CN108641044B - Acid modified C5 petroleum resin and molecular weight controllable preparation method thereof - Google Patents
Acid modified C5 petroleum resin and molecular weight controllable preparation method thereof Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 126
- 239000011347 resin Substances 0.000 title claims abstract description 126
- 239000003208 petroleum Substances 0.000 title claims abstract description 78
- 239000002253 acid Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims abstract description 50
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 150000003440 styrenes Chemical class 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 6
- -1 monoolefine Natural products 0.000 claims abstract 3
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 32
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 24
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 17
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 16
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 16
- 239000012467 final product Substances 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 15
- PMJHHCWVYXUKFD-PLNGDYQASA-N (3z)-penta-1,3-diene Chemical compound C\C=C/C=C PMJHHCWVYXUKFD-PLNGDYQASA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012745 toughening agent Substances 0.000 claims description 9
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical compound CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-N 0.000 claims description 4
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 claims description 4
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims description 4
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 claims description 4
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 abstract description 14
- 230000001105 regulatory effect Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 28
- 150000005673 monoalkenes Chemical class 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 125000002015 acyclic group Chemical group 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 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 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 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 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
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- 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)
- 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 acid modified C5 petroleum resin and a molecular weight controllable preparation method thereof, belonging to the technical field of petroleum resin preparation. The preparation method comprises the following steps: accurately weighing substances such as a decyclization C5 compound, piperylene, recycled piperylene, monoolefine, styrene and styrene derivatives according to a certain proportion relation, dissolving the substances in solvent oil, adding the solvent oil into a cold polymerization reaction kettle, uniformly stirring, controlling the reaction temperature of polymerization to be 45-80 ℃, controlling the reaction time to be 0.5-4 h, and preparing a base resin after polymerization; finally, the basic resin is grafted to obtain the final acid modified petroleum resin product. The invention regulates and controls the molecular weight of the base resin by regulating the content of each material component in the reaction material, and then controls the molecular weight of the petroleum resin by the grafting technology, thereby finally realizing the control of the molecular weight of the petroleum resin and having wider regulation and control range.
Description
Technical Field
The invention belongs to the technical field of petroleum resin preparation, and particularly relates to an acid modified C5 petroleum resin and a molecular weight controllable preparation method thereof.
Background
Petroleum resin (hydrocarbon resin) is a thermoplastic resin produced by the processes of pretreatment, polymerization, distillation and the like of C5 and C9 fractions which are by-products produced by petroleum cracking, and is not a high polymer but an oligomer with the molecular weight of 300-3000. The petroleum resin is named as a petroleum derivative, has the characteristics of low acid value, good miscibility, water resistance, ethanol resistance, chemical resistance and the like, has chemical stability to acid and alkali, and has the characteristics of good viscosity regulation and thermal stability. Petroleum resins are generally not used alone but as accelerators, regulators, modifiers and other resins together.
Petroleum resins are classified into aliphatic resins (C5), alicyclic resins (DCPD), aromatic resins (C9), aliphatic/aromatic copolymer resins (C5/C9) and hydrogenated petroleum resins depending on the raw materials. The hydrogenated petroleum resin comprises C5 hydrogenated petroleum resin and C9 hydrogenated petroleum resin. Among them, the C5 petroleum resin is also called carbon five resin and aliphatic hydrocarbon resin, and is divided into 3 types of general type, blend type and colorless transparent type, and has good viscosity increasing property, heat resistance, stability, water resistance, acid and alkali resistance, and the viscosity increasing effect is generally better than that of the C9 resin, and the resin has good compatibility with phenolic resin, terpene resin, coumarone resin, natural rubber, synthetic rubber, etc., especially good compatibility with Styrene Butadiene Rubber (SBR). At present, the C5 petroleum resin has been widely used in production as an accelerator, a regulator and a modifier, and has been gradually substituted for natural resin tackifiers (rosin and terpene resins) due to its characteristics of high peel adhesion strength, good quick adhesion, stable adhesion, moderate melt viscosity, good heat resistance, good compatibility with high polymer matrix, and low cost.
However, petroleum resin has the disadvantages of high brittleness, poor film-forming property, structural lack of polar groups, deep color and the like, so that the application of the petroleum resin in a plurality of fields is limited. The prior art generally overcomes the above disadvantages by modification, wherein the modification methods mainly include two methods: the first is hydrogenation modification, and the second is chemical modification. The chemical modification is to introduce polar groups into C5 petroleum resin molecules or add modifiers into raw materials to prepare petroleum resin with special properties. The common modification mode of modifying C5 petroleum resin into C5 petroleum resin by taking maleic anhydride as a grafting flexibilizer is characterized in that the polarity of the C5 petroleum resin is enhanced by introducing polar groups into a main chain of the C5 petroleum resin, and the modified C5 petroleum resin macroscopically shows that the softening point of the C5 petroleum resin is improved, the color is deepened, the adhesive force to steel is increased, and the like. The petroleum resin grafted by maleic anhydride is widely applied to the aspects of pressure-sensitive adhesives, hot melt adhesives, traffic marking paints, rubber tackifiers, coatings, paper sizing agents and the like.
The molecular weight and the molecular weight distribution of the petroleum resin directly reflect the structural difference of the polymer, and the molecular weight distribution can influence the compatibility of the petroleum resin and the elastomer, the melt viscosity of the PSA and the cohesion/adhesion balance, so that the molecular weight requirements of different application fields on petroleum resin products are different. In the prior art, the molecular weight of a petroleum resin product is usually adjusted by changing process parameters such as polymerization temperature and the like, but the molecular weight is sensitive to temperature and greatly changes along with the temperature, so that the molecular weight is difficult to finely adjust. At present, researchers have also studied the regulation of the molecular weight of petroleum resin products by the addition of monoolefin-based molecular weight regulators. For example, the chinese patent application No. 2009100226153 is to use a mixed monoolefin as a molecular weight regulator to regulate the molecular weight of polydicyclopentadiene petroleum resin, but the molecular weight regulating range of the petroleum resin product obtained by using the monoolefin molecular weight regulator is relatively narrow, which is difficult to meet the use requirements of different fields.
Therefore, exploring key factors that control molecular weight magnitude is invaluable to study polymerization principles, petroleum resin structural features, and to service downstream production.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to overcome the defects in the prior art and provides an acid modified C5 petroleum resin and a molecular weight controllable preparation method thereof. According to the invention, the content of each material component in the reaction material is blended, so that the molecular weight of the obtained acid modified C5 petroleum resin can be freely regulated and controlled within a certain range, and different use requirements of different customers on the acid modified petroleum resin can be met.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
according to the acid modified C5 petroleum resin, the acid modified C5 petroleum resin product is obtained by grafting the base resin obtained by polymerization, the softening point of the acid modified C5 petroleum resin can be controlled to be 88-110 ℃, and the molecular weight Mz can be controlled to be 6000-15000.
The invention relates to a molecular weight controllable preparation method of acid modified C5 petroleum resin, which comprises the steps of taking a decyclization C5 compound, piperylene, recovered piperylene, monoolefin, styrene and styrene derivatives as main raw materials, preparing a base resin through polymerization reaction, and then taking maleic anhydride as a grafting flexibilizer for grafting treatment to obtain the acid modified C5 petroleum resin.
Furthermore, the method comprises the following specific steps:
1) accurately weighing each reaction raw material according to a certain proportion relation, and dissolving the reaction raw materials in solvent oil;
2) adding the weighed reaction materials into a cold polymerization reaction kettle, uniformly stirring, controlling the polymerization reaction temperature to be 45-80 ℃, and the reaction time to be 0.5-4 h, and polymerizing to obtain a base resin;
3) and finally, grafting the base resin by taking maleic anhydride as a grafting toughening agent to prepare the final product, namely the acid modified petroleum resin.
Furthermore, the solvent oil is one or more of benzene, toluene, xylene, pentane, hexane, cyclohexane, heptane, octane, nonane, decane, solvent D40 and solvent D60.
Furthermore, the mass ratio of the acyclic C5 compound, the piperylene, the recovered piperylene, the monoolefin, the styrene and the styrene derivative in the reaction raw materials is (1-150): 1-60: (1-150): (1-80): (0-60).
Further, the decyclization C5 compound mainly comprises the following effective components: 1-20% of trans-1, 3-pentadiene, 1-10% of cis-1, 3-pentadiene, 1-30% of isoprene, 1-10% of cyclopentene, 1-10% of 1-pentene and 1-5% of 1, 4-pentadiene.
Furthermore, the piperylene mainly contains the following effective components: 1-50% of trans-1, 3-pentadiene, 1-30% of cis-1, 3-pentadiene, 0-1% of cyclopentadiene, 1-20% of cyclopentene and 1-10% of 2-methyl-2-butene.
Furthermore, the recovered piperylene mainly contains the following effective components: 1-10% of trans-1, 3-pentadiene, 1-50% of cis-1, 3-pentadiene, 1-40% of cyclopentene, 1-5% of isoprene and 1-5% of 2-methyl-2-butene.
Furthermore, the monoolefine mainly comprises the following effective components: 1-5% of 1-pentene, 1-15% of 2-methyl-1-butene, 1-25% of 2-methyl-2-butene, 1-5% of cyclopentene, 1-20% of trans-2-pentene and 1-10% of cis-2-pentene.
Furthermore, the softening point of the base resin obtained by polymerization can be controlled within 80-100 ℃, and the molecular weight Mz can be controlled within 5000-10000.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) the softening point of the acid modified C5 petroleum resin can be controlled to be 88-110 ℃, the molecular weight Mz can be regulated and controlled within the range of 6000-15000, and the adjustable range of the molecular weight is wider on the basis of ensuring that the fluctuation of the softening point is small, so that different requirements of different customers on the acid modified C5 petroleum resin can be met.
(2) The invention relates to a controllable preparation method of molecular weight of acid modified C5 petroleum resin, which takes a decyclization C5 compound, piperylene, recycled piperylene, monoolefin, styrene and styrene derivatives as main raw materials, and regulates and controls the mass ratio of the reaction raw materials, thereby ensuring the softening point of the petroleum resin product, enabling the molecular weight of the product to be freely regulated and controlled within a certain range, having a wider regulation and control range, meeting the requirements of different application fields on the molecular weight of the acid modified C5 petroleum resin, and having simpler regulation and control operation.
(3) According to the controllable preparation method of the molecular weight of the acid modified C5 petroleum resin, the mass ratio of each reaction raw material is regulated, and particularly, the contents of trans-1, 3-pentadiene and cis-1, 3-pentadiene in isoprene and m-pentadiene are regulated, so that the molecular weight of the obtained resin product can be freely regulated in a large range, and the method is simple, convenient, easy to operate and suitable for large-scale and automatic production.
(4) According to the preparation method for the acid-modified C5 petroleum resin with the controllable molecular weight, the temperature and the time of the polymerization reaction are optimally designed, so that the softening point and the molecular weight of the obtained acid-modified petroleum resin product can be further ensured, the softening point of the base resin obtained by polymerization can be controlled to be 80-100 ℃, and the molecular weight Mz can be controlled to be 5000-10000; the softening point of the final acid modified petroleum resin prepared by the basic resin through a grafting technology can be controlled to be 88-110 ℃, and the molecular weight Mz can be controlled to be 6000-15000.
Detailed Description
The invention relates to a molecular weight controllable preparation method of acid modified C5 petroleum resin, which comprises the steps of taking a decyclization C5 compound, piperylene, recovered piperylene, monoolefin, styrene and styrene derivatives as main raw materials, preparing a base resin through polymerization reaction, and then taking maleic anhydride as a grafting flexibilizer for grafting treatment to obtain the acid modified C5 petroleum resin. The acid modified C5 petroleum resin comprises the following steps:
1) accurately weighing each reaction raw material according to a certain proportion relation, and dissolving the reaction raw materials in solvent oil; wherein the mass ratio of the acyclic C5 compound, the piperylene, the recycled piperylene, the monoolefin, the styrene and the derivatives of the styrene to the solvent oil is (1-150): (1-60): 1-150): (1-80): (0-60) < 100-200 >.
In the prior art, the molecular weight of a petroleum resin product is usually adjusted by adjusting the process parameters of a polymerization reaction or adding a monoolefin molecular weight regulator, but on the one hand, on the basis of ensuring the requirement of the softening point of the product, the method has a limited adjustment range of the molecular weight of the resin product and is difficult to meet the requirements of different fields and different manufacturers on the resin product, and on the other hand, the method is difficult to finely adjust the molecular weight of the petroleum resin product. The invention adjusts the raw material proportion in the polymer material, optimally controls the reaction process parameters, particularly adjusts the contents of trans-1, 3-pentadiene and cis-1, 3-pentadiene in isoprene and m-pentadiene, and grafts maleic anhydride by a grafting technology, thereby finally realizing the control of the molecular weight of the acid modified petroleum resin on the basis of ensuring the softening point of the obtained product, enabling the molecular weight to be freely regulated and controlled in a larger range, and further meeting different use requirements of different customers on the molecular weight of the petroleum resin.
2) Adding the weighed reaction materials into a cold polymerization reaction kettle, uniformly stirring, controlling the polymerization reaction temperature to be 45-80 ℃, reacting for 0.5-4 h, and then carrying out steam stripping on the polymerized reaction materials to recover solvent oil to obtain base resin; the softening point of the obtained base resin can be controlled to be 80-100 ℃, and the molecular weight Mz can be controlled to be 5000-10000.
3) And finally, grafting the base resin by using maleic anhydride as a grafting toughening agent, and washing by using a melt grafting means to obtain the final product, namely the acid modified petroleum resin, wherein the softening point of the acid modified petroleum resin can be controlled to be 88-110 ℃, and the molecular weight Mz can be controlled to be 6000-15000.
For a further understanding of the invention, reference will now be made in detail to specific embodiments of the invention. It should be noted that the acyclic C5 compound of the present invention mainly contains the following effective components: 1-20% of trans-1, 3-pentadiene, 1-10% of cis-1, 3-pentadiene, 1-30% of isoprene, 1-10% of cyclopentene, 1-10% of 1-pentene and 1-5% of 1, 4-pentadiene. The piperylene mainly contains the following effective components: 1-50% of trans-1, 3-pentadiene, 1-30% of cis-1, 3-pentadiene, 0-1% of cyclopentadiene, 1-20% of cyclopentene and 1-10% of 2-methyl-2-butene. The recovered piperylene mainly contains the following effective components: 1-10% of trans-1, 3-pentadiene, 1-50% of cis-1, 3-pentadiene, 1-40% of cyclopentene, 1-5% of isoprene and 1-5% of 2-methyl-2-butene. The monoolefine mainly comprises the following effective components: 1-5% of 1-pentene, 1-15% of 2-methyl-1-butene, 1-25% of 2-methyl-2-butene, 1-5% of cyclopentene, 1-20% of trans-2-pentene and 1-10% of cis-2-pentene. The solvent oil is one or more of benzene, toluene, xylene, pentane, hexane, cyclohexane, heptane, octane, nonane, decane, solvent D40 and solvent D60. For the sake of brevity, the present invention is intended to cover only some of the illustrative embodiments, but not limited to the particular materials and values recited in the illustrative embodiments. Examples 1-6 the main effective components of the decyclized C5 compound used were: 10-15% of trans-1, 3-pentadiene, 4-8% of cis-1, 3-pentadiene, 15-30% of isoprene, 4-8% of cyclopentene, 4-8% of 1-pentene and 1-5% of 1, 4-pentadiene. The main effective components of the piperylene comprise: 35-45% of trans-1, 3-pentadiene, 20-30% of cis-1, 3-pentadiene, 0-1% of cyclopentadiene, 15-25% of cyclopentene and 1-10% of 2-methyl-2-butene. The main effective components of the recovered piperylene comprise: 1-10% of trans-1, 3-pentadiene, 35-45% of cis-1, 3-pentadiene, 25-40% of cyclopentene, 1-4% of isoprene and 1-5% of 2-methyl-2-butene. The main effective components of the mono-olefin are as follows: 1-5% of 1-pentene, 10-15% of 2-methyl-1-butene, 20-25% of 2-methyl-2-butene, 1-5% of cyclopentene, 10-20% of trans-2-pentene and 5-10% of cis-2-pentene.
Example 1
130g of decyclization C5 compound, 60g of piperylene, 90g of recovered piperylene, 20g of monoolefin and 50g of styrene are respectively weighed and dissolved in 150g of solvent oil; then adding the reaction materials into a cold polymerization reaction kettle and uniformly stirring, controlling the reaction temperature of polymerization to be 60 ℃, controlling the reaction time to be 2 hours, and after the reaction is finished, carrying out steam stripping on the reaction product of polymerization to recover solvent oil to obtain base resin; and finally, taking maleic anhydride as a grafting toughening agent for the base resin, and obtaining the final product, namely the acid modified petroleum resin by means of melt grafting and washing. The molecular weight Mz of the base resin was found to be 6500, the softening point 90 ℃, the molecular weight Mz of the final product 9100, and the softening point 100 ℃.
Example 2
150g of decyclization C5 compound, 60g of piperylene, 60g of recycled piperylene, 30g of monoolefin and 30g of styrene are respectively weighed and dissolved in 170g of solvent oil; then adding the reaction materials into a cold polymerization reaction kettle and uniformly stirring, controlling the reaction temperature of polymerization to be 70 ℃, controlling the reaction time to be 2 hours, and after the reaction is finished, carrying out steam stripping on the reaction product of polymerization to recover solvent oil to obtain base resin; and finally, taking maleic anhydride as a grafting toughening agent for the base resin, and obtaining the final product, namely the acid modified petroleum resin by means of melt grafting and washing. The molecular weight Mz of the base resin was found to be 9800, the softening point was found to be 99 ℃, the molecular weight Mz of the final product was found to be 14600, and the softening point was found to be 110 ℃.
Example 3
100g of acyclic C5 compound, 40g of piperylene, 120g of recovered piperylene, 50g of mono-olefin and 50g of styrene are respectively weighed and dissolved in 140g of solvent oil; then adding the reaction materials into a cold polymerization reaction kettle and uniformly stirring, controlling the polymerization reaction temperature to be 58 ℃ and the reaction time to be 3h, and after the reaction is finished, recovering solvent oil from the polymerized reaction product through steam stripping to obtain base resin; and finally, taking maleic anhydride as a grafting toughening agent for the base resin, and obtaining the final product, namely the acid modified petroleum resin by means of melt grafting and washing. The molecular weight Mz of the base resin was determined to be 7200, the softening point 85 ℃, the molecular weight Mz of the final product 9500, and the softening point 98 ℃.
Example 4
80g of decyclization C5 compound, 50g of piperylene, 150g of recovered piperylene, 50g of mono-olefin and 50g of styrene are respectively weighed and dissolved in 120g of solvent oil; then adding the reaction materials into a cold polymerization reaction kettle and uniformly stirring, controlling the polymerization reaction temperature to be 75 ℃, controlling the reaction time to be 4h, and after the reaction is finished, carrying out steam stripping on the polymerized reaction product to recover solvent oil to obtain base resin; and finally, taking maleic anhydride as a grafting toughening agent for the base resin, and obtaining the final product, namely the acid modified petroleum resin by means of melt grafting and washing. The molecular weight Mz of the base resin was found to be 6200, the softening point was 87 ℃, the molecular weight Mz of the final product was 6500, and the softening point was 95 ℃.
Example 5
Respectively weighing 95g of decyclization C5 compound, 30g of piperylene, 100g of recovered piperylene, 60g of monoolefin and 40g of styrene, and dissolving the obtained materials in 150g of solvent oil; then adding the reaction materials into a cold polymerization reaction kettle and uniformly stirring, controlling the reaction temperature of polymerization to be 45 ℃ and the reaction time to be 1.5h, and after the reaction is finished, carrying out steam stripping on the reaction product of polymerization to recover solvent oil to obtain base resin; and finally, taking maleic anhydride as a grafting toughening agent for the base resin, and obtaining the final product, namely the acid modified petroleum resin by means of melt grafting and washing. The molecular weight Mz of the base resin was found to be 5000, the softening point 80 ℃, the molecular weight Mz of the final product was found to be 6000, and the softening point was found to be 89 ℃.
Example 6
Respectively weighing 90g of acyclic C5 compound, 55g of piperylene, 142g of recovered piperylene, 40g of mono-olefin and 40g of styrene, and dissolving the materials in 120g of solvent oil; then adding the reaction materials into a cold polymerization reaction kettle and uniformly stirring, controlling the reaction temperature of polymerization to be 80 ℃, controlling the reaction time to be 0.5h, and after the reaction is finished, carrying out steam stripping on the reaction product of polymerization to recover solvent oil to obtain base resin; and finally, taking maleic anhydride as a grafting toughening agent for the base resin, and obtaining the final product, namely the acid modified petroleum resin by means of melt grafting and washing. The molecular weight Mz of the base resin was found to be 7000, the softening point was 96 ℃, the molecular weight Mz of the final product was 8000, and the softening point was 107 ℃.
Claims (4)
1. A molecular weight controllable preparation method of acid modified C5 petroleum resin is characterized in that: the method comprises the following steps of preparing base resin by taking a decyclization C5 compound, piperylene, recycled piperylene, monoolefine, styrene and styrene derivatives as main raw materials through polymerization, and then taking maleic anhydride as a grafting flexibilizer to carry out grafting treatment to obtain acid modified C5 petroleum resin; the mass ratio of a decyclization C5 compound, piperylene, recycled piperylene, monoolefine, styrene and styrene derivatives in the reaction raw materials is (1-150): (1-60): 1-150): (1-80): (0-60), wherein the softening point of the obtained acid modified C5 petroleum resin is 88-110 ℃, and the molecular weight Mz is 6000-15000; the decyclization C5 compound mainly comprises the following effective components: 1-20% of trans-1, 3-pentadiene, 1-10% of cis-1, 3-pentadiene, 1-30% of isoprene, 1-10% of cyclopentene, 1-10% of 1-pentene and 1-5% of 1, 4-pentadiene; the piperylene mainly contains the following effective components: 1-50% of trans-1, 3-pentadiene, 1-30% of cis-1, 3-pentadiene, 0-1% of cyclopentadiene, 1-20% of cyclopentene and 1-10% of 2-methyl-2-butene; the recovered piperylene mainly contains the following effective components: 1-10% of trans-1, 3-pentadiene, 1-50% of cis-1, 3-pentadiene, 1-40% of cyclopentene, 1-5% of isoprene and 1-5% of 2-methyl-2-butene; the monoolefine mainly comprises the following effective components: 1-5% of 1-pentene, 1-15% of 2-methyl-1-butene, 1-25% of 2-methyl-2-butene, 1-5% of cyclopentene, 1-20% of trans-2-pentene and 1-10% of cis-2-pentene.
2. The method for preparing acid-modified C5 petroleum resin with controllable molecular weight according to claim 1, which comprises the following steps:
1) accurately weighing each reaction raw material according to a certain proportion relation, and dissolving the reaction raw materials in solvent oil;
2) adding the weighed reaction materials into a cold polymerization reaction kettle, uniformly stirring, controlling the polymerization reaction temperature to be 45-80 ℃, and the reaction time to be 0.5-4 h, and polymerizing to obtain a base resin;
3) and finally, grafting the base resin by taking maleic anhydride as a grafting toughening agent to prepare the final product, namely the acid modified petroleum resin.
3. The method for preparing acid-modified C5 petroleum resin with controllable molecular weight according to claim 2, wherein the method comprises the following steps: the solvent oil is one or more of benzene, toluene, xylene, pentane, hexane, cyclohexane, heptane, octane, nonane, decane, solvent D40 and solvent D60.
4. The controllable preparation method of the molecular weight of the acid modified C5 petroleum resin according to any one of claims 1-3, wherein the method comprises the following steps: the softening point of the base resin obtained by polymerization can be controlled to be 80-100 ℃, and the molecular weight Mz can be controlled to be 5000-10000.
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