CN112794962B - Preparation method of flexible hydrogenated C9 petroleum resin - Google Patents
Preparation method of flexible hydrogenated C9 petroleum resin Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 88
- 239000011347 resin Substances 0.000 title claims abstract description 88
- 239000003208 petroleum Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 54
- -1 alcohol ester Chemical class 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011976 maleic acid Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006477 desulfuration reaction Methods 0.000 claims description 7
- 230000023556 desulfurization Effects 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 239000007870 radical polymerization initiator Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 4
- 125000004018 acid anhydride group Chemical group 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 229910020068 MgAl Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XHSDDKAGJYJAQM-KXYMVQBMSA-N dioctadecyl (z)-but-2-enedioate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)\C=C/C(=O)OCCCCCCCCCCCCCCCCCC XHSDDKAGJYJAQM-KXYMVQBMSA-N 0.000 description 2
- DYVHFPDDBMMBAX-DQSJHHFOSA-N ditetradecyl (z)-but-2-enedioate Chemical compound CCCCCCCCCCCCCCOC(=O)\C=C/C(=O)OCCCCCCCCCCCCCC DYVHFPDDBMMBAX-DQSJHHFOSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- YQGINXRZRCSDGG-FPLPWBNLSA-N CCCCCCC(OC(/C=C\C(O)=O)=O)=O Chemical compound CCCCCCC(OC(/C=C\C(O)=O)=O)=O YQGINXRZRCSDGG-FPLPWBNLSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HFUSECPXGUISGB-UHFFFAOYSA-N benzoyl benzenecarboperoxoate;2-tert-butylperoxy-2-methylpropane Chemical compound CC(C)(C)OOC(C)(C)C.C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 HFUSECPXGUISGB-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 125000001511 cyclopentyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HEJZJSIRBLOWPD-VHXPQNKSSA-N didodecyl (z)-but-2-enedioate Chemical compound CCCCCCCCCCCCOC(=O)\C=C/C(=O)OCCCCCCCCCCCC HEJZJSIRBLOWPD-VHXPQNKSSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- IACKKVBKKNJZGN-UHFFFAOYSA-N pentacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCO IACKKVBKKNJZGN-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of petroleum resin processing, and particularly relates to a preparation method of flexible hydrogenated C9 petroleum resin. The preparation method of the flexible hydrogenated C9 petroleum resin sequentially comprises the preparation of the maleic acid double-long-chain alcohol ester, the preparation of the flexible C9 petroleum resin and the preparation of the flexible hydrogenated C9 petroleum resin. According to the invention, the acid anhydride group of maleic anhydride and long-chain alcohol are used for synthesizing the flexible monomer, the double bond of the flexible monomer and the unsaturated double bond of the C9 petroleum resin are subjected to free radical copolymerization to generate the flexible petroleum resin, and the flexible petroleum resin is subjected to hydrogenation modification to synthesize the flexible hydrogenated petroleum resin.
Description
Technical Field
The invention belongs to the technical field of petroleum resin processing, and particularly relates to a preparation method of flexible hydrogenated C9 petroleum resin.
Background
The C9 resin is insoluble in water and soluble in organic solvents, has excellent performances of acid resistance, alkali resistance, ageing resistance and the like, has wide sources and low price, has wide application fields, and can be applied to the industries of road marking paint, adhesives, rubber, tires, plastics, papermaking, printing ink and the like. However, the common petroleum resin stone has the defects of dark color, low thermal stability, large brittleness and the like due to the existence of more unsaturated double bonds, aromatic hydrocarbons, halide impurities in the polymerization process and the like, so that the industrial application is limited.
In order to solve the problems, hydrogenation modification is mostly adopted at present to modify the petroleum resin, the hydrogenation modification can saturate unsaturated double bonds and aromatic hydrocarbons in the petroleum resin and remove residual halogen elements, the modified resin is colorless and has no special smell, and the performances such as weather resistance, adhesion, stability and the like of the modified resin can be improved, but the hydrogenation modification still does not overcome the problem of large brittleness of the petroleum resin, but the resin becomes nonpolar after hydrogenation to influence the application of the resin, for example, the hydrogenation modified C9 petroleum resin such as Chinese patent CN2019103862953, CN2017100737577, CN2018114110240 and the like. Therefore, it is imperative to find a new modification method which can ensure light color and good thermal stability of the C9 petroleum resin and overcome the defect of large brittleness.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a preparation method of flexible hydrogenated C9 petroleum resin, which not only solves the problems of dark color and poor thermal stability of C9 petroleum resin, but also solves the problem of high brittleness, and can realize the regulation and control of the flexibility of the petroleum resin through the control of a reaction process.
The above object of the present invention can be achieved by the following technical solutions: a preparation method of flexible hydrogenated C9 petroleum resin sequentially comprises the preparation of maleic acid double-long-chain alcohol ester, the preparation of flexible C9 petroleum resin and the preparation of flexible hydrogenated C9 petroleum resin.
Preferably, the preparation of the maleic acid di-long-chain alcohol ester specifically comprises the following steps: adding maleic anhydride, long-chain alcohol, toluenesulfonic acid and water carrying agent into a four-mouth bottle with a stirrer, heating to 100 ℃ and 140 ℃ for esterification reaction, and after the reaction is finished, carrying out reduced pressure distillation, alkaline washing, water washing and vacuum drying on the product to obtain milky waxy maleic acid di-long-chain alcohol ester.
More preferably, the long-chain alcohol is a normal alcohol having no branch on the carbon chain, and the number of carbon atoms on the carbon chain is 5 to 25. For the purposes of this application, too small a molecular weight does not contribute to the modification, but too large a molecular weight also affects the modification.
More preferably, the mass percentages of the maleic anhydride, the long-chain alcohol, the toluenesulfonic acid and the water carrying agent are 18-40%, 58-80%, 0.5-2% and 1-1.5% in sequence.
Still more preferably, the water carrying agent is at least one of petroleum ether, benzene, toluene, cyclohexane, chloroform and carbon tetrachloride.
Preferably, the preparation of the flexible C9 petroleum resin is specifically as follows: adding C9 petroleum resin into a four-mouth bottle with a stirrer, heating to melt, adding maleic acid double-long-chain alcohol ester, adding a radical polymerization initiator in batches at 250 ℃ in equal amount, heating to 300 ℃ after the initiator is added, and carrying out grafting reaction to obtain the flexible petroleum resin. According to the invention, the initiator is added in batches, so that the reaction process can be carried out stably and safely, and in the actual operation process, the reaction liquid is splashed when the initiator is added at one time, so that the reaction process is unstable, more byproducts are generated, and the yield and the performance of the product are reduced.
More preferably, the adding amount of the maleic acid double-long-chain alcohol ester is 5-30% of the total mass of the C9 petroleum resin, and the adding amount of the free radical polymerization initiator is 0.5-2.5% of the total mass of the C9 petroleum resin.
More preferably, the radical polymerization initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert-butyl peroxide, and methyl ethyl ketone peroxide.
Preferably, the preparation of the flexible hydrogenated petroleum resin is specifically as follows: dissolving flexible petroleum resin with saturated alkane or saturated cycloalkane at concentration of 1-20%, and performing two-stage hydrogenation with nickel catalyst with high sulfur poisoning resistance at 150-350 deg.C under 3-8MPa and liquid space velocity of 0.1-1.0h-1To complete the unsaturated conditionAnd double bond hydrogenation and desulfurization; the second stage hydrogenation adopts palladium catalyst with the temperature of 150 ℃ and 350 ℃, the pressure of 6-16MPa and the liquid space velocity of 0.1-1.0h-1And finishing the hydrogenation of the aromatic hydrocarbon to finally obtain the flexible hydrogenated petroleum resin. The invention adopts two-stage hydrogenation to avoid that the arene in the flexible hydrogenated petroleum resin can not be hydrogenated only by adopting the first-stage hydrogenation on one hand, and avoids that the palladium catalyst is poisoned only by adopting the second-stage hydrogenation for too long reaction time.
The beneficial effects of the invention are as follows:
according to the invention, the acid anhydride group of maleic anhydride and long-chain alcohol are used for synthesizing the flexible monomer, the double bond of the flexible monomer and the unsaturated double bond of the C9 petroleum resin are subjected to free radical copolymerization to generate the flexible petroleum resin, and the flexible petroleum resin is subjected to hydrogenation modification to synthesize the flexible hydrogenated petroleum resin.
Detailed Description
The following are specific examples of the present invention and illustrate the technical solutions of the present invention for further description, but the present invention is not limited to these examples. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
Example 1
Weighing the following components in percentage by mass: 28 percent of maleic anhydride, 69 percent of n-octadecyl alcohol, 1.5 percent of toluenesulfonic acid and 1.5 percent of petroleum ether are sequentially added into a four-mouth bottle with a stirring device, a reflux condenser pipe and a water separator are arranged on the four-mouth bottle, then an electrothermal insulating sleeve is used for heating to 120 ℃ for esterification reaction, water generated by the reaction and a water carrying agent form an azeotrope to be evaporated out, the water is separated by the water separator, when the water yield removed by a system is equal to the theoretical water yield or the water yield is not increased any more, the esterification reaction is finished, and a product is subjected to reduced pressure distillation, alkali washing, water washing and vacuum drying to obtain milky waxy maleic acid di-n-octadecyl ester;
placing 100g of C9 petroleum resin into a four-mouth bottle with a stirring device, heating the bottle in an oil bath to a molten state, adding 10g of the prepared maleic acid di-n-octadecyl ester, then adding 1.5g of azobisisobutyronitrile in batches at 200 ℃, after the addition of the azobisisobutyronitrile is finished, heating the mixture to 280 ℃ for grafting reaction, and obtaining flexible petroleum resin after the reaction is finished;
dissolving the obtained flexible petroleum resin with saturated heptane to obtain solution with concentration of 15%, and placing in fixed bed reactor (stainless steel tubular reactor with all sizes
) The hydrogenation reaction is carried out in the middle, two-stage hydrogenation is adopted, two stainless steel tube type reactors are completely the same, and NiMoS/gamma-Al for the first-stage hydrogenation2O3The catalyst has the temperature of 250 ℃, the pressure of 5MPa and the liquid space velocity of 0.6h-1Completing unsaturated double bond hydrogenation and desulfurization; Pd/MgAl for second-stage hydrogenation2O4-Al2O3The catalyst has the temperature of 260 ℃, the pressure of 10MPa and the liquid space velocity of 0.6h-1And finishing the hydrogenation of the aromatic hydrocarbon to obtain the flexible hydrogenated petroleum resin.
Example 2
Weighing the following components in percentage by mass: 18 percent of maleic anhydride, 80 percent of n-heptanol, 0.5 percent of toluenesulfonic acid and 1.5 percent of toluene are sequentially added into a four-mouth bottle with a stirring device, a reflux condenser pipe and a water separator are arranged on the four-mouth bottle, then an electric heating insulation sleeve is used for heating to 100 ℃ for esterification reaction, water generated by the reaction and a water carrying agent form an azeotrope to be evaporated, the water is separated by the water separator, when the water amount removed by a system is equal to the theoretical water yield or the water yield is not increased any more, the esterification reaction is finished, and a product is subjected to reduced pressure distillation, alkali washing, water washing and vacuum drying to obtain milky waxy n-heptanoyl maleate;
placing 100g of C9 petroleum resin into a four-mouth bottle with a stirring device, heating the bottle in an oil bath to a molten state, adding 5g of the prepared n-heptanol maleate, adding 0.5g of benzoyl peroxide in batches at 150 ℃, heating the mixture to 260 ℃ after the benzoyl peroxide is added, and carrying out grafting reaction to obtain flexible petroleum resin after the reaction is finished;
dissolving the obtained flexible petroleum resin with saturated C12 alkane to obtain a solution with a concentration of 10%, and placing the solution in a fixed bed reactor (the sizes of stainless steel tubular reactors are all equal)
) The hydrogenation reaction is carried out in the middle, two sections of hydrogenation are adopted, the two sections of stainless steel tube reactors are completely the same, and NiMoS/gamma-Al is used for the hydrogenation in the first section2O3Catalyst with temperature of 150 ℃, pressure of 3MPa and liquid space velocity of 0.1h-1Completing unsaturated double bond hydrogenation and desulfurization; Pd/MgAl for second-stage hydrogenation2O4-Al2O3Catalyst with temperature of 350 ℃, pressure of 6MPa and liquid space velocity of 0.1h-1And finishing the hydrogenation of aromatic hydrocarbon to obtain the flexible hydrogenated petroleum resin.
Example 3
Weighing the following components in percentage by mass: 28 percent of maleic anhydride, 69 percent of n-pentacosanol, 1.5 percent of toluenesulfonic acid and 1.5 percent of cyclohexane are sequentially added into a four-mouth bottle with a stirring device, a reflux condenser pipe and a water separator are arranged on the four-mouth bottle, then an electric heating insulating sleeve is used for heating to 120 ℃ for esterification reaction, the water generated by the reaction and a water carrying agent form an azeotrope to be evaporated, the water is separated by the water separator, when the water amount removed from the system is equal to the theoretical water yield or the water yield is not increased any more, the esterification reaction is finished, and the product is subjected to reduced pressure distillation, alkali washing, water washing and vacuum drying to obtain milky waxy maleic acid di-n-pentacosanol ester;
placing 100g of C9 petroleum resin into a four-mouth bottle with a stirring device, heating the bottle in an oil bath to a molten state, adding 15g of the prepared maleic acid di-n-pentacosanol ester, adding dimethyl azodiisobutyrate in batches at 180 ℃, heating the solution to 270 ℃ after the dimethyl azodiisobutyrate is added, and carrying out grafting reaction to obtain flexible petroleum resin after the reaction is finished;
dissolving the obtained flexible petroleum resin with cyclohexane to a concentration of 15%, and placing in a fixed bed reactor (without adding water)The size of the steel tube reactor is
) The hydrogenation reaction is carried out in the middle, two-stage hydrogenation is adopted, two stainless steel tube type reactors are completely the same, and NiMoS/gamma-Al for the first-stage hydrogenation2O3Catalyst with temperature of 180 ℃, pressure of 4MPa and liquid space velocity of 0.4h-1Completing unsaturated double bond hydrogenation and desulfurization; Pd/MgAl for second-stage hydrogenation2O4-Al2O3The catalyst has the temperature of 160 ℃, the pressure of 8MPa and the liquid space velocity of 0.4h-1And finishing the hydrogenation of the aromatic hydrocarbon to obtain the flexible hydrogenated petroleum resin.
Example 4
Weighing the following components in percentage by mass: 35 percent of maleic anhydride, 63 percent of n-dodecanol, 0.8 percent of toluenesulfonic acid and 1.2 percent of carbon tetrachloride are sequentially added into a four-mouth bottle with a stirring device, a reflux condenser pipe and a water separator are arranged on the four-mouth bottle, then an electric heating insulation sleeve is used for heating to 130 ℃ for esterification reaction, water generated by the reaction and a water carrying agent form an azeotrope to be evaporated, the water is separated by the water separator, when the water yield removed by a system is equal to the theoretical water yield or the water yield is not increased any more, the esterification reaction is finished, and a product is subjected to reduced pressure distillation, alkali washing, water washing and vacuum drying to obtain milky waxy di-n-dodecanol maleate;
placing 100g of C9 petroleum resin into a four-mouth bottle with a stirring device, heating the bottle in an oil bath to a molten state, adding 20g of the prepared di-n-dodecyl maleate, then adding 2g of benzoyl peroxide tert-butyl ester for 3 times at 230 ℃, after finishing adding the benzoyl peroxide tert-butyl ester, heating the solution to 290 ℃ for grafting reaction, and obtaining flexible petroleum resin after the reaction is finished;
dissolving the obtained flexible petroleum resin saturated cyclopentane with concentration of 18%, and placing in a fixed bed reactor (the sizes of stainless steel tubular reactors are all equal)
) The hydrogenation reaction is carried out in the middle, two-stage hydrogenation is adopted, and the two-stage hydrogenation is finished in a stainless steel tube type reactorAll the same, NiMoS/gamma-Al for hydrogenation in the first stage2O3Catalyst with temperature of 300 ℃, pressure of 7MPa and liquid space velocity of 0.8h-1Completing unsaturated double bond hydrogenation and desulfurization; Pd/MgAl for second-stage hydrogenation2O4-Al2O3Catalyst with temperature of 300 ℃, pressure of 15MPa and liquid space velocity of 0.8h-1And finishing the hydrogenation of the aromatic hydrocarbon to obtain the flexible hydrogenated petroleum resin.
Example 5
Weighing the following components in percentage by mass: 40% of maleic anhydride, 58% of n-tetradecanol, 1% of toluenesulfonic acid and 1% of benzene are sequentially added into a four-mouth bottle with a stirring device, a reflux condenser pipe and a water separator are arranged on the four-mouth bottle, then an electrothermal insulating sleeve is used for heating to 140 ℃ for esterification reaction, water generated by the reaction and a water carrying agent form an azeotrope to be evaporated, water is separated by the water separator, when the water amount removed from a system is equal to the theoretical water yield or the water yield is not increased any more, the esterification reaction is finished, and a product is subjected to reduced pressure distillation, alkali washing, water washing and vacuum drying to obtain milky waxy di-n-tetradecyl maleate;
placing 100g of C9 petroleum resin into a four-mouth bottle with a stirring device, heating the bottle in oil bath to a molten state, adding 30g of the prepared maleic acid di-n-tetradecyl ester, then adding 2.5g of methyl ethyl ketone peroxide 3 times at 250 ℃, after the methyl ethyl ketone peroxide is added, heating the mixture to 300 ℃ for grafting reaction, and obtaining flexible petroleum resin after the reaction is finished;
dissolving the obtained flexible petroleum resin with saturated C18 alkane to obtain a solution with a concentration of 20%, and placing the solution in a fixed bed reactor (the stainless steel tubular reactor has the same size as the fixed bed reactor)
) The hydrogenation reaction is carried out in the middle, two-stage hydrogenation is adopted, two stainless steel tube type reactors are completely the same, and NiMoS/gamma-Al for the first-stage hydrogenation2O3The catalyst has the temperature of 350 ℃, the pressure of 8MPa and the liquid space velocity of 1.0h-1Completing unsaturated double bond hydrogenation and desulfurization; Pd/MgAl for second-stage hydrogenation2O4-Al2O3Catalyst with temperature of 150 ℃, pressure of 16MPa and liquid space velocity of 1.0h-1And finishing the hydrogenation of the aromatic hydrocarbon to obtain the flexible hydrogenated petroleum resin.
Comparative example 1
C9 petroleum resin body.
Comparative example 2
The only difference from example 1 is that the C9 petroleum resin was directly subjected to a two-stage hydrogenation reaction to obtain a hydrogenated C9 petroleum resin.
Comparative example 3
The only difference from example 1 is that azobisisobutyronitrile, a radical polymerization initiator, was added at one time during the preparation of the flexible petroleum resin.
Comparative example 4
The only difference from example 1 is that only the first stage hydrogenation reaction was used.
Comparative example 5
The only difference from example 1 is that only the second stage hydrogenation reaction was used.
Comparative example 6
A polypropylene body.
The detection method of each technical index of the invention comprises the following steps:
(1) measurement of softening point: the determination is carried out according to the method of the asphalt softening point determination method, namely the global method (national standard GB/T4507-1999).
(2) Measurement of chromaticity: the color is measured according to the method of measuring the color of the epoxy resin and the method of the Nardy colorimetric method (national standard GB/T222295-2008).
(3) The notched impact strength is tested according to GB/T1043-2008, the flexibility or brittleness of the flexible hydrogenated C9 petroleum resin is mainly measured by blending the flexible hydrogenated petroleum resin with other substances and then testing the notched impact strength of the blended material, therefore, the flexible hydrogenated petroleum resin accounting for 1 wt% of the total mass of the materials and 99 wt% of polypropylene are blended for 0.5h at 120 ℃, then the notched impact strength of the blended material is tested, and the flexibility or brittleness of the resin is evaluated through the numerical change of the impact strength.
The results of the property test of the flexible hydrogenated petroleum resins of examples 1 to 5 and comparative examples 1 to 6 are shown in Table 1:
table 1: results of Performance test of Flexible hydrogenated Petroleum resins in examples 1 to 5 and comparative examples 1 to 6
As can be seen from the test results in Table 1, the flexible hydrogenated petroleum resin prepared by the technical scheme of the invention has light color, small color change at high temperature and good high-temperature stability; the blending of the untreated C9 petroleum resin and the polypropylene not only does not improve the notch impact strength of the polypropylene, but also deteriorates the notch impact strength, but the blending of the modified flexible hydrogenated C9 petroleum resin and the polypropylene obviously improves the notch impact strength of the polypropylene, which indicates that the flexible hydrogenated petroleum resin has good flexibility or less brittleness. Therefore, the invention solves the problems of dark color, poor thermal stability and large brittleness by modifying the C9 petroleum resin, and has good industrial application value.
The technical scope of the invention claimed by the embodiments herein is not exhaustive and new solutions formed by equivalent replacement of single or multiple technical features in the embodiments are also within the scope of the invention, and all parameters involved in the solutions of the invention do not have mutually exclusive combinations if not specifically stated.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (7)
1. The preparation method of the flexible hydrogenated C9 petroleum resin is characterized by sequentially comprising the preparation of the maleic acid double-long-chain alcohol ester, the preparation of the flexible C9 petroleum resin and the preparation of the flexible hydrogenated C9 petroleum resin;
the preparation method of the flexible C9 petroleum resin comprises the following steps: adding C9 petroleum resin into a four-mouth bottle with a stirrer, heating to melt, adding maleic acid double-long-chain alcohol ester, adding a free radical polymerization initiator in batches at the temperature of 150-250 ℃, heating to the temperature of 260-300 ℃ after the initiator is added, and carrying out a grafting reaction to obtain flexible petroleum resin after the reaction is finished;
the preparation method of the flexible hydrogenated petroleum resin comprises the following steps: dissolving flexible petroleum resin with saturated alkane or saturated cycloalkane, and then carrying out two-stage hydrogenation reaction to prepare flexible hydrogenated petroleum resin;
the long-chain alcohol is normal alcohol without branched chains on carbon chains, and the number of carbon atoms on the carbon chains is 5-25.
2. The method according to claim 1, wherein the preparation of the bis-long chain alcohol maleate specifically comprises: adding maleic anhydride, long-chain alcohol, toluenesulfonic acid and water carrying agent into a four-mouth bottle with a stirrer, heating to 100 ℃ and 140 ℃ for esterification reaction, and after the reaction is finished, carrying out reduced pressure distillation, alkaline washing, water washing and vacuum drying on the product to obtain milky waxy maleic acid di-long-chain alcohol ester.
3. The preparation method according to claim 2, wherein the mass percentages of the maleic anhydride, the long-chain alcohol, the toluenesulfonic acid and the water carrying agent are 18-40%, 58-80%, 0.5-2% and 1-1.5% in sequence.
4. The method according to claim 2 or 3, wherein the water carrying agent is at least one of petroleum ether, benzene, toluene, cyclohexane, chloroform and carbon tetrachloride.
5. The method according to claim 1, wherein the amount of the dilong chain alcohol maleate is 5-30% of the total mass of the C9 petroleum resin, and the amount of the radical polymerization initiator is 0.5-2.5% of the total mass of the C9 petroleum resin.
6. The production method according to claim 1 or 5, wherein the radical polymerization initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate initiator, benzoyl peroxide, benzoyl t-butyl peroxide, and methyl ethyl ketone peroxide.
7. The preparation method according to claim 1, wherein the two-stage hydrogenation reaction is specifically: the first stage hydrogenation adopts a nickel catalyst, the temperature is 150-350 ℃, the pressure is 3-8MPa, and the liquid space velocity is 0.1-1.0h-1Completing unsaturated double bond hydrogenation and desulfurization; the second stage hydrogenation adopts palladium catalyst with the temperature of 150 ℃ and 350 ℃, the pressure of 6-16MPa and the liquid space velocity of 0.1-1.0h-1And finishing the hydrogenation of aromatic hydrocarbon.
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