CN115894799B - Preparation method of modified hydrogenated resin - Google Patents
Preparation method of modified hydrogenated resin Download PDFInfo
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- CN115894799B CN115894799B CN202211544448.0A CN202211544448A CN115894799B CN 115894799 B CN115894799 B CN 115894799B CN 202211544448 A CN202211544448 A CN 202211544448A CN 115894799 B CN115894799 B CN 115894799B
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- 229920005989 resin Polymers 0.000 title claims abstract description 100
- 239000011347 resin Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000003208 petroleum Substances 0.000 claims abstract description 55
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 28
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 23
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 20
- 239000002952 polymeric resin Substances 0.000 claims description 20
- 229920003002 synthetic resin Polymers 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 18
- 150000001721 carbon Chemical class 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007701 flash-distillation Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- -1 piperylene modified DCPD Chemical class 0.000 claims description 3
- XPVIQPQOGTVMSU-UHFFFAOYSA-N (4-acetamidophenyl)arsenic Chemical compound CC(=O)NC1=CC=C([As])C=C1 XPVIQPQOGTVMSU-UHFFFAOYSA-N 0.000 abstract description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 abstract description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 2
- 229920013640 amorphous poly alpha olefin Polymers 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 101000805129 Homo sapiens Protein DPCD Proteins 0.000 description 1
- 102100037836 Protein DPCD Human genes 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of modified hydrogenated resin, which comprises the following steps of S1: batching, S2: heat-polymerizing, S3: primary desolventizing, S4: stripping, S5: primary hydrogenation, S6: secondary desolventizing and S7: and (5) secondary stripping. The preparation method is simple to operate, adopts a thermal polymerization method to avoid using aluminum trichloride catalyst in the polymerization stage, does not generate a large amount of wastewater, has higher economic product added value than the traditional DCPD resin product and is suitable for industrial continuous production, and the modified DCPD hydrogenated petroleum resin prepared by the preparation method has light color number, yellow index of about 2.5YI, better softening point and melt viscosity, and better compatibility with EVA, IR, APAO, rosin, wax, SBS and SIS compared with unmodified DCPD hydrogenated petroleum resin.
Description
Technical Field
The invention relates to the field of petroleum resin modification, in particular to a preparation method of modified hydrogenated resin.
Background
The petroleum resin is usually prepared by adopting raw materials with higher concentration of polymerized monomers to prepare the polymerized resin, and then is produced by cold polymerization mode used by most resin manufacturers in China, and then is hydrogenated to prepare hydrogenated petroleum resin with higher performance.
Disclosure of Invention
The present invention is directed to a method for preparing a modified hydrogenated resin, which solves the problems set forth in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions: a process for the preparation of a modified hydrogenated resin, said process comprising the steps of;
S1: preparing materials, wherein the materials comprise dicyclopentadiene as a raw material a, piperylene as a raw material b, a hydrogenated carbon nine solvent as a raw material c, and mixing the raw material a, the raw material b and the raw material c in proportion to obtain a reaction raw material c;
s2: heat-gathering; the thermal polymerization comprises the steps of putting a reaction raw material c into a reaction kettle with a stirrer, and reacting to obtain a polymerization solution;
s3: removing solvent once; the primary desolventizing comprises the steps of placing the polymerization solution into a flash tower for solvent removal to obtain a resin mixed solution;
S4: stripping; the steam stripping comprises the steps of carrying out superheated steam stripping on the polymer resin mixed solution in a rectifying tower to remove oligomers, so as to obtain polymer resin solution;
s5: primary hydrogenation; the primary hydrogenation comprises the steps of mixing a polymer resin liquid and a carbon nine hydrogenation solvent according to a mass ratio, and adding the mixture into a hydrogenation reactor together with a catalyst accounting for 1-5% of the mass of the polymer resin liquid to obtain a hydrogenated petroleum resin mixed liquid;
S6: secondary desolventizing; the secondary desolventizing comprises the steps of removing the solvent of the hydrogenated petroleum resin mixed solution in a flash tower to obtain the hydrogenated petroleum resin mixed solution;
S7: secondary steam stripping; the secondary stripping comprises the step of carrying out superheated steam stripping on the hydrogenated petroleum resin mixed solution in a rectifying tower to remove the oligomer, thus obtaining modified DCPD hydrogenated petroleum resin, and obtaining the piperylene modified DCPD hydrogenated petroleum resin.
Preferably, the dicyclopentadiene content in the S1 step is 84-85%, and the mass ratio of dicyclopentadiene, piperylene and hydrogenated carbon nine solvent is 30-57:3-10:40-60.
Preferably, the temperature of the reaction kettle in the step S2 is 220-280 ℃ and the reaction time is 180-360 min.
Preferably, the operation pressure of the flash distillation tower in the step S3 is micro positive pressure, the temperature of the tower bottom is 180-230 ℃, and the temperature of the tower top is 160-190 ℃.
Preferably, in the step S4, the operation pressure of the rectifying tower is-0.08 MPa, the temperature of the tower bottom is 200-240 ℃, the temperature of the tower top is 170-240 ℃, and the reflux ratio is 1-12.
Preferably, the mass ratio of the polymer resin liquid to the carbon nine hydrogenation solvent in the step S5 is 4-6:6-4, and the reaction temperature is 220-270 ℃ and the reaction time is 150-360 min under the conditions that the hydrogen pressure is 3-8MPa and the mass airspeed is 2-10 hr-1 in the hydrogenation reactor.
Preferably, in the step S6, the operation pressure of the flash distillation tower is micro positive pressure, the temperature of the tower bottom is 180-230 ℃, and the temperature of the tower top is 160-190 ℃.
Preferably, in the step S7, the operation pressure of the rectifying tower is-0.08 MPa, the temperature of the tower bottom is 200-240 ℃, the temperature of the tower top is 170-240 ℃, and the reflux ratio is 1-12.
The invention has the technical effects and advantages that:
the preparation method is simple to operate, adopts a thermal polymerization method to avoid using aluminum trichloride catalyst in the polymerization stage, does not generate a large amount of wastewater, has higher economic product added value than the traditional DCPD resin product and is suitable for industrial continuous production, and the modified DCPD hydrogenated petroleum resin prepared by the preparation method has light color number, yellow index of about 2.5YI, better softening point and melt viscosity, and better compatibility with EVA, IR, APAO, rosin, wax, SBS and SIS compared with unmodified DCPD hydrogenated petroleum resin.
Drawings
FIG. 1 is a flow chart of the operational steps of the present invention.
Fig. 2 is a process flow diagram of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The present invention provides a method for producing a modified hydrogenated resin as shown in FIGS. 1-2, comprising the steps of;
S1: preparing materials, wherein the materials comprise dicyclopentadiene as a raw material a, piperylene as a raw material b, a hydrogenated carbon nine solvent as a raw material c, and mixing the raw material a, the raw material b and the raw material c in proportion to obtain a reaction raw material c;
s2: heat-gathering; the thermal polymerization comprises the steps of putting a reaction raw material c into a reaction kettle with a stirrer, and reacting to obtain a polymerization solution;
s3: removing solvent once; the primary desolventizing comprises the steps of placing the polymerization solution into a flash tower for solvent removal to obtain a resin mixed solution;
S4: stripping; the steam stripping comprises the steps of carrying out superheated steam stripping on the polymer resin mixed solution in a rectifying tower to remove oligomers, so as to obtain polymer resin solution;
s5: primary hydrogenation; the primary hydrogenation comprises the steps of mixing a polymer resin liquid and a carbon nine hydrogenation solvent according to a mass ratio, and adding the mixture into a hydrogenation reactor together with a catalyst accounting for 1-5% of the mass of the polymer resin liquid to obtain a hydrogenated petroleum resin mixed liquid;
S6: secondary desolventizing; the secondary desolventizing comprises the steps of removing the solvent of the hydrogenated petroleum resin mixed solution in a flash tower to obtain the hydrogenated petroleum resin mixed solution;
S7: secondary steam stripping; the secondary stripping comprises the steps of carrying out superheated steam stripping on the hydrogenated petroleum resin mixed solution in a rectifying tower to remove oligomers, so as to obtain modified DCPD hydrogenated petroleum resin, and thus obtaining piperylene modified DCPD hydrogenated petroleum resin;
In the step S1, the dicyclopentadiene accounts for 84-85 percent, and the mass ratio of dicyclopentadiene, piperylene and hydrogenated carbon nine solvent is 30-57:3-10:40-60;
the temperature of the reaction kettle in the step S2 is 220-280 ℃ and the reaction time is 180-360 min;
the operation pressure of the flash distillation tower in the step S3 is micro positive pressure, the temperature of the tower bottom is 180-230 ℃, and the temperature of the tower top is 160-190 ℃;
in the step S4, the operating pressure of the rectifying tower is-0.08 MPa, the temperature of the tower bottom is 200-240 ℃, the temperature of the tower top is 170-240 ℃, and the reflux ratio is 1-12;
The mass ratio of the polymerized resin liquid to the carbon nine hydrogenation solvent in the step S5 is 4-6:6-4, and the reaction temperature is 220-270 ℃ and the reaction time is 150-360 min under the conditions that the hydrogen pressure is 3-8MPa and the mass airspeed is 2-10 hr-1 in the hydrogenation reactor;
In the step S6, the operation pressure of the flash distillation tower is micro positive pressure, the temperature of the tower bottom is 180-230 ℃, and the temperature of the tower top is 160-190 ℃;
In the step S7, the operating pressure of the rectifying tower is-0.08 MPa, the temperature of the tower bottom is 200-240 ℃, the temperature of the tower top is 170-240 ℃, and the reflux ratio is 1-12.
The S1 dicyclopentadiene component
The S1 piperylene component
| Component (A) | Content of |
| Piperylene | 63％ |
| Trans-1, 3-pentadiene | 30％ |
| Dicyclopentadiene + cyclopentadiene | 1％ |
The S1 hydrogenated carbon nine solvent component
Example 1
Mixing piperylene, DCPD and hydrogenated carbon nine solvent according to the mass ratio of 1:49:50, adding the mixture into a reaction kettle with a stirrer, enabling the materials to react for 240min at the temperature of 260 ℃ to obtain a polymerization solution, removing the solvent from the polymerization solution in a flash evaporation tower, wherein the operation pressure is micro positive pressure, the temperature of the kettle is 210 ℃, the temperature of the top of the tower is 190 ℃, obtaining a mixed solution of resin and oligomer, adding the mixed solution into a rectifying tower, carrying out superheated steam stripping to remove the oligomer, the operation pressure is-0.08 MPa, the temperature of the kettle is 240 ℃, the temperature of the top of the tower is 210 ℃, the reflux ratio is 6, obtaining a polymerization resin solution, mixing the polymerization resin solution with the carbon nine hydrogenation solvent according to the mass ratio of 4:6, adding the polymerization resin solution into the hydrogenation reactor together with a catalyst accounting for 1.5% of the mass of the polymerization resin solution, and obtaining a hydrogenated petroleum resin mixed solution under the conditions of hydrogen pressure of 5MPa and mass space velocity of 7hr < -1 >, the reaction temperature is 250 ℃ and the reaction time is 240 min; removing solvent from the hydrogenated petroleum resin mixed solution in a flash distillation tower, wherein the operation pressure is micro positive pressure, the temperature of a tower kettle is 210 ℃, the temperature of a tower top is 190 ℃, the obtained hydrogenated resin and oligomer mixed solution is added into a rectifying tower, the superheated steam stripping is carried out to remove the oligomer, the operation pressure is-0.08 MPa, the temperature of the tower kettle is 240 ℃, the temperature of the tower top is 210 ℃, the reflux ratio is 6, the hydrogenated petroleum resin solution is obtained, and the obtained hydrogenated petroleum resin solution is granulated by a granulator, so as to obtain m-pentadiene modified DCPD hydrogenated petroleum resin particles;
Example two
Mixing piperylene, DCPD and hydrogenated carbon nine solvent according to the mass ratio of 3:47:50, adding the mixture into a reaction kettle with a stirrer, enabling the materials to react for 240min at the temperature of 260 ℃ to obtain a polymerization solution, removing the solvent from the polymerization solution in a flash evaporation tower, wherein the operation pressure is micro positive pressure, the temperature of the tower kettle is 210 ℃, the temperature of the tower top is 190 ℃, adding the obtained mixed solution of resin and oligomer into a rectifying tower, and carrying out superheated steam stripping to remove the oligomer, the operation pressure is-0.08 MPa, the temperature of the tower kettle is 240 ℃, the temperature of the tower top is 210 ℃, and the reflux ratio is 6, thereby obtaining a polymerized resin solution; mixing the polymer resin liquid with a carbon nine hydrogenation solvent according to a mass ratio of 4:6, adding the mixture into a hydrogenation reactor together with a catalyst accounting for 1.5% of the mass of the polymer resin liquid, and obtaining a hydrogenated petroleum resin mixed liquid under the conditions of a hydrogen pressure of 5MPa and a mass space velocity of 7hr < -1 >, wherein the reaction temperature is 250 ℃ and the reaction time is 240 min; removing solvent from the hydrogenated petroleum resin mixed solution in a flash distillation tower, wherein the operation pressure is micro positive pressure, the temperature of a tower kettle is 210 ℃, the temperature of a tower top is 190 ℃, the obtained hydrogenated resin and oligomer mixed solution is added into a rectifying tower, the superheated steam stripping is carried out to remove the oligomer, the operation pressure is-0.08 MPa, the temperature of the tower kettle is 240 ℃, the temperature of the tower top is 210 ℃, the reflux ratio is 6, the hydrogenated petroleum resin liquid is obtained, and the obtained hydrogenated petroleum resin liquid is granulated by a granulator, so as to obtain m-pentadiene modified DCPD hydrogenated petroleum resin particles.
Example III
Mixing piperylene, DCPD and hydrogenated carbon nine solvent according to the mass ratio of 5:45:50, adding the mixture into a reaction kettle with a stirrer, enabling the materials to react for 240min at the temperature of 260 ℃ to obtain a polymerization solution, removing the solvent from the polymerization solution in a flash evaporation tower, wherein the operation pressure is micro positive pressure, the temperature of the tower kettle is 210 ℃, the temperature of the tower top is 190 ℃, adding the obtained mixed solution of resin and oligomer into a rectifying tower, and carrying out superheated steam stripping to remove the oligomer, the operation pressure is-0.08 MPa, the temperature of the tower kettle is 240 ℃, the temperature of the tower top is 210 ℃, and the reflux ratio is 6, thereby obtaining a polymerized resin solution; mixing the polymer resin liquid and a carbon nine hydrogenation solvent according to the mass ratio of 4:6, adding the mixture into a hydrogenation reactor together with a catalyst which is 1.5 percent of the mass of the polymer resin liquid, under the conditions of the hydrogen pressure of 5MPa and the mass airspeed of 7hr < -1 >, the reaction temperature of 250 ℃ and the reaction time of 240min to obtain hydrogenated petroleum resin mixed liquid, removing the solvent of the hydrogenated petroleum resin mixed liquid in a flash evaporation tower, operating the pressure of micro positive pressure, the temperature of a tower kettle of 210 ℃, the temperature of a tower top of 190 ℃, obtaining the mixed liquid of hydrogenated resin and oligomer, adding the mixed liquid into a rectifying tower, performing superheated steam stripping to remove the oligomer, the operating pressure of-0.08 MPa, the temperature of the tower kettle of 240 ℃, the temperature of the tower top of 210 ℃, and the reflux ratio of 6, granulating by a granulator to obtain the m-pentadiene modified DCPD hydrogenated petroleum resin particles.
Example IV
Mixing piperylene, DCPD and hydrogenated carbon nine solvent according to the mass ratio of 8:42:50, adding the mixture into a reaction kettle with a stirrer, enabling the materials to react for 240min at 260 ℃ to obtain a polymerization solution, removing the solvent from the polymerization solution in a flash evaporation tower, wherein the operation pressure is micro positive pressure, the temperature of the kettle is 210 ℃, the temperature of the top of the tower is 190 ℃, obtaining a mixed solution of resin and oligomer, adding the mixed solution into a rectifying tower, carrying out superheated steam stripping to remove the oligomer, the operation pressure is-0.08 MPa, the temperature of the top of the tower is 240 ℃, the temperature of the top of the tower is 210 ℃, the reflux ratio is 6, obtaining a polymerization resin solution, mixing the polymerization resin solution with the carbon nine hydrogenation solvent according to the mass ratio of 4:6, adding the catalyst accounting for 1.5% of the mass of the polymerization resin solution into the hydrogenation reactor, and under the conditions that the hydrogen pressure is 5MPa and the mass space velocity is 7hr-1, the reaction temperature is 250 ℃, and the reaction time is 240min, thus obtaining a hydrogenated petroleum resin mixed solution; removing solvent from the hydrogenated petroleum resin mixed solution in a flash distillation tower, wherein the operation pressure is micro positive pressure, the temperature of a tower kettle is 210 ℃, the temperature of a tower top is 190 ℃, the obtained hydrogenated resin and oligomer mixed solution is added into a rectifying tower, the superheated steam stripping is carried out to remove the oligomer, the operation pressure is-0.08 MPa, the temperature of the tower kettle is 240 ℃, the temperature of the tower top is 210 ℃, the reflux ratio is 6, the hydrogenated petroleum resin liquid is obtained, and the obtained hydrogenated petroleum resin liquid is granulated by a granulator, so as to obtain m-pentadiene modified DCPD hydrogenated petroleum resin particles.
Example five
Mixing piperylene, DCPD and hydrogenated carbon nine solvent according to the mass ratio of 10:40:50, adding the mixture into a reaction kettle with a stirrer, enabling the materials to react for 240min at the temperature of 260 ℃ to obtain a polymerization solution, removing the solvent from the polymerization solution in a flash evaporation tower, wherein the operation pressure is micro positive pressure, the temperature of the tower kettle is 210 ℃, the temperature of the tower top is 190 ℃, adding the obtained mixed solution of resin and oligomer into a rectifying tower, and carrying out superheated steam stripping to remove the oligomer, the operation pressure is-0.08 MPa, the temperature of the tower kettle is 240 ℃, the temperature of the tower top is 210 ℃, and the reflux ratio is 6, thereby obtaining a polymerized resin solution; mixing the polymer resin liquid and a carbon nine hydrogenation solvent according to the mass ratio of 4:6, adding the mixture into a hydrogenation reactor together with a catalyst which is 1.5 percent of the mass of the polymer resin liquid, under the conditions of the hydrogen pressure of 5MPa and the mass airspeed of 7hr < -1 >, the reaction temperature of 250 ℃ and the reaction time of 240min to obtain hydrogenated petroleum resin mixed liquid, removing the solvent of the hydrogenated petroleum resin mixed liquid in a flash evaporation tower, operating the pressure of micro positive pressure, the temperature of a tower kettle of 210 ℃, the temperature of a tower top of 190 ℃, obtaining the mixed liquid of hydrogenated resin and oligomer, adding the mixed liquid into a rectifying tower, performing superheated steam stripping to remove the oligomer, the operating pressure of-0.08 MPa, the temperature of the tower kettle of 240 ℃, the temperature of the tower top of 210 ℃, and the reflux ratio of 6, granulating by a granulator to obtain the m-pentadiene modified DCPD hydrogenated petroleum resin particles.
Example six
Mixing piperylene, DCPD and hydrogenated carbon nine solvent according to the mass ratio of 30:20:50, adding the mixture into a reaction kettle with a stirrer, enabling the materials to react for 240min at 260 ℃ to obtain a polymerization solution, removing the solvent from the polymerization solution in a flash evaporation tower, wherein the operation pressure is micro positive pressure, the temperature of the kettle is 210 ℃, the temperature of the top of the tower is 190 ℃, obtaining a mixed solution of resin and oligomer, adding the mixed solution into a rectifying tower, carrying out superheated steam stripping to remove the oligomer, the operation pressure is-0.08 MPa, the temperature of the top of the tower is 240 ℃, the temperature of the top of the tower is 210 ℃, the reflux ratio is 6, obtaining a polymerization resin solution, mixing the polymerization resin solution with the carbon nine hydrogenation solvent according to the mass ratio of 4:6, adding the catalyst accounting for 1.5% of the mass of the polymerization resin solution into the hydrogenation reactor, and under the conditions that the hydrogen pressure is 5MPa and the mass space velocity is 7hr-1, the reaction temperature is 250 ℃, and the reaction time is 240min, thus obtaining a hydrogenated petroleum resin mixed solution; removing solvent from the hydrogenated petroleum resin mixed solution in a flash distillation tower, wherein the operation pressure is micro positive pressure, the temperature of a tower kettle is 210 ℃, the temperature of a tower top is 190 ℃, the obtained hydrogenated resin and oligomer mixed solution is added into a rectifying tower, the superheated steam stripping is carried out to remove the oligomer, the operation pressure is-0.08 MPa, the temperature of the tower kettle is 240 ℃, the temperature of the tower top is 210 ℃, the reflux ratio is 6, the hydrogenated petroleum resin liquid is obtained, and the obtained hydrogenated petroleum resin liquid is granulated by a granulator, so as to obtain m-pentadiene modified DCPD hydrogenated petroleum resin particles.
Wherein, in the preparation of DCPD hydrogenated petroleum resin, the specific gravity of the modified component piperylene in the raw material has a great influence on the chromaticity, softening point, melt viscosity and compatibility of the hydrogenated petroleum resin, and the influence of the proportion of piperylene and DCPD on the properties of the hydrogenated petroleum resin is shown in table 1.
TABLE 1
As shown in the above list, as the content of piperylene and DPCD in the reaction raw materials is changed, the amount of piperylene added is increased, and the softening point and melt viscosity of the hydrogenated petroleum resin are gradually reduced, and the chromaticity and compatibility are normally distributed, so that the preferable proportion of the amount of piperylene added in the raw materials is 3% -8%.
Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principles of the present invention.
Claims (5)
1. A process for producing a modified hydrogenated resin, characterized by comprising the steps of;
s1: preparing materials, wherein the materials comprise dicyclopentadiene as a raw material a, piperylene as a raw material b, a hydrogenated carbon nine solvent as a raw material c, and mixing the raw material a, the raw material b and the raw material c in proportion to obtain a reaction raw material c;
s2: heat-gathering; the thermal polymerization comprises the steps of putting a reaction raw material c into a reaction kettle with a stirrer, and reacting to obtain a polymerization solution;
s3: removing solvent once; the primary desolventizing comprises the steps of placing the polymerization solution into a flash tower for solvent removal to obtain a resin mixed solution;
S4: stripping; the steam stripping comprises the steps of carrying out superheated steam stripping on the polymer resin mixed solution in a rectifying tower to remove oligomers, so as to obtain polymer resin solution;
s5: primary hydrogenation; the primary hydrogenation comprises the steps of mixing a polymer resin liquid and a carbon nine hydrogenation solvent according to a mass ratio, and adding the mixture into a hydrogenation reactor together with a catalyst accounting for 1-5% of the mass of the polymer resin liquid to obtain a hydrogenated petroleum resin mixed liquid;
S6: secondary desolventizing; the secondary desolventizing comprises the steps of removing the solvent of the hydrogenated petroleum resin mixed solution in a flash tower to obtain the hydrogenated petroleum resin mixed solution;
S7: secondary steam stripping; the secondary stripping comprises the steps of carrying out superheated steam stripping on the hydrogenated petroleum resin mixed solution in a rectifying tower to remove oligomers, so as to obtain modified DCPD hydrogenated petroleum resin, and thus obtaining piperylene modified DCPD hydrogenated petroleum resin;
In the step S1, the dicyclopentadiene accounts for 84-85 percent, and the mass ratio of dicyclopentadiene, piperylene and hydrogenated carbon nine solvent is 30-57:3-10:40-60;
the temperature of the reaction kettle in the step S2 is 220-280 ℃ and the reaction time is 180-360 min;
in the step S3, the operation pressure of the flash distillation tower is micro positive pressure, the temperature of the tower bottom is 180-230 ℃, and the temperature of the tower top is 160-190 ℃.
2. The process for producing a modified hydrogenated resin according to claim 1, wherein the rectifying column in step S4 is operated at a pressure of-0.08 MPa, a column bottom temperature of 200 to 240℃and a column top temperature of 170 to 240℃and a reflux ratio of 1 to 12.
3. The process for producing a modified hydrogenated resin according to claim 1, wherein the mass ratio of the polymer resin liquid to the carbon nine hydrogenation solvent in the step S5 is 4-6:6-4, and the reaction temperature is 220 to 270℃and the reaction time is 150 to 360 minutes under the conditions of a hydrogen pressure of 3 to 8MPa and a mass space velocity of 2 to 10hr-1 in the hydrogenation reactor.
4. The process for producing a modified hydrogenated resin according to claim 1, wherein the operation pressure of the flash column in step S6 is a micro positive pressure, the temperature of the column bottom is 180 to 230℃and the temperature of the column top is 160 to 190 ℃.
5. The process for producing a modified hydrogenated resin according to claim 1, wherein the rectifying column in step S7 is operated at a pressure of-0.08 MPa, a column bottom temperature of 200 to 240℃and a column top temperature of 170 to 240℃and a reflux ratio of 1 to 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211544448.0A CN115894799B (en) | 2022-12-04 | 2022-12-04 | Preparation method of modified hydrogenated resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211544448.0A CN115894799B (en) | 2022-12-04 | 2022-12-04 | Preparation method of modified hydrogenated resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115894799A CN115894799A (en) | 2023-04-04 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54117591A (en) * | 1978-03-03 | 1979-09-12 | Toyo Soda Mfg Co Ltd | Preparation of petroleum resin |
| CN101613438A (en) * | 2009-07-29 | 2009-12-30 | 宁波甬华树脂有限公司 | A kind of preparation method of m-pentadiene modified DCPD petroleum resin |
| WO2021125837A1 (en) * | 2019-12-17 | 2021-06-24 | 코오롱인더스트리 주식회사 | Hydrogenated petroleum resin and rubber composition comprising same |
| CN114835855A (en) * | 2022-05-16 | 2022-08-02 | 新疆昊辰汇德新材料科技有限责任公司 | Method for modifying DCPD petroleum resin |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54117591A (en) * | 1978-03-03 | 1979-09-12 | Toyo Soda Mfg Co Ltd | Preparation of petroleum resin |
| CN101613438A (en) * | 2009-07-29 | 2009-12-30 | 宁波甬华树脂有限公司 | A kind of preparation method of m-pentadiene modified DCPD petroleum resin |
| WO2021125837A1 (en) * | 2019-12-17 | 2021-06-24 | 코오롱인더스트리 주식회사 | Hydrogenated petroleum resin and rubber composition comprising same |
| CN114835855A (en) * | 2022-05-16 | 2022-08-02 | 新疆昊辰汇德新材料科技有限责任公司 | Method for modifying DCPD petroleum resin |
Non-Patent Citations (2)
| Title |
|---|
| Assessment of the compatibility in hot melts by using different thermoanalytical methods. Ethylene/n-butyl acrylate (EBA) hot melts containing tackifiers of different nature;Marı´a Alejandra Moyano et al;《J Therm Anal Calorim》;20171231;第129卷;第1495-1503页 * |
| 双环戊二烯石油树脂的合成研究;姜丹蕾 等;《化工科技》;20121231;第20卷(第5期);第24-27页 * |
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