CN110078847B - Preparation method of high-softening-point hydrogenated petroleum resin - Google Patents
Preparation method of high-softening-point hydrogenated petroleum resin Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention relates to a preparation method of hydrogenated petroleum resin with high softening point, which adopts C5 olefin as raw material to obtain C through high-temperature thermal polymerization10、C15Polymerizing the polymer under catalysis to obtain dark petroleum resin; the hydrogenated petroleum resin with high softening point is prepared under the action of a hydrogenation catalyst and a certain hydrogenation process condition. The hydrogenated petroleum resin prepared by the invention has very high softening point and relatively low molecular weight, has excellent compatibility with amorphous alpha-olefin copolymer (APAO), and is suitable for the fields of BOPP films, sealants, paper laminating agents, high-grade asphalt modifiers and the like.
Description
Technical Field
The invention belongs to the field of petroleum resin, and particularly relates to a preparation method of hydrogenated petroleum resin with a high softening point.
Background
The petroleum resin is a solid or viscous liquid medium-low relative molecular weight polymer obtained by catalytic polymerization or free radical polymerization of byproducts C5, C9 fractions and the like of an ethylene device serving as main raw materials. The monomers and molecular structures constituting the resin can be roughly classified into aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, and the like.
The aliphatic petroleum resin and the alicyclic petroleum resin are respectively obtained by different C5 raw materials and polymerization processes, wherein the structure of the aliphatic petroleum resin and the alicyclic petroleum resin is mainly straight-chain alkane with a branched chain structure and is mainly obtained by direct Friedel-Crafts alkylation catalytic polymerization; the latter structure is based on a multi-ring structure, and usually requires prepolymerization to obtain C10、C15、C20And performing catalytic polymerization on the prepolymer to obtain the petroleum resin.
Wanfushan et al studied the preparation of high-performance alicyclic petroleum resin from cracking C5 fraction by hydrogenation pretreatment, polymerization, catalyst removal, resin hydrogenation and other steps. A method for preparing C5 petroleum resin by cracking C5 raw material through high-temperature thermal dimerization is disclosed in German patent GB 752884; canadian patent CA1039673 discloses a method for obtaining C5 petroleum resin with high softening point by thermal dimerization and Friedel-Crafts catalysis of C5 monoolefin and diolefin; patent CN100513528 discloses a medicineCracking C5 fraction as raw material to prepare C-containing10、C15、C20A method of olefin prepolymer; patent CN101555307 discloses a thermal polymerization method for preparing polydicyclopentadiene petroleum resin with adjustable softening point, molecular weight and distribution; patent CN101319030 discloses a method for synthesizing C5 petroleum resin by using the above thermopolymer in a catalyst-dispersant composite catalytic system; patent CN10122012 discloses a method for preparing decyclization C5 hydrogenated resin by thermal dimerization and catalytic polymerization of decyclization C5 and monoolefine raw material to obtain molten petroleum resin, and then catalytic hydrogenation; patent CN103450401 discloses a method for obtaining C5 hydrogenated petroleum resin raw material through dimerization, rectification and extraction.
In the preparation method of the alicyclic C5 petroleum resin, the process flow of C5 thermal polymerization → cationic catalytic polymerization is commonly adopted, the softening point of the prepared resin is usually 80-120 ℃, and the Gardner color number is 7-12 #, and further hydrogenation treatment is needed; and the resin molecule mainly adopts a multi-ring structure similar to polydicyclopentadiene (PDCPD), has poor compatibility with various base materials, and is limited to use in high-end application fields.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of hydrogenated petroleum resin with high softening point, the prepared hydrogenated petroleum resin has very high softening point and relatively low molecular weight, has excellent compatibility with amorphous alpha-olefin copolymer (APAO), and is suitable for the fields of BOPP films, sealants, paper laminating agents, high-grade asphalt modifiers and the like.
The invention provides a preparation method of hydrogenated petroleum resin with high softening point, which comprises the following steps:
(1) mixing cyclopentadiene, n-pentene, cyclopentene, 2-pentene and a diluting solvent to obtain a C5 ingredient; wherein, the ingredient composition of C5 is: 6.0-12.0 wt% of cyclopentadiene, 4.0-10.0 wt% of cyclopentene, 4.0-8.0 wt% of n-pentene, 0-5.0 wt% of 2-pentene and the balance of a diluting solvent;
(2) reacting the C5 ingredient obtained in the step (1) at 200-270 ℃ for 4-10 h, and flashing the obtained polymerization solution at the vacuum degree of-0.080-0.095 MPa and the temperature of 70-150 ℃ to respectively obtain a light component C5 so as to obtain a light component C5And a heavy fraction C10Mixing the materials;
(3) c obtained in the step (2)10Reacting the mixed material at 110-180 ℃ for 24-40 h under the action of a catalyst, removing the catalyst from the obtained polymerization reaction liquid, repeatedly washing the polymerization reaction liquid to be neutral, sending the polymerization reaction liquid into a rectifying tower, rectifying the polymerization reaction liquid at the vacuum degree of-0.080-0.095 MPa and the temperature of 200-260 ℃, obtaining a recovered solvent at the tower top, and obtaining a resin liquid from a tower kettle;
(4) diluting the resin liquid obtained in the step (3) and refined mineral oil according to the mass ratio of 1: 3-9, feeding the diluted resin liquid and refined mineral oil into a hydrogenation reactor, and reacting the diluted resin liquid and refined mineral oil with H under the action of a hydrogenation catalyst at the pressure of 14-16 MPa and the temperature of 200-300 DEG C2Reacting at a liquid hourly space velocity LSHV of 0.2-0.8 h-1Obtaining hydrogenated resin liquid;
(5) feeding the hydrogenated resin liquid obtained in the step (4) into a rectifying tower, and rectifying at the vacuum degree of-0.080 to-0.095 MPa and the temperature of 200 to 260 ℃ to obtain a recovered solvent at the tower top; and granulating the tower material to obtain the hydrogenated petroleum resin with the high softening point.
The diluting solvent in the step (1) is C5-C8 saturated alkane.
C in the step (2)10The composition of the mixed material is as follows: with tricyclo [5.2.1.02,6]Dec-8-ene, 5-propyl- [2.2.2]Hept-2-ene based C10、C15Mixing; wherein, C1085-98 wt% of C15The content is 2-15 wt%.
The catalyst in the step (3) is anhydrous aluminum trichloride.
And (3) removing the catalyst by using 15% alkali liquor.
The refined mineral oil in the step (4) is low-viscosity saturated mineral oil, the distillation range is 250-400 ℃, and the dynamic viscosity (40 ℃) is 4-10 cP.
The hydrogenation catalyst in the step (4) is Pd/P-gamma-Al2O3。
The Pd/P-gamma-Al2O3Is eggshell-shaped, the Pd content is 0.8-2.5 wt%, the carrier is phosphorus modified activated alumina, the P content is 0.75-1.5 wt%, and the BET specific surface area is 90-150 m2G, averageThe pore diameter is 20 to 33 nm.
The softening point of the hydrogenated petroleum resin obtained in the step (5) is 120-155 ℃, and the Gardner color number is less than or equal to 2 #.
The invention adopts Cyclopentadiene (CPD) and C5 monoolefin to generate C by Diels-Alder reaction at high temperature10And further side reaction to form C15And C20. The reaction product can be used as a raw material for preparing petroleum resin by cationic catalytic polymerization.
The hydrogenation catalyst adopts P-gamma-Al modified by phosphorus2O3The catalyst is used as a carrier, so that the total acid amount is reduced, the weak acid center proportion is increased, and the degradation effect of the high-palladium catalyst on petroleum resin can be effectively improved.
Advantageous effects
(1) The invention uses cyclopentadiene and a plurality of C5 monoolefins to generate petroleum resin polymerization raw materials through thermal polymerization, prepares hydrogenated petroleum resin with low molecular weight distribution and high softening point, and has excellent compatibility with APAO base materials;
(2) the precursor for the hydrogenated modified resin is prepared by a thermal polymerization method, the content of impurities such as halogen, sulfur, nitrogen and the like is low, the poisoning failure of a hydrogenation catalyst is relieved, and the difficulty of a hydrogenation process is reduced;
(3) the invention adopts a modified hydrogenation catalyst Pd/P-gamma-Al2O3The cracking of the petroleum resin in the deep hydrogenation process is reduced, and the higher softening point and hydrogenation yield of the petroleum resin are ensured;
(4) according to the invention, low-viscosity refined mineral oil is used as a diluting solvent, so that the dissolving capacity of gel is improved, the poison of the gel to a hydrogenation catalyst is slowed down, and the service life of the catalyst is prolonged;
(5) the hydrogenated petroleum resin obtained by the invention is suitable for the fields of BOPP films, sealants, paper laminating agents, high-grade asphalt modifiers and the like.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The C5 thermal dimerization batch consisted of: 10.0 wt% of cyclopentadiene, 7.0 wt% of cyclopentene, 3.0 wt% of n-pentene, 1.5 wt% of 2-pentene, and the balance being a diluting solvent methylcyclohexane.
C5 thermal dimerization ingredient is reacted for 10 hours in a high-pressure polymerization kettle with a stirrer at the temperature of 250 ℃, the obtained polymerization liquid is flashed at the vacuum degree of-0.090 MPa and the temperature of 95 ℃ to obtain a light component C5 and a heavy component C10And (4) mixing the materials. Mixing the above C10Reacting the mixed material at 125 ℃ for 36h under the action of an anhydrous aluminum trichloride catalyst to obtain a polymerization reaction solution; then washing with 15% alkali liquor to remove catalyst, repeatedly washing with water to neutrality, rectifying in a rectifying tower at 240 deg.C under-0.085 MPa to obtain recovered solvent at the tower top, and collecting yellow to brown resin liquid in the tower. Diluting the resin liquid and the refined mineral oil according to the mass ratio of 1:4, then feeding the diluted resin liquid and the refined mineral oil into a hydrogenation reactor, and adding the diluted resin liquid and the refined mineral oil into a hydrogenation catalyst Pd/P-gamma-Al2O3Under the action of the reaction, reacting with H at the temperature of 255 ℃ under the pressure of 15MPa2The liquid hourly space velocity LSHV is 0.5h-1. Feeding the hydrogenated resin liquid into a rectifying tower, rectifying at the vacuum degree of-0.095 MPa and the temperature of 250 ℃, and obtaining a recovered solvent at the tower top; the tower material was pelletized to obtain hydrogenated petroleum resin having a softening point of 135 ℃ and a Gardner color number 1 #.
Examples 2 to 5
Adopting different C5 ingredients, under the same thermal dimerization reaction condition and resin hydrogenation process to obtain C10The composition and properties of the hydrogenated petroleum resin are as follows:
thermal dimerization of C5 to C10The reaction conditions are as follows: the temperature is 245 ℃, and the reaction time is 10 h; the flash evaporation vacuum degree is-0.085 MPa, and the temperature is 110 ℃;
hydrogenation ofThe process conditions are as follows: the hydrogenation temperature is 275 ℃, the pressure is 15MPa, and the LSHV is 0.5h-1。
As can be seen from the above table, the greater the monoolefin/diolefin ratio (O/D value) in the feed, the lower the probability of side reactions and the C in the product10The higher the ratio, C15The lower the ratio. The ratio of CPD to cyclopentene, n-pentene, etc. in the formulation directly affects the softening point and molecular weight distribution (Mw/Mn) of the hydrogenated petroleum resin.
Examples 6 to 8
The same deep color petroleum resin liquid to be hydrogenated is mixed with refined mineral oil with the distillation range of 280-350 ℃ and the dynamic viscosity of 6.6cP according to the mass ratio of 1:5.5 to obtain a hydrogenation raw material, and the influence of different hydrogenation processes on the performance of the hydrogenated petroleum resin is examined as follows:
from the above table, it can be seen that the influence of hydrogenation temperature on the resin hydrogenation decomposition rate, i.e. the final softening point, is the greatest influence factor of the resin molecular bond breakage, and then the liquid hourly space velocity, and the influence of reaction pressure on the resin hydrogenation decomposition rate, i.e. the final softening point, is smaller. Liquid Hourly Space Velocity (LHSV) is the largest influence factor of hydrogenation reaction depth, and the color number is the lightest; and secondly, the hydrogenation temperature and the hydrogenation pressure are respectively, and the influence is relatively small. The reaction temperature is high, and the liquid hourly space velocity is large, so as to reduce the color number and the average molecular weight of the petroleum resin and improve the product performance.
Claims (7)
1. A method for preparing a high softening point hydrogenated petroleum resin, comprising:
(1) mixing cyclopentadiene, n-pentene, cyclopentene, 2-pentene and a diluting solvent to obtain a C5 ingredient; wherein, the ingredient composition of C5 is: 6.0-12.0 wt% of cyclopentadiene, 4.0-10.0 wt% of cyclopentene, 4.0-8.0 wt% of n-pentene, 0-5.0 wt% of 2-pentene and the balance of a diluting solvent;
(2) reacting the C5 ingredient obtained in the step (1) at 200-270 ℃ for 4-10 h, and flashing the obtained polymer liquid at the vacuum degree of-0.080-0.095 MPa and the temperature of 70-150 ℃ to respectively obtain a light component C5 and a heavy component C510Mixing the materials; wherein, the composition of the C10 mixed material is as follows: with tricyclo [5.2.1.02,6]Dec-8-ene, 5-propyl- [2.2.2]Mixtures of C10, C15 with hept-2-ene as the main component; wherein the content of C10 is 85-98 wt%, and the content of C15 is 2-15 wt%;
(3) c obtained in the step (2)10Reacting the mixed material at 110-180 ℃ for 24-40 h under the action of a catalyst, removing the catalyst from the obtained polymerization reaction liquid, repeatedly washing the polymerization reaction liquid to be neutral, sending the polymerization reaction liquid into a rectifying tower, rectifying the polymerization reaction liquid at the vacuum degree of-0.080-0.095 MPa and the temperature of 200-260 ℃, obtaining a recovered solvent at the tower top, and obtaining a resin liquid from a tower kettle; wherein the catalyst is anhydrous aluminum trichloride;
(4) diluting the resin liquid obtained in the step (3) and refined mineral oil according to the mass ratio of 1: 3-9, feeding the diluted resin liquid and refined mineral oil into a hydrogenation reactor, and reacting the diluted resin liquid and refined mineral oil with H under the action of a hydrogenation catalyst at the pressure of 14-16 MPa and the temperature of 200-300 DEG C2Reacting at a liquid hourly space velocity LSHV of 0.2-0.8 h-1Obtaining hydrogenated resin liquid;
(5) feeding the hydrogenated resin liquid obtained in the step (4) into a rectifying tower, and rectifying at the vacuum degree of-0.080 to-0.095 MPa and the temperature of 200 to 260 ℃ to obtain a recovered solvent at the tower top; and granulating the tower material to obtain the hydrogenated petroleum resin with the high softening point.
2. The method of claim 1, wherein: the diluting solvent in the step (1) is C5-C8 saturated alkane.
3. The method of claim 1, wherein: and (3) removing the catalyst by using 15% alkali liquor.
4. The method of claim 1, wherein: the refined mineral oil in the step (4) is low-viscosity saturated mineral oil, the distillation range is 250-400 ℃, and the dynamic viscosity is 4-10 cP.
5. The method of claim 1, wherein: the hydrogenation catalyst in the step (4) is Pd/P-gamma-Al2O3。
6. The method of claim 5, wherein: the Pd/P-gamma-Al2O3Is eggshell-shaped, the Pd content is 0.8-2.5 wt%, the carrier is phosphorus modified activated alumina, the P content is 0.75-1.5 wt%, and the BET specific surface area is 90-150 m2(ii)/g, the average pore diameter is 20 to 33 nm.
7. The method of claim 1, wherein: the softening point of the hydrogenated petroleum resin obtained in the step (5) is 120-155 ℃, and the Gardner color number is less than or equal to 2 #.
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| US6605680B1 (en) * | 2000-04-07 | 2003-08-12 | Eastman Chemical Resins, Inc. | Low color, aromatic modified C5 hydrocarbon resins |
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| CN107876051A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of hydrogenation of petroleum resin palladium series catalyst, preparation method and applications |
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| US10294175B2 (en) * | 2015-11-04 | 2019-05-21 | Exxonmobil Chemical Patents Inc. | Process for conversion of acyclic C5 compounds to cyclic C5 compounds and catalyst composition for use therein |
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| US6605680B1 (en) * | 2000-04-07 | 2003-08-12 | Eastman Chemical Resins, Inc. | Low color, aromatic modified C5 hydrocarbon resins |
| CN1928025A (en) * | 2006-08-30 | 2007-03-14 | 中国石油兰州石油化工公司 | Prepolymer containing mixture of C10, C15, C20 olefin, preparation and application thereof |
| CN104959136A (en) * | 2015-06-30 | 2015-10-07 | 大连理工大学 | Preparation method for resin hydrogenation eggshell type catalyst |
| CN107876051A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of hydrogenation of petroleum resin palladium series catalyst, preparation method and applications |
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