JP2022016982A - Method for producing petroleum resin - Google Patents
Method for producing petroleum resin Download PDFInfo
- Publication number
- JP2022016982A JP2022016982A JP2020120006A JP2020120006A JP2022016982A JP 2022016982 A JP2022016982 A JP 2022016982A JP 2020120006 A JP2020120006 A JP 2020120006A JP 2020120006 A JP2020120006 A JP 2020120006A JP 2022016982 A JP2022016982 A JP 2022016982A
- Authority
- JP
- Japan
- Prior art keywords
- boron trifluoride
- petroleum resin
- static mixer
- complex catalyst
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003208 petroleum Substances 0.000 title claims abstract description 82
- 239000011347 resin Substances 0.000 title claims abstract description 80
- 229920005989 resin Polymers 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 177
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 89
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 230000003068 static effect Effects 0.000 claims abstract description 41
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 59
- 238000000197 pyrolysis Methods 0.000 abstract 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 32
- 239000002994 raw material Substances 0.000 description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000003446 ligand Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- FXVQIAPSJGBLJJ-UHFFFAOYSA-N butan-1-ol;trifluoroborane Chemical compound FB(F)F.CCCCO FXVQIAPSJGBLJJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- VENBJVSTINLYEU-UHFFFAOYSA-N phenol;trifluoroborane Chemical compound FB(F)F.OC1=CC=CC=C1 VENBJVSTINLYEU-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 241000862969 Stella Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical compound CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- -1 phenol Chemical class 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-PLNGDYQASA-N (3z)-penta-1,3-diene Chemical compound C\C=C/C=C PMJHHCWVYXUKFD-PLNGDYQASA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GUOAPVPPPVLIQQ-UHFFFAOYSA-N dimethyldicyclopentadiene Chemical compound C1=CC2CC1C1C2C(C)C(C)=C1 GUOAPVPPPVLIQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- MVJKXJPDBTXECY-UHFFFAOYSA-N trifluoroborane;hydrate Chemical compound O.FB(F)F MVJKXJPDBTXECY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
Description
本発明は、石油樹脂の製造方法に関するものであり、更に詳しくは、石油樹脂の製造工程中に、三フッ化ホウ素と配位子から三フッ化ホウ素錯体触媒を調製する工程を有することから、重合収率や色相の改善された石油樹脂を製造する方法に関するものである。 The present invention relates to a method for producing a petroleum resin, and more specifically, a step of preparing a boron trifluoride complex catalyst from boron trifluoride and a ligand is included in the process of producing the petroleum resin. It relates to a method for producing a petroleum resin having an improved polymerization yield and hue.
石油類の分解、精製の際に得られる不飽和炭化水素含有留分を原料油として、含酸素有機化合物を配位子とした三フッ化ホウ素錯体触媒の存在下に重合を行い、石油樹脂を製造する方法は工業的に実施されている。その際、三フッ化ホウ素錯体触媒として、市販の三フッ化ホウ素フェノール錯体、三フッ化ホウ素ブタノール錯体などが一般的には用いられる。 The unsaturated hydrocarbon-containing distillate obtained during the decomposition and purification of petroleum is used as a raw material oil, and polymerization is carried out in the presence of a boron trifluoride complex catalyst using an oxygen-containing organic compound as a ligand to obtain a petroleum resin. The method of manufacture is industrially practiced. At that time, as a boron trifluoride complex catalyst, a commercially available boron trifluoride phenol complex, a boron trifluoride butanol complex, or the like is generally used.
そして、重合収率や樹脂色相の改良方法として、複数の配位子から成る三フッ化ホウ素錯体触媒を用いることが提案されている(例えば特許文献1~3参照)。 Then, as a method for improving the polymerization yield and the resin hue, it has been proposed to use a boron trifluoride complex catalyst composed of a plurality of ligands (see, for example, Patent Documents 1 to 3).
また、原料油と配位子の混合物に三フッ化ホウ素ガスを吹き込み、重合反応器内にて三フッ化ホウ素錯体触媒の調製と重合とを同時に実施する、石油樹脂の製造方法が提案されている(例えば特許文献4参照)。 Further, a method for producing a petroleum resin has been proposed in which boron trifluoride gas is blown into a mixture of raw material oil and a ligand, and the preparation and polymerization of a boron trifluoride complex catalyst are simultaneously carried out in a polymerization reactor. (See, for example, Patent Document 4).
しかし、従来、石油樹脂の製造においては、一般的に三フッ化ホウ素錯体触媒を触媒タンクにて長期保管を行うことが必要であった。そして、その際に三フッ化ホウ素錯体触媒の組成や濃度が変化して、触媒活性の低下や樹脂品質の低下に繋がっていた。この課題は、特許文献1~3に提案の複数の配位子から成る三フッ化ホウ素錯体触媒においても解決されないものであった。 However, conventionally, in the production of petroleum resins, it has generally been necessary to store the boron trifluoride complex catalyst in a catalyst tank for a long period of time. At that time, the composition and concentration of the boron trifluoride complex catalyst changed, leading to a decrease in catalytic activity and a decrease in resin quality. This problem has not been solved even in the boron trifluoride complex catalyst composed of a plurality of ligands proposed in Patent Documents 1 to 3.
また、特許文献4に提案の重合器に原料と配位子と三フッ化ホウ素ガスを供給し、三フッ化ホウ素錯体触媒の調製とそれを用いた重合を同時に実施する方法においては、原料中に含まれる水分や不純物なども配位子となり所望しない三フッ化ホウ素錯体を形成するため、目的とする三フッ化ホウ素錯体触媒の収率や純度の低下を誘引し、石油樹脂の収率や品質を低下させる原因となるという課題を有するものであった。 Further, in the method of supplying the raw material, the ligand and the boron trifluoride gas to the polymerizer proposed in Patent Document 4, preparing the boron trifluoride complex catalyst and simultaneously performing the polymerization using the raw material, the raw material is used. Since water and impurities contained in the above also act as ligands to form an undesired boron trifluoride complex, it induces a decrease in the yield and purity of the target boron trifluoride complex catalyst, and the yield of petroleum resin and the like. It had the problem of causing deterioration in quality.
そこで、より重合収率や色相の改善された石油樹脂を製造する方法の出現が切望されていた。 Therefore, the emergence of a method for producing a petroleum resin having an improved polymerization yield and hue has been eagerly desired.
本発明者らは、上記課題に関して、鋭意検討した結果、三フッ化ホウ素錯体触媒を用い石油樹脂を製造する際に、三フッ化ホウ素と含酸素有機化合物とを接触混合し、三フッ化ホウ素錯体触媒を調製する工程を付随した石油樹脂の製造方法とすることにより、高純度の三フッ化ホウ素錯体触媒が得られ、該高純度三フッ化ホウ素錯体触媒により、重合収率や色相の改善された石油樹脂の製造方法となることを見出し、本発明を完成させた。 As a result of diligent studies on the above problems, the present inventors contact-mix boron trifluoride and an oxygen-containing organic compound when producing a petroleum resin using a boron trifluoride complex catalyst, and boron trifluoride. A high-purity boron trifluoride complex catalyst can be obtained by using a method for producing a petroleum resin accompanied by a step of preparing a complex catalyst, and the high-purity boron trifluoride complex catalyst improves the polymerization yield and hue. The present invention has been completed by finding that it is a method for producing a petroleum resin.
即ち、本発明は、三フッ化ホウ素錯体触媒を用い石油類の熱分解及び/又は精製により得られる炭化水素留分より石油樹脂を製造する際に、少なくとも気体状の三フッ化ホウ素1モルに対し、液状の含酸素有機化合物1.0~3.5モルをスタティックミキサーにて気液接触混合し、三フッ化ホウ素錯体触媒を調製する工程、を有する製造方法とすることを特徴とする石油樹脂の製造方法に関するものである。 That is, the present invention makes at least 1 mol of gaseous boron trifluoride when producing a petroleum resin from a hydrocarbon distillate obtained by thermal decomposition and / or purification of petroleum using a boron trifluoride complex catalyst. On the other hand, petroleum is characterized by comprising a step of preparing a boron trifluoride complex catalyst by gas-liquid contact mixing 1.0 to 3.5 mol of a liquid oxygen-containing organic compound with a static mixer. It relates to a resin manufacturing method.
以下に、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の石油樹脂の製造方法は、三フッ化ホウ素錯体触媒を用い炭化水素留分の重合を行い、石油樹脂を製造する際に、少なくとも気体状の三フッ化ホウ素1モルに対し、液状の含酸素有機化合物1.0~3.5モルをスタティックミキサーにて気液接触混合し、三フッ化ホウ素錯体触媒を調製する工程、を有する製造方法とするものである。 In the method for producing a petroleum resin of the present invention, a hydrocarbon distillate is polymerized using a boron trifluoride complex catalyst, and when the petroleum resin is produced, it is liquid with respect to at least 1 mol of gaseous boron trifluoride. The production method comprises a step of preparing a boron trifluoride complex catalyst by gas-liquid catalytic mixing of 1.0 to 3.5 mol of an oxygen-containing organic compound with a static mixer.
ここで、気体状の三フッ化ホウ素とは、常温常圧で気体状を示す三フッ化ホウ素であればよく、その純度としては99wt%以上のものであることが好ましく、特に純度99.5wt%以上のものであることが好ましい。 Here, the gaseous boron trifluoride may be boron trifluoride which is gaseous at normal temperature and pressure, and its purity is preferably 99 wt% or more, and particularly, the purity is 99.5 wt. % Or more is preferable.
また、含酸素有機化合物とは、三フッ化ホウ素錯体触媒において配位子となるものであり、該含酸素有機化合物としては、メタノール,エタノール,1-プロパノール,2-プロパノール,1-ブタノール,2-ブタノール,イソブタノール,t-ブタノール,1-ペンタノール、2-ペンタノール、3-ペンタノール、イソペンタノール、ネオペンチルアルコール、3-メチル-2-ブタノール等のアルコール類、ジメチルエーテル,ジエチルエーテル,ジブチルエーテル,テトラヒドロフラン等のエーテル類、酢酸,プロピオン酸,ヒドロキシ安息香酸,安息香酸等のカルボン酸類、フェノール,アルキルフェノール,レゾルシン,等のフェノール類、等を挙げることができる。 The oxygen-containing organic compound serves as a ligand in the boron trifluoride complex catalyst, and the oxygen-containing organic compound includes methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2. -Alcohols such as butanol, isobutanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, isopentanol, neopentyl alcohol, 3-methyl-2-butanol, dimethyl ether, diethyl ether, Examples thereof include ethers such as dibutyl ether and tetrahydrofuran, carboxylic acids such as acetic acid, propionic acid, hydroxybenzoic acid and benzoic acid, and phenols such as phenol, alkylphenol and resorcin.
三フッ化ホウ素錯体触媒を調製する際の該三フッ化ホウ素と該含酸素有機化合物との割合は、三フッ化ホウ素1モルに対して、含酸素有機化合物1.0~3.5モルの範囲であり、該範囲とすることにより、重合収率に優れ、得られる石油樹脂が色相に優れるものとなる。ここで、含酸素有機化合物のモル比が1.0モル未満である場合、含酸素有機化合物が不足し、錯体を形成しない三フッ化ホウ素が発生してロスとなるばかりか、悪影響を及ぼし得られる石油樹脂は色調に劣るものとなる。一方、3.5モルを超える場合、充分な性能を発現する触媒とはならず、充分な重合収率が得られない。なお、三フッ化ホウ素の供給量は、後述する石油類の熱分解及び/又は精製により得られる炭化水素留分である原料油に対して0.01~1質量%の範囲内とすることが好ましく、特に0.02~0.7質量%の範囲内、さらに0.03~0.5質量%の範囲内とすることが好ましい。 The ratio of the boron trifluoride to the oxygen-containing organic compound in preparing the boron trifluoride complex catalyst is 1.0 to 3.5 mol of the oxygen-containing organic compound with respect to 1 mol of boron trifluoride. It is a range, and by setting the range, the polymerization yield is excellent and the obtained petroleum resin is excellent in hue. Here, when the molar ratio of the oxygen-containing organic compound is less than 1.0 mol, the oxygen-containing organic compound is insufficient, and boron trifluoride that does not form a complex is generated, which not only causes loss but also has an adverse effect. The resulting petroleum resin is inferior in color. On the other hand, if it exceeds 3.5 mol, the catalyst does not exhibit sufficient performance and a sufficient polymerization yield cannot be obtained. The supply amount of boron trifluoride may be in the range of 0.01 to 1% by mass with respect to the raw material oil which is a hydrocarbon fraction obtained by thermal decomposition and / or purification of petroleums described later. It is preferable that the content is preferably in the range of 0.02 to 0.7% by mass, more preferably in the range of 0.03 to 0.5% by mass.
本発明の製造方法においては、三フッ化ホウ素錯体触媒はスタティックミキサーにおいて調製されるものである。その際に、気体状の三フッ化ホウ素と液状の含酸素有機化合物のそれぞれをスタティックミキサーの上流側に供給し、スタティックミキサー入口では気体状の三フッ化ホウ素の連続相に、含酸素有機化合物の液体が分散した状態でスタティックミキサーに供給される。そして、スタティックミキサー内で気液接触混合を繰り返し、出口では液状の三フッ化ホウ素錯体が触媒として調製される。 In the production method of the present invention, the boron trifluoride complex catalyst is prepared in a static mixer. At that time, each of the gaseous boron trifluoride and the liquid oxygen-containing organic compound is supplied to the upstream side of the static mixer, and at the inlet of the static mixer, the oxygen-containing organic compound is added to the continuous phase of the gaseous boron trifluoride. The liquid is supplied to the static mixer in a dispersed state. Then, gas-liquid contact mixing is repeated in the static mixer, and a liquid boron trifluoride complex is prepared as a catalyst at the outlet.
三フッ化ホウ素錯体触媒を調製する際の条件としては、三フッ化ホウ素錯体の調製が可能であれば如何なる条件であってもよく、効率的な三フッ化ホウ素錯体の調製が可能となることからスタティックミキサー入口においては、気体状の三フッ化ホウ素と液状の含酸素有機化合物との混合物の管内流速を0.1~15m/秒とすることが好ましい。また、三フッ化ホウ素と含酸素有機化合物の錯化反応は発熱反応のため、スタティックミキサー出口温度を0~50℃の範囲に保持できる条件、例えば除熱を行うことが好ましい。 The conditions for preparing the boron trifluoride complex catalyst may be any condition as long as the boron trifluoride complex can be prepared, and the boron trifluoride complex can be efficiently prepared. Therefore, at the inlet of the static mixer, the in-pipe flow velocity of the mixture of gaseous boron trifluoride and the liquid oxygen-containing organic compound is preferably 0.1 to 15 m / sec. Further, since the complexing reaction between boron trifluoride and the oxygen-containing organic compound is an exothermic reaction, it is preferable to carry out conditions under which the static mixer outlet temperature can be maintained in the range of 0 to 50 ° C., for example, heat removal.
本発明におけるスタティックミキサーとは、駆動部のないラインミキサーと称されるものであり、気体状の三フッ化ホウ素と液状の含酸素有機化合物の高い気液接触効率を有するものであれば、特に限定されない。そして、スタティックミキサーは、流体の流れを乱すために、1個のスタティックミキサーの内部が複数の部材(以下、「エレメント」という場合がある)で構成されている。例えば、平板を捩ったエレメントを、角度を変えて交互に配置する等して、流体の流れを乱すことができる。スタティックミキサーのエレメント数は、スタティックミキサー出口で液状の三フッ化ホウ素錯体を得ることができれば特に限定されないが、10~40の範囲が好ましい。 The static mixer in the present invention is referred to as a line mixer without a driving unit, and is particularly capable of having high gas-liquid contact efficiency between gaseous boron trifluoride and a liquid oxygen-containing organic compound. Not limited. In the static mixer, the inside of one static mixer is composed of a plurality of members (hereinafter, may be referred to as "elements") in order to disturb the flow of fluid. For example, the elements obtained by twisting the flat plate can be arranged alternately at different angles to disturb the fluid flow. The number of elements of the static mixer is not particularly limited as long as a liquid boron trifluoride complex can be obtained at the outlet of the static mixer, but is preferably in the range of 10 to 40.
さらに、本発明におけるスタティックミキサーは、混合が充分で三フッ化ホウ素の錯化が効率的に進行すると共に、圧力損失の課題が発生しにくいことから内径(d)と長さ(L)との比(L/d)が2~200であることが好ましく、5~100であることがより好ましい。 Further, in the static mixer of the present invention, since the mixing is sufficient, the complexation of boron trifluoride proceeds efficiently, and the problem of pressure loss is unlikely to occur, the inner diameter (d) and the length (L) are different. The ratio (L / d) is preferably 2 to 200, more preferably 5 to 100.
スタティックミキサーにより調製された三フッ化ホウ素錯体触媒をそのままで、石油樹脂の製造方法に適用(in situ)する製造方法、例えば石油類の熱分解及び/又は精製により得られる炭化水素留分を原料油とした重合反応に、上記した三フッ化ホウ素錯体触媒の調製工程を付随・適用することにより、分子量、軟化点、色相に優れる石油樹脂を生産効率よく製造することができる。 A production method in which the boron trifluoride complex catalyst prepared by a static mixer is applied as it is to a method for producing petroleum resin, for example, a hydrocarbon fraction obtained by thermal decomposition and / or purification of petroleum is used as a raw material. By accompanying and applying the above-mentioned preparation step of the boron trifluoride complex catalyst to the polymerization reaction using oil, a petroleum resin having excellent molecular weight, softening point, and hue can be produced efficiently.
その際の原料油としては、例えば石油類の熱分解及び/又は精製により得られる、沸点範囲20~110℃のC5留分、沸点範囲140~280℃のC9留分、等を挙げることができる。 Examples of the raw material oil at that time include a C5 fraction having a boiling point range of 20 to 110 ° C., a C9 fraction having a boiling point range of 140 to 280 ° C., and the like, which are obtained by thermal decomposition and / or refining of petroleums. ..
該C5留分としては、一般的に石油類の熱分解及び/又は精製により得られる沸点範囲20~110℃の留分として知られているものであれば如何なるものを用いることも可能であり、例えばイソプレン、トランス-1,3-ペンタジエン、シス-1,3-ペンタジエン、シクロペンタジエン、メチルシクロペンタジエン等に代表される炭素数4~6の共役ジオレフィン性不飽和炭化水素類;ブテン、2-メチル-1-ブテン、2-メチル-2-ブテン、1-ペンテン、2-ペンテン、シクロペンテン等に代表される炭素数4~6のモノオレフィン性不飽和炭化水素類;シクロペンタン、2-メチルペンタン、3-メチルペンタン、n-ヘキサン等の脂肪族系飽和炭化水素;これらの混合物、等が挙げられる。 As the C5 distillate, any distillate generally known as a distillate having a boiling point range of 20 to 110 ° C. obtained by thermal decomposition and / or refining of petroleum can be used. Conjugated diolefinically unsaturated hydrocarbons having 4 to 6 carbon atoms represented by isoprene, trans-1,3-pentadiene, cis-1,3-pentadiene, cyclopentadiene, methylcyclopentadiene, etc .; butene, 2- Monoolefinically unsaturated hydrocarbons having 4 to 6 carbon atoms represented by methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, cyclopentene and the like; cyclopentane, 2-methylpentane , 3-Methylpentane, n-hexane and other aliphatic saturated hydrocarbons; mixtures thereof, and the like.
該C9留分としては、一般的に石油類の熱分解及び/又は精製により得られる沸点範囲140~280℃の留分として知られているものであれば如何なるものを用いることも可能であり、例えばスチレン、α-メチルスチレン、β-メチルスチレン、ビニルトルエン、インデン、インデンのアルキル誘導体等に代表される炭素数8~10のビニル芳香族炭化水素類;炭素数10以上のオレフィン類;炭素数9以上の飽和芳香族類;ジシクロペンタジエン、メチルジシクロペンタジエン、ジメチルジシクロペンタジエン等のジシクロペンタジエン類;これらの混合物、等が挙げられる。 As the C9 fraction, any fraction generally known as a fraction having a boiling point range of 140 to 280 ° C. obtained by thermal decomposition and / or refining of petroleum can be used. For example, vinyl aromatic hydrocarbons having 8 to 10 carbon atoms represented by alkyl derivatives such as styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, indene, and indene; olefins having 10 or more carbon atoms; carbon atoms. 9 or more saturated aromatics; dicyclopentadiene such as dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene; mixtures thereof, and the like.
該原料油として、該C5留分を主成分として用いた場合、得られる石油樹脂は脂肪族系石油樹脂と称されるものとなる。また、該C9留分を主成分として用いた場合、得られる石油樹脂は芳香族系石油樹脂と称されるものとなる。該C5留分と該C9留分の混合物(その際の混合割合は任意である。)を用いた場合、得られる石油樹脂は脂肪族/芳香族系石油樹脂と称されるものとなる。 When the C5 fraction is used as the main component of the raw material oil, the obtained petroleum resin is referred to as an aliphatic petroleum resin. When the C9 fraction is used as a main component, the obtained petroleum resin is called an aromatic petroleum resin. When a mixture of the C5 fraction and the C9 fraction (the mixing ratio at that time is arbitrary) is used, the obtained petroleum resin is referred to as an aliphatic / aromatic petroleum resin.
そして、石油樹脂を製造する際には、スタティックミキサーを用いて気体状の三フッ化ホウ素と液状の含酸素有機化合物とから三フッ化ホウ素錯体触媒を調製し、原料油に対して供給し、重合を行うこと以外の如何なる制限を受けることはなく、例えば原料油に該三フッ化ホウ素錯体触媒を加え加熱し重合することにより石油樹脂を製造することができる。その際の重合温度としては、任意であり、特に色相に優れる石油樹脂を生産効率よく製造できることから、0~100℃が好ましく、特に0~80℃であることが好ましい。重合時間としては、0.1~10時間の範囲が好ましい。反応圧力は大気圧~1MPaが好ましい。また、特に生産効率に優れる製造方法となることから、スタティックミキサーを用いて気体状の三フッ化ホウ素と液状の含酸素有機化合物とから連続的に三フッ化ホウ素錯体触媒を調製すると共に、重合反応場に連続的に供給する原料油に対して連続的に供給し、重合反応を行う連続製造方法とすることが好ましい。 Then, when producing the petroleum resin, a boron trifluoride complex catalyst is prepared from gaseous boron trifluoride and a liquid oxygen-containing organic compound using a static mixer, and supplied to the raw material oil. It is not subject to any restrictions other than the polymerization, and for example, a petroleum resin can be produced by adding the boron trifluoride complex catalyst to the raw material oil, heating the mixture, and polymerizing the oil. The polymerization temperature at that time is arbitrary, and is preferably 0 to 100 ° C., particularly preferably 0 to 80 ° C., because a petroleum resin having an excellent hue can be produced with high production efficiency. The polymerization time is preferably in the range of 0.1 to 10 hours. The reaction pressure is preferably atmospheric pressure to 1 MPa. In addition, since it is a production method with particularly excellent production efficiency, a boron trifluoride complex catalyst is continuously prepared from gaseous boron trifluoride and a liquid oxygen-containing organic compound using a static mixer, and polymerization is performed. It is preferable to use a continuous production method in which the feedstock oil continuously supplied to the reaction field is continuously supplied and the polymerization reaction is carried out.
本発明の石油樹脂の製造方法においては、重合反応後は、塩基による中和処理により触媒を除去し、溶媒及び未反応モノマーを留去して石油樹脂として回収・製造することが来出る。 In the method for producing a petroleum resin of the present invention, after the polymerization reaction, the catalyst is removed by a neutralization treatment with a base, and the solvent and the unreacted monomer are distilled off to recover and produce the petroleum resin.
そして、得られる石油樹脂は、色相および重合収率に優れることを特徴とするものであり、特に色相10以下、全モノマーの重合収率が40%以上であることが好ましい。また、軟化点60~160℃、特に70~150℃を有するものであることが好ましい。特に加工性に優れるものとなることから重量平均分子量(Mw)500~5000である石油樹脂が好ましい。 The obtained petroleum resin is characterized by being excellent in hue and polymerization yield, and it is particularly preferable that the hue is 10 or less and the polymerization yield of all the monomers is 40% or more. Further, it preferably has a softening point of 60 to 160 ° C, particularly 70 to 150 ° C. In particular, a petroleum resin having a weight average molecular weight (Mw) of 500 to 5000 is preferable because it is excellent in processability.
スタティックミキサーを用い気体状の三フッ化ホウ素と液状の含酸素有機化合物から三フッ化ホウ素錯体触媒を調製する工程を有することから、高純度の三フッ化ホウ素錯体触媒の調製と石油樹脂の製造を一貫して実施することで、重合収率、樹脂色相の優れる石油樹脂を製造することができる。 Since it has a step of preparing a boron trifluoride complex catalyst from gaseous boron trifluoride and a liquid oxygen-containing organic compound using a static mixer, preparation of a high-purity boron trifluoride complex catalyst and production of petroleum resin By consistently carrying out the above, it is possible to produce a petroleum resin having excellent polymerization yield and resin hue.
以下、本発明を実施例により説明するが、本発明はこれらの実施例により何ら制限を受けるものではない。尚、実施例、比較例において用いた原料油、得られた石油樹脂の分析方法は下記の通りである。 Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. The methods for analyzing the raw material oil and the obtained petroleum resin used in Examples and Comparative Examples are as follows.
<原料油>
ナフサの分解・精製により得られた沸点範囲140~280℃のC9留分(表1)、沸点範囲20~110℃のC5留分(表2)のそれぞれの組成を表1~2に示す。なお、表1~2中のDCPDはジシクロペンタジエン、CPDはシクロペンタジエンの略記である。
<Raw material oil>
Tables 1 and 2 show the compositions of the C9 fraction having a boiling point range of 140 to 280 ° C. (Table 1) and the C5 fraction having a boiling point range of 20 to 110 ° C. (Table 2) obtained by decomposing and purifying naphtha. In Tables 1 and 2, DCPD is an abbreviation for dicyclopentadiene and CPD is an abbreviation for cyclopentadiene.
<三フッ化ホウ素錯体触媒及びその原料>
三フッ化ホウ素:(ステラケミファ(株)製)、純度99.7%
三フッ化ホウ素フェノール錯体:三フッ化ホウ素30重量%(ステラケミファ(株)製)。
三フッ化ホウ素ブタノール錯体:三フッ化ホウ素30重量%(ステラケミファ(株)製)。
フェノール:(和光純薬(株)製、試薬特級)。
1-ブタノール:(和光純薬(株)製、試薬特級)。
2-プロパノール:(和光純薬(株)製、試薬特級)。
<Boron trifluoride complex catalyst and its raw materials>
Boron trifluoride: (manufactured by Stella Chemipha Co., Ltd.), purity 99.7%
Boron trifluoride phenol complex: 30% by weight boron trifluoride (manufactured by STELLA CHEMIFA CO., LTD.).
Boron trifluoride butanol complex: 30% by weight of boron trifluoride (manufactured by STELLA CHEMIFA CO., LTD.).
Phenol: (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent).
1-Butanol: (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent).
2-propanol: (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent).
~分析方法~
<各原料油中の成分分析>
JIS K-0114(2000年)に準拠してガスクロマトグラフ法を用いて分析した。
<重合収率の測定>
仕込み原料と重合後に得られる石油樹脂の重量を秤量し、原料に対する石油樹脂の比率を重合収率とした。
<重量平均分子量(Mw)の測定>
ポリスチレンを標準物質とし、JIS K-0124(1994年)に準拠してゲル浸透クロマトグラフィーにより測定した。
<軟化点の測定>
JIS K-2531(1960)(環球法)に準拠した方法で測定した。
<色相(ガードナー)の測定>
得られた石油樹脂を50重量%トルエン溶液として、ASTM D-1544-63Tに従って測定した。
~ Analysis method ~
<Analysis of components in each raw material oil>
Analysis was performed using a gas chromatograph method according to JIS K-0114 (2000).
<Measurement of polymerization yield>
The weights of the charged raw material and the petroleum resin obtained after the polymerization were weighed, and the ratio of the petroleum resin to the raw material was taken as the polymerization yield.
<Measurement of weight average molecular weight (Mw)>
Polystyrene was used as a standard material, and the measurement was performed by gel permeation chromatography according to JIS K-0124 (1994).
<Measurement of softening point>
The measurement was carried out by a method according to JIS K-2531 (1960) (ring ball method).
<Measurement of hue (Gardner)>
The obtained petroleum resin was measured as a 50 wt% toluene solution according to ASTM D-1544-63T.
実施例1
上流部にガス供給口と混合槽を設置した液体供給口とを有するスタティックミキサーと共に、別途原料油の混合槽をも設置する重合槽を有し、さらに該重合槽の下流部には重合反応後の重合液を中和するための中和槽、及びその後の未反応油を蒸留除去するための濃縮器のそれぞれを有する連続製造装置にて石油樹脂の製造を行った。
Example 1
A static mixer having a gas supply port and a liquid supply port having a mixing tank installed in the upstream portion has a polymerization tank in which a mixing tank for raw material oil is separately installed, and a polymerization tank is further installed in the downstream portion of the polymerization tank after the polymerization reaction. The petroleum resin was produced by a continuous production apparatus having a neutralization tank for neutralizing the polymerized liquid and a concentrator for distilling and removing the unreacted oil thereafter.
スタティックミキサーのガス供給口に三フッ化ホウ素を0.75g/分(11mmol/分)で供給すると共に、フェノールを1.96g/分(21mmol/分)、1-ブタノール0.45g/分(6mmol/分)を混合槽に供給し混合液を2.41g/分の条件にてスタティックミキサーA(L/D=100mm/3.4mm=29、エレメント数17)に供給し、三フッ化ホウ素錯体の調製を行った。その際の条件を表3に示す通りとすると共に、スタティックミキサーの出口温度は冷却により25℃とした。スタティックミキサー出口からは三フッ化ホウ素錯体の均一液体が吐出され、三フッ化ホウ素錯体触媒として3.16g/分で重合槽へ供給した。 Boron trifluoride is supplied to the gas supply port of the static mixer at 0.75 g / min (11 mmol / min), phenol is 1.96 g / min (21 mmol / min), and 1-butanol is 0.45 g / min (6 mmol). / Min) is supplied to the mixing tank, and the mixed solution is supplied to the static mixer A (L / D = 100 mm / 3.4 mm = 29, number of elements 17) under the condition of 2.41 g / min to form a boron trifluoride complex. Was prepared. The conditions at that time were as shown in Table 3, and the outlet temperature of the static mixer was set to 25 ° C. by cooling. A uniform liquid of the boron trifluoride complex was discharged from the outlet of the static mixer and supplied to the polymerization tank at 3.16 g / min as a boron trifluoride complex catalyst.
一方、表2に示すC5留分を192g/分と表1に示すC9留分を108g/分の条件にて原料油の混合槽に供給し混合原料油とし、該混合原料を300g/分で重合槽へ供給することにより石油樹脂の重合を行った。その際、重合温度を40℃、滞留時間を2時間とした。 On the other hand, the C5 fraction shown in Table 2 was supplied to the mixing tank of the raw material oil under the conditions of 192 g / min and the C9 fraction shown in Table 1 was 108 g / min to prepare the mixed raw material oil, and the mixed raw material was used at 300 g / min. The petroleum resin was polymerized by supplying it to the polymerization tank. At that time, the polymerization temperature was set to 40 ° C. and the residence time was set to 2 hours.
そして、重合後の重合液を303.16g/分で連続的に重合槽から中和槽に移送し、苛性ソーダ水溶液を添加して中和した後、濃縮器に移送し油相の未反応油を蒸留して石油樹脂を得た。得られた石油樹脂の物性を表3に示す。重合収率は41%であり、色相も8と優れるものであった。 Then, the polymerized liquid after polymerization is continuously transferred from the polymerization tank to the neutralization tank at 303.16 g / min, neutralized by adding a caustic soda aqueous solution, and then transferred to a concentrator to remove unreacted oil in the oil phase. Distillation was performed to obtain petroleum resin. Table 3 shows the physical characteristics of the obtained petroleum resin. The polymerization yield was 41%, and the hue was also excellent at 8.
比較例1
スタティックミキサーを用いず、三フッ化ホウ素錯体触媒3.16g/分の代わりに、30%三フッ化ホウ素フェノール錯体2.81g/分および30%三フッ化ホウ素ブタノール錯体0.65g/分の混合物を3.51g/分で重合槽へ供給し、重合液を303.46g/分で連続的に重合槽から中和槽に移送した以外は、実施例1と同様の方法にて石油樹脂の製造を行った。得られた石油樹脂の物性を表4に示す。重合収率は38%と低く、色相は11と悪いものであった。
Comparative Example 1
A mixture of 30% boron trifluoride phenol complex 2.81 g / min and 30% boron trifluoride butanol complex 0.65 g / min instead of the boron trifluoride complex catalyst 3.16 g / min without a static mixer. Was supplied to the polymerization tank at 3.51 g / min, and the polymerization solution was continuously transferred from the polymerization tank to the neutralization tank at 303.46 g / min. Was done. Table 4 shows the physical characteristics of the obtained petroleum resin. The polymerization yield was as low as 38%, and the hue was as bad as 11.
実施例2
三フッ化ホウ素、フェノール、1-ブタノールの供給量、スタティックミキサーの条件を表3に示すものとすると共に、三フッ化ホウ素錯体触媒の供給量を4.755g/分とし、C9留分、C5留分の供給量を表3に示すものするとともに、重合槽からの移送量を454.755g/分とした以外は、実施例1と同様の方法により石油樹脂を製造した。得られた石油樹脂の物性を表3に示す。重合収率は40%であり、色相7と良好であった。
Example 2
Table 3 shows the supply amounts of boron trifluoride, phenol, and 1-butanol, and the conditions of the static mixer. The supply amount of the boron trifluoride complex catalyst is 4.755 g / min, and the C9 fraction and C5 are used. A petroleum resin was produced by the same method as in Example 1 except that the supply amount of the distillate was shown in Table 3 and the transfer amount from the polymerization tank was 454.755 g / min. Table 3 shows the physical characteristics of the obtained petroleum resin. The polymerization yield was 40%, which was good with a hue of 7.
比較例2
スタティックミキサーを用いず、三フッ化ホウ素錯体触媒4.755g/分の代わりに、30%三フッ化ホウ素フェノール錯体4.21g/分および30%三フッ化ホウ素ブタノール錯体0.97g/分の混合物を5.18g/分で重合槽へ供給し、重合液を455.18g/分で連続的に重合槽から中和槽に移送した以外は、実施例2と同様の方法により石油樹脂を製造した。得られた石油樹脂の物性を表4に示す。重合収率は36%と低く、色相11と悪いものであった。
Comparative Example 2
A mixture of 30% boron trifluoride phenol complex 4.21 g / min and 30% boron trifluoride butanol complex 0.97 g / min instead of the boron trifluoride complex catalyst 4.755 g / min without a static mixer. Was supplied to the polymerization tank at 5.18 g / min, and the polymerization solution was continuously transferred from the polymerization tank to the neutralization tank at 455.18 g / min, but the petroleum resin was produced by the same method as in Example 2. .. Table 4 shows the physical characteristics of the obtained petroleum resin. The polymerization yield was as low as 36%, and the hue was as bad as 11.
実施例3
スタティックミキサーB(L/D=310mm/9mm=34、エレメント数18)とし、三フッ化ホウ素、フェノール、1-ブタノールの供給量、スタティックミキサーの条件を表3に示すものとすると共に、三フッ化ホウ素錯体触媒の供給量を444g/分とし、C9留分、C5留分の供給量を表3に示すものするとともに、重合槽からの移送量を42444g/分とした以外は、実施例1と同様の方法により石油樹脂を製造した。得られた石油樹脂の物性を表3に示す。重合収率は42%であり、色相は7と良好であった。
Example 3
The static mixer B (L / D = 310 mm / 9 mm = 34, number of elements 18) is used, and the supply amounts of boron trifluoride, phenol, and 1-butanol, and the conditions of the static mixer are shown in Table 3, and three hooks are used. Example 1 except that the supply amount of the boron trifluoride complex catalyst was 444 g / min, the supply amounts of the C9 fraction and the C5 distillate were shown in Table 3, and the transfer amount from the polymerization tank was 42444 g / min. Petroleum resin was produced by the same method as above. Table 3 shows the physical characteristics of the obtained petroleum resin. The polymerization yield was 42%, and the hue was as good as 7.
実施例4
三フッ化ホウ素、フェノール、1-ブタノールの供給量、スタティックミキサーの条件を表3に示すものとすると共に、三フッ化ホウ素錯体触媒の供給量を1.8g/分とし、C9留分、C5留分の供給量を表3に示すものするとともに、重合槽からの移送量を301.8g/分とした以外は、実施例1と同様の方法により石油樹脂を製造した。得られた石油樹脂の物性を表3に示す。重合収率は42%であり、色相は8と良好であった。
Example 4
Table 3 shows the supply amounts of boron trifluoride, phenol, and 1-butanol, and the conditions of the static mixer. The supply amount of the boron trifluoride complex catalyst is 1.8 g / min, and the C9 fraction and C5 are used. A petroleum resin was produced by the same method as in Example 1 except that the supply amount of the distillate was shown in Table 3 and the transfer amount from the polymerization tank was 301.8 g / min. Table 3 shows the physical characteristics of the obtained petroleum resin. The polymerization yield was 42%, and the hue was as good as 8.
実施例5
三フッ化ホウ素、フェノール、1-ブタノールの供給量、スタティックミキサーの条件を表3に示すものとすると共に、三フッ化ホウ素錯体触媒の供給量を3.98g/分とし、C9留分、C5留分の供給量を表3に示すものするとともに、重合槽からの移送量を303.98g/分とした以外は、実施例1と同様の方法により石油樹脂を製造した。得られた石油樹脂の物性を表3に示す。重合収率は40%であり、色相は7と良好であった。
Example 5
Table 3 shows the supply amounts of boron trifluoride, phenol, and 1-butanol, and the conditions of the static mixer. The supply amount of the boron trifluoride complex catalyst is 3.98 g / min, and the C9 fraction and C5 are used. A petroleum resin was produced by the same method as in Example 1 except that the supply amount of the distillate was shown in Table 3 and the transfer amount from the polymerization tank was 303.98 g / min. Table 3 shows the physical characteristics of the obtained petroleum resin. The polymerization yield was 40%, and the hue was as good as 7.
実施例6
三フッ化ホウ素、フェノール、2-プロパノールの供給量、スタティックミキサーの条件を表3に示すものとすると共に、三フッ化ホウ素錯体触媒の供給量を3.08g/分とし、C9留分、C5留分の供給量を表3に示すものするとともに、重合槽からの移送量を303.08g/分とした以外は、実施例1と同様の方法により石油樹脂を製造した。得られた石油樹脂の物性を表3に示す。重合収率は42%であり、色相は8と良好であった。
Example 6
Table 3 shows the supply amounts of boron trifluoride, phenol, and 2-propanol, and the conditions of the static mixer. The supply amount of the boron trifluoride complex catalyst is 3.08 g / min, and the C9 fraction and C5 are used. A petroleum resin was produced by the same method as in Example 1 except that the supply amount of the distillate was shown in Table 3 and the transfer amount from the polymerization tank was 303.08 g / min. Table 3 shows the physical characteristics of the obtained petroleum resin. The polymerization yield was 42%, and the hue was as good as 8.
比較例3
三フッ化ホウ素、フェノール、1-ブタノールの供給量、スタティックミキサーの条件を表4に示すものとすると共に、三フッ化ホウ素錯体触媒の供給量を1.62g/分とし、C9留分、C5留分の供給量を表4に示すものするとともに、重合槽からの移送量を301.62g/分とした以外は、実施例1と同様の方法により石油樹脂を製造した。得られた石油樹脂の物性を表4に示す。重合収率は33%であり、色相は11と悪いものであった。
Comparative Example 3
Table 4 shows the supply amounts of boron trifluoride, phenol, and 1-butanol, and the conditions of the static mixer. The supply amount of the boron trifluoride complex catalyst is 1.62 g / min, and the C9 fraction and C5 are used. A petroleum resin was produced by the same method as in Example 1 except that the supply amount of the distillate was shown in Table 4 and the transfer amount from the polymerization tank was 301.62 g / min. Table 4 shows the physical characteristics of the obtained petroleum resin. The polymerization yield was 33%, and the hue was as bad as 11.
比較例4
三フッ化ホウ素、フェノール、1-ブタノールの供給量、スタティックミキサーの条件を表4に示すものとすると共に、三フッ化ホウ素錯体触媒の供給量を4.44g/分とし、C9留分、C5留分の供給量を表4に示すものするとともに、重合槽からの移送量を304.44g/分とした以外は、実施例1と同様の方法により石油樹脂を製造した。得られた石油樹脂の物性を表4に示す。重合収率は30%であり、色相は12と悪いものであった。
Comparative Example 4
Table 4 shows the supply amounts of boron trifluoride, phenol, and 1-butanol, and the conditions of the static mixer. The supply amount of the boron trifluoride complex catalyst is 4.44 g / min, and the C9 fraction and C5 are used. A petroleum resin was produced by the same method as in Example 1 except that the supply amount of the distillate was shown in Table 4 and the transfer amount from the polymerization tank was 304.44 g / min. Table 4 shows the physical characteristics of the obtained petroleum resin. The polymerization yield was 30%, and the hue was as bad as 12.
比較例5
スタティックミキサーを用いずに、三フッ化ホウ素、フェノール、1-ブタノール、C9留分、C5留分を重合槽に同時に供給した以外は、実施例3と同じ条件で石油樹脂を製造した。得られた石油樹脂は、重合収率は40%であり、色相は12と悪いものであった。原料油中に含まれる水と三フッ化ホウ素が、色相を悪化させる三フッ化ホウ素-水錯体を副生したためと推定した。
Comparative Example 5
A petroleum resin was produced under the same conditions as in Example 3 except that boron trifluoride, phenol, 1-butanol, a C9 fraction, and a C5 fraction were simultaneously supplied to the polymerization tank without using a static mixer. The obtained petroleum resin had a polymerization yield of 40% and a hue as poor as 12. It is presumed that the water and boron trifluoride contained in the raw material oil produced a boron trifluoride-water complex that deteriorates the hue.
本発明によれば、調製直後の高純度の三フッ化ホウ素錯体触媒を石油樹脂の製造に利用することが可能になり、重合収率や樹脂色相が大幅に改善される。本技術を石油樹脂プロセスに応用することで原料原単位の低減、樹脂品質の改善が図られ、その産業的価値は極めて高いものである。 According to the present invention, a high-purity boron trifluoride complex catalyst immediately after preparation can be used for producing a petroleum resin, and the polymerization yield and the resin hue are significantly improved. By applying this technology to the petroleum resin process, the raw material basic unit can be reduced and the resin quality can be improved, and its industrial value is extremely high.
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020120006A JP2022016982A (en) | 2020-07-13 | 2020-07-13 | Method for producing petroleum resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020120006A JP2022016982A (en) | 2020-07-13 | 2020-07-13 | Method for producing petroleum resin |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2022016982A true JP2022016982A (en) | 2022-01-25 |
Family
ID=80185685
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2020120006A Pending JP2022016982A (en) | 2020-07-13 | 2020-07-13 | Method for producing petroleum resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2022016982A (en) |
-
2020
- 2020-07-13 JP JP2020120006A patent/JP2022016982A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPH01284586A (en) | Selective catalytic hydrogenation of usually gaseous raw material containing ethylene and acetylene in liquid phase | |
TW574240B (en) | Deactivation and recovery of boron trifluoride in the preparation of polyisobutenes | |
TW201938594A (en) | Method for producing hydrocarbon resins and hydrogenation products thereof | |
JP4264416B2 (en) | Anionic polymerization method | |
WO2019040549A1 (en) | Process to produce blown asphalt | |
TW200936565A (en) | Process for purification of an aqueous phase containing polyaromatics | |
JP2022016982A (en) | Method for producing petroleum resin | |
EP1980575B1 (en) | A method of gel inhibition for the homopolymerization or copolymerization process of conjugated diene | |
JP2019007003A (en) | Polymerization initiation system and method for manufacturing high reactive olefin functional polymer | |
CN107325228A (en) | A kind of tetrahydroindene is modified the preparation method of C 9 petroleum resin | |
US4113931A (en) | Process for the continuous production of indene resins | |
CN107879873B (en) | Method and device for producing ethylene and propylene from n-butane | |
CN101497569A (en) | Method for synthesizing allyl alcohol polyethenoxy ether metacrylic acid ester | |
JP6083196B2 (en) | Catalyst for producing petroleum resin and method for producing petroleum resin using the same | |
EP1608722A1 (en) | Integrated process for the production of olefin derivatives | |
JP6326749B2 (en) | Catalyst for producing petroleum resin and method for producing petroleum resin using the same | |
JP6179095B2 (en) | Catalyst for producing petroleum resin and method for producing petroleum resin using the same | |
EP3395792B1 (en) | Method for producing methyl tertiary-butyl ether | |
US7041862B2 (en) | Thermal cracking of Diels-Alder adducts | |
CN107879875B (en) | Method and device for producing ethylene and propylene from propane | |
US20230048953A1 (en) | Naphtha catalytic cracking process | |
JPS63260913A (en) | Manufacture of cyclopentadiene petroleum resin with high softening point | |
JP6326734B2 (en) | Catalyst for producing petroleum resin and method for producing petroleum resin using the same | |
JP6194648B2 (en) | Catalyst for producing petroleum resin and method for producing petroleum resin using the same | |
CN117843458A (en) | Cracking carbon four antioxidant and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230614 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20240315 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240326 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240408 |