JPH02215802A - Production of decolored petroleum resin - Google Patents
Production of decolored petroleum resinInfo
- Publication number
- JPH02215802A JPH02215802A JP3621589A JP3621589A JPH02215802A JP H02215802 A JPH02215802 A JP H02215802A JP 3621589 A JP3621589 A JP 3621589A JP 3621589 A JP3621589 A JP 3621589A JP H02215802 A JPH02215802 A JP H02215802A
- Authority
- JP
- Japan
- Prior art keywords
- petroleum resin
- hydrogenation
- hydrogenated
- reaction
- catalyst
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 73
- 239000011347 resin Substances 0.000 title claims abstract description 73
- 239000003208 petroleum Substances 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 52
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 22
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004042 decolorization Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- -1 printing Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (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)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、石油樹脂を水素化することにより脱色した脱
色石油樹脂の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a decolorized petroleum resin, which is obtained by hydrogenating a petroleum resin.
更に詳しくは、水素化反応時、メチルシクロヘキサン及
び／またはエチルシクロヘキサンから選ばれた溶媒を用
いることにより水添脱色を効率的に行うことを特徴とす
る脱色石油樹脂の製造方法に関する。More specifically, the present invention relates to a method for producing a decolorized petroleum resin, characterized in that hydrogen decolorization is efficiently carried out by using a solvent selected from methylcyclohexane and/or ethylcyclohexane during the hydrogenation reaction.
石油樹脂は、−船釣には石油類の熱分解等により得られ
る分解油留分に含まれるジオレフィン類、モノオレフィ
ン類などの重合性勧賞を、フリーデルクラフト型触媒の
存在下、カチオン重合させるか、あるいはラジカル重合
法、熱重合法により製造される。これらの石油樹脂は粘
着性、接着性、他樹脂との相溶性などに特異な物性を有
する機能性樹脂として、各種の樹脂類、ゴム、油性物質
に混溶され、塗料、印刷、インキ、トラフィックペイン
ト、接着剤、粘着剤等の広い用途に用いられている。Petroleum resins are produced by cationically polymerizing polymerizable compounds such as diolefins and monoolefins contained in cracked oil fractions obtained by thermal decomposition of petroleum in the presence of Friedel-Crafts catalysts. Alternatively, it can be produced by radical polymerization or thermal polymerization. These petroleum resins are functional resins with unique physical properties such as tackiness, adhesion, and compatibility with other resins, and are mixed with various resins, rubbers, and oil-based substances, and are used in paints, printing, inks, and traffic. It is used in a wide range of applications such as paints, adhesives, and adhesives.
石油樹脂はもともと淡黄色ないしは淡褐色の色相を有し
ている。Petroleum resins originally have a pale yellow or light brown hue.
石油樹脂とその分子骨格中の不飽和二重結合を水素化す
ることにより脱色できることは公知であり、透明性を要
求される紙オムツ、生理用品用のホットメルト接着、粘
着剤、食品包装用の粘着剤、ＰＰフィルム用改質剤等に
は水素化した脱色石油樹脂が好んで用いられており、近
年これら分野の需要はさらに増加する傾向にある。It is well known that petroleum resins can be decolored by hydrogenating the unsaturated double bonds in their molecular skeletons, and can be used for disposable diapers that require transparency, hot melt adhesives for sanitary products, pressure-sensitive adhesives, and food packaging. Hydrogenated decolorized petroleum resins are preferably used as adhesives, modifiers for PP films, and the like, and demand in these fields has been on the rise in recent years.
また、水素化した脱色石油樹脂は熱安定性、耐候性も改
善されるという利点を有している。Additionally, hydrogenated decolorized petroleum resins have the advantage of improved thermal stability and weather resistance.
しかしながら、石油樹脂の分子量は４００〜ｔｏｏｏ。 However, the molecular weight of petroleum resin is 400 to too much.
程度と大きいこと、あるいは石油樹脂中には５０〜１０
００ｐｐＬ１ もの水素化反応用触媒の触媒毒になる硫
黄が含まれているために、水素化反応を行うには高温、
高圧の非常に厳しい反応条件を一般的に採用しなければ
ならない。degree and large, or 50 to 10 in petroleum resin.
Because it contains 00ppL1 of sulfur, which poisons the hydrogenation reaction catalyst, high temperatures and high temperatures are required to carry out the hydrogenation reaction.
Very harsh reaction conditions at high pressures generally have to be employed.
他方、低温、低圧の穏和な反応条件で水素化を行うには
、多量の触媒の使用か、長時間の反応時間を必要とする
という問題点がある。On the other hand, hydrogenation under mild reaction conditions at low temperature and low pressure requires the use of a large amount of catalyst or a long reaction time.
石油樹脂の水素化反応においては、シクロヘキサン、ヘ
プタン、ヘキサン等の通常の飽和炭化水素が溶媒として
一般的に使用されているが、これらの溶媒を用いた場合
、穏和な条件下での効率的な水添脱色がむづかしい。In the hydrogenation reaction of petroleum resins, ordinary saturated hydrocarbons such as cyclohexane, heptane, and hexane are generally used as solvents. Hydrogenation decolorization is difficult.
［課題を解決するための手段〕
本発明者らは、できるだけ穏和な反応条件で、更に少な
い触媒使用量で石油樹脂の水素化反応による脱色が可能
な方法を鋭意検討した結果、意外にも、石油樹脂を水素
加圧下、水素化触媒で水添脱色するに際し、特定の溶媒
中で水素化反応を行うことにより前記の問題点を解決で
きることを見い出し本発明を完成させた。[Means for Solving the Problems] As a result of intensive study by the present inventors on a method capable of decolorizing a petroleum resin by a hydrogenation reaction under as mild reaction conditions and using a smaller amount of catalyst, surprisingly, The present inventors have discovered that the above-mentioned problems can be solved by carrying out the hydrogenation reaction in a specific solvent when a petroleum resin is hydrogenated and decolorized with a hydrogenation catalyst under hydrogen pressure, and the present invention has been completed.
即ち、本発明は石油樹脂を水素加圧下、水素化触媒で水
添脱色するに際し、メチルシクロヘキサン及び／または
エチルシクロヘキサンから選ばれる溶媒中で水素化反応
を行うことを特徴とする脱色石油樹脂の製造方法に関す
る。That is, the present invention relates to the production of a decolorized petroleum resin, which is characterized in that when a petroleum resin is hydrogenated and decolorized with a hydrogenation catalyst under hydrogen pressure, the hydrogenation reaction is carried out in a solvent selected from methylcyclohexane and/or ethylcyclohexane. Regarding the method.
本発明の方法を実施する上で、溶媒として、メチルシク
ロヘキサン及び／またはエチルシクロヘキサンが特に有
効な理由は明らかではないが、石油樹脂の溶解性が他の
溶媒と異なること、あるいは、石油樹脂中に含まれる硫
黄の量が水素化反応活性に及ぼす影響が非常に大きく、
硫黄の量が多くなると水素化反応が進み難くなることか
ら、メチルシクロヘキサン及び／またはエチルシクロヘ
キサンを溶媒として用いることにより、他の溶媒に比較
して石油樹脂の中に含まれる硫黄が触媒毒としてより働
き難い状態にある可能性も考えられる。The reason why methylcyclohexane and/or ethylcyclohexane are particularly effective as a solvent in carrying out the method of the present invention is not clear, but it may be that the solubility of petroleum resin is different from other solvents, or that petroleum resin is The amount of sulfur contained has a very large effect on the hydrogenation reaction activity.
When the amount of sulfur increases, it becomes difficult for the hydrogenation reaction to proceed, so by using methylcyclohexane and/or ethylcyclohexane as a solvent, the sulfur contained in petroleum resin becomes more catalytic poison than other solvents. It is also possible that they are in a condition that makes it difficult for them to work.
本発明において、石油樹脂とは、スチレン、ビニルトル
エン、α−メチルスチレン、インデン等の主としてＣ９
留分を共重合して得られるＣ９系または芳香族系石油樹
脂、イソプレン、ピペリレン、２−メチルブテン−１お
よび２などの主としてＣ３留分を共重合して得られるＣ
２系または脂肪族系石油樹脂、Ｃ９留分、Ｃ３留分を共
重合して得られるＣ８Ｃ９系石油樹脂をさしている。In the present invention, petroleum resins include mainly C9 resins such as styrene, vinyltoluene, α-methylstyrene, and indene.
C9-based or aromatic petroleum resins obtained by copolymerizing fractions, C9-based or aromatic petroleum resins obtained by copolymerizing mainly C3 fractions, such as isoprene, piperylene, and 2-methylbutene-1 and 2.
It refers to a C8C9 petroleum resin obtained by copolymerizing a di- or aliphatic petroleum resin, a C9 fraction, and a C3 fraction.
本発明において、水素添加反応における最適な溶媒量は
、石油樹脂に対して重量比で０．３〜３．０倍量が好ま
しい。In the present invention, the optimum amount of solvent in the hydrogenation reaction is preferably 0.3 to 3.0 times the weight of the petroleum resin.
０．３倍量より少なくなると水素化反応の進行が遅くな
り、水添率が高くなりにくい。If the amount is less than 0.3 times, the progress of the hydrogenation reaction will be slow and the hydrogenation rate will be difficult to increase.
また、３．０倍量より多くなると水素化反応は進むもの
の、最終的に水添樹脂を溶媒から分離する時の費用が高
くなる。Moreover, if the amount is more than 3.0 times, although the hydrogenation reaction will proceed, the cost for finally separating the hydrogenated resin from the solvent will increase.
石油樹脂に対して同量以下の溶媒を用いる場合、反応液
の粘度が比較的高くなるので、水素化反応終了後、ろ過
により触媒を分離する際、少量の溶媒を加えろ過性を良
くすることは可能である。If less than the same amount of solvent is used for the petroleum resin, the viscosity of the reaction liquid will become relatively high, so when separating the catalyst by filtration after the hydrogenation reaction, it is necessary to add a small amount of solvent to improve filtration performance. is possible.
−船釣に、石油樹脂の色相はガードナー色数４〜１２程
度の淡黄色ないし淡褐色であるが、本発明の方法によれ
ば、脱色石油樹脂の色相をハーゼン色数２５０以下とす
ることができる。- For boat fishing, the hue of petroleum resin is pale yellow to light brown with a Gardner color number of 4 to 12, but according to the method of the present invention, the hue of decolorized petroleum resin can be reduced to a Hazen color number of 250 or less. can.
（石油樹脂の色相はＪＩＳ Ｋ６９０１ のハーゼン色
数法、ガードナー色数法に準じ測定した。ハーゼン色数
４００がほぼガードナー色数１に相当する。）脱色石油
樹脂の脱色の程度と水添率の間には比較的良い相関があ
る。(The hue of the petroleum resin was measured according to the Hazen color number method and the Gardner color number method of JIS K6901. A Hazen color number of 400 approximately corresponds to a Gardner color number of 1.) The degree of decolorization of the decolorized petroleum resin and the hydrogenation rate There is a relatively good correlation between them.
出発原料となる石油樹脂の種類によって異なるが、ハー
ゼン色数２５０以下に脱色するためには少なくとも１５
％以上の水添率が必要となる。It varies depending on the type of petroleum resin used as the starting material, but in order to decolorize to a Hazen color number of 250 or less, at least 15
% or more is required.
更に脱色しようと思えば、水添率を上げることにより可
能となる。水添率は触媒量、水素圧、反応温度、反応時
間などの反応条件を変えることにより、任意に調節する
ことが可能である。Further decolorization can be achieved by increasing the hydrogenation rate. The hydrogenation rate can be arbitrarily adjusted by changing reaction conditions such as catalyst amount, hydrogen pressure, reaction temperature, and reaction time.
特に、穏和な反応条件で水添率を上げるためには、石油
樹脂中に含まれる硫黄分が少ない方がより好ましい０石
油樹脂中には５０〜１１０００ｐｐ程度の硫黄が含まれ
ているが、好ましくは１５０ｐｐｍ以下、より好ましく
は１００ｐｐ＋ｗ以下であることが望ましい。In particular, in order to increase the hydrogenation rate under mild reaction conditions, it is more preferable that the sulfur content in the petroleum resin is small.The petroleum resin contains about 50 to 11,000 pp of sulfur, but it is preferable. is preferably 150 ppm or less, more preferably 100 pp+w or less.
石油樹脂中の硫黄含有量が多い場合、公知の方法で硫黄
含有量を減らし、水素化反応に供することもできる。When the sulfur content in the petroleum resin is high, the sulfur content can be reduced by a known method and then subjected to a hydrogenation reaction.
なお、本発明での水添率とは、石油樹脂の分子骨格中の
不飽和二重結合を水素化した割合を表わし、プロトンの
Ｎ）’ＩＲスペクトルの測定から次式により算出した値
である。The hydrogenation rate in the present invention refers to the rate at which unsaturated double bonds in the molecular skeleton of petroleum resin are hydrogenated, and is a value calculated from the measurement of the proton N)' IR spectrum using the following formula. .
ＡｉＯ〜４．０ｐｐｍの飽和炭化水素の積分領域Ｂｉ４
．２〜ａ、ｏｐｐ−の不飽和炭化水素の積分領域本発明
における水素化触媒としては、水素化能力を有する触媒
であればいずれも使用でき、特に限定されない、オレフ
ィン化合物の水素化に一般的に使用されるものであれば
、いずれも使用可能である。Integral region Bi4 of saturated hydrocarbons from AiO to 4.0 ppm
．． 2-a, opp- integral region of unsaturated hydrocarbons As the hydrogenation catalyst in the present invention, any catalyst can be used as long as it has hydrogenation ability, and is not particularly limited. Any one can be used as long as it is used.
たとえば、ニッケル、もしくはパラジウム、ロジウム、
白金、ルテニウムなどの白金属触媒、あるいはこれら主
触媒に助触媒としてコバルト、鉄、クロム、銅、亜鉛、
アルカリ金属、アルカリ土類金属の１種以上を混合した
触媒、またはこれらの金属をケイソウ土、カーボン、シ
リカ、アルミナ等の担体の上に担持した担持触媒が挙げ
られる、 多くの場合、金属を担体上に担持した担持触
媒が使用される。For example, nickel, palladium, rhodium,
Platinum metal catalysts such as platinum and ruthenium, or cobalt, iron, chromium, copper, zinc,
These include catalysts containing a mixture of one or more of alkali metals and alkaline earth metals, or supported catalysts in which these metals are supported on a carrier such as diatomaceous earth, carbon, silica, or alumina. A supported catalyst is used.
水素化反応の型式は、特に限定されず、通常の方法で行
われる。たとえば、回分式の懸濁床方式、流通式の固定
床方式等がある。The type of hydrogenation reaction is not particularly limited and can be carried out by a conventional method. For example, there are a batch type suspended bed system, a flow type fixed bed system, etc.
水素化反応における触媒量、水素圧、反応温度、反応時
間等の反応条件は石油樹脂の種類、硫黄含有量、あるい
は目的とする水添脱色石油樹脂の性状に応じて定めるべ
きであるが、一般に触媒量は石油樹脂に対して０．１〜
３５重量％、水素圧は５〜２５０ｋｇ／ｃ＋ａＧ 、反
応温度は１００〜２７０°６１反応時間は１〜１０時間
とするのが適当である。Reaction conditions such as catalyst amount, hydrogen pressure, reaction temperature, and reaction time in the hydrogenation reaction should be determined depending on the type of petroleum resin, sulfur content, or properties of the target hydrogenated and decolorized petroleum resin, but in general, Catalyst amount is 0.1 to petroleum resin
35% by weight, hydrogen pressure of 5 to 250 kg/c+aG, reaction temperature of 100 to 270°61, and reaction time of 1 to 10 hours.
水素化反応終了後、ろ過により触媒を、蒸留等の操作に
より溶媒を分離することにより、目的とする水添脱色石
油樹脂を得ることができる。After the hydrogenation reaction is completed, the desired hydrogenated decolorized petroleum resin can be obtained by separating the catalyst by filtration and the solvent by distillation or the like.
本発明の方法に従えば、石油樹脂の水添脱色を効率的に
行うことができる。According to the method of the present invention, petroleum resin can be efficiently decolorized by hydrogenation.
換言すれば、同一水素化反応条件において、メチルシク
ロヘキサン及び／またはエチルシクロヘキサンから選ば
れる溶媒を用いることにより、他の飽和炭化水素溶媒に
比較して一層高い水添率となし得る。In other words, under the same hydrogenation reaction conditions, by using a solvent selected from methylcyclohexane and/or ethylcyclohexane, a higher hydrogenation rate can be achieved compared to other saturated hydrocarbon solvents.
以下、実施例を挙げて本発明を具体的に説明するが、こ
れは１例であり、本発明はこれに限定されるものではな
い。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but these are just examples and the present invention is not limited thereto.
実施例１
２００ｄオートクレーブ中に市販の石油樹脂（東邦化学
型「ハイレジン＃９０」硫黄含有量９３９９ｍ、色相ガ
ードナー色数８）２７ｇを、メチルシクロヘキサ４０ｇ
を溶解し、それに水素化触媒として安定化ニッケル触媒
（８渾化学製Ｎ−１１３触媒）０゜２７ｇを仕込み窒素
ガスにて系内を置換した後、水素にて１００ｋｇ／ｃ４
Ｇに加圧した。Example 1 In a 200 d autoclave, 27 g of commercially available petroleum resin (Toho Kagaku type "HiResin #90" sulfur content 9399 m, hue Gardner color number 8) was mixed with 40 g of methyl cyclohexa.
After dissolving 0.27 g of stabilized nickel catalyst (N-113 catalyst manufactured by 8Hun Chemical Co., Ltd.) as a hydrogenation catalyst and purging the system with nitrogen gas, 100 kg/c4 of hydrogen was added.
Pressure was applied to G.
二〇伏態で２５０’Ｃに昇温し、全圧１００ｋｇ／ｃ＋
ｄＧ温度２５０°Ｃにて５．５時間水素化反応を行った
。Temperature raised to 250'C in 20°C, total pressure 100kg/c+
The hydrogenation reaction was carried out at a dG temperature of 250°C for 5.5 hours.
反応終了後、触媒をろ別した。After the reaction was completed, the catalyst was filtered off.
メチルシクロヘキサンを最初常圧で、その後減圧下で除
去し水添石油樹脂を得た。Methylcyclohexane was removed first at normal pressure and then under reduced pressure to obtain a hydrogenated petroleum resin.
こうして得られた水添石油樹脂の水添率は６７．２％で
あった。The hydrogenation rate of the hydrogenated petroleum resin thus obtained was 67.2%.
色相はハーゼン色数２０であり、十分に脱色されていた
。The hue was Hazen color number 20 and was sufficiently bleached.
実施例２
実施例１のメチルシクロヘキサンの代りにエチルシクロ
ヘキサンを用いたほか実施例１と同様に行い水添石油樹
脂を得た。この水添石油樹脂の水添率は６１．６％であ
った０色相はハーゼン色数２０テあり、十分脱色されて
いた。Example 2 A hydrogenated petroleum resin was obtained in the same manner as in Example 1 except that ethylcyclohexane was used instead of methylcyclohexane. The hydrogenation rate of this hydrogenated petroleum resin was 61.6%, and the 0 hue had a Hazen color number of 20, indicating that it was sufficiently decolored.
比較例１
実施例１のメチルシクロヘキサンの代りにシクロヘキサ
ンを用いたほかは実施例１と同様に行い水添石油樹脂を
得た。Comparative Example 1 A hydrogenated petroleum resin was obtained in the same manner as in Example 1 except that cyclohexane was used instead of methylcyclohexane.
この水添石油樹脂の水添率は４９．３％であった。The hydrogenation rate of this hydrogenated petroleum resin was 49.3%.
色相はハーゼン色数４０であった。The hue was Hazen color number 40.
比較例２
実施例１のメチルシクロヘキサンの代りにｎ−へブタン
を用いたほかは実施例１と同様に行い、水添石油樹脂を
得た。Comparative Example 2 A hydrogenated petroleum resin was obtained in the same manner as in Example 1, except that n-hebutane was used instead of methylcyclohexane.
この水添石油樹脂の水添率は４４．７％であった。The hydrogenation rate of this hydrogenated petroleum resin was 44.7%.
色相はハーゼン色数４０であった。The hue was Hazen color number 40.
実施例３
２００ｄオートクレーブ中に市販の石油樹脂（東邦化学
部「ハイレジン１２０ＳＪ硫黄含有量５０ｐｐ−１色相
ガードナー色数１１）２０ｇをエチルシクロヘキサン５
０ｇに溶解し、それに水素化触媒として安定化ニッケル
（８揮化学製ＮＮ−１１３）６を仕込み、窒素ガスにて
系内をｉｆＷ！した後水素にて１０ｋｇ／ｃｊＧに加圧
した。Example 3 In a 200 d autoclave, 20 g of a commercially available petroleum resin (Toho Kagakubu Hi-Resin 120SJ sulfur content 50 pp-1, hue Gardner color number 11) was mixed with ethylcyclohexane 5
Stabilized nickel (NN-113 manufactured by 8Koku Kagaku Co., Ltd.) 6 was added as a hydrogenation catalyst, and the system was heated with nitrogen gas ifW! After that, the pressure was increased to 10 kg/cjG with hydrogen.
この状態で１４０℃に昇温し、全圧１０ｋｇ／ｃｄＧ
。In this state, the temperature was raised to 140℃, and the total pressure was 10kg/cdG.
.
温度１４０”ｃにて６時間水素化反応を行った。The hydrogenation reaction was carried out at a temperature of 140"C for 6 hours.
反応終了後、触媒をろ別した。After the reaction was completed, the catalyst was filtered off.
エチルシクロヘキサン溶媒を、初め常圧でその後減圧下
除去し、水添石油樹脂を得た。The ethylcyclohexane solvent was removed first at normal pressure and then under reduced pressure to obtain a hydrogenated petroleum resin.
こうして得られた水添石油樹脂の水添率は３７．１％で
あった。The hydrogenation rate of the hydrogenated petroleum resin thus obtained was 37.1%.
色相はハーゼン色数６０であった。The hue was Hazen color number 60.
比較例３
実施例３のエチルシクロヘキサンの代りにジオキサンを
用いたほかは実施例３と同様に行い水添石油樹脂を得た
。Comparative Example 3 A hydrogenated petroleum resin was obtained in the same manner as in Example 3, except that dioxane was used instead of ethylcyclohexane.
水添石油樹脂の水添率は１６．２％であった。The hydrogenation rate of the hydrogenated petroleum resin was 16.2%.
色相はハーゼン色数２５０であった。The hue was Hazen color number 250.
実施例４
２００ ｄオートクレーブ中に、市販の石油樹脂（東邦
化学部「ハイレジン＃９０」硫黄含有量１１００ｐｐ
、色相ガードナー色数８）２７ｇをメチルシクロヘキサ
ン４０ｇに溶解し、それに水素化触媒としてＰｄ（５χ
）活性炭担持触媒（水分５０．３χ）含有、８揮化学製
） ６．３ｇを仕込み、窒素ガスにて系内を置換した後
、水素にて３０ｋｇ／ｃｄＧに加圧した。Example 4 In a 200 d autoclave, a commercially available petroleum resin (Toho Chemical Co., Ltd. “Hi-Resin #90” with a sulfur content of 1100 pp.
, hue Gardner color number 8) was dissolved in 40 g of methylcyclohexane, and Pd (5χ
) 6.3 g of activated carbon-supported catalyst (containing water content 50.3x, manufactured by 8Ki Kagaku Co., Ltd.) was charged, and after replacing the inside of the system with nitrogen gas, it was pressurized to 30 kg/cdG with hydrogen.
この状態で１７０°Ｃに昇温し、全圧３０ｋｇ／ｅ＋ｊ
Ｇ温度１７０℃にて６時間水添反応を行った。In this state, the temperature is raised to 170°C and the total pressure is 30kg/e+j
Hydrogenation reaction was carried out at a G temperature of 170° C. for 6 hours.
反応終了後、触媒をろ別した。After the reaction was completed, the catalyst was filtered off.
メチルシクロヘキサン溶媒を初め常圧で、その後減圧下
で除去し水添石油樹脂を得た。The methylcyclohexane solvent was first removed at normal pressure and then under reduced pressure to obtain a hydrogenated petroleum resin.
こうして得られた水添石油樹脂の水添率は６２．０％で
あった０色相はハーゼン色数３０であった。The hydrogenation rate of the thus obtained hydrogenated petroleum resin was 62.0%, and the zero hue had a Hazen color number of 30.
実施例５．６
実施例１において、メチルシクロヘキサン４０ｇをそれ
ぞれメチルシクロヘキサン２７ｇ 、 １８ｇ とした
ほかは実施例１と同様に行い水添石油樹脂を得た。Example 5.6 A hydrogenated petroleum resin was obtained in the same manner as in Example 1, except that 40 g of methylcyclohexane in Example 1 was changed to 27 g and 18 g of methylcyclohexane, respectively.
水添石油樹脂の水添率は、それぞれ６４．３％、及び５
１．２％であった。The hydrogenation rate of hydrogenated petroleum resin is 64.3% and 5%, respectively.
It was 1.2%.
色相はそれぞれハーゼン色数３０、及び４０であった。The hues were Hazen color numbers 30 and 40, respectively.
本発明によれば、他の溶媒を用いるよりも効率的に脱色
石油樹脂が得られることは実施例、比較例から明らかで
ある。It is clear from the Examples and Comparative Examples that according to the present invention, a decolorized petroleum resin can be obtained more efficiently than when using other solvents.
したがって、目的の性状を有する脱色石油樹脂を製造す
る場合、同一反応温度、水素圧条件では触媒量を減らす
こと、反応時間を短くすることが可能となり、製造上の
改善効果は非常に大きなものである。Therefore, when producing a decolorized petroleum resin with the desired properties, it is possible to reduce the amount of catalyst and shorten the reaction time under the same reaction temperature and hydrogen pressure conditions, which is a huge improvement in production. be.
特許出願人 日本化薬株式会社Patent applicant: Nippon Kayaku Co., Ltd.
Claims (1)
に際し、メチルシクロヘキサン及び／またはエチルシク
ロヘキサンから選ばれる溶媒中で水素化反応を行うこと
を特徴とする脱色石油樹脂の製造方法。1. A method for producing a decolorized petroleum resin, which comprises carrying out the hydrogenation reaction in a solvent selected from methylcyclohexane and/or ethylcyclohexane when the petroleum resin is decolorized by hydrogenation using a hydrogenation catalyst under hydrogen pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3621589A JPH02215802A (en) | 1989-02-17 | 1989-02-17 | Production of decolored petroleum resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3621589A JPH02215802A (en) | 1989-02-17 | 1989-02-17 | Production of decolored petroleum resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02215802A true JPH02215802A (en) | 1990-08-28 |
Family
ID=12463538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3621589A Pending JPH02215802A (en) | 1989-02-17 | 1989-02-17 | Production of decolored petroleum resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02215802A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021031568A (en) * | 2019-08-22 | 2021-03-01 | Ｅｎｅｏｓ株式会社 | Sulfur-containing unsaturated hydrocarbon polymer, method for manufacturing same, additive for rubber, rubber composition, and tire |
-
1989
- 1989-02-17 JP JP3621589A patent/JPH02215802A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021031568A (en) * | 2019-08-22 | 2021-03-01 | Ｅｎｅｏｓ株式会社 | Sulfur-containing unsaturated hydrocarbon polymer, method for manufacturing same, additive for rubber, rubber composition, and tire |
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