil to obtain the C9 thermal polymerized petroleum resin. The Gardner color number of the resin was found to be 9#, and the softening point was found to be 128.2 ℃.
Example 4
Firstly, distilling the C9 raw material to remove 13 percent of heavier components in the C9 raw material (accounting for the total mass of the C9 raw material). Then respectively weighing 900g of the weight-removed C9 raw material, 300g of dicyclopentadiene, 50g of methyl dicyclopentadiene and 150g of indene and indane, and dissolving the raw material and the methyl dicyclopentadiene in 100g of solvent oil; adding 30% of reaction initiator into a reaction kettle, then adding the reaction material into a thermal polymerization reaction kettle, uniformly stirring, controlling the polymerization reaction temperature to be 250 ℃ under the protection of nitrogen atmosphere and normal pressure, controlling the reaction time to be 10h, and after the reaction is finished, recovering solvent oil from the polymerized reaction product through steam stripping to obtain the C9 thermal polymerized petroleum resin. The resin was found to have a Gardner color number of 13# and a softening point of 138.1 ℃.
Example 5
Firstly, distilling the C9 raw material to remove 10 percent of heavier components in the C9 raw material (accounting for the total mass of the C9 raw material). Then 1200g of the raw material C9, 500g of dicyclopentadiene, 80g of methyl dicyclopentadiene and 200g of indene and indane which are subjected to weight removal treatment are respectively weighed and dissolved in 100g of solvent oil; adding 15% of reaction initiator into a reaction kettle, then adding the reaction material into a thermal polymerization reaction kettle, uniformly stirring, controlling the reaction temperature of polymerization to be 247 ℃ under the protection of nitrogen atmosphere and normal pressure, controlling the reaction time to be 14h, and after the reaction is finished, carrying out steam stripping on the reaction product of polymerization to recover solvent oil to obtain the C9 thermal polymerization petroleum resin. The Gardner color number of the resin was found to be 12# and the softening point was found to be 135 ℃.
Claims (10)
1. A preparation process of a C9 heat polymerized petroleum resin product with light color and high softening point is characterized in that: by-product C9 aromatic hydrocarbon fraction of a cracking ethylene preparation device is taken as a main raw material, and C9 raw oil is rectified to remove heavier components in C9 raw oil; then mixing the C9 raw material, dicyclopentadiene, methyl dicyclopentadiene, indene and solvent oil which are subjected to de-weighting treatment according to a certain proportion, placing the mixture into a thermal polymerization reaction kettle, adding a certain reaction initiator into the thermal polymerization reaction kettle, and carrying out thermal polymerization reaction to obtain a C9 thermal polymerization petroleum resin product with a light color number and a high softening point; the mixing mass ratio of the heavy component removing C9 raw material, dicyclopentadiene, methyl dicyclopentadiene, indene, indan and solvent oil is (800-1200) to (100-500) to (50-100) to (100-200) to 100; the reaction initiator adopts a reaction polymerization liquid reserved by the previous thermal polymerization reaction, and the addition amount of the reaction initiator accounts for 10-30% of the total mass of the reaction raw materials.
2. The process for preparing a light-colored, high softening point C9 hot polymeric petroleum resin product according to claim 1, wherein: when the C9 raw oil is rectified, naphthalene and other polycyclic aromatic hydrocarbon substances in the C9 raw material are mainly removed, and the removal amount of heavy components accounts for 10-15% of the total weight of the raw material.
3. The process for preparing the light-color C9 heat-polymerized petroleum resin product with high softening point according to claim 2, wherein the process comprises the following steps: when the C9 raw oil is rectified, the removal amount of heavy components accounts for 12-15% of the total weight of the raw oil.
4. The process for preparing a light-colored, high softening point C9 hot polymeric petroleum resin product according to claim 1, wherein: the main components of the raw material C9 after weight removal are 5-15% of styrene and derivatives thereof, 10-20% of methyl styrene and derivatives thereof, 20-30% of dicyclopentadiene, 10-20% of indene and indane, 5-15% of methyl dicyclopentadiene and 1-30% of alkane compounds below C9.
5. The process for preparing a light-gauge, high softening point C9 hot polymeric petroleum resin product according to any one of claims 1-4, wherein: the addition amount of the reaction trigger accounts for 15-25% of the total mass of the reaction raw materials.
6. The process for preparing a light-gauge, high softening point C9 hot polymeric petroleum resin product according to any one of claims 1-4, wherein: the temperature of the thermal polymerization reaction is 230-260 ℃, and the reaction time is controlled to be 5-24 h.
7. The process for preparing a light-colored, high softening point C9 hot-polymerized petroleum resin product according to claim 6, wherein: the polymerization temperature is 240-250 ℃, and the polymerization time is 10-18 h.
8. The process for preparing a light-gauge, high softening point C9 hot polymeric petroleum resin product according to any one of claims 1-4, wherein: the solvent oil is one or more of benzene, toluene, xylene, n-pentane, isopentane, hexane, cyclohexane, heptane, octane, nonane, decane, solvent D40 and solvent D60; the polymerization solution obtained by thermal polymerization is stripped to recover the solvent oil.
9. A light-colored, high softening point C9 heat polymerized petroleum resin product, characterized by: the petroleum resin is prepared by the method of any one of claims 1 to 8.
10. A light-gauge, high softening point C9 heat polymerized petroleum resin product according to claim 9, wherein: the Gardner color number of the C9 heat polymerized petroleum resin is 9-13, and the softening point is 120-140 ℃.
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| CN102443103B (en) * | 2011-09-16 | 2013-07-03 | 中国海洋石油总公司 | Preparation method of low-chroma high-softening-point dicyclopentadiene petroleum resin |
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