CN106916264B - Aromatic hydrocarbon modified C5 petroleum resin and synthetic method thereof - Google Patents
Aromatic hydrocarbon modified C5 petroleum resin and synthetic method thereof Download PDFInfo
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- CN106916264B CN106916264B CN201510994275.6A CN201510994275A CN106916264B CN 106916264 B CN106916264 B CN 106916264B CN 201510994275 A CN201510994275 A CN 201510994275A CN 106916264 B CN106916264 B CN 106916264B
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- 239000011347 resin Substances 0.000 title claims abstract description 39
- 229920005989 resin Polymers 0.000 title claims abstract description 39
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 29
- 238000010189 synthetic method Methods 0.000 title claims abstract description 23
- 239000003208 petroleum Substances 0.000 title abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000010790 dilution Methods 0.000 claims abstract description 9
- 239000012895 dilution Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000005292 vacuum distillation Methods 0.000 claims description 8
- -1 arene compound Chemical class 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 230000011218 segmentation Effects 0.000 claims description 3
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 10
- 239000004831 Hot glue Substances 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 11
- 239000002480 mineral oil Substances 0.000 description 8
- 235000010446 mineral oil Nutrition 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 239000012943 hotmelt Substances 0.000 description 4
- 235000005128 Sapium sebiferum Nutrition 0.000 description 3
- 244000057114 Sapium sebiferum Species 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- 206010024769 Local reaction Diseases 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000008601 oleoresin Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- 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
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
- C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
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 discloses an aromatic hydrocarbon modified C5 petroleum resin and a synthetic method thereof, which comprises the following steps: taking a mixed component with C10, C15 and C20 as main components as a raw material, taking an aromatic hydrocarbon compound as a modifier, mixing the raw material and the modifier, adding the mixture into a reactor, adding a catalyst accounting for 0.3-2.5% of the weight of the mixed component, reacting for 4-10 hours at the temperature of 100-140 ℃ and the pressure of 0-8 MPa, heating to 150-190 ℃ and the pressure of 0-8 MPa, and continuously reacting for 4-10 hours to obtain crude resin; adding a solvent into the crude resin for dilution, washing with water, settling, and distilling under reduced pressure to obtain the petroleum resin. The aromatic hydrocarbon modified petroleum resin synthesized by the invention has good compatibility with SIS, SEBS and SBS, improves the initial viscosity of the hot melt adhesive and other sanitary materials and the bonding strength of the hot melt adhesive, and can be applied to the adhesive product industries such as the hot melt adhesive and the like and the field of sanitary material products.
Description
Technical field
The invention belongs to chemical products field, the new synthetic method more particularly to one kind for being related to a kind of Petropols are adopted
It is main material composition to C 5 fraction after pre-processing, passes through the new method of arene compound modified synthesis Petropols.
Background technique
With the development of ethylene industry, by-product C5 and the C9 fraction of ethylene unit is increasing.Utilize C5 and C9 fraction
Various Petropols are synthesized, are the important channels for making full use of C5, C9 fraction resource.C5 Petropols increase with preferable pour point depression
Performance that is viscous and improving viscosity coefficient, is commonly used in hot melt adhesive, pressure sensitive adhesive, traffic paint, paper sizing agent etc..C5 petroleum tree
Rouge is usually used in mixed way with other mixtures, it is desirable that Petropols have good compatibility, while hot melt adhesive being required to have one
Fixed adhesive strength, therefore Petropols performance is improved using the method being modified to Petropols, to improve petroleum
The compatibility of resin and other hot melt adhesive ingredients, to meet it in the application demand in different application field.
There are grafting modification and blending and modifying to the main method of modifying of C5 Petropols at present.Grafting modification
It is that it is anti-to be participated in C5 raw material using modified monomer such as C9 fraction, maleic anhydride, amide and esters etc. jointly for cationic polymerization
It answers, new functional group is introduced by polymerization process to achieve the purpose that improve Petropols compatibility.Blending and modifying is usually to adopt
It is blended or is crosslinked under certain condition with Petropols with modifying agent, reach improvement petroleum by introducing new functional molecular chain
The purpose of resin compatible.
Chinese patent CN 201110116550 describe it is a kind of by Petropols, maleic anhydride rising temperature for dissolving, 100~
Initiator is added dropwise between 200 DEG C, the method for preparing maleic anhydride grafted petroleum resin.Chinese patent CN 200910192163 is situated between
One kind continued using waste polystyrene foam as modifying agent, the mass ratio with Petropols is 1: (0.1~99), 30~150
After being stirred 0.5~1.5 hour at DEG C, then be warming up to 180~280 DEG C and maintain 1.5~2.5 hours, pressure control 0~
1.5MPa, the method for preparing Polystyrene Petropols.Chinese patent CN 200910055554 describes one kind will split
Solution ethylene by-product C 5 fraction raw material and DCPD rich material in mass ratio 1: 0.6~1.2 are mixed to get reaction raw materials, 180~
It is reacted 20~30 hours under the conditions of 240 DEG C, the method for preparing C5 modified DCPD petroleum resin.
United States Patent (USP) US5,939,268 introduce it is a kind of using by Diels-Alder reaction product as raw material, amide, esters
Deng the method for function monomer synthetic resin.United States Patent (USP) US20140058033 describe it is a kind of with cyclopentadiene compound and
The mixture of vinyl aromatic compound is raw material, and by heat polymerization, hydrogenation reaction removes dissolving agent process and granulation etc.
Technique obtains the preparation method of granular hydrogenated petroleum resin.
Chinese patent CN200610104530.6 describes one kind with C10, C15, C20 mixed composition as main component
The method of Material synthesis Petropols, using the Petropols that this method synthesizes can be improved resin and hot melt adhesive SIS, SBS,
The compatibility of EVA.But aromatic component content is low in the Petropols molecular structure of such process synthesis, is unable to satisfy hot melt
Performance requirement of the glue special industry to the high arene content of Petropols.
Summary of the invention
The main purpose of the present invention is to provide a kind of modified C5 Petropols of aromatic hydrocarbon and its synthetic methods, to overcome
The Petropols defect low with the poor compatibility of hot melt gum base materials and adhesive strength in the prior art.
The object of the present invention is achieved like this, a kind of synthetic method for the C5 Petropols that aromatic hydrocarbon is modified, this method
Specifically: it, will be described using arene compound as modifying agent using C10, C15, C20 mixed composition as main component as raw material
After raw material and modifying agent mixing, reactor is added, the catalyst of mixed composition weight 0.3~2.5% is then added, in temperature
100 DEG C~140 DEG C, pressure is react 4~10 hours under 0~8Mpa, then heats to 150 DEG C~190 DEG C, pressure for 0~
8MPa, the reaction was continued 4~10 hours obtains crude resin；Stone is obtained to the dilution of crude resin addition solvent, washing, sedimentation, vacuum distillation
Oleoresin.
The synthetic method of the modified C5 Petropols of aromatic hydrocarbon of the present invention, wherein preferably, with weight percent
Than meter, the raw material includes C1075~95%, C152~15%, C203~10%.
The synthetic method of the modified C5 Petropols of aromatic hydrocarbon of the present invention, wherein the modifying agent is preferably second
C9 in alkene cracking process cuts fraction (fraction between 120-200 DEG C), styrene, α-methylstyrene, 4- methylbenzene second
One or more of alkene and the formed group of propenylbenzene.
The synthetic method of the modified C5 Petropols of aromatic hydrocarbon of the present invention, wherein the additional amount of the modifying agent
Preferably the 1~30% of mixed composition weight.
The synthetic method of the modified C5 Petropols of aromatic hydrocarbon of the present invention, wherein the reaction is using segmentation
What method carried out.
The synthetic method of the modified C5 Petropols of aromatic hydrocarbon of the present invention, wherein the catalyst is preferably nothing
Water alchlor.
The synthetic method of the modified C5 Petropols of aromatic hydrocarbon of the present invention, wherein described C10, C15, C20 are excellent
It is selected as cyclic olefins.
The present invention also provides a kind of modified C5 Petropols of aromatic hydrocarbon, are the modified C5 petroleum trees of above-mentioned aromatic hydrocarbon
The synthetic method synthesis of rouge.
The modified C5 Petropols of aromatic hydrocarbon of the present invention, wherein the softening point of the C5 Petropols is 80~
110 DEG C, coloration is 2~12, and number-average molecular weight is 550~700, and molecular weight distribution is 1.3~2.6.
The synthetic method of the modified C5 Petropols of aromatic hydrocarbon of the present invention, wherein based on described C10, C15, C20
The mixed composition for wanting ingredient is to carry out cracking of ethylene C5 fraction under 140~300 DEG C of temperature, 1.0~12.0MPa of pressure
Cooling discharge after Diels-Alder reacts 3~12 hours, rectifying remove unreacted C5Component and obtain.
The synthetic method of the modified C5 Petropols of aromatic hydrocarbon of the present invention, wherein the solvent is high boiling
Add hydrogen saturated alkane mineral oil, pentane, naphtha etc..
Beneficial effects of the present invention:
The invention is found through experiments that, using C10, C15, C20 mixed composition as main component as raw material, using aromatic series
Olefines modifying agent can further enhance the compatibility of resin and other hot melt gum base materials SIS, SEBS, SBS, improve heat
The tack of melten gel and other hygienic materials and the adhesive strength for improving hot melt adhesive.
The present invention carries out the modification of Petropols using two sections of polymerization techniques, can effectively control the stabilization of polymerization process
Property, control polymer molecular weight and its distribution.Low temperature (lower than 70 DEG C) is generallyd use in C5 Petropols resin industry at present to close
At technology, effective concentration of olefin is low (55-70% percentage composition, rest part are saturated alkane) in raw material, and local reaction is violent,
Condensation product is easy to appear in polymerization process causes polymer performance unstable, and polymer molecular weight distribution is wide.It polymerize in the present invention
Raw material is 99% cycloolefin, and almost all is that effective alkene participates in polymerization process, and polymerization process raw material availability is high.
It is tested and is found by the invention, the resin after polymerization is purified, the solvent after analysis abjection does not find fragrance
Race's olefines modifying agent illustrates that modifying agent participates in reacting completely, not will lead to introduce free benzene-like compounds in naval stores and
Influence product quality.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Embodiment 1
It will be with C10, C15, C20 mixed composition as main component (mixed composition mass percentage composition: C10 content
85%, C15 content 9%, C20 content 5%, other components 1%.) with 3% modifying agent C9 cutting fraction mix that (modifying agent adds
Dosage is mass percent) reactor is added, the aluminum trichloride (anhydrous) of mixed composition weight 2.5% is added under stiring, in temperature
125 DEG C of degree, pressure are polymerization reaction 6 hours under 1MPa；Reaction temperature is increased to 150 DEG C later, pressure is controlled in 1.2MPa
Lower polymerization reaction 8 hours obtains petroleum tree to the dilution of crude resin addition mineral oil, washing, sedimentation, vacuum distillation after reaction
Rouge.After measured, the softening point of the petroleum resin products is 98 DEG C；Coloration is 4.3；Number-average molecular weight is 575；Molecular weight distribution is
1.61。
Embodiment 2
It will be with C10, C15, C20 mixed composition as main component (mixed composition mass percentage composition: C10 content
87%, C15 content 8%, C20 content 4%, other components 1%.) (styrene and C9 press 95:5 mass ratio with 5% modifying agent
Example mixing) mixing (modifying agent additive amount is mass percent) addition reactor, mixed composition weight 2.5% is added under stiring
Aluminum trichloride (anhydrous), 120 DEG C of temperature, pressure be 1MPa under polymerization reaction 9 hours；Reaction temperature is increased to 145 later
DEG C, pressure control polymerization reaction 10 hours at 1.1MPa are added mineral oil dilution to crude resin after reaction, washing, sink
Drop, vacuum distillation obtain Petropols.After measured, the softening point of the petroleum resin products is 104 DEG C；Coloration is 4.1；Number is divided equally
Son amount is 573；Molecular weight distribution is 1.43.
Embodiment 3
It will be with C10, C15, C20 mixed composition as main component (mixed composition mass percentage composition: C10 content
90%, C15 content 5%, C20 content 4%, other components 1%.) with 7% modifying agent styrene mix (modifying agent additive amount
For mass percent) reactor is added, the aluminum trichloride (anhydrous) of mixed composition weight 1.0% is added under stiring, in temperature 135
DEG C, pressure be 1.1MPa under polymerization reaction 8 hours；Reaction temperature is increased to 155 DEG C later, pressure control gathers at 1.3MPa
Reaction 7 hours is closed, Petropols are obtained to the dilution of crude resin addition mineral oil, washing, sedimentation, vacuum distillation after reaction.
After measured, the softening point of the petroleum resin products is 106 DEG C；Coloration is 5.0；Number-average molecular weight is 563；Molecular weight distribution is
1.63。
Embodiment 4
It will be with C10, C15, C20 mixed composition as main component (mixed composition mass percentage composition: C10 content
85%, C15 content 10%, C20 content 4%, other components 1%.) (modifying agent addition is mixed with 10% modifying agent C9 fraction
Amount is mass percent) reactor is added, the aluminum trichloride (anhydrous) of mixed composition weight 0.90% is added under stiring, in temperature
125 DEG C, pressure be 1.0MPa under polymerization reaction 8 hours；Reaction temperature is increased to 150 DEG C later, pressure is controlled in 1.2MPa
Lower polymerization reaction 10 hours obtains petroleum to the dilution of crude resin addition mineral oil, washing, sedimentation, vacuum distillation after reaction
Resin.After measured, the softening point of the petroleum resin products is 106 DEG C；Coloration is 5.3；Number-average molecular weight is 617；Molecular weight point
Cloth is 1.76.
Embodiment 5
It will be with C10, C15, C20 mixed composition as main component (mixed composition mass percentage composition: C10 content
88%, C15 content 9%, C20 content 2%, other components 1%.) with 10% modifying agent (α-methylstyrene and C9 press 90:
The mixing of 10 mass ratios) mixing (modifying agent additive amount is mass percent) addition reactor, mixed composition is added under stiring
The aluminum trichloride (anhydrous) of weight 0.80%, polymerization reaction 9 hours under being 1.1MPa in 120 DEG C of temperature, pressure；It later will reaction temperature
Degree is increased to 145 DEG C, and it is dilute that mineral oil is added to crude resin after reaction in pressure control polymerization reaction 11 hours at 1.3MPa
It releases, wash, settling, being evaporated under reduced pressure and obtain Petropols.After measured, the softening point of the petroleum resin products is 103.2 DEG C；Coloration
It is 5.1；Number-average molecular weight is 609；Molecular weight distribution is 1.63.
Comparative example 1
It will be with C10, C15, C20 mixed composition as main component (mixed composition mass percentage composition: C10 content
87%, C15 content 8%, C20 content 4%, other components 1%.) (styrene and C9 press 95:5 mass ratio with 5% modifying agent
Example mixing) mixing (modifying agent additive amount is mass percent) addition reactor, mixed composition weight 2.5% is added under stiring
Aluminum trichloride (anhydrous), 140 DEG C of temperature, pressure be 1.2MPa under polymerization reaction 18 hours, crude resin is added after reaction
Enter mineral oil dilution, filtering has 2% condensation product impurity, obtains petroleum to the washing of filtered resin liquid, sedimentation, vacuum distillation
Resin.After measured, the softening point of the petroleum resin products is 97 DEG C；Coloration is 5.8；Number-average molecular weight is 547；Molecular weight distribution
It is 1.87.
Comparative example 2
It will be with C10, C15, C20 mixed composition as main component (mixed composition mass percentage composition: C10 content
85%, C15 content 10%, C20 content 4%, other components 1%.) (modifying agent addition is mixed with 10% modifying agent C9 fraction
Amount is mass percent) reactor is added, the aluminum trichloride (anhydrous) of mixed composition weight 0.90% is added under stiring, in temperature
145 DEG C, pressure be 1.2MPa under polymerization reaction 18 hours；Mineral oil dilution is added to crude resin after reaction, filtering has
1.6% condensation product impurity obtains Petropols to the washing of filtered resin liquid, sedimentation, vacuum distillation.After measured, the stone
The softening point of oleoresin product is 100 DEG C；Coloration is 5.9；Number-average molecular weight is 535；Molecular weight distribution is 1.97.
By comparative example and comparative example it is found that segmentation reaction can be to avoid generation cohesion in upgrading processes in embodiment
Object impurity, and the molecular weight distribution of upgraded products obtained by embodiment is also more excellent than comparative example.
Beneficial effects of the present invention:
The invention is found through experiments that, using C10, C15, C20 mixed composition as main component as raw material, using aromatic series
Olefines modifying agent can further enhance the compatibility of resin and other hot melt gum base materials SIS, SEBS, SBS, improve heat
The tack of melten gel and other hygienic materials and the adhesive strength for improving hot melt adhesive.
The present invention carries out the modification of Petropols using two sections of polymerization techniques, can effectively control the stabilization of polymerization process
Property, control polymer molecular weight and its distribution.Low temperature (lower than 70 DEG C) is generallyd use in C5 Petropols resin industry at present to close
At technology, effective concentration of olefin is low (55--70% percentage composition, rest part are saturated alkane) in raw material, and local reaction is violent
Condensation product is easy to appear in polymerization process causes polymer performance unstable, and polymer molecular weight distribution is wide.It polymerize in the present invention
Raw material is 99% cycloolefin, and almost all is that effective alkene participates in polymerization process, and polymerization process raw material availability is high.
It is tested and is found by the invention, the resin after polymerization is purified, the solvent after analysis abjection does not find fragrance
Race's olefines modifying agent illustrates that modifying agent participates in reacting completely, not will lead to introduce free benzene-like compounds in naval stores and
Influence product quality.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (9)
1. a kind of synthetic method of the modified C5 Petropols of aromatic hydrocarbon, which is characterized in that this method specifically: with C10, C15,
C20 mixed composition as main component is raw material, and using arene compound as modifying agent, the raw material and modifying agent are mixed
Afterwards, reactor is added, the catalyst of mixed composition weight 0.3~2.5%, at 100 DEG C~140 DEG C of temperature, pressure is then added
To react 4~10 hours under 0~8MPa, 150 DEG C~190 DEG C are then heated to, pressure is 0~8MPa, and the reaction was continued 4~10
Hour obtains crude resin；Petropols are obtained to the dilution of crude resin addition solvent, washing, sedimentation, vacuum distillation.
2. the synthetic method of the modified C5 Petropols of aromatic hydrocarbon according to claim 1, which is characterized in that with weight hundred
Divide than meter, the raw material includes C10 content 75~95%, C15 content 2~15%, C20 content 3~10%.
3. the synthetic method of the modified C5 Petropols of aromatic hydrocarbon according to claim 1, which is characterized in that the modification
Agent cuts fraction, styrene, α-methylstyrene, 4- methyl styrene and propenylbenzene institute group for the C9 during cracking of ethylene
At one or more of group.
4. the synthetic method of the modified C5 Petropols of aromatic hydrocarbon according to claim 1, which is characterized in that the modification
The additional amount of agent is the 1~30% of mixed composition weight.
5. the synthetic method of the modified C5 Petropols of aromatic hydrocarbon according to claim 1, which is characterized in that the reaction
It is to be carried out using segmentation method.
6. the synthetic method of the modified C5 Petropols of aromatic hydrocarbon according to claim 1, which is characterized in that the catalysis
Agent is aluminum trichloride (anhydrous).
7. the synthetic method of the modified C5 Petropols of aromatic hydrocarbon according to claim 1, which is characterized in that the C10,
C15, C20 are cyclic olefins.
8. a kind of modified C5 Petropols of aromatic hydrocarbon are the modified C5 of aromatic hydrocarbon described in claim 1 to 7 any one
The synthetic method synthesis of Petropols.
9. the modified C5 Petropols of aromatic hydrocarbon according to claim 8, which is characterized in that the C5 Petropols it is soft
Changing point is 80~110 DEG C, and coloration is 2~12, and number-average molecular weight is 550~700, and molecular weight distribution is 1.3~2.6.
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| CN109880109B (en) * | 2019-01-28 | 2021-07-13 | 陶乐敏 | Aromatic modified petroleum resin and preparation method thereof |
| CN110003388B (en) * | 2019-03-26 | 2021-09-07 | 恒河材料科技股份有限公司 | Preparation method of hydrogenated modified C5 petroleum resin |
| CN109912744B (en) * | 2019-03-26 | 2021-10-22 | 恒河材料科技股份有限公司 | Preparation method of monomer modified C5 petroleum resin |
| WO2022255314A1 (en) * | 2021-06-01 | 2022-12-08 | Ｅｎｅｏｓ株式会社 | Petroleum resin, additive for rubber, uncrosslinked rubber composition, and crosslinked rubber |
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