JPH049353A - Production of dicyclopentadiene methacrylate - Google Patents
Production of dicyclopentadiene methacrylateInfo
- Publication number
- JPH049353A JPH049353A JP2111333A JP11133390A JPH049353A JP H049353 A JPH049353 A JP H049353A JP 2111333 A JP2111333 A JP 2111333A JP 11133390 A JP11133390 A JP 11133390A JP H049353 A JPH049353 A JP H049353A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- salt
- solvent
- reaction
- methacrylic 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 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 title claims abstract 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 title claims description 18
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 26
- 229910001868 water Inorganic materials 0.000 claims abstract description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000011651 chromium Substances 0.000 claims abstract description 6
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 239000003112 inhibitor Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000011572 manganese Substances 0.000 abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 4
- 150000008043 acidic salts Chemical class 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 2
- 229920000058 polyacrylate Polymers 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 229940116318 copper carbonate Drugs 0.000 description 4
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- NFMHSPWHNQRFNR-UHFFFAOYSA-N hyponitrous acid Chemical class ON=NO NFMHSPWHNQRFNR-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、シンクロペンタジエンメタクリレートの製造
方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing synchropentadiene methacrylate.
本発明で得られるシンクロペンタジエンメタクリレート
は、透明性、耐熱性、熱安定性、耐溶剤性、誘電特性等
の物理的、化学的特性に優れた新規なアクリレート系重
合体を製造するのに用いられる極めて有用な化学物質で
ある。The synchropentadiene methacrylate obtained in the present invention can be used to produce a new acrylate polymer with excellent physical and chemical properties such as transparency, heat resistance, thermal stability, solvent resistance, and dielectric properties. It is an extremely useful chemical substance.
その具体的用途としては、光硬化性樹脂、熱硬化性樹脂
、アクリル系塗料、アクリル系接着材の改質用途などが
挙げられる（例えば、特開昭６１−１５９４０８号公報
参照）。Specific uses thereof include modifying photocurable resins, thermosetting resins, acrylic paints, and acrylic adhesives (see, for example, Japanese Patent Laid-Open No. 159408/1983).
（従来の技術）
シンクロペンタジエンメタクリレートの製造方法として
は、シンクロペンタジエンとメタクリル酸とを、三弗化
ホウ素のエーテル錯体の存在下、反応させる方法が知ら
れている（特開昭５４−９７６９５号−、ケミカル・ア
ブストラクト６３−９０５５頁（１９６６年））。これ
とは別に、弗素含有イオン交換樹脂を触媒として用いる
方法もある（特開昭５６−５９７３６号）。(Prior Art) As a method for producing synchropentadiene methacrylate, a method is known in which synchropentadiene and methacrylic acid are reacted in the presence of an ether complex of boron trifluoride (JP-A-54-97695- , Chemical Abstracts, pp. 63-9055 (1966)). Apart from this, there is also a method using a fluorine-containing ion exchange resin as a catalyst (Japanese Patent Application Laid-open No. 59736/1983).
しかし、前者は、装置の腐食の問題があり、煩雑な後処
理を必要とし、後者は、シンクロペンタジエン（以下、
ＤＣＰＤと略記することがある）に対して過剰量のメタ
クリル酸を必要とし、効率的でないという欠点があった
。However, the former has problems with equipment corrosion and requires complicated post-treatment, and the latter uses synchropentadiene (hereinafter referred to as
This method requires an excessive amount of methacrylic acid (sometimes abbreviated as DCPD) and has the drawback of being inefficient.
これに対して、特開昭５６−５９７３５号に開示されて
いる、タングステンのへテロポリ酸を触媒として用いて
シンクロペンタジエンメタクリレートを製造する方法で
は、上記の装置の腐食および反応の非効率性は改善され
る。On the other hand, in the method for producing synchropentadiene methacrylate using tungsten heteropolyacid as a catalyst, which is disclosed in JP-A No. 56-59735, the corrosion of the above-mentioned equipment and the inefficiency of the reaction are improved. be done.
（発明が解決しようとする課題）
ところが特開昭５６−５９７３５号に記載の方法では、
シンクロペンタジエンメタクリレートの収率が約５０％
と低かった。(Problem to be solved by the invention) However, in the method described in JP-A No. 56-59735,
The yield of synclopentadiene methacrylate is approximately 50%.
It was low.
そこで本発明の目的は、タングステンのへテロポリ酸を
用いてシンクロペンタジエンとメタクリル酸とから、高
転化率及び高選択率で、従って高収率でシンクロペンタ
ジエンメタクリレートを、製造する方法を提供すること
にある。Therefore, an object of the present invention is to provide a method for producing synchropentadiene methacrylate from synchropentadiene and methacrylic acid using a tungsten heteropolyacid with high conversion and high selectivity, and therefore with high yield. be.
（課題を解決するための手段）
本発明は、シンクロペンタジエンとメタクリル酸との反
応用触媒として、物理吸着水を除去したリンタングステ
ン酸又はその酸性塩を用いることにより、上記目的を達
成した。(Means for Solving the Problems) The present invention has achieved the above object by using phosphotungstic acid or an acid salt thereof from which physically adsorbed water has been removed as a catalyst for the reaction between synchlopentadiene and methacrylic acid.
以下、本発明について詳説する。The present invention will be explained in detail below.
本発明において触媒としてヘテロポリ酸構造を有するリ
ンタングステン酸（Ｈ３ＰＷ、□Ｏ，。） 又はその酸
性塩を用いる。酸触媒としての活性を有する必要がある
ため、酸性塩であり、リンタングステン酸の金属塩であ
ることが好ましい。酸性塩は、例えば組成式ＭＸ／ＩＩ
ＩＨＩ−０［ＰＷ、２０４．Ｉ Ｃ但し、Ｍは金属原
子を表し、ｍは、金属原子の原子価を表し、Ｘは０より
大きく２又は２より小さい数である）で表すことができ
る。塩を形成するための金属としては、特に銅、クロム
、マンガン及びナトリウムであることが好ましい。酸性
塩の具体例としては、ＮａＨ２ＰＷ１２０４０、Ｎａ２
ＨＰＷｔ２０＋ｏ、ＣＬＩＨＰＷ１２０１０、ＣＬＩＨ
２［ＰＷｔ２０＜ｏ］ ２ 、ＣｒＨＩｌ［ＰＷ１２０
４０］ ３、ＭｎＨ４［：ＰＷ１２０４゜コ。等を挙げ
ることができる。In the present invention, phosphotungstic acid (H3PW, □O, .) having a heteropolyacid structure or an acid salt thereof is used as a catalyst. Since it is necessary to have activity as an acid catalyst, it is an acid salt, and preferably a metal salt of phosphotungstic acid. The acidic salt has, for example, the composition formula MX/II
IHI-0 [PW, 204. IC (where M represents a metal atom, m represents a valence of the metal atom, and X is a number greater than 0 and 2 or less than 2). Particularly preferred metals for forming the salt are copper, chromium, manganese and sodium. Specific examples of acid salts include NaH2PW12040, Na2
HPWt20+o, CLIHPW12010, CLIH
2[PWt20<o] 2 , CrHIl[PW120
40] 3, MnH4[:PW1204゜co. etc. can be mentioned.
リンタングステン酸の酸性塩は、水溶液中で金属のハロ
ゲン塩、炭酸塩、酢酸塩、硫酸塩等と反応させ、沈澱ま
たは蒸発乾固させることにより得ることができる。The acidic salt of phosphotungstic acid can be obtained by reacting with a metal halide, carbonate, acetate, sulfate, etc. in an aqueous solution, followed by precipitation or evaporation to dryness.
本発明において触媒として用いるリンタングステン酸又
はその酸性塩は物理吸着水を有さないものである。リン
タングステン酸は潮解性を有し、一般に多量の物理吸着
水を有する。シンクロペンタジエンとメタクリル酸から
シンクロペンタジエンメタクリレートを製造する際には
、この物理吸着水を除去したリンタングステン酸又はそ
の酸性塩を用いることで、高収率でシンクロペンタジェ
ンメタクリレートを製造することができる。リンタング
ステン酸の物理吸着水の除去は、例えば常圧では８０℃
以上に加熱することにより行うことができる。この温度
は、リンタングステン酸及び酸性塩の種類により異なる
が、熱分析をすることにより容易に求めることができる
。又、リンタングステン酸は、多量の結晶水も有する。The phosphotungstic acid or its acid salt used as a catalyst in the present invention does not have physically adsorbed water. Phosphortungstic acid has deliquescent properties and generally has a large amount of physically adsorbed water. When producing synclopentadiene methacrylate from synclopentadiene and methacrylic acid, synclopentadiene methacrylate can be produced in high yield by using phosphotungstic acid or its acid salt from which this physically adsorbed water has been removed. Physically adsorbed water of phosphotungstic acid can be removed at, for example, 80°C at normal pressure.
This can be done by heating above. This temperature varies depending on the type of phosphotungstic acid and acid salt, but can be easily determined by thermal analysis. Phosphortungstic acid also has a large amount of water of crystallization.
例えばＨｓＰＷ１２０４−では、１ユニツト当たり最大
２９コの結晶水を有する。そして加熱条件によっては物
理吸着水に次いで結晶水も離脱することがある。シンク
ロペンタジエン及びメタクリル酸の転化率並びにシンク
ロペンタジエンメタクリレートの選択率を考慮すると結
晶水の数が、リンタングステン酸１ユニツト当たり１〜
２０コ、好ましくは３〜ｌＯコであることが特に好まし
い。結晶水の数と加熱処理条件との関係は、熱分析を行
うことにより求めることかできる。例えばＨ３ＰＷ、、
Ｏ，、の場合、常圧で約１５０〜３００°Ｃ１好ましく
は２００〜３００°Ｃで加熱することにより所望の数の
結晶水を有するＨ３ＰＷ、□０４０を得ることができる
。For example, HsPW1204- has a maximum of 29 crystal waters per unit. Depending on the heating conditions, water of crystallization may also be released next to physically adsorbed water. Considering the conversion rate of synchropentadiene and methacrylic acid and the selectivity of synchropentadiene methacrylate, the number of water of crystallization is 1 to 1 per unit of phosphotungstic acid.
It is particularly preferred that the number is 20, preferably 3 to 10. The relationship between the number of water of crystallization and the heat treatment conditions can be determined by thermal analysis. For example, H3PW,
In the case of O,, H3PW, □040, having a desired number of water of crystallization can be obtained by heating at about 150 to 300°C, preferably 200 to 300°C, at normal pressure.
尚、上記加熱脱水処理は、減圧下でも行うことかでき、
但し、加熱温度は、減圧度に応じて、常圧の場合よりも
低くすることができる。In addition, the above heating dehydration treatment can also be performed under reduced pressure.
However, the heating temperature can be lower than that at normal pressure depending on the degree of pressure reduction.
また、リンタングステン酸の酸性塩は、反応の前に、脱
水処理されたリンタングステン酸と、金属のハロゲン塩
、炭酸塩、酢酸塩又は硫酸塩とを反応系内へ導入するこ
とにより形成させることもできる。Furthermore, the acid salt of phosphotungstic acid may be formed by introducing dehydrated phosphotungstic acid and a metal halide, carbonate, acetate, or sulfate into the reaction system before the reaction. You can also do it.
触媒の使用量は、シンクロペンタジェンとメタクリル酸
の合計重量に対して０．１〜５ｗｔ％が好ましく、１〜
３ｗｔ％とすることか特に好ましい。この使用範囲を越
えて多量に使用すると、シンクロペンタジエンのカチオ
ン重合が促進することかあり、好ましくない。The amount of the catalyst used is preferably 0.1 to 5 wt%, and 1 to 5 wt% based on the total weight of synclopentadiene and methacrylic acid.
It is particularly preferable to set the content to 3 wt%. If it is used in an amount exceeding this usage range, the cationic polymerization of synchropentadiene may be accelerated, which is not preferable.
反応温度は、４０６Ｃ〜９０℃、好ましくは６０〜８０
℃の範囲が好ましい。４０°Ｃ未満では反応を十分に進
行させるのに長時間を要することになる。また、１００
°Ｃ以上では、シンクロペンタジエンのカチオン重合お
よび生成したメタクリレートの重合が促進されるので好
ましくない。反応時間は、通常２〜１０時間の範囲とす
ることが適当である。The reaction temperature is 406C to 90C, preferably 60 to 80C.
A range of 0.degree. C. is preferred. If the temperature is lower than 40°C, it will take a long time for the reaction to proceed sufficiently. Also, 100
If the temperature is above .degree. C., the cationic polymerization of synchropentadiene and the polymerization of the produced methacrylate are promoted, which is not preferable. It is appropriate that the reaction time is usually in the range of 2 to 10 hours.
本発明の反応は、溶媒中で行う。リンタングステン酸が
シンクロペンタジエン及びメタクリル酸に溶解せず、不
均一な系になり、反応が進行しないからである。そこで
、溶媒としては、リンタングステン酸又はその酸性塩を
溶解するものを用いる。例えば、メチルエチルケトン、
メチルイソブチルケトン等のケトン類、酢酸エチル、酢
酸イソプロピル等のエステル類等を挙げることができる
。The reaction of the present invention is carried out in a solvent. This is because phosphotungstic acid is not dissolved in synchlopentadiene and methacrylic acid, resulting in a non-uniform system, and the reaction does not proceed. Therefore, a solvent that dissolves phosphotungstic acid or its acid salt is used as the solvent. For example, methyl ethyl ketone,
Examples include ketones such as methyl isobutyl ketone, and esters such as ethyl acetate and isopropyl acetate.
溶媒の使用量は、シンクロペンタジエンの仕込み重量１
００に対して２０〜１００（重量比）とすることが、リ
ンタングステン酸又はその酸性塩を溶解し、反応を進行
させるという観点から好ましい。The amount of solvent used is 1 by weight of synchropentadiene.
It is preferable to set the ratio to 20 to 100 (weight ratio) to 0.00 from the viewpoint of dissolving phosphotungstic acid or its acid salt and allowing the reaction to proceed.
シンクロペンタジエンとメタクリル酸の使用量は、実質
的に等量とすることが、高収率を挙げるために好ましい
。例えば、シンクロペンタジエン１に対してメタクリル
酸をモル比で０．８〜１．２の範囲内にすることが適当
である。It is preferable that the amounts of synclopentadiene and methacrylic acid used are substantially equal in order to obtain a high yield. For example, it is appropriate that the molar ratio of methacrylic acid to 1 part of synchropentadiene be within the range of 0.8 to 1.2.
シンクロペンタジエン及びメタクリル酸並びに生成する
メタクリレートは、熱的に不安定な物質であるため重合
禁止剤を添加して反応を行うのが好ましい。重合禁止剤
としては、ヒドロキノン、メトキシフェノール、カテコ
ール類、フェノチアジン、ナフトール類等が挙げられる
。その使用量は、反応基質の合計重量に対して１００〜
５００Ｏｐｐｍが好ましい。この範囲以上の添加は、反
応液の着色および触媒活性の劣化が著しくなるので好ま
しくなく、この範囲以下の添加では効果がでない。Since synchronopentadiene, methacrylic acid, and the methacrylate produced are thermally unstable substances, it is preferable to carry out the reaction by adding a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, methoxyphenol, catechols, phenothiazine, naphthols, and the like. The amount used is 100 to 100% based on the total weight of reaction substrates.
500 Oppm is preferred. Addition in excess of this range is undesirable, as coloring of the reaction liquid and deterioration of catalyst activity will become significant, while addition in below this range will not be effective.
また、酸素含有気体を反応液に吹き込んでも良く、その
量には特に限定はない。このとき、上記重合禁止剤のう
ち、アルコール系のものを併用することが特に好ましい
。Further, an oxygen-containing gas may be blown into the reaction liquid, and the amount thereof is not particularly limited. At this time, among the above-mentioned polymerization inhibitors, it is particularly preferable to use alcohol-based ones together.
反応は、回分式、半回分式及び連続式のいずれの方法で
も実施される。但し、回分式及び半回分式が好ましい。The reaction is carried out in any of the batch, semi-batch and continuous methods. However, batch type and semi-batch type are preferred.
回分式の場合は、触媒を溶解した溶媒にメタクリル酸及
びシンクロペンタジエンを供給するか、シンクロペンタ
ジエン、メタクリル酸及び溶媒の混合液に、触媒を溶解
した溶媒を供給するか、あるいは、触媒、メタクリル酸
及び溶媒の混合液に、シンクロペンタジエンを滴下する
ことができる。特に、触媒、メタクリル酸及び溶媒の混
合液に、シンクロペンタジエンを滴下する方法が、シン
クロペンタジエンの重合を抑制できるという観点から好
ましい。In the case of a batch method, methacrylic acid and synchropentadiene are supplied to a solvent in which the catalyst is dissolved, or a solvent in which the catalyst is dissolved is supplied to a mixture of synchropentadiene, methacrylic acid, and a solvent, or the catalyst, methacrylic acid Synchropentadiene can be added dropwise to the mixture of the compound and the solvent. In particular, a method in which synchropentadiene is dropped into a mixed solution of a catalyst, methacrylic acid, and a solvent is preferred from the viewpoint of suppressing polymerization of synchropentadiene.
反応は、常圧下またはオートクレーブ中で加圧下で行う
ことができる。The reaction can be carried out under normal pressure or under pressure in an autoclave.
反応終了後は、例えば以下のようにして生成物を回収す
ることができる。反応液容量に対して５〜１０倍量のノ
ルマルヘキサンに投入し、重合物を沈澱濾過する。回収
されるる液は、純水で洗浄後、５ｗｔ％炭酸水素ナトリ
ウム水溶液等のアルカリ水溶液で洗浄、さらに純水で洗
浄した後、低沸点成分を減圧除去することにより高純度
の粗製品か高収率で回収される。After the reaction is completed, the product can be recovered, for example, as follows. The reaction solution is poured into 5 to 10 times the volume of normal hexane, and the polymer is precipitated and filtered. The recovered liquid is washed with pure water, then washed with an alkaline aqueous solution such as a 5 wt % sodium bicarbonate aqueous solution, further washed with pure water, and then the low-boiling components are removed under reduced pressure to produce a high-purity crude product or a high-yield product. recovered at a rate.
さらに必要であれば、減圧蒸留することにより更に高純
度の製品を回収することができる。Furthermore, if necessary, a product of even higher purity can be recovered by distillation under reduced pressure.
得られるメタクリレートは、重合性が高いためできるか
ぎり短時間で蒸留を行うことが好ましく、薄膜蒸留等の
方法を用いることが好ましい。この際、重合禁止剤を添
加して行うのがよい。重合禁止剤としては、ターシャリ
ブチルカテコール、Ｎニトロンフェニルアミン、Ｎ−ニ
トロソヒドロキシルアミン塩、フェノチアジン、ジ−β
−ナフトール、Ｎ、Ｎ−ジ−β−ナフチル−Ｐ−フエニ
レンジアミン等が挙げられ、これらの単独または２種以
上の併用がよい。Since the obtained methacrylate has high polymerizability, it is preferable to distill it in as short a time as possible, and it is preferable to use a method such as thin film distillation. At this time, it is preferable to add a polymerization inhibitor. Polymerization inhibitors include tert-butylcatechol, N-nitron phenylamine, N-nitrosohydroxylamine salt, phenothiazine, di-β
-naphthol, N,N-di-β-naphthyl-P-phenylenediamine, etc., and these may be used alone or in combination of two or more.
以上の本発明の方法により、一般式（Ｉ）で表わされる
メタクリレートを高収率で得ることができる。尚、一般
式（Ｉ）のメタクリレートは、具体的には、以下の化合
物である。By the method of the present invention described above, the methacrylate represented by general formula (I) can be obtained in high yield. In addition, the methacrylate of general formula (I) is specifically the following compound.
（発明の効果）
本発明によれば、高い転化率かつ高い選択率でシンクロ
ペンタジエンメタクリレートを合成でき、その結果高収
率でシンクロペンタジエンメタクリレートを得ることか
できる。(Effects of the Invention) According to the present invention, synchropentadiene methacrylate can be synthesized with a high conversion rate and high selectivity, and as a result, synchropentadiene methacrylate can be obtained with a high yield.
（実施例） 以下、実施例により本発明をさらに説明する。(Example) The present invention will be further explained below with reference to Examples.
但し、本発明はこれに限定されるものではない。However, the present invention is not limited to this.
参考例１
撹拌器及び温度計を備えた１００−のガラス製フラスコ
中で、市販のＨ３ＰＷ、２０．．５、Ｏｇを純水２５−
に完全に溶解した。この溶液に、塩基性炭酸銅（Ｃｕ（
ＯＨ）２・ＣＨ３ＣＯＯ）０．０８ ｇを溶解した水溶
液１０−を滴下した。滴下終了後、室温で２時間攪拌し
、ついで１２０℃で加熱し、蒸発乾固して水分及び炭酸
を除去した。Reference Example 1 In a 100-mm glass flask equipped with a stirrer and a thermometer, commercially available H3PW, 20. ．． 5. Og in pure water 25-
completely dissolved in. Add basic copper carbonate (Cu(
An aqueous solution 10- in which 0.08 g of OH)2.CH3COO) was dissolved was added dropwise. After the dropwise addition was completed, the mixture was stirred at room temperature for 2 hours, then heated at 120°C and evaporated to dryness to remove water and carbonic acid.
このようにして、定量的にリンタングステン酸の銅の酸
性塩（ＣｕＨ４［ＰＷ１２０４０］ ２）を得た。In this way, a copper acid salt of phosphotungstic acid (CuH4[PW12040] 2) was obtained quantitatively.
参考例２
参考例１における塩基性炭酸銅の代わりに酢酸銅（ＣＬ
Ｉ（ＣＨ３ＣＯＯ）２ ・Ｈ２０）０．０７２ ｇを用
いた以外は参考例１と同様にしてリンタングステン酸の
銅の酸性塩（ＣｕＨ４［ＰＷｌ ２０４６１２ ）を得
た。Reference Example 2 Copper acetate (CL) was used instead of basic copper carbonate in Reference Example 1.
A copper acid salt of phosphotungstic acid (CuH4[PWl 204612 ) was obtained in the same manner as in Reference Example 1 except that 0.072 g of I(CH3COO)2 .H20) was used.
参考例３
塩基性炭酸銅（ＣＬＩ（ＯＨ）２ ・ＣｕＣ０３）０．
１６ ｇ （リンタングステン酸と等モル量）を用いた
以外は参考例２と同様にしてリンタングステン酸の銅の
酸性塩（ＣｕＨＰＷ＋ ２０４ Ｇ ）を得た。Reference Example 3 Basic copper carbonate (CLI(OH)2 ・CuC03) 0.
A copper acid salt of phosphotungstic acid (CuHPW+ 204 G) was obtained in the same manner as in Reference Example 2 except that 16 g (equimolar amount of phosphotungstic acid) was used.
参考例４
参考例１における塩基性炭酸銅の代わりに炭酸ナトリウ
ム０．０３８ ｇを用いた以外は参考例１と同様にして
リンタングステン酸のナトリウムの酸性塩（Ｎａｌ（２
ＰＷｌ ２０４０）を得た。Reference Example 4 An acid salt of sodium phosphotungstic acid (Nal(2
PWl 2040) was obtained.
参考例５及び６
参考例２における酢酸銅の代わりに酢酸クロム（Ｃｒ（
ＣＨａＣＯＯ）２” Ｈ２０）０．１６ ｇ （参考例
５）又は酢酸マンガン（Ｍｎ（ＣＨ３ＣＯＯ）２６４Ｈ
２０）０．０８９ ｇ（参考例６）を用いた以外は参考
例１と同様にしてリンタングステン酸のクロムの酸性塩
（ＣｒＨｓ ［ＰＷ１２０４０］ ａ）及びマンガンの
酸性塩（ＭｎＨ＊ ［ＰＷ＋□０４ｏ］ ２）を得た。Reference Examples 5 and 6 Chromium acetate (Cr(
CHaCOO)2” H20) 0.16 g (Reference Example 5) or manganese acetate (Mn(CH3COO)264H
20) Chromium acid salt of phosphotungstic acid (CrHs [PW12040] a) and manganese acid salt (MnH* [PW+□04o ] 2) was obtained.
実施例１
冷却装置、撹拌器、温度計を備えた２００−の四つロフ
ラスコにメタクリル酸２８．７ ｇ （０，３３ｍｏｂ
）、メチルエチルケトン２４ｙｄ、ノ１イトロキノン０
．０３ ｇ、触媒として参考例２で調製したリンタング
ステン酸の銅の酸性塩１．０ｇを加え、攪拌して均一溶
液とした。Example 1 28.7 g of methacrylic acid (0.33 mob
), methyl ethyl ketone 24yd, noitroquinone 0
．． 03 g, and 1.0 g of the copper acid salt of phosphotungstic acid prepared in Reference Example 2 as a catalyst were added and stirred to form a homogeneous solution.
７０°Ｃのオイルバス中で、滴下ロートを用いてシンク
ロペンタジエン４４ ｇ （０，３３ｍｏｌ）を２時間
かけて滴下した。滴下終了後、更に５時間反応させた。In a 70°C oil bath, 44 g (0.33 mol) of synchropentadiene was added dropwise using a dropping funnel over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 5 hours.
反応終了後、放冷し、未反応物及びメチルエチルケトン
をロータリーエバポレーターで減圧下除去した。残渣を
をｎ−ヘキサン中に投入し、重合物を沈澱ろ過した。ろ
液を回収し、５ｗｔ％Ｎａ２ＣＯ３水溶液及び純水で洗
浄した後、ｎ−ヘキサンを減圧除去し、粗製品を回収し
た。After the reaction was completed, the mixture was allowed to cool, and unreacted substances and methyl ethyl ketone were removed under reduced pressure using a rotary evaporator. The residue was poured into n-hexane, and the polymer was precipitated and filtered. The filtrate was collected and washed with a 5 wt % Na2CO3 aqueous solution and pure water, and then n-hexane was removed under reduced pressure and a crude product was collected.
この粗製品のガスクロマトグラフィによる分析により収
率、転化率および選択率を求めた。その結果を表１に示
す。The yield, conversion rate, and selectivity were determined by analyzing this crude product by gas chromatography. The results are shown in Table 1.
実施例２
リンタングステン酸の銅の酸性塩を３００℃で１２時間
加熱処理した以外は実施例１と同様にして反応を行った
。結果を表１に示す。Example 2 A reaction was carried out in the same manner as in Example 1, except that the copper acid salt of phosphotungstic acid was heat-treated at 300° C. for 12 hours. The results are shown in Table 1.
実施例３〜８
触媒として、参考例３で調製したリンタングステン酸の
銅の酸性塩（実施例３）、参考例１で調製したリンタン
グステン酸の銅の酸性塩（実施例４）、市販のリンタン
グステン酸（Ｈ３ＰＷ、２０４゜）（実施例５）、参考
例５で調製したリンタングステン酸のクロムの酸性塩（
実施例７）又は参考例６で調製したリンタングステン酸
のマンガンの酸性塩（実施例８）をそれぞれ３００℃で
１２時間加熱処理したもの、若しくは参考例４で調製し
たリンタングステン酸のナトリウムの酸性塩（実施例６
）を触媒として用いた以外、実施例１と同様にして反応
を行った。結果を表１に示す。Examples 3 to 8 As a catalyst, the acidic copper salt of phosphotungstic acid prepared in Reference Example 3 (Example 3), the acidic copper salt of phosphotungstic acid prepared in Reference Example 1 (Example 4), and the commercially available Phosphotungstic acid (H3PW, 204°) (Example 5), chromium acid salt of phosphotungstic acid prepared in Reference Example 5 (
Example 7) or the manganese acid salt of phosphotungstic acid prepared in Reference Example 6 (Example 8) heat-treated at 300°C for 12 hours, or the acid salt of sodium phosphotungstic acid prepared in Reference Example 4 Salt (Example 6
) was used as a catalyst, but the reaction was carried out in the same manner as in Example 1. The results are shown in Table 1.
比較例
市販のリンタングステン酸を加熱処理することなくその
まま触媒として用いた以外は、実施例１と同様にして反
応を行った。結果を表１に示す。Comparative Example A reaction was carried out in the same manner as in Example 1, except that commercially available phosphotungstic acid was used as a catalyst without heat treatment. The results are shown in Table 1.
実施例９
メタクリル酸２８．７ ｇ （０，３３ｍｏＡ ） 、
メチルエチルケトン２４−、ハイドロキノン０．０３ｇ
、触媒として市販のリンタングステン酸（Ｈ３ＰＷ、
、０．、）を３００°Ｃで１２時間加熱処理したものを
１．０ｇと塩基性炭酸銅（Ｃｕ（ＣＨ３ＣＯＯ）、 ”
Ｈ２Ｏ）を０．１ ｇの均一溶液を用いた以外は実施
例１と同様にして反応を行った。結果を表１に示す。Example 9 28.7 g (0.33 moA) of methacrylic acid,
Methyl ethyl ketone 24-, hydroquinone 0.03g
, commercially available phosphotungstic acid (H3PW,
,0. ,) heated at 300°C for 12 hours and 1.0g of basic copper carbonate (Cu(CH3COO)).
The reaction was carried out in the same manner as in Example 1 except that a homogeneous solution of 0.1 g of H2O) was used. The results are shown in Table 1.
Claims (2)
せて一般式（ I ） ▲数式、化学式、表等があります▼（ I ） で表わされるジシクロペンタジエンメタクリレートを製
造する方法であって、上記反応を、溶媒、及びヘテロポ
リ酸構造を有し、かつ物理吸着水を有さないリンタング
ステン酸又はその酸性塩の存在下、行うことを特徴とす
る上記方法。(1) A method for producing dicyclopentadiene methacrylate represented by the general formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) by reacting synchronopentadiene and methacrylic acid, in which the above reaction is carried out, The above method is characterized in that it is carried out in the presence of a solvent and phosphotungstic acid or an acid salt thereof having a heteropolyacid structure and not having physically adsorbed water.
ンガン及びナトリウムから成る群から選ばれる少なくと
も１種の金属塩である請求項１記載の製造方法。(2) The manufacturing method according to claim 1, wherein the acid salt of phosphotungstic acid is at least one metal salt selected from the group consisting of copper, chromium, manganese, and sodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2111333A JPH049353A (en) | 1990-04-26 | 1990-04-26 | Production of dicyclopentadiene methacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2111333A JPH049353A (en) | 1990-04-26 | 1990-04-26 | Production of dicyclopentadiene methacrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH049353A true JPH049353A (en) | 1992-01-14 |
Family
ID=14558550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2111333A Pending JPH049353A (en) | 1990-04-26 | 1990-04-26 | Production of dicyclopentadiene methacrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH049353A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011007514A1 (en) * | 2009-07-15 | 2011-01-20 | パナソニック株式会社 | Analysis reagent and analysis device having the analysis reagent carried therein |
| JP2011047835A (en) * | 2009-08-28 | 2011-03-10 | Panasonic Corp | Analysis reagent and analysis device |
| CN113083337A (en) * | 2019-12-23 | 2021-07-09 | 万华化学集团股份有限公司 | Catalyst for methacrylic acid production and preparation method and application thereof |
-
1990
- 1990-04-26 JP JP2111333A patent/JPH049353A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011007514A1 (en) * | 2009-07-15 | 2011-01-20 | パナソニック株式会社 | Analysis reagent and analysis device having the analysis reagent carried therein |
| JP2011047835A (en) * | 2009-08-28 | 2011-03-10 | Panasonic Corp | Analysis reagent and analysis device |
| CN113083337A (en) * | 2019-12-23 | 2021-07-09 | 万华化学集团股份有限公司 | Catalyst for methacrylic acid production and preparation method and application thereof |
| CN113083337B (en) * | 2019-12-23 | 2022-04-19 | 万华化学集团股份有限公司 | Catalyst for methacrylic acid production and preparation method and application thereof |
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