CN111234106A - Preparation method of liquid modified aromatic hydrocarbon petroleum resin - Google Patents
Preparation method of liquid modified aromatic hydrocarbon petroleum resin Download PDFInfo
- Publication number
- CN111234106A CN111234106A CN202010166512.0A CN202010166512A CN111234106A CN 111234106 A CN111234106 A CN 111234106A CN 202010166512 A CN202010166512 A CN 202010166512A CN 111234106 A CN111234106 A CN 111234106A
- Authority
- CN
- China
- Prior art keywords
- liquid
- resin
- polymerization
- aromatic hydrocarbon
- petroleum resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011347 resin Substances 0.000 title claims abstract description 52
- 229920005989 resin Polymers 0.000 title claims abstract description 52
- 239000007788 liquid Substances 0.000 title claims abstract description 50
- 239000003208 petroleum Substances 0.000 title claims abstract description 22
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- 239000011973 solid acid Substances 0.000 claims abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002952 polymeric resin Substances 0.000 claims description 6
- 229920003002 synthetic resin Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000011964 heteropoly acid Substances 0.000 claims description 5
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 4
- 150000005673 monoalkenes Chemical class 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 4
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 claims description 3
- ANSIWEGOCFWRSC-UHFFFAOYSA-N 1,2-dimethyl-1h-indene Chemical compound C1=CC=C2C(C)C(C)=CC2=C1 ANSIWEGOCFWRSC-UHFFFAOYSA-N 0.000 claims description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002469 indenes Chemical class 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 238000010074 rubber mixing Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/22—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of chromium, molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a preparation method of liquid modified aromatic hydrocarbon petroleum resin, which comprises the following steps: mixing indene, styrene and a C5 olefin saturated solvent to obtain a polymerization raw material, carrying out catalytic polymerization by using a foamed ceramic supported solid acid catalyst to obtain a polymerization resin liquid, and carrying out adsorption filtration and rectification to remove the solvent to obtain the catalyst. The preparation method has simple and convenient process and mild polymerization conditions, reduces the generation of three wastes, and the obtained liquid modified resin has good compatibility and is suitable for the fields of rubber mixing, plastic modification and the like.
Description
Technical Field
The invention belongs to the field of petroleum resin, and particularly relates to a preparation method of liquid modified aromatic hydrocarbon petroleum resin.
Background
The ethylene cracking C9 fraction is rich in polymerizable monomers such as styrene, methyl styrene, dicyclopentadiene, indene and the like. The aromatic petroleum resin obtained by thermal free radical polymerization or Lewis acid catalytic polymerization of the components has excellent tackifying performance, certain polarity, good compatibility with various rubbers, elastomers and the like, and can improve the viscosity, strength and ductility of products.
The liquid aromatic petroleum resin is a special petroleum resin which has a lower softening point and an average molecular weight and is in a flowing state at normal temperature, is an excellent rubber tackifier and hot melt adhesive auxiliary agent developed in recent years, and has wide market application potential. However, at present, liquid resins are generally derived from byproducts of solid petroleum resins, and the production process is similar to the process: inorganic acid or Lewis acid is used as a catalyst, the reaction is mainly carried out in a kettle type and batch reaction, and the catalyst needs to be removed by alkali washing and water washing in the post-treatment process, so that the properties of the liquid resin product, such as color number, average molecular weight, melt viscosity and the like, are unstable, a large amount of waste water containing acid, alkali or halide is generated in the process, and the influence on the environment is increased.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of liquid modified aromatic hydrocarbon petroleum resin, which is environment-friendly, reduces the generation of three wastes, and the prepared petroleum resin has good compatibility.
The invention provides a preparation method of liquid modified aromatic hydrocarbon petroleum resin, which comprises the following steps:
(1) preparing and mixing indene or derivatives thereof, styrene or derivatives thereof and C5 olefin according to the mass ratio of 1: 0.05-0.5: 0-0.5, uniformly mixing with a saturated solvent accounting for 25-50% of the total mass of the materials to obtain a polymerization raw material, drying and dehydrating the raw material through an alumina bed, and carrying out catalytic polymerization by using a foamed ceramic supported solid acid catalyst at the reaction temperature of 35-75 ℃, the reaction pressure of 101.3-120.0 kPa and the reaction time of 3-12 h to obtain a polymerization resin liquid;
(2) and adsorbing and filtering the polymeric resin liquid by a packed tower, then feeding the polymeric resin liquid into a rectifying tower, and removing the solvent at the vacuum degree of-0.080 to-0.095 Mpa and the temperature of 175-210 ℃ to obtain the liquid modified aromatic hydrocarbon petroleum resin.
The indene derivative in the step (1) is at least one of methyl indene and dimethyl indene.
The styrene derivative in the step (1) is at least one of α -methyl styrene and vinyl toluene.
The C5 olefin in the step (1) is C5 monoolefin or C5 diolefin. The C5 monoolefin is at least one of n-pentene, isopentene and cyclopentene; the C5 diolefin is at least one of piperylene, isoprene and cyclopentadiene.
The saturated solvent in the step (1) is at least one of n-pentane, cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane.
The solid acid catalyst in the step (1) is a heteropolyacid catalyst, such as a phosphotungstic acid or phosphomolybdic acid catalyst. Preferably, the heteropolyacid catalyst is H6P2W18O62、H3PW12O40、H3PO4·12MoO3At least one of (1).
The packed tower in the step (2) is of a two-layer packing structure, and the average diameter of the packing is 13-25 mm; wherein, the upper layer is gamma-activated alumina, and the lower layer is foamed ceramic.
The Gardner color number of the liquid modified aromatic hydrocarbon petroleum resin obtained in the step (2) is less than or equal to 4#, and the melt viscosity at 60 ℃ is 30-350 mPa · s.
The heteropolyacid catalyst of the present invention has good catalytic activity and thermal stability (as previously applied), acid strength (H)0) Far greater than H of molecular sieve catalyst and ion exchange resin catalyst, especially supported phosphotungstic acid catalyst0Can reach-2.5 to-3.8. Ceramic foam, as a type of porous medium, is usually made of Al2O3And materials such as SiC and the like are prepared by an organic foam impregnation method, a pore-forming agent adding method and the like, and have the advantages of high permeability, high specific surface area, low density, high temperature resistance, corrosion resistance and the like. Heteropolyacids such as phosphotungstic acid or phosphomolybdic acid and the like are loaded in pores of the foamed ceramic to prepare a solid acid catalyst, so that the liquid resin can realize high-efficiency polymerization reaction capable of being continuously operated without complex subsequent treatment, the production efficiency is improved, and the product performance is stabilized.
Advantageous effects
(1) The invention adopts C5 olefin to modify liquid aromatic hydrocarbon petroleum resin, so that the structure has both aliphatic hydrocarbon group and aromatic hydrocarbon group, and the compatibility of the resin is improved;
(2) according to the invention, the foamed ceramic supported solid acid catalyst is used as a polymerization catalyst, so that the liquid resin can realize high-efficiency polymerization reaction capable of being continuously operated without complex subsequent treatment, the production efficiency is improved, and the product performance is stabilized;
(3) the solid acid catalyst is adopted, so that acid-containing wastewater generated in a catalyst removal process can be avoided, and the green and environment-friendly properties of the process are improved;
(4) the method adopts a multistage packed tower to separate impurities in the liquid resin polymerization liquid, and ensures the continuity and stability of the subsequent solvent removal process;
(5) the melt viscosity of the liquid modified aromatic hydrocarbon petroleum resin can be adjusted according to different requirements, the application field and range are expanded, and the liquid modified aromatic hydrocarbon petroleum resin is suitable for the fields of rubber mixing, plastic modification and the like.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
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
Mixing indene, styrene and piperylene according to the mass ratio of 1:0.25:0.1, then uniformly mixing with methylcyclohexane accounting for 30% of the total mass of the materials to obtain a polymerization raw material, and drying and dehydrating through alumina until the water content of the raw material is 110 ppm; then loading phosphotungstic acid H through foamed ceramic6P2W18O62Catalyzing and polymerizing to obtain a polymer resin liquid, wherein the reaction temperature is 45 ℃, the reaction pressure is 110kPa, and the reaction time is 8 h. Filtering the resin liquid by a packed tower to remove impurities, then feeding the resin liquid into a rectifying tower, and removing the solvent at the vacuum degree of-0.090 MPa and the temperature of 185 ℃ to obtain the liquid petroleum resin with the Gardner color number of 3.0 and the melt viscosity (60 ℃) of 175 mPas. The resin has good compatibility with IR, BR rubber and the like, and the cohesive strength of the product is improved.
Examples 2 to 5
In examples 2 to 5, indene, styrene and different C5 olefins were prepared in a mass ratio of 1:0.25:0.1, and the other process conditions were the same as in example 1.
| Example 2 | Example 3 | Example 4 | Example 5 | |
| C5 olefin monomer | Isoprene (I) | Cyclopentadiene | Isoamylene | Cyclopentene |
| Gardner color number, # | 3.2 | 3.9 | 1.9 | 2.3 |
| Melt viscosity (60 ℃ C.) mPas | 238 | 118 | 57 | 104 |
| DACP cloud Point, deg.C | -13 | 3 | -5 | 10 |
The DACP cloud point, namely the diacetone alcohol cloud point, is obtained by uniformly mixing resin, xylene and diacetone alcohol according to equal mass ratio; the samples were then heated and furnace cooled, and the temperature at which the solution was completely cloudy was used as a measure. This index reflects the polarity of the resin itself. Too high a DACP cloud point affects the initial compatibility with NR, SIS, SBS, SBR, etc. elastomers, leading to a decrease in cohesive properties and exudation.
From examples 2 to 5, it can be seen that liquid aromatic resins with different melt viscosities and compatibility properties can be obtained by using polyolefins with different C5 as modifying components. The isoamylene and cyclopentene modified liquid aromatic resin has lighter color number and lower melt viscosity, and is suitable for raising the cohesive strength of low density and low rigidity elastomer. The isoprene modified liquid aromatic resin has higher melt viscosity, and is suitable for modifying elastomers with stronger rigidity.
The liquid resin respectively modified by isoprene and isoamylene with lower DACP cloud point has better initial compatibility with partial elastomer, and can enhance the cohesive strength and toughness thereof.
Example 6
The preparation method comprises the steps of preparing and mixing methyl indene, α -methyl styrene and piperylene according to the mass ratio of 1:0.40:0.05, then uniformly mixing the materials with methylcyclohexane accounting for 35% of the total mass of the materials to obtain a polymerization raw material, drying and dehydrating the polymerization raw material by using alumina until the water content of the raw material is 120ppm, then carrying out catalytic polymerization by using ceramic foam loaded dodecaphosphomolybdic acid to obtain a polymerization resin liquid, wherein the reaction temperature is 60 ℃, the reaction pressure is 114kPa, the reaction time is 5h, filtering the resin liquid by using a packed tower to remove impurities, then feeding the resin liquid into a rectifying tower, and removing a solvent at the vacuum degree of-0.090 MPa and the temperature of 185 ℃ to obtain the Gardner color number 0.9, and the melt viscosity (60 ℃) is 267 mPas.
Example 7
Indene and α -methylstyrene are prepared and mixed according to the mass ratio of 1:0.55, then are uniformly mixed with methylcyclohexane accounting for 35 percent of the total mass of the materials to obtain a polymerization raw material, firstly, alumina is used for drying and dehydration until the water content of the raw material reaches 60ppm, then the raw material is catalyzed and polymerized by foam ceramic loaded dodecaphosphomolybdic acid to obtain a polymerization resin liquid, the reaction temperature is 50 ℃, the reaction pressure is 110kPa, the reaction time is 4h, the resin liquid is filtered by a packed tower to remove impurities, then the resin liquid enters a rectifying tower, and the solvent is removed at the temperature of 200 ℃ under the vacuum degree of-0.090 MPa, so that the liquid petroleum resin with the Gardner color number of 1.2 and the melt viscosity (60 ℃) of 323 mPas is obtained.
Examples 8 to 10
The polymer resin liquid with the Gardner color number of 1.5# and the melt viscosity (60 ℃) of 22mPa & s is obtained through the step (1), and in the embodiment 8-10, the product performance of the liquid resin is influenced by different post-treatment conditions.
The operating conditions of the rectifying tower are vacuum degree of-0.090 MPa and operating temperature of 200 ℃.
The polymerization resin liquid contains about 55% by weight of a saturated solvent, so that the initial viscosity is low. As can be seen from the above examples, by adjusting the adsorption temperature and residence time of the packed column, liquid resins with different properties can be obtained: the adsorption temperature is increased, and the color number and the melt viscosity of the liquid resin are both obviously reduced; while shorter adsorption temperatures and residence times result in higher viscosity liquid resin products.
Claims (10)
1. A method for preparing liquid modified aromatic hydrocarbon petroleum resin comprises the following steps:
(1) preparing and mixing indene or derivatives thereof, styrene or derivatives thereof and C5 olefin according to the mass ratio of 1: 0.05-0.5: 0-0.5, uniformly mixing with a saturated solvent accounting for 25-50% of the total mass of the materials to obtain a polymerization raw material, drying and dehydrating the raw material through an alumina bed, and carrying out catalytic polymerization by using a foamed ceramic supported solid acid catalyst at the reaction temperature of 35-75 ℃, the reaction pressure of 101.3-120.0 kPa and the reaction time of 3-12 h to obtain a polymerization resin liquid;
(2) and adsorbing and filtering the polymeric resin liquid by a packed tower, then feeding the polymeric resin liquid into a rectifying tower, and removing the solvent at the vacuum degree of-0.080 to-0.095 Mpa and the temperature of 175-210 ℃ to obtain the liquid modified aromatic hydrocarbon petroleum resin.
2. The method of claim 1, wherein: the indene derivative in the step (1) is at least one of methyl indene and dimethyl indene.
3. The method according to claim 1, wherein the styrene derivative in the step (1) is at least one of α -methylstyrene and vinyltoluene.
4. The method of claim 1, wherein: the C5 olefin in the step (1) is C5 monoolefin or C5 diolefin.
5. The method of claim 4, wherein: the C5 monoolefin is at least one of n-pentene, isopentene and cyclopentene; the C5 diolefin is at least one of piperylene, isoprene and cyclopentadiene.
6. The method of claim 1, wherein: the saturated solvent in the step (1) is at least one of n-pentane, cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane.
7. The method of claim 1, wherein: the solid acid catalyst in the step (1) is a heteropoly acid catalyst.
8. The production process according to claim 7, wherein,the method is characterized in that: the heteropoly acid catalyst is H6P2W18O62、H3PW12O40、H3PO4·12MoO3At least one of (1).
9. The method of claim 1, wherein: the packed tower in the step (2) is of a two-layer packing structure, and the average diameter of the packing is 13-25 mm; wherein, the upper layer is gamma-activated alumina, and the lower layer is foamed ceramic.
10. The method of claim 1, wherein: the Gardner color number of the liquid modified aromatic hydrocarbon petroleum resin obtained in the step (2) is less than or equal to 4#, and the melt viscosity at 60 ℃ is 30-350 mPa · s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010166512.0A CN111234106A (en) | 2020-03-11 | 2020-03-11 | Preparation method of liquid modified aromatic hydrocarbon petroleum resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010166512.0A CN111234106A (en) | 2020-03-11 | 2020-03-11 | Preparation method of liquid modified aromatic hydrocarbon petroleum resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111234106A true CN111234106A (en) | 2020-06-05 |
Family
ID=70879104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010166512.0A Pending CN111234106A (en) | 2020-03-11 | 2020-03-11 | Preparation method of liquid modified aromatic hydrocarbon petroleum resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111234106A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1348414A (en) * | 1970-03-23 | 1974-03-20 | Nippon Petrochemicals Co Ltd | Aromatic hydrocarbon resin |
| CN1249733A (en) * | 1997-01-08 | 2000-04-05 | 赫尔克里士公司 | Metal oxide solid acids as catalysts for preparation of hydrocarbon resins |
| CN101732883A (en) * | 2010-01-21 | 2010-06-16 | 天津天大天海化工新技术有限公司 | Adsorptive rectification tower for decoloring aromatic solvent oil and process method thereof |
-
2020
- 2020-03-11 CN CN202010166512.0A patent/CN111234106A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1348414A (en) * | 1970-03-23 | 1974-03-20 | Nippon Petrochemicals Co Ltd | Aromatic hydrocarbon resin |
| CN1249733A (en) * | 1997-01-08 | 2000-04-05 | 赫尔克里士公司 | Metal oxide solid acids as catalysts for preparation of hydrocarbon resins |
| CN101732883A (en) * | 2010-01-21 | 2010-06-16 | 天津天大天海化工新技术有限公司 | Adsorptive rectification tower for decoloring aromatic solvent oil and process method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1277620A (en) | Process for producing hydrogenated C9 petroleum resin and hydrogenated C9 petroleum resin obtained by the process | |
| CN102140153B (en) | Preparation method for Carbon 5/Carbon 9 hydrogenated petroleum resin | |
| WO2001060771A1 (en) | Process for purifying a liquid hydrocarbon product | |
| KR101104741B1 (en) | Method for manufacturing hydrogenated block copolymer | |
| CN109400922B (en) | Preparation method and application of super-crosslinked porous polyion liquid material | |
| KR101487107B1 (en) | Pervaporation system using organic-inorganic composite membranes for dehydration of glycol ether | |
| CN105062085A (en) | Addition-type organosilicone mould rubber and preparation method thereof | |
| CN108484896A (en) | A kind of preparation method of low VOC high-activity high molecular weight polyether polyols | |
| CN111234106A (en) | Preparation method of liquid modified aromatic hydrocarbon petroleum resin | |
| CN108329444B (en) | Solid acid catalytic synthesis method of tackifying alkyl phenolic resin | |
| CN108017759B (en) | Modified pentadiene hydrogenated petroleum resin and preparation method thereof | |
| CN102151495B (en) | Preparation method of Polyvinyl Butyral (PVB) microfiltration membrane | |
| CN101590375B (en) | Composite membrane for removing organic sulfide from liquefied gas and preparation method thereof | |
| CN112679297A (en) | Preparation method of high-purity dicyclopentadiene | |
| CN104892840A (en) | Styrene modified dicyclopentadiene petroleum resin and preparing method thereof | |
| CN109400807B (en) | Production method of petroleum resin | |
| CN113372503A (en) | Acid modified C9 petroleum resin and preparation method thereof with controllable molecular weight | |
| CN106893056A (en) | A kind of styrene butadiene styrene is modified dicyclopentadiene petroleum resin and preparation method | |
| KR102393363B1 (en) | Petroleum resin and preparation method thereof | |
| CN102093511A (en) | Method for preparing dicyclopentadiene hydrogenated petroleum resin | |
| CN113185632B (en) | Preparation method of benzene-free high-solid-content thermoplastic acrylic resin | |
| CN112439323A (en) | Preparation method of support layer-removed low-cost high-flux silicon carbide ceramic ultrafiltration membrane | |
| CN109675447A (en) | A kind of enhancement type hollow fiber film and preparation method thereof for being not easy to strip off | |
| CN1190449C (en) | Application of novel dispersion system in preparing polyvinyl chloride resin dedicated for pipes with high apparent density | |
| CN109054077B (en) | Method for recycling macroporous ion exchange resin pore-foaming agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200605 |
|
| RJ01 | Rejection of invention patent application after publication |