JP4240239B2 - Method for producing alicyclic compound - Google Patents
Method for producing alicyclic compound Download PDFInfo
- Publication number
- JP4240239B2 JP4240239B2 JP35468797A JP35468797A JP4240239B2 JP 4240239 B2 JP4240239 B2 JP 4240239B2 JP 35468797 A JP35468797 A JP 35468797A JP 35468797 A JP35468797 A JP 35468797A JP 4240239 B2 JP4240239 B2 JP 4240239B2
- Authority
- JP
- Japan
- Prior art keywords
- methylstyrenes
- hydrogenation
- reaction
- alicyclic compound
- acid
- 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.)
- Expired - Fee Related
Links
- 150000001334 alicyclic compounds Chemical class 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000005984 hydrogenation reaction Methods 0.000 claims description 23
- 239000013638 trimer Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000007868 Raney catalyst Substances 0.000 claims description 4
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical class CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000004014 plasticizer Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- -1 phthalate ester Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UXZZHVLZNFQJMN-UHFFFAOYSA-N 1,3-dimethyl-1-(2-methyl-2-phenylpropyl)-3-phenyl-2h-indene Chemical compound C=1C=CC=CC=1C(C)(C)CC(C1=CC=CC=C11)(C)CC1(C)C1=CC=CC=C1 UXZZHVLZNFQJMN-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- IBTHFIILQIUOEK-UHFFFAOYSA-N 1-ethyl-4-prop-1-en-2-ylbenzene Chemical compound CCC1=CC=C(C(C)=C)C=C1 IBTHFIILQIUOEK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PZAGQUOSOTUKEC-UHFFFAOYSA-N acetic acid;sulfuric acid Chemical compound CC(O)=O.OS(O)(=O)=O PZAGQUOSOTUKEC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/45—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing nine carbon atoms
- C07C13/465—Indenes; Completely or partially hydrogenated indenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、可塑剤、造核剤、プロセスオイル、動力伝達用オイル及び熱媒体等に好適な脂環式化合物の製造法に関する。
【０００２】
【従来の技術】
従来、各種熱可塑性樹脂の可塑性付与のために、一次可塑剤としてフタル酸エステル、脂肪族二塩基酸エステル、塩素化パラフィン、二次可塑剤としてポリエステル系可塑剤、エポキシ系可塑剤、リン酸エステル系可塑剤、トリメリット酸系可塑剤等が使用されてきた。しかし従来の一次可塑剤には一長一短があり、相溶性、耐熱性、耐寒性、耐ブリード性、耐候性を同時に満足できる材料がなかった。
特公昭６１−４６０１４号公報にはポリオレフィン用の可塑剤として３個または４個のシクロヘキシル環を有する可塑剤の使用例が記載されている。また自動車等の動力伝達用オイルとしては動作温度範囲で液体であること、長期間の熱安定性及び酸化安定性に優れること、動力伝達性能が優れていることが求められ、特公昭８−２３２９号公報にはα−メチルスチレンを重合して得られるトリアリールアルカン及びテトラアリールアルカンの核水添物が記載されている。
このように可塑剤や動力伝達用オイルには一般的にシクロヘキサン環等の複数の脂環構造を有する化合物が使用されてきた。また熱媒体用のオイルも動力伝達用オイルと同様な化合物が使用されている。
【０００３】
これらシクロヘキサン環を数個有する化合物のなかでヒドロインダン型又はインデンの構造を有する化合物はその剛直な構造からシクロヘキサン環を線状に有する化合物よりも高い動力伝達性能や可塑剤としての耐熱性が期待できる。しかしながら特公昭８−２３０２９号公報、Polymer Journal、Vol.13、No.10、P947等に記載されているようにヒドロインダン型又はインデン構造を持つα−メチルスチレン三量体の核水添物を高収率で合成する方法がなかった。特公平８−２３０２９号公報に記載ではヒドロインダン構造を有するα−メチルスチレン類三量体の収率は約３％から６％である。
【０００４】
【発明が解決しようとする課題】
請求項１、２及び３記載の発明は、目的とする脂環式化合物を高収率、高純度で製造することができる脂環式化合物の製造法を提供するものである。
【０００５】
【課題を解決するための手段】
本発明は、酸のα−メチルスチレン類に対するモル比が０．０００５〜０．１となるようにして、酸を含む有機溶媒中にα−メチルスチレン類を滴下し、反応温度−１５〜３０℃でα−メチルスチレン類を三量化してα−メチルスチレン類の三量体を得、さらに得られたα−メチルスチレン類の三量体の芳香環に水素添加を行なうことを特徴とする一般式（Ｉ）
【化２】
で表される脂環式化合物の製造法に関する。
【０００６】
また、本発明は、酸がＡｌＣｌ3である前記脂環式化合物の製造法に関する。 また、本発明は、水素添加において触媒として安定化ニッケル又はラネーニッケルを用い、反応温度１４０℃〜２２０℃で水素添加を行なう前記脂環式化合物の製造法に関する。
【０００７】
【発明の実施の形態】
本発明におけるα−メチルスチレン類は、下記一般式（II）で表される化合物である。
【０００８】
また、α−メチルスチレン類の三量体は、下記の一般式（III）で表される化合物である。
【化４】
【０００９】
具体的には、α−メチルスチレン類としては、例えば、α−メチルスチレン、ｍ−又はｐ−メチル−α−メチルスチレン、ｍ−又はｐ−エチル−α−メチルスチレン、ｍ−又はｐ−イソプロピル−α−メチルスチレン等が挙げられ、これらを出発原料としてα−メチルスチレン類の三量体を合成する。原料にα−メチルスチレンを使用すると、その三量体としての１，３−ジメチル−３−フェニル−１−（２−メチル−２−フェニルプロピル）インダン体が得られる。
【００１０】
本発明において、α−メチルスチレン類の三量体の合成に用いられる酸としては、例えば、ＡｌＣｌ3、ＡｌＣｌ3−ＣＨ3ＮＯ2、ＳｎＣｌ4、ＴｉＣｌ4、Ａｌ2Ｏ3−ＴｉＯ2、ＳｉＯ2−Ａｌ2Ｏ3、ＴｉＯ2−ＺｒＯ2等のルイス酸、Ｈ2ＳＯ4、トリクロロ酢酸等のプロトン酸、酸性白土、活性白土、モンモリオナイト型粘土などを使用することができるが、純率、純度の点からルイス酸が好ましく、中でもＡｌＣｌ3が好ましい。ＡｌＣｌ3は単体のままで用いてもよいが、ＣＨ3ＮＯ2（ニトロメタン）等に均一に溶解してから用いると、反応系が均一となり好ましい。
【００１１】
使用する酸の量は、α−メチルスチレン類に対するモル比が０．０００５〜０．１であることが必要であり、０．００１〜０．０５であることが好ましく、０．００２〜０．０１であることがより好ましい。モル比が０．０００５未満の場合は反応速度が遅く、反応率が大きく低下する。一方、モル比が０．１を超えると、α−メチルスチレン類の三量体の収率が低下する。
三量化の反応温度は、−１５〜３０℃とすることが必要であり、−１０〜２０℃とすることが好ましく、−５〜１０℃とすることがより好ましい。反応温度が−１５℃未満であると、α−メチルスチレン類の四量体以上のオリゴマーの生成量が増え、三量体の収率が低下する。一方、反応温度が３０℃を超えるとα−メチルスチレン類の二量体の生成量が増え、三量体の収率が低下する。
また、三量化の反応時間は、０．２５〜５時間程度である。
【００１２】
本発明においては、まず三量化の触媒となる酸を有機溶媒中に分散あるいは溶解し、ここにα−メチルスチレン類、あるいは有機溶媒にα−メチルスチレン類を溶解したものを滴下し、反応させることが必須である。酸とα−メチルスチレン類を有機溶媒中で同時に混合したり、α−メチルスチレン類の中にあるいは有機溶媒にα−メチルスチレンを溶解したものの中に、酸あるいは酸を有機溶剤に分散あるいは溶解したものを滴下すると、α−メチルスチレン類の三量体の収率が低くなり、α−メチルスチレン類の三量体を水素添加（核水添）して得られる前記一般式（Ｉ）で表される脂環式化合物の収率が低下する。
【００１３】
本発明における有機溶媒としては、石油エーテル、ヘキサン、メチルシクロヘキサン等の飽和脂肪族炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素、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などが挙げられる。
【００１４】
α−メチルスチレン類の三量体の芳香環へ水素添加（核水添）を行う際、触媒を使用できる。水素添加の触媒として、例えば、ルテニウム−カーボン、安定化ニッケル、ラネーニッケル、ラネーニッケル−モリブデン、ニッケル珪藻土、白金、白金−アルミナ、ロジウム、ロジウム−アルミナ等の触媒を使用することができるが、収率、純度の点から安定化ニッケル及びラネーニッケルが好ましい。安定化ニッケルは、例えば、堺化学工業(株)から商品名、安定化ニッケル触媒；ＳＮ−１１０、ＳＮ−１５０、ＳＮ−２５０、ＳＮ−７５０、ＳＮ−３００、ＳＴ−１００等として商業的に入手できる。また、ラネーニッケルは、例えば、デグッサ社から商品名、ＦＢ−ＡＭＣ等として商業的に入手できる。
触媒を使用する場合、その使用量はα−メチルスチレン類の三量体に対して０．１〜５．０重量％とすることが好ましく、０．２５〜２．０重量％とすることがより好ましい。この触媒の使用量が０．１重量％未満では反応時間が長くなる傾向があり、５重量％を超えると副成物が増加する傾向がある。
水素添加の反応温度は１４０℃〜２２０℃とすることが好ましく、１６０℃〜２００℃とすることがより好ましい。２２０℃を超えると副成物が増加する傾向があり、１４０℃未満では反応時間が長くなる傾向がある。
【００１５】
水素添加の反応圧力は４．９０×１０5〜１．４７×１０7Paとすることが好ましく、１．９６×１０6〜９．８１×１０6Paとすることがより好ましい。反応圧力が４．９０×１０5Pa未満では副成物が増加する傾向があり、反応時間が長くなる傾向がある。反応圧力は１．４７×１０7Paを超えると量産性が困難となる傾向がある。水素添加の反応時間は０．５〜２０時間とすることが好ましく、１〜１０時間とすることがより好ましい。反応時間が０．５時間未満では核水添が不充分となる傾向があり、２０時間を超えても収率が向上しない傾向がある。
【００１６】
このようにして得られた一般式（Ｉ）で表される脂環式化合物は、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリアクリルニトリル、ポリエステル、ポリアミド、ＡＢＳ樹脂、ポリアセタール、ポリフェニレンエーテル、ポリカーボネート、ポリウレタン、メタクリル樹脂また各種熱可塑性樹脂の可塑剤として好適である。
【００１７】
また、本発明の製造法で得られる脂環式化合物は、−４０℃〜１４０℃の広い温度範囲で性状が安定（液体など）しており、耐熱性、耐寒性、酸化安定性、耐候性の向上に有利な化合物であり、射出成形時のプロセスオイル、熱媒体や動力伝達用オイルとしても好適である。
【００１８】
【実施例】
以下、実施例により本発明を説明する。
実施例１
〔１，３−ジメチル−３−フェニル−１−(２−メチル−２−フェニルプロピル)インダン（一般式(III)でｐ、ｑ及びｒは０の化合物）(以下ＭＴＩと略す)の合成〕
撹拌装置、滴下ロート、ジムロート冷却管及び温度計を具備した２００mlの四つ口フラスコに、触媒としてＡｌＣｌ3のＣＨ3ＮＯ2溶液（１５重量％）０．４６ｇ（ＡｌＣｌ3０．０６９ｇ＝０．５１７ミリモル）、溶媒としてトルエン１００mlを仕込んだ。そして滴下ロートにα−メチルスチレン３０ｇ（２５４ミリモル）を含むトルエン溶液５０mlを仕込んだ（ＡｌＣｌ3のα−メチルスチレンに対するモル比は０．００２）。
【００１９】
フラスコ内を０℃に保ち、撹拌しながらα−メチルスチレンのトルエン溶液を約３５分かけて滴下した。滴下終了後さらに２５分間反応を続けた。反応終了後、水をゆっくり滴下し、触媒を分解した。有機層を水洗した後、生成物をクライゼン型分留器及びリービッヒ冷却管を具備した２００mlの四つ口フラスコに投入して蒸留を行い、温度２０３℃、圧力１．５トールの条件下でＭＴＩを単離した。
なお、有機層を水洗した後の生成物を高速液体クロマトグラフィー（ＨＰＬＣ）で分析したところ、α−メチルスチレンは、ほぼ１００％反応し多量化されており、そのうち三量体の割合は７５％と高いものであった。
【００２０】
〔１，３−ジメチル−３−シクロヘキシル−１−（２−メチル−２−シクロヘキシルプロピル）インデン（一般式（Ｉ）で、ｐ、ｑ及びｒは０の化合物）（以下ＭＨＩと略す）の合成（ＭＴＩへの水素添加）〕
ＭＴＩ１００ｇと安定化ニッケル（堺化学工業(株)製、安定化ニッケル触媒ＳＮ−７５０）０．５ｇをオートクレーブ中にいれて、水素を導入した。１８０℃に昇温し、４．９０×１０6Paの圧力下で２時間反応を行なった。室温に温度が下がった後、圧力をさげて反応物を取り出した。ＮＭＲ及びＩＲで反応物の分析を行なった結果、ＮＭＲスペクトルの６．９〜７．４ppmのベンゼン環の水素に由来するピークが消え、またＩＲスペクトルでは波数７００、７６０、１５００及び１６００のピークが消え、ベンゼン環に水素が付加していることが確認され、反応物はＭＨＩであることが確認できた。
また、ガスクロマトグラフで分析した結果、ＭＨＩの収率は９９．８％（ＭＴＩに対して）であった。この結果を表１に示した。
【００２１】
得られたＭＨＩをクリーブランド解放式試験で引火点を測定した結果、引火点は２２８℃であり、ＡＳＴＭ Ｅ６５９に準じて発火点を測定した結果、発火点は３７５℃であった。
また、carri-medc.s.Rheometerで粘度を測定した結果、粘度は３０℃で１５４６Pa・s、４０℃で２８５Pa・s、５０℃で５１．２Pa・s、５９．９℃で１１．１Pa・s、６９．９℃で２．８７Pa・s、８０．２℃で０．８６７Pa・s、９０．１℃で０．３３０Pa・sであった。また、ＭＨＩの流動点は３０．０℃、沸点は２２３℃〜２２８℃（１トール）、比重は１．０００g/cm3であった。
【００２２】
実施例２
実施例１においてＡｌＣｌ3のＣＨ3ＮＯ2溶液（１５重量％）を０．９１３ｇ用いること以外は実施例１と同様に反応を行った。このときＡｌＣｌ3のα−メチルスチレンに対するモル比は０．００４である。この結果を表１に示した。
【００２３】
実施例３
実施例１においてＡｌＣｌ3をＣＨ3ＮＯ2には溶解せず、そのまま０．０６９ｇ用いること以外は実施例１と同様に反応を行った。このとき不均一系での反応となるが、反応は問題なく進行した。この結果を表１に示した。
【００２４】
実施例４
実施例１において反応温度を１５℃にすること以外は実施例１と同様に反応を行った。この結果を表１に示した。
【００２５】
比較例１
実施例１においてまずフラスコに、α−メチルスチレン３０ｇ（２５４ミリモル）を含むトルエン溶液１００mlを仕込み、滴下ロートにＡｌＣｌ3のＣＨ3ＮＯ2溶液（１５重量％）を０．４６ｇとトルエン５０mlを仕込んで、α−メチルスチレン溶液中に触媒を滴下するということ以外は実施例１と同様に反応を行い、水素添加を行なった。このときＡｌＣｌ3のα−メチルスチレンに対するモル比は０．００２である。この結果を表１に示した。
【００２６】
比較例２
実施例１においてＡｌＣｌ3のＣＨ3ＮＯ2溶液（１５重量％）を０．１ｇ用いること以外は実施例１と同様に反応を行い、水素添加を行なった。ＡｌＣｌ3のα−メチルスチレンに対するモル比は０．０００４４である。この結果を表１に示した。
【００２７】
比較例３
実施例１においてＡｌＣｌ3のＣＨ3ＮＯ2溶液（３０重量％）を１２．４ｇ用いること以外は実施例１と同様に反応を行い、水素添加を行なった。ＡｌＣｌ3のα−メチルスチレンに対するモル比は０．１１である。この結果を表１に示した。
【００２８】
比較例４
実施例１において反応温度を−２０℃にすること以外は実施例１と同様に反応を行い、水素添加を行なった。この結果を表１に示した。
【００２９】
比較例５
実施例１において反応温度を３５℃にすること以外は実施例１と同様に反応を行い、水素添加を行なった。この結果を表１に示した。
【００３０】
実施例５
実施例１において水素添加時の反応温度を１８０℃から２２０℃に変更した以外は実施例１と同様に反応を行なった。水素添加によるのＭＨＩの収率は８６．０％であった。この結果を表１に示した。
【００３１】
実施例６
実施例１において水素添加時の触媒量を０．５ｇから６．０ｇに変更した以外は実施例１と同様に反応を行なった。水素添加によるのＭＨＩの収率は９２．０％であった。この結果を表１に示した。
【００３２】
【表１】
【発明の効果】
請求項１、２及び３記載の脂環式化合物の製造法は、目的とする脂環式化合物を高収率、高純度で製造することのできるものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an alicyclic compound suitable for a plasticizer, a nucleating agent, a process oil, a power transmission oil, a heat medium and the like.
[0002]
[Prior art]
Conventionally, phthalate ester, aliphatic dibasic acid ester, chlorinated paraffin as primary plasticizer, polyester plasticizer, epoxy plasticizer, phosphate ester as secondary plasticizer for imparting plasticity to various thermoplastic resins Plasticizers, trimellitic acid plasticizers, and the like have been used. However, conventional primary plasticizers have advantages and disadvantages, and there is no material that can simultaneously satisfy compatibility, heat resistance, cold resistance, bleed resistance, and weather resistance.
Japanese Examined Patent Publication No. 61-46014 describes use examples of plasticizers having 3 or 4 cyclohexyl rings as plasticizers for polyolefins. Further, power transmission oil for automobiles and the like is required to be liquid in the operating temperature range, excellent in long-term thermal stability and oxidation stability, and excellent in power transmission performance. The publication describes a nuclear hydrogenated product of triarylalkane and tetraarylalkane obtained by polymerizing α-methylstyrene.
As described above, compounds having a plurality of alicyclic structures such as cyclohexane rings have generally been used for plasticizers and power transmission oils. Also, the same oil as the power transmission oil is used for the heat medium oil.
[0003]
Among these compounds having several cyclohexane rings, compounds having a hydroindane type or indene structure are expected to have higher power transmission performance and heat resistance as a plasticizer than compounds having a cyclohexane ring in a linear form due to its rigid structure. it can. However, as described in Japanese Patent Publication No. 8-23029, Polymer Journal, Vol. 13, No. 10, P947, etc., a nuclear hydrogenated product of α-methylstyrene trimer having a hydroindane type or indene structure is used. There was no way to synthesize in high yield. In Japanese Patent Publication No. 8-23029, the yield of α-methylstyrene trimer having a hydroindane structure is about 3% to 6%.
[0004]
[Problems to be solved by the invention]
The inventions according to claims 1, 2 and 3 provide a method for producing an alicyclic compound capable of producing a target alicyclic compound with high yield and high purity.
[0005]
[Means for Solving the Problems]
In the present invention, α-methylstyrenes are dropped into an organic solvent containing an acid so that the molar ratio of acid to α-methylstyrene is 0.0005 to 0.1, and the reaction temperature is 15 to 30. The α-methylstyrenes are trimerized at a temperature of ℃ to obtain α-methylstyrenes trimer, and the aromatic ring of the resulting α-methylstyrenes trimer is hydrogenated. Formula (I)
[Chemical formula 2]
It relates to the manufacturing method of the alicyclic compound represented by these.
[0006]
The present invention also relates to a method for producing the alicyclic compound, wherein the acid is AlCl 3 . Moreover, this invention relates to the manufacturing method of the said alicyclic compound which uses hydrogenation at reaction temperature 140-220 degreeC, using stabilized nickel or Raney nickel as a catalyst in hydrogenation.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The α-methylstyrenes in the present invention are compounds represented by the following general formula (II).
[0008]
Moreover, the trimer of α-methylstyrenes is a compound represented by the following general formula (III).
[Formula 4]
[0009]
Specific examples of the α-methylstyrenes include α-methylstyrene, m- or p-methyl-α-methylstyrene, m- or p-ethyl-α-methylstyrene, m- or p-isopropyl. -Α-methylstyrene and the like are mentioned, and a trimer of α-methylstyrenes is synthesized using these as starting materials. When α-methylstyrene is used as a raw material, 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane as a trimer is obtained.
[0010]
In the present invention, examples of acids used for the synthesis of α-methylstyrene trimers include AlCl 3 , AlCl 3 —CH 3 NO 2 , SnCl 4 , TiCl 4 , Al 2 O 3 —TiO 2 , SiO 2 . Lewis acids such as 2- Al 2 O 3 and TiO 2 —ZrO 2 , proton acids such as H 2 SO 4 and trichloroacetic acid, acidic clay, activated clay, montmorillonite type clay and the like can be used. Lewis acid is preferable from the viewpoint of the ratio and purity, and AlCl 3 is particularly preferable. AlCl 3 may be used as it is, but if it is used after it is uniformly dissolved in CH 3 NO 2 (nitromethane) or the like, the reaction system becomes uniform, which is preferable.
[0011]
The amount of the acid to be used must be such that the molar ratio with respect to α-methylstyrenes is 0.0005 to 0.1, preferably 0.001 to 0.05, and 0.002 to 0.00. More preferably, it is 01. When the molar ratio is less than 0.0005, the reaction rate is slow and the reaction rate is greatly reduced. On the other hand, when the molar ratio exceeds 0.1, the yield of trimers of α-methylstyrenes decreases.
The trimerization reaction temperature is required to be −15 to 30 ° C., preferably −10 to 20 ° C., and more preferably −5 to 10 ° C. When the reaction temperature is less than −15 ° C., the amount of oligomers that are tetramers or more of α-methylstyrenes increases, and the yield of trimers decreases. On the other hand, when reaction temperature exceeds 30 degreeC, the production amount of the dimer of (alpha) -methylstyrenes will increase and the yield of a trimer will fall.
The trimerization reaction time is about 0.25 to 5 hours.
[0012]
In the present invention, first, an acid serving as a trimerization catalyst is dispersed or dissolved in an organic solvent, and α-methylstyrenes or those in which α-methylstyrenes are dissolved in an organic solvent are dropped and reacted. It is essential. Acid or α-methylstyrenes are mixed in an organic solvent at the same time, or an acid or acid is dispersed or dissolved in an α-methylstyrenes or a solution in which α-methylstyrene is dissolved in an organic solvent. When the product is added dropwise, the yield of α-methylstyrenes trimer decreases, and the general formula (I) obtained by hydrogenation (nuclear hydrogenation) of the trimer of α-methylstyrenes. The yield of the represented alicyclic compound is reduced.
[0013]
Examples of the organic solvent in the present invention include petroleum ether, saturated aliphatic hydrocarbons such as hexane and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, dibutyl ether and tetrahydrofuran. .
[0014]
A catalyst can be used when hydrogenation (nuclear hydrogenation) is performed on an aromatic ring of a trimer of α-methylstyrenes. As a catalyst for hydrogenation, for example, a catalyst such as ruthenium-carbon, stabilized nickel, Raney nickel, Raney nickel-molybdenum, nickel diatomaceous earth, platinum, platinum-alumina, rhodium, rhodium-alumina, etc. can be used. Stabilized nickel and Raney nickel are preferred from the standpoint of purity. Stabilized nickel is commercially available from Sakai Chemical Industry Co., Ltd. under the trade name, stabilized nickel catalyst; SN-110, SN-150, SN-250, SN-750, SN-300, ST-100, etc. Available. Raney nickel is commercially available from Degussa, for example, under the trade name, FB-AMC.
When a catalyst is used, the amount used is preferably 0.1 to 5.0% by weight, preferably 0.25 to 2.0% by weight, based on the trimer of α-methylstyrenes. More preferred. If the amount of the catalyst used is less than 0.1% by weight, the reaction time tends to be long, and if it exceeds 5% by weight, the by-products tend to increase.
The reaction temperature for hydrogenation is preferably 140 ° C. to 220 ° C., more preferably 160 ° C. to 200 ° C. If it exceeds 220 ° C, by-products tend to increase, and if it is less than 140 ° C, the reaction time tends to be long.
[0015]
The reaction pressure for hydrogenation is preferably 4.90 × 10 5 to 1.47 × 10 7 Pa, more preferably 1.96 × 10 6 to 9.81 × 10 6 Pa. When the reaction pressure is less than 4.90 × 10 5 Pa, by-products tend to increase and the reaction time tends to be long. If the reaction pressure exceeds 1.47 × 10 7 Pa, mass productivity tends to be difficult. The reaction time for hydrogenation is preferably 0.5 to 20 hours, more preferably 1 to 10 hours. If the reaction time is less than 0.5 hours, the nuclear hydrogenation tends to be insufficient, and if it exceeds 20 hours, the yield tends not to improve.
[0016]
The alicyclic compounds represented by the general formula (I) thus obtained are polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyester, polyamide, ABS resin, polyacetal, polyphenylene. Suitable as a plasticizer for ethers, polycarbonates, polyurethanes, methacrylic resins and various thermoplastic resins.
[0017]
The alicyclic compound obtained by the production method of the present invention has stable properties (liquid, etc.) over a wide temperature range of −40 ° C. to 140 ° C., and has heat resistance, cold resistance, oxidation stability, and weather resistance. It is a compound that is advantageous for improving the temperature and is also suitable as a process oil, a heat medium, and a power transmission oil during injection molding.
[0018]
【Example】
Hereinafter, the present invention will be described by way of examples.
Example 1
[Synthesis of 1,3-dimethyl-3-phenyl-1- (2-methyl-2-phenylpropyl) indane (compound of general formula (III) where p, q and r are 0) (hereinafter abbreviated as MTI)]
In a 200 ml four-necked flask equipped with a stirrer, a dropping funnel, a Dimroth condenser and a thermometer, 0.46 g of a CH 3 NO 2 solution (15 wt%) of AlCl 3 as a catalyst (AlCl 3 0.069 g = 0. 517 mmol) and 100 ml of toluene as a solvent. A dropping funnel was charged with 50 ml of a toluene solution containing 30 g (254 mmol) of α-methylstyrene (the molar ratio of AlCl 3 to α-methylstyrene was 0.002).
[0019]
While maintaining the inside of the flask at 0 ° C., a toluene solution of α-methylstyrene was dropped over about 35 minutes while stirring. The reaction was continued for another 25 minutes after completion of the dropwise addition. After completion of the reaction, water was slowly added dropwise to decompose the catalyst. After the organic layer was washed with water, the product was placed in a 200 ml four-necked flask equipped with a Claisen type fractionator and a Liebig condenser, and distilled, and the MTI was performed at a temperature of 203 ° C. and a pressure of 1.5 torr. Was isolated.
The product after the organic layer was washed with water was analyzed by high performance liquid chromatography (HPLC). As a result, α-methylstyrene was reacted and almost in an amount of 100%, of which the proportion of trimer was 75%. It was expensive.
[0020]
Synthesis of [1,3-dimethyl-3-cyclohexyl-1- (2-methyl-2-cyclohexylpropyl) indene (compound of general formula (I), p, q and r are 0) (hereinafter abbreviated as MHI) (Hydrogen addition to MTI)]
100 g of MTI and 0.5 g of stabilized nickel (manufactured by Sakai Chemical Industry Co., Ltd., stabilized nickel catalyst SN-750) were placed in an autoclave to introduce hydrogen. The temperature was raised to 180 ° C., and the reaction was performed for 2 hours under a pressure of 4.90 × 10 6 Pa. After the temperature dropped to room temperature, the pressure was reduced and the reaction product was removed. As a result of analysis of the reaction product by NMR and IR, peaks derived from hydrogen in the benzene ring at 6.9 to 7.4 ppm disappeared from the NMR spectrum, and peaks at wave numbers 700, 760, 1500 and 1600 were observed in the IR spectrum. It disappeared and it was confirmed that hydrogen was added to the benzene ring, and it was confirmed that the reaction product was MHI.
As a result of analysis by gas chromatography, the yield of MHI was 99.8% (relative to MTI). The results are shown in Table 1.
[0021]
As a result of measuring the flash point of the obtained MHI by the Cleveland release test, the flash point was 228 ° C., and the ignition point was measured according to ASTM E659. As a result, the ignition point was 375 ° C.
As a result of measuring the viscosity with a carri-medc.s.Rheometer, the viscosity was 1546 Pa · s at 30 ° C., 285 Pa · s at 40 ° C., 51.2 Pa · s at 50 ° C., 11.1 Pa · s at 59.9 ° C. s, 2.9.9 Pa · s at 69.9 ° C., 0.867 Pa · s at 80.2 ° C., and 0.330 Pa · s at 90.1 ° C. Further, the pour point of MHI was 30.0 ° C., the boiling point was 223 ° C. to 228 ° C. (1 torr), and the specific gravity was 1.000 g / cm 3 .
[0022]
Example 2
The reaction was carried out in the same manner as in Example 1 except that 0.913 g of a CH 3 NO 2 solution (15% by weight) of AlCl 3 was used in Example 1. At this time, the molar ratio of AlCl 3 to α-methylstyrene is 0.004. The results are shown in Table 1.
[0023]
Example 3
In Example 1, the reaction was carried out in the same manner as in Example 1 except that 0.069 g of AlCl 3 was not dissolved in CH 3 NO 2 and was used as it was. At this time, the reaction was heterogeneous, but the reaction proceeded without problems. The results are shown in Table 1.
[0024]
Example 4
The reaction was performed in the same manner as in Example 1 except that the reaction temperature was changed to 15 ° C. in Example 1. The results are shown in Table 1.
[0025]
Comparative Example 1
In Example 1, a flask was charged with 100 ml of a toluene solution containing 30 g (254 mmol) of α-methylstyrene, and a dropping funnel was charged with 0.46 g of an AlCl 3 CH 3 NO 2 solution (15% by weight) and 50 ml of toluene. Then, the reaction was conducted in the same manner as in Example 1 except that the catalyst was dropped into the α-methylstyrene solution, and hydrogenation was performed. At this time, the molar ratio of AlCl 3 to α-methylstyrene is 0.002. The results are shown in Table 1.
[0026]
Comparative Example 2
The reaction was performed in the same manner as in Example 1 except that 0.1 g of a CH 3 NO 2 solution (15% by weight) of AlCl 3 was used in Example 1, and hydrogenation was performed. The molar ratio of AlCl 3 to α-methylstyrene is 0.00044. The results are shown in Table 1.
[0027]
Comparative Example 3
The reaction was carried out in the same manner as in Example 1 except that 12.4 g of a CH 3 NO 2 solution (30 wt%) of AlCl 3 was used in Example 1, and hydrogenation was performed. The molar ratio of AlCl 3 to α-methylstyrene is 0.11. The results are shown in Table 1.
[0028]
Comparative Example 4
The reaction was performed in the same manner as in Example 1 except that the reaction temperature was set to −20 ° C. in Example 1, and hydrogenation was performed. The results are shown in Table 1.
[0029]
Comparative Example 5
The reaction was conducted in the same manner as in Example 1 except that the reaction temperature was 35 ° C. in Example 1, and hydrogenation was performed. The results are shown in Table 1.
[0030]
Example 5
In Example 1, the reaction was performed in the same manner as in Example 1 except that the reaction temperature at the time of hydrogenation was changed from 180 ° C to 220 ° C. The yield of MHI by hydrogenation was 86.0%. The results are shown in Table 1.
[0031]
Example 6
The reaction was carried out in the same manner as in Example 1 except that the amount of catalyst at the time of hydrogenation in Example 1 was changed from 0.5 g to 6.0 g. The yield of MHI by hydrogenation was 92.0%. The results are shown in Table 1.
[0032]
[Table 1]
【The invention's effect】
The method for producing an alicyclic compound according to claims 1, 2 and 3 is capable of producing the target alicyclic compound in high yield and high purity.
Claims (3)
で表される脂環式化合物の製造法。The α-methylstyrenes are dropped into an organic solvent containing the acid so that the molar ratio of the acid to the α-methylstyrenes is 0.0005 to 0.1, and the α-methylstyrenes are reacted at −15 to 30 ° C. Trimethylation of methylstyrenes yields trimers of α-methylstyrenes, and hydrogenation is carried out on the aromatic ring of the trimer of the obtained α-methylstyrenes (I )
The manufacturing method of the alicyclic compound represented by these.
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| JP35468797A JP4240239B2 (en) | 1997-12-24 | 1997-12-24 | Method for producing alicyclic compound |
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| JP35468797A JP4240239B2 (en) | 1997-12-24 | 1997-12-24 | Method for producing alicyclic compound |
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