CN108219068B - High-performance polymer resin with controllable melt viscosity and preparation method thereof - Google Patents
High-performance polymer resin with controllable melt viscosity and preparation method thereof Download PDFInfo
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- 239000002952 polymeric resin Substances 0.000 title claims abstract description 17
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- 239000002904 solvent Substances 0.000 claims abstract description 37
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000155 melt Substances 0.000 claims abstract description 19
- 150000005673 monoalkenes Chemical class 0.000 claims abstract description 19
- 150000001993 dienes Chemical class 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 28
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 24
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 23
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000012467 final product Substances 0.000 claims description 17
- PMJHHCWVYXUKFD-PLNGDYQASA-N (3z)-penta-1,3-diene Chemical compound C\C=C/C=C PMJHHCWVYXUKFD-PLNGDYQASA-N 0.000 claims description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 150000003440 styrenes Chemical class 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 241000208818 Helianthus Species 0.000 claims description 3
- 235000003222 Helianthus annuus Nutrition 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 230000037452 priming Effects 0.000 claims 1
- 239000003208 petroleum Substances 0.000 abstract description 39
- 230000001105 regulatory effect Effects 0.000 abstract description 9
- 239000011968 lewis acid catalyst Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 14
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 9
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 7
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 7
- 239000004831 Hot glue Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000006837 decompression Effects 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- CPBKRGKKLKNFAI-UHFFFAOYSA-N C=CC=CC.[C] Chemical compound C=CC=CC.[C] CPBKRGKKLKNFAI-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000002087 whitening effect Effects 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
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a high-performance polymer resin with controllable melt viscosity and a preparation method thereof, belonging to the technical field of petrochemical industry. The method can realize the production of petroleum resin with the softening point index close to that of the petroleum resin and the melt viscosity controllably regulated through the adjustment of the process, and comprises the following steps: the oil product raw materials adopted comprise carbon five diolefin, monoolefin, styrene and solvent oil, the oil product is added into a reaction kettle in a dropwise adding mode, meanwhile, a Lewis acid catalyst is added, the reaction temperature is controlled to be 50-90 ℃, the reaction pressure is controlled to be less than 1Mpa, the reaction is carried out for 0.5-4 h under the condition, and after the reaction is finished, the final petroleum resin product is obtained through water washing and solvent removal. The Gardner color number of the petroleum resin prepared by the invention is 2-5, the softening point is 70-104 ℃, and the melt viscosity is 40-300cps at 200 ℃. The invention can prepare petroleum resin with different viscosities, thereby meeting the requirements of different application fields.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a petroleum resin product with a controllable melt viscosity index and a preparation method thereof.
Background
The petroleum resin is a thermoplastic resin polymerized by taking C5 and C9 fractions of byproducts in the ethylene cracking process as main raw materials, has the relative molecular mass of 300-5000, and has the characteristics of high peel strength, good quick-adhesion, stable adhesive property, good compatibility and the like. Wherein the physical properties of the C5 petroleum resin are as follows: softening point, chromaticity, melt viscosity, acid value, etc. are all important factors affecting the field of application of C5 petroleum resins, and the melt viscosity index of C5 petroleum resins is critical for its specific application.
For example, the melt viscosity of the C5 petroleum resin can influence the infiltration capacity of the hot melt adhesive and the pressure-sensitive adhesive, and if the melt viscosity of the resin is too high, the infiltration capacity of the hot melt adhesive and the pressure-sensitive adhesive is reduced, so that the adhesion of the hot melt adhesive and the coating of the pressure-sensitive adhesive are not facilitated; on the one hand, the excessively low melt viscosity may cause sedimentation of the filler in the hot melt adhesive system, which may cause uneven distribution of material components, and on the other hand, the decrease of cohesive strength of the hot melt adhesive may cause adverse effect on adhesion. In the aspect of resin for ink, in particular to screen ink, the viscosity of the resin is required to be smaller, and the drying rate is slower so as to prevent screen blocking; the petroleum resin used for preparing the transparent putty is required to have high molecular weight and high viscosity, and is thick-coated to prevent pigment and filler from precipitating. Thus, in general, low viscosity resins are commonly used as varnishes and varnishes, medium viscosity resins are used as solid paints and topcoats, and high viscosity resins are used in many applications in silver paints and primers. In view of the above, the melt viscosity of petroleum resin is required to be different depending on the application of the resin.
Along with technological development and advocation of green and environment-friendly products, new requirements are put forward on materials and use environments in the application field of the products, further, new requirements are put forward on the viscosity of petroleum resin products, the requirement cannot be met by the melt viscosity of original petroleum resin, effective regulation and control of the viscosity of the petroleum resin are achieved, the distribution of molecular weight is effectively controlled, and the stability of the softening point of the petroleum resin products is guaranteed to have great significance for development of the petroleum resin and expansion of the application field of the products.
At present, in the prior art, the adjustment of melt viscosity is usually realized by adjusting the polymerization temperature, the adjustment range is relatively small, and the use requirements of various application fields are difficult to meet, so that resin products in different application fields also need to be prepared by adopting different reaction raw materials. Meanwhile, when the melt viscosity is adjusted by adjusting the polymerization temperature, fine adjustment is difficult to be carried out, so that the quality and performance of resin products in various fields cannot be ensured. In addition, the mode is adjusted by changing the polymerization degree, so that uneven reaction is easy to cause, and the application performance of the product is greatly influenced.
For example, chinese patent 201310197007.2 discloses a petroleum resin rotary offset printing news ink and a preparation method thereof, and the petroleum resin rotary offset printing news ink of the application contains the following components in parts by mass: 10-15 parts of dark petroleum resin, 23-30 parts of ink solvent oil, 2-5 parts of isoprene oligomer, 15-20 parts of refined linseed oil, 7-11 parts of pigment carbon black, 6-10 parts of iron blue, 1-3 parts of phthalocyanine blue B, 4.5-7 parts of low aromatic petroleum solvent, 1.5-3.5 parts of aluminum hydroxide and 0.005-0.015 part of odor masking and flavoring agent. For another example, chinese patent 201210096726.0 discloses a polyethylene hot melt adhesive composition comprising a matrix material, an initiator, a modifier, a grafting monomer, a whitening agent, a viscosity modifier, and an antioxidant. The viscosity of the obtained resin product can be adjusted by adding the ink solvent oil or the viscosity regulator respectively in the two applications, but the viscosity is adjusted by the additive, so that the adjustment range of the viscosity of petroleum resin is limited, and the adjustment in the mode is generally applied to the corresponding field, namely the application field is limited.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to overcome the defect that the viscosity of resin is difficult to be greatly and finely adjusted by adopting the existing preparation method, so that the requirements of different application fields on the viscosity of the resin cannot be met, and provides a high-performance polymer resin with controllable melt viscosity and a preparation method thereof. The technical scheme of the invention is convenient for greatly and finely adjusting the viscosity of the obtained petroleum resin product, thereby preparing petroleum resins with various different viscosities, meeting the requirements of different application fields and ensuring the quality and performance of the obtained resin product.
2. Technical proposal
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
the invention relates to a preparation method of high-performance polymer resin with controllable melt viscosity, which comprises the following steps:
1) Taking carbon five diolefin, monoolefin and styrenes as reaction raw materials, respectively weighing the reaction raw materials and solvent oil according to mass ratio, and uniformly mixing;
2) Firstly, pumping a solvent into a reaction kettle, and then adding a catalyst accounting for 0.6-3% of the total mass of reaction materials;
3) After the temperature in the reaction kettle reaches the synthesis temperature, adding the mixed materials into the reaction kettle for reaction;
4) The reaction time is controlled to be 1-5 h, after the reaction is finished, the reaction is carried out, water washing is carried out, and then the polymerization liquid after water washing is subjected to reduced pressure suction filtration and steam stripping to obtain the final product.
Further, the mass ratio of the reaction raw materials to the solvent oil is that the carbon five diene: mono-olefins: styrenes: solvent oil is (1-20): (1-15): (0-10): (1-15).
Further, the reaction temperature is controlled to be 50-90 ℃, and the reaction pressure is controlled to be less than 1Mpa.
Furthermore, in the step 3), the mixed materials are added in a dropwise adding mode by a metering pump, and the dropwise adding is controlled to be completed within 0.5-2 hours.
Further, the carbon-five diene is one or more of piperylene, isoprene, butadiene and cyclopentadiene, and the mass ratio of trans-1, 3-pentadiene to cis-1, 3-pentadiene in the piperylene is 0.1-2.0.
Still further, the mono-olefin is one or more of isobutylene, isoamylene, n-pentene and cyclopentene.
Further, the styrenes are one or more of styrene, alpha-methylstyrene, beta-methylstyrene and styrene derivatives.
Further, the solvent is one or more of benzene, toluene, xylene, trimethylbenzene, pentane, hexane, cyclohexane, heptane, octane, nonane, sunflower, undecane, dodecane, no. 100 solvent oil, no. 200 solvent oil, solvent D40 and solvent D60.
Further, the catalyst is aluminum trichloride powder or liquid aluminum trichloride catalyst.
The high-performance polymer resin with controllable melt viscosity has a Gardner color number of 2-5, a softening point of 70-104 ℃ and a melt viscosity of 40-300 cps.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) According to the preparation method of the high-performance polymer resin with controllable melt viscosity, the carbon penta-diene, the mono-olefin and the styrenes are used as reaction raw materials, the ratio of the reaction raw materials and the reaction technological parameters are regulated, the controllable regulation and control of the melt viscosity of the petroleum resin can be realized under a lower reaction temperature system, the softening point index is ensured to be close, and the fluctuation is small.
(2) The method for preparing the high-performance polymer resin with controllable melt viscosity has the advantages that the Gardner color number of the petroleum resin prepared by the method is 2-5, the softening point is 70-104 ℃, the melt viscosity of 200 ℃ is 40-300cps, the regulating range of the viscosity of the petroleum resin is wider, and the petroleum resin with different melt viscosities can be produced according to application requirements, so that the requirements of different application fields can be met.
(3) According to the preparation method of the high-performance polymer resin with controllable melt viscosity, resin products with different viscosities can be prepared by adjusting the addition amount of the carbon five diene and the styrene, and meanwhile, under the same polymerization condition, the stability of the softening point of petroleum resin can be effectively ensured and the softening point of the petroleum resin is prevented from generating larger fluctuation by ensuring the ratio (D/O) of the diene and the mono-olefin. Meanwhile, the preparation process is simple, the operation is convenient and easy to control, and the defects that the regulation and control range is narrow and the regulation precision is difficult to be effectively ensured when the resin viscosity is regulated by regulating the polymerization temperature or adding the viscosity regulator in the prior art are overcome.
Detailed Description
The invention relates to a preparation method of high-performance polymer resin with controllable melt viscosity, which comprises the following steps:
1) Takes carbon-five diolefin, monoolefin and styrenes as reaction raw materials, and the mass ratio of the carbon-five diolefin is as follows: mono-olefins: styrenes: solvent oil is (1-20): (1-15): (0-10): (1-15) respectively weighing the reaction raw materials and solvent oil, and uniformly mixing;
2) Firstly, pumping a solvent into a reaction kettle, and then adding aluminum trichloride powder or liquid aluminum trichloride accounting for 0.6-3% of the total mass of the reaction materials as a catalyst;
3) After the temperature in the reaction kettle reaches the synthesis temperature of 50-90 ℃, dropwise adding the mixed materials into the reaction kettle by using a metering pump for reaction, controlling the dropwise adding time to be 0.5-2 h, and controlling the reaction pressure to be less than 1Mpa;
4) The reaction time is controlled to be 1-5 h, after the reaction is finished, the reaction is washed for 3-5 times, and then the polymer liquid after washing is subjected to vacuum filtration and steam stripping to obtain the final product. The polymer resin prepared by the method has the gardner color number of 2-5, the softening point of 70-104 ℃ and the melt viscosity of 40-300 cps.
Aiming at the defects that the viscosity of petroleum resin is usually regulated by regulating the polymerization temperature or adding a viscosity regulator in the prior art, the regulating range is smaller, and the viscosity requirement of petroleum resin in various application fields is difficult to meet, the invention innovatively uses the carbon five diene, the mono-olefin and the styrene as reaction raw materials, adopts a low-temperature polymerization process, and can prepare the petroleum resin with various viscosities according to application requirements by regulating the proportion of each reaction raw material, the polymerization temperature, the reaction time and the use amount of the catalyst, thereby meeting the requirements of different application fields. In addition, the invention can realize fine adjustment of the viscosity of the petroleum resin, and has simple adjustment operation, thereby being beneficial to ensuring the quality of the obtained petroleum resin product. Specifically, the invention can prepare various resin products with different viscosities by adjusting the addition amount of the carbon five diene and the styrene so as to meet the use requirements of different application fields, wherein the carbon five diene is one or more of piperylene, isoprene, butadiene and cyclopentadiene, and the viscosity of petroleum resin is obviously influenced by the ratio of trans-1, 3-pentadiene to cis-1, 3-pentadiene in the piperylene and the ratio of isoprene to cis-1, 3-pentadiene. As the ratio between trans-1, 3-pentadiene and cis-1, 3-pentadiene, and between isoprene and cis-1, 3-pentadiene increases, the viscosity of the resulting resin product increases. The presence of styrene reduces the softening point and viscosity of the petroleum resin product. The petroleum resin with different viscosities can be prepared by matching the three components. In addition, the invention can ensure the stability of the softening points of the obtained resin products with different viscosities by strictly controlling the ratio (D/O) of the carbon five diolefin to the monoolefin under the same polymerization condition, and prevent the softening points from greatly fluctuating so as to ensure the quality and the service performance of the obtained resin products.
For a further understanding of the present invention, the present invention will now be described in detail with reference to specific examples. The mono-olefin in the invention is one or more of isobutene, isoamylene, n-pentene and cyclopentene. The styrene is one or more of styrene, alpha-methylstyrene, beta-methylstyrene and styrene derivatives, and the solvent is one or more of benzene, toluene, xylene, trimethylbenzene, pentane, hexane, cyclohexane, heptane, octane, nonane, sunflower, undecane, dodecane, no. 100 solvent oil, no. 200 solvent oil, solvent D40 and solvent D60. The catalyst is aluminum trichloride powder or liquid aluminum trichloride catalyst. With limited space, only a few examples are listed below, and the actual scope of protection is not limited to the following specific examples.
Example 1
150g of piperylene (trans-1, 3-pentadiene: cis-1, 3-pentadiene=1.54), 120g of isopentene and 50g of n-pentane are weighed and mixed uniformly. 100g of n-pentane was then added to the reactor, followed by 4g of aluminum trichloride as catalyst. And after the reaction temperature reaches 55 ℃, dropwise adding the mixed materials by using a metering pump, and controlling the dropwise adding within 30 min. After 1h of reaction, the reaction product was washed 3 times with water. And then the obtained water-washed polymer solution is subjected to steam stripping, decompression and suction filtration to obtain a final product, wherein the softening point of the final product is 95 ℃, the Gardner color number is 2.5, and the melt viscosity of the final product is 80cps at 200 ℃.
Example 2
100g of isoprene, 50g of piperylene, 150g of mono-olefin (mass ratio of isoamylene: cyclopentene: n-pentene=3:1:1) and 100g of solvent (mass ratio of n-pentane: heptane=1:1) are respectively weighed and uniformly mixed, and the trans-1, 3-pentadiene in the reaction ingredients: cis-1, 3-pentadiene = 0.12, isoprene: cis-1, 3-pentadiene = 2.24. 100g of n-pentane was then added to the reactor, followed by 6g of aluminum trichloride as catalyst. After the reaction temperature reaches 60 ℃, adding the mixed materials by a metering pump in a dripping way, and controlling the dripping to be completed within 60 minutes. After 0.5h of reaction, the reaction product was washed with water 5 times. And then the obtained water-washed polymer solution is subjected to steam stripping, decompression and suction filtration to obtain a final product, wherein the softening point of the final product is 95 ℃, the Gardner color number is 3, and the melt viscosity of the final product is 200cps at 200 ℃.
Example 3
Respectively weighing 150g of piperylene, 150g of mono-olefin (mass ratio of isoamylene to cyclopentene to n-pentene=3:1:1), 20g of styrene and 100g of solvent (mass ratio of n-pentane to heptane=1:1), uniformly mixing, and reacting to obtain trans-1, 3-pentadiene in the ingredients: cis-1, 3-pentadiene = 0.93. 100g of n-pentane was then added to the reactor, followed by 6g of aluminum trichloride as catalyst. After the reaction temperature reaches 50 ℃, adding the mixed materials by a metering pump in a dripping way, and controlling the dripping to be completed within 60 minutes. After 0.5h of reaction, the reaction product was washed with water for 4 times. Then the obtained water-washed polymer solution is subjected to steam stripping, decompression and suction filtration to obtain a final product, wherein the softening point of the final product is 75 ℃, the Gardner color number is 3, and the melt viscosity is 55cps at 200 ℃.
Example 4
100g of isoprene, 50g of piperylene, 100g of mono-olefin (mass ratio of isoamylene: cyclopentene: n-pentene=1:1:1) and 100g of solvent (mass ratio of benzene: toluene: xylene=1:1:1) are respectively weighed and uniformly mixed, and trans-1, 3-pentadiene is reacted in a mixture: cis-1, 3-pentadiene = 1.54, isoprene: cis-1, 3-pentadiene = 5.09. Then 100g of n-pentane was added to the reactor followed by 6g of liquid aluminium trichloride as catalyst. After the reaction temperature reaches 50 ℃, adding the mixed materials by a metering pump in a dropwise adding mode, controlling the completion of dropwise adding within 60 minutes, and adding 3g of catalyst once again in the process of dropwise adding the materials. After 2h of reaction, the reaction product was washed with water 5 times. And then the obtained water-washed polymer solution is subjected to steam stripping, decompression and suction filtration to obtain a final product, wherein the softening point of the final product is 101 ℃, the Gardner color number is 4, and the melt viscosity is 280cps at 200 ℃.
Example 5
80g of isoprene, 40g of piperylene, 60g of mono-olefin (mass ratio of isoamylene: cyclopentene: n-pentene=2:1:1), 10g of styrene (mass ratio of styrene: alpha-methylstyrene=1:1) and 100g of solvent (mass ratio of benzene: toluene: xylene=1:1:1) are respectively weighed and uniformly mixed, and the trans-1, 3-pentadiene in the reaction mixture: cis-1, 3-pentadiene = 1.54, isoprene: cis-1, 3-pentadiene = 5.09. Then 100g of n-pentane was added to the reactor followed by 3g of liquid aluminium trichloride as catalyst. After the reaction temperature reaches 70 ℃, adding the mixed materials by a metering pump in a dropwise adding mode, controlling the completion of dropwise adding within 60 minutes, and adding 3g of catalyst once again in the process of dropwise adding the materials. After 2h of reaction, the reaction product is washed with water for 3 times, and then the obtained water-washed polymerization solution is subjected to steam stripping and reduced pressure suction filtration to obtain the final product, wherein the softening point of the final product is 103 ℃, the Gardner color number is No. 4, and the melt viscosity is 210cps at 200 ℃.
Example 6
100g of carbon five-diene (mass ratio of piperylene to isoprene to butadiene: cyclopentadiene=4:2:1:0.5), 100g of mono-olefin (mass ratio of isoamylene to cyclopentene: n-pentene=1:1:1) and 100g of solvent (mass ratio of benzene to toluene to xylene: no. 100 solvent oil=1:1:1:1) are respectively weighed and uniformly mixed, and trans-1, 3-pentadiene is reacted in a mixture: cis-1, 3-pentadiene = 1.54, isoprene: cis-1, 3-pentadiene = 1.28. 100g of n-pentane was then added to the reactor, followed by 3g of aluminum trichloride as catalyst. After the reaction temperature reaches 65 ℃, dropwise adding the mixed materials by using a metering pump, controlling the completion of dropwise adding within 60 minutes, and adding the catalyst twice in the process of dropwise adding the materials, wherein 1.5g of the catalyst is added each time. After the reaction is carried out for 1h, the reaction product is washed with water for 3 times, and then the obtained water-washed polymerization liquid is subjected to steam stripping and reduced pressure suction filtration to obtain the final product, wherein the softening point of the final product is 98 ℃, the Gardner color number is No. 5, and the melt viscosity is 150cps at 200 ℃.
Claims (6)
1. A method for preparing a high-performance polymer resin with controllable melt viscosity, which is characterized by comprising the following steps:
1) The method comprises the steps of taking carbon five diolefin, monoolefin and styrenes as reaction raw materials, respectively weighing the reaction raw materials and solvent oil according to mass ratio, and uniformly mixing, wherein the mass ratio of the reaction raw materials to the solvent oil is that the carbon five diolefin: mono-olefins: styrenes: solvent oil is (1-20): (1-15): (0-10): (1-15); the carbon-five diene is piperylene or the mixture of piperylene and at least one of isoprene, butadiene and cyclopentadiene, and the mass ratio of trans-1, 3-pentadiene to cis-1, 3-pentadiene in piperylene is 0.1-2.0; the mono-olefin is an isoamylene,
2) Firstly, pumping a solvent into a reaction kettle for priming, and then adding a catalyst accounting for 0.6-3% of the total mass of reaction materials;
3) After the temperature in the reaction kettle reaches the synthesis temperature, adding the mixed materials into the reaction kettle for reaction;
4) The reaction time is controlled to be 1-5 h, after the reaction is finished, the reaction is carried out, water washing is carried out, and then the polymer liquid after the water washing is subjected to reduced pressure suction filtration and steam stripping to obtain a final product; the softening point of the obtained resin is 70-104 ℃, the melt viscosity at 200 ℃ is 40-300cps, and the Gardner color number is 2-5.
2. The method for producing a high-performance polymer resin with controllable melt viscosity according to claim 1, wherein: the reaction temperature is controlled between 50 and 90 ℃, and the reaction pressure is controlled to be less than 1Mpa.
3. The method for producing a high-performance polymer resin with controllable melt viscosity according to claim 1, wherein: and 3) adding the mixed materials by a metering pump in a dropwise adding mode, and controlling the completion of dropwise adding within 0.5-2 h.
4. The method for producing a high-performance polymer resin with controllable melt viscosity according to claim 2, wherein: the styrenes are at least one of styrene and styrene derivatives.
5. The method for producing a high-performance polymer resin with controllable melt viscosity according to claim 2, wherein: the solvent is one or more of benzene, toluene, xylene, trimethylbenzene, pentane, hexane, cyclohexane, heptane, octane, nonane, sunflower alkane, undecane, dodecane, no. 100 solvent oil, no. 200 solvent oil, solvent D40 and solvent D60.
6. The method for producing a high-performance polymer resin with controllable melt viscosity according to claim 2, wherein: the catalyst is aluminum trichloride powder or liquid aluminum trichloride catalyst.
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