CN113087845B - Preparation method of long-chain olefin modified C9 petroleum resin - Google Patents
Preparation method of long-chain olefin modified C9 petroleum resin Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 81
- 229920005989 resin Polymers 0.000 title claims abstract description 81
- 239000003208 petroleum Substances 0.000 title claims abstract description 64
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 40
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000009826 distribution Methods 0.000 claims abstract description 17
- 239000012442 inert solvent Substances 0.000 claims abstract description 7
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 6
- 239000012043 crude product Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 42
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 15
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 15
- 229940069096 dodecene Drugs 0.000 claims description 15
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical group FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 33
- 239000007788 liquid Substances 0.000 abstract description 16
- 239000000047 product Substances 0.000 abstract description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 239000010865 sewage Substances 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 239000000806 elastomer Substances 0.000 abstract description 4
- 229920001971 elastomer Polymers 0.000 abstract description 4
- 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 3
- 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 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 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 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 abstract description 2
- 150000005673 monoalkenes Chemical class 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 abstract 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 18
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 description 9
- 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 9
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 9
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- AQLBDEAOQUJAIE-UHFFFAOYSA-N 10-methylundec-1-ene Chemical compound CC(C)CCCCCCCC=C AQLBDEAOQUJAIE-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-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
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of petroleum resin, and particularly discloses a preparation method of long-chain olefin modified C9 petroleum resin. Specifically, in the presence of a catalyst and an inert solvent and under an inert atmosphere, the C9 fraction and the long-chain olefin undergo a cationic polymerization reaction to obtain a crude product of the long-chain olefin modified C9 petroleum resin. The invention has mild polymerization conditions, utilizes the structural characteristics of long-chain olefin as long-chain monoolefin, has the property of chain transfer, and adjusts the molecular weight and the crosslinking degree of resin, thereby improving the molecular weight distribution of resin products, having the molecular weight distribution of 1.3-1.6, finally improving the compatibility with elastomers, and expanding the application range of the products in adhesives. The invention adopts long-chain olefin for product modification, and compared with the modification processes of piperylene, rosin and the like, the long-chain olefin has the advantages of low cost and price of raw materials and economic advantage; compared with the maleic anhydride modification process, the raw material long-chain olefin is liquid, so that the operation is easy, and the workload of workers is reduced; in addition, the long-chain olefin does not react with sodium hydroxide, so that the oily sewage is less generated, and the sewage treatment cost is reduced.
Description
Technical Field
The invention relates to the field of petroleum resin, in particular to a preparation method of long-chain olefin modified C9 petroleum resin.
Background
The C9 petroleum resin is prepared by polymerizing active components with double bonds such as methyl styrene, dicyclopentadiene, indene, methyl indene and the like in the ethylene byproduct C9 fraction by cationic polymerization reaction in the presence of a Lewis acid catalyst. The C9 petroleum resin is widely applied to the industries of paint, printing ink, adhesive and the like.
In recent years, the market demand of domestic petroleum resins is rapidly increasing, and particularly the annual demand of a large amount of petroleum resins used in various fields such as rubber processing, paint coating, printing ink, adhesive and the like is remarkably increased, but compared with petroleum resins produced abroad, the petroleum resins produced at home have single domestic variety and type, lower product quality level, more product cross-linking structure and large molecular weight distribution, seriously affect the compatibility of the products and Elastomers (EVA), and greatly restrict the application of the products in the adhesive.
At present, the modification method of C9 petroleum resin mainly comprises blending modification, modified monomers mainly comprise maleic anhydride, itaconic acid, amide, esters and the like, and the aim of improving the compatibility of the petroleum resin is achieved by introducing a new functional molecular chain. For example, CN20111011655.0 and CN1813008A introduce a method for preparing maleic anhydride grafted petroleum resin by heating and dissolving petroleum resin and maleic anhydride, the compatibility of the petroleum resin in an elastomer can be improved to a certain extent by using the method, but the molecular weight of the resin cannot be adjusted to reduce the cross-linking structure in the resin, the purpose of improving the viscosity of an adhesive cannot be achieved, in addition, the resin is easy to darken in the thermal polymerization process, the application of the product in sanitary products and environment-friendly products cannot be met, and the application range of the product is reduced.
CN200410056912.7 discloses a method for obtaining C9 petroleum resin by using maleic anhydride as a polymerization raw material and catalyzing C9 fractions with boron trifluoride diethyl etherate, but the maleic anhydride is easy to react with sodium hydroxide, so that not only is the ash content of the product influenced, but also oily wastewater is generated, and the sewage treatment cost is increased.
Zhang Kun et al disclose a method for modifying C9 petroleum resin with rosin in CN106967201, wang Bin et al disclose a method for improving compatibility of petroleum resin with tetrahydroindene modified C9 petroleum resin in CN107325228, but the modifier used in the method is expensive in raw material cost.
Disclosure of Invention
The invention provides a preparation method of long-chain olefin modified C9 petroleum resin, and the C9 petroleum resin prepared by the method has narrower molecular weight distribution and excellent compatibility with EVA.
The purpose of the invention is realized by the following technical scheme:
in the presence of a catalyst and an inert solvent and under an inert atmosphere, a C9 fraction and long-chain olefin undergo a cationic polymerization reaction to obtain a crude product of the long-chain olefin modified C9 petroleum resin.
The dosage of the long-chain olefin is 5-20% of the mass fraction of the C9 fraction.
The long-chain olefin is one or the combination of two of isomeric dodecene and isomeric hexadecene. The isomeric dodecene is tetrapropylene or trimerized isobutene. The isomeric hexadecene is a tetrameric isobutene body.
The catalyst is a Friedel-Crafts catalyst, and comprises boron trifluoride diethyl etherate or aluminum trichloride. The amount of the Friedel-Crafts catalyst is 0.2-1.5% of the mass fraction of the C9 fraction.
The using amount of the inert solvent is 20-200% of the mass fraction of the C9 fraction. The inert solvent is toluene, xylene or cyclohexane. The C9 fraction comprises the following components in percentage by mass: 10-40% of methyl styrene, 1-10% of dicyclopentadiene, 5-25% of indene and 15-45% of methyl indene.
The inert atmosphere is nitrogen, and other inert gases can also be used.
The reaction temperature of the cationic polymerization reaction is 10-50 ℃, and the reaction time is 1-6h.
The method also comprises the step of purifying the obtained crude long-chain olefin modified C9 petroleum resin, and specifically, after the obtained crude long-chain olefin modified C9 petroleum resin is subjected to alkali washing and water washing, the crude long-chain olefin modified C9 petroleum resin is subjected to reduced pressure distillation to obtain the purified long-chain olefin modified C9 petroleum resin. Wherein, the reduced pressure distillation pressure is-0.08 to-0.1 Mpa, and the distillation temperature is 220 to 250 ℃.
The alkali liquor for alkali washing is a sodium hydroxide or potassium hydroxide aqueous solution, the alkali liquor is an aqueous solution with the solid alkali content of 2-5% by mass fraction, and the molar weight of the solid alkali is larger than that of a Friedel-Crafts catalyst.
The invention also aims to provide the long-chain olefin modified C9 petroleum resin prepared by the preparation method, wherein the molecular weight distribution of the long-chain olefin modified C9 petroleum resin is 1.3-1.6.
The invention has the beneficial effects that:
(1) The invention has mild polymerization conditions, utilizes the structural characteristics of long-chain olefin as long-chain mono-olefin, has the property of chain transfer, and adjusts the molecular weight and the crosslinking degree of resin, thereby improving the molecular weight distribution of resin products, having the molecular weight distribution of 1.3-1.6, finally improving the compatibility with elastomers and expanding the application range of the products in adhesives.
(2) Compared with the maleic anhydride modification process, the long-chain olefin serving as the raw material is liquid, so that the operation is easy, and the workload of workers is reduced; in addition, the long-chain olefin does not react with sodium hydroxide, so that less oily sewage is generated, and the sewage treatment cost is reduced.
(3) The invention adopts long-chain olefin to modify products, compared with modification processes such as pentadiene, rosin and the like, the price of raw materials is low, and the invention has more obvious economic advantages.
Detailed Description
The following embodiments are given as examples of the present invention, and are not intended to limit the present invention in any way, and it will be understood by those skilled in the art that the present invention may be embodied in many forms without departing from the spirit and scope of the present invention.
The test method of each index in the invention comprises the following steps:
softening point: the measurement is carried out according to the ring and ball method specified in the GB/t2294-2019 standard.
Weight average molecular weight and molecular weight distribution: the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were determined by gel permeation chromatography analysis, and the molecular weight distribution was represented by the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
Compatibility (cloud point): taking the weight of 1:1, respectively, mixing the resin with EVA with the content of 28%, heating until the mixture is clear, cooling, and observing the turbidity temperature. The lower the haze point temperature, the better the compatibility of the resin and the EVA.
In the present invention, all parts and percentages (%) are by mass unless otherwise specified.
In the invention, the long-chain olefin is one or the combination of two of isomeric dodecene and isomeric hexadecene. The isomeric dodecenes may be tetrapropylene or trimerized isobutylene. The isomeric hexadecene is an isobutylene tetramer.
Example 1
(1) Adding 100g of dimethylbenzene into a reaction kettle with a stirrer, adding 100g of C9 fraction and 5g of isododecene (tetrapropylene), controlling the temperature of reaction materials to be 20 ℃, slowly dropwise adding a boron trifluoride ether complex catalyst with 1.5 mass percent of C9 fraction into the reaction kettle at a constant speed within 10min, reacting for 3h, and using nitrogen for protection in the process to obtain dodecene modified C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with the concentration of 3 percent into a reaction kettle to remove the catalyst, washing the reaction kettle to be neutral by distilled water to obtain light yellow clear resin liquid, and then distilling the resin liquid under reduced pressure of-0.09 Mpa to 230 ℃ to remove oligomers to obtain the dodecene modified C9 petroleum resin.
The C9 fraction contained: 30% of methyl styrene, 2.5% of dicyclopentadiene, 18.5% of indene, 27.5% of methyl indene and 21.5% of the other.
The softening point of the dodecene modified C9 petroleum resin is measured to be 128 ℃, the weight average molecular weight is 2875, the molecular weight distribution is 1.57, and the haze point is measured to be 145 ℃.
Example 2
(1) Adding 50g of dimethylbenzene into a reaction kettle with a stirrer, adding 100g of C9 fraction and 10g of isomeric dodecene (trimeric isobutylene), controlling the temperature of reaction materials to 10 ℃, slowly dropwise adding a boron trifluoride ether complex catalyst with 0.8 mass percent of C9 fraction into the reaction kettle at a constant speed within 10min, reacting for 3h, and protecting with nitrogen in the reaction process to obtain dodecene modified C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with the concentration of 3 percent into a reaction kettle to remove the catalyst, washing the reaction kettle to be neutral by distilled water to obtain light yellow clear resin liquid, and then carrying out reduced pressure distillation under the pressure of-0.1 Mpa to 240 ℃ to remove oligomers to obtain the dodecene modified C9 petroleum resin.
The C9 fraction contained: 30% of methyl styrene, 2.5% of dicyclopentadiene, 18.5% of indene, 27.5% of methyl indene and 21.5% of the other.
The softening point of the dodecene modified C9 petroleum resin is 120 ℃, the weight average molecular weight is 2160, the molecular weight distribution is 1.38, and the fog point is 137 ℃.
Example 3
(1) Adding 100g of toluene into a reaction kettle with a stirrer, adding 100g of C9 fraction and 15g of isomeric hexadecene, controlling the temperature of reaction materials to 30 ℃, slowly dropwise adding a boron trifluoride ether complex catalyst with 0.8 mass percent of C9 fraction into the reaction kettle at a constant speed within 10min, reacting for 2h, and using nitrogen for protection in the reaction process to obtain the hexadecene modified C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with concentration of 5% to the reaction kettle to remove the catalyst, washing with distilled water to neutrality to obtain a light yellow clear resin solution, and then distilling under reduced pressure of-0.1 MPa to 235 ℃ to remove oligomers to obtain the hexadecene modified C9 petroleum resin.
The C9 fraction contained: 25% of methyl styrene, 3% of dicyclopentadiene, 20.5% of indene, 25.5% of methyl indene and 26% of the rest.
The softening point of the hexadecene modified C9 petroleum resin is 118 ℃, the weight-average molecular weight is 2057, the molecular weight distribution is 1.37, and the fog point is 127 ℃.
Example 4
(1) Adding 200g of toluene into a reaction kettle with a stirrer, adding 100g of C9 fraction and 10g of isomeric dodecene (trimeric isobutene), controlling the temperature of the reaction materials to 40 ℃, slowly adding an aluminum trichloride catalyst with 0.2 mass percent of C9 fraction into the reaction kettle, reacting for 6 hours, and using nitrogen for protection in the reaction process to obtain dodecene modified C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with the concentration of 2 percent into a reaction kettle to remove the catalyst, washing the reaction kettle to be neutral by distilled water to obtain light yellow clear resin liquid, and then carrying out reduced pressure distillation under-0.08 Mpa to 240 ℃ to remove oligomers to obtain the dodecene modified C9 petroleum resin.
The C9 fraction contained: 25% of methyl styrene, 3% of dicyclopentadiene, 20.5% of indene, 25.5% of methyl indene and 26% of the rest.
The softening point of the dodecene modified C9 petroleum resin is 123 ℃, the weight average molecular weight is 2257, the molecular weight distribution is 1.40, and the haze point is 146 ℃.
Comparative example 1
(1) Adding 100g of dimethylbenzene into a reaction kettle with a stirrer, then adding 100g of C9 fraction, controlling the temperature of reaction materials to be 20 ℃, slowly dropwise adding boron trifluoride diethyl etherate catalyst with 1.5% mass fraction of C9 fraction into the reaction kettle at a constant speed, reacting for 3 hours, and using nitrogen for protection in the process to obtain C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with the concentration of 5 percent into a reaction kettle to remove the catalyst, washing the reaction kettle to be neutral by distilled water to obtain light yellow clear resin liquid, and then carrying out reduced pressure distillation under the pressure of-0.1 Mpa to 230 ℃ to remove oligomers to obtain the C9 petroleum resin.
The C9 fraction contained: 30% of methyl styrene, 2.5% of dicyclopentadiene, 18.5% of indene, 27.5% of methyl indene and 21.5% of the rest.
The C9 petroleum resin softening point was found to be 142 ℃, the weight average molecular weight was 4218, the molecular weight distribution was 2.21, and the haze point was 215 ℃.
Comparative example 2
(1) Adding 100g of dimethylbenzene into a reaction kettle with a stirrer, adding 100g of C9 fraction, controlling the temperature of reaction materials to be 10 ℃, slowly dripping boron trifluoride diethyl etherate complex catalyst with the mass fraction of 0.8% of reaction raw materials into the reaction kettle at a constant speed, reacting for 3 hours, and using nitrogen for protection in the reaction process to obtain C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with the concentration of 3 percent into a reaction kettle to remove the catalyst, washing the reaction kettle to be neutral by distilled water to obtain light yellow clear resin liquid, and then carrying out reduced pressure distillation under the pressure of-0.08 Mpa to 240 ℃ to remove oligomers to obtain the C9 petroleum resin.
The C9 fraction contained: 30% of methyl styrene, 2.5% of dicyclopentadiene, 18.5% of indene, 27.5% of methyl indene and 21.5% of the other.
The softening point of the C9 petroleum resin was found to be 135 ℃, the weight average molecular weight was found to be 3860, the molecular weight distribution was found to be 2.16, and the haze point was found to be 202 ℃.
Comparative example 3
(1) Adding 100g of dimethylbenzene into a reaction kettle with a stirrer, adding 100g of C9 fraction, controlling the temperature of reaction materials to be 30 ℃, slowly dropwise adding a boron trifluoride diethyl etherate complex catalyst with 0.3% mass fraction of the C9 fraction into the reaction kettle at a constant speed, reacting for 2 hours, and protecting with nitrogen in the reaction process to obtain the C9 petroleum resin liquid.
(2) Adding 100g of NaOH aqueous solution with the concentration of 2 percent into a reaction kettle to remove the catalyst, washing the reaction kettle to be neutral by distilled water to obtain light yellow clear resin liquid, and then carrying out reduced pressure distillation under-0.09 Mpa to 220 ℃ to remove oligomers to obtain the C9 petroleum resin.
The C9 fraction contained: 30% of methyl styrene, 2.5% of dicyclopentadiene, 18.5% of indene, 27.5% of methyl indene and 21.5% of the rest.
The C9 petroleum resin softening point was 137 ℃, the weight average molecular weight was 3957, the molecular weight distribution was 2.18, and the haze point was 208 ℃.
Claims (9)
1. A preparation method of long-chain olefin modified C9 petroleum resin is characterized in that in the presence of a catalyst and an inert solvent and under an inert atmosphere, C9 fraction and long-chain olefin undergo a cationic polymerization reaction to obtain a crude product of the long-chain olefin modified C9 petroleum resin; the dosage of the long-chain olefin is 5-20% of the mass fraction of the C9 fraction; the long-chain olefin is one or the combination of two of isomeric dodecene and isomeric hexadecene.
2. The method for preparing a long-chain olefin modified C9 petroleum resin according to claim 1, wherein the catalyst is a Friedel-Crafts catalyst and is used in an amount of 0.2 to 1.5% by mass of the C9 fraction.
3. The method for preparing a long-chain olefin modified C9 petroleum resin according to claim 2, wherein the Friedel-Crafts catalyst is boron trifluoride diethyl etherate or aluminum trichloride.
4. The method for preparing a long-chain olefin modified C9 petroleum resin as claimed in claim 1, wherein the amount of the inert solvent is 20-200% by mass of the C9 fraction.
5. The method for preparing a long-chain olefin modified C9 petroleum resin as claimed in claim 1, wherein the inert solvent is toluene, xylene or cyclohexane.
6. The method for producing a long-chain olefin-modified C9 petroleum resin according to claim 1, wherein the inert atmosphere is nitrogen.
7. The method for preparing a long-chain olefin modified C9 petroleum resin as claimed in claim 1, wherein the reaction temperature of the cationic polymerization is 10-50 ℃ and the reaction time is 1-6h.
8. The method for preparing a long-chain olefin modified C9 petroleum resin according to any one of claims 1 to 7, wherein the purified long-chain olefin modified C9 petroleum resin is obtained by subjecting the crude long-chain olefin modified C9 petroleum resin to alkali washing, water washing and reduced pressure distillation.
9. The long-chain olefin-modified C9 petroleum resin produced by the production process according to any one of claims 1 to 8, characterized in that it has a molecular weight distribution of 1.3 to 1.6.
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