JPH0764787B2 - Method for producing high-purity methacrylic acid ester - Google Patents
Method for producing high-purity methacrylic acid esterInfo
- Publication number
- JPH0764787B2 JPH0764787B2 JP63074602A JP7460288A JPH0764787B2 JP H0764787 B2 JPH0764787 B2 JP H0764787B2 JP 63074602 A JP63074602 A JP 63074602A JP 7460288 A JP7460288 A JP 7460288A JP H0764787 B2 JPH0764787 B2 JP H0764787B2
- Authority
- JP
- Japan
- Prior art keywords
- methacrylic acid
- esterification
- solvent
- alcohol
- column
- 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 - Lifetime
Links
- 125000005397 methacrylic acid ester group Chemical group 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 121
- 238000005886 esterification reaction Methods 0.000 claims description 105
- 238000009835 boiling Methods 0.000 claims description 54
- 239000002904 solvent Substances 0.000 claims description 46
- 230000032050 esterification Effects 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 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 claims description 32
- 238000004821 distillation Methods 0.000 claims description 31
- 239000003729 cation exchange resin Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 27
- 239000007795 chemical reaction product Substances 0.000 claims description 20
- 230000003197 catalytic effect Effects 0.000 claims description 19
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 12
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 claims description 11
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 8
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 description 47
- 238000000605 extraction Methods 0.000 description 43
- 238000000926 separation method Methods 0.000 description 36
- 239000000047 product Substances 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 20
- 235000019198 oils Nutrition 0.000 description 20
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 18
- 239000008346 aqueous phase Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 239000012535 impurity Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 230000007774 longterm Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 239000007809 chemical reaction catalyst Substances 0.000 description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- 238000009825 accumulation Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- -1 Here Chemical compound 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、メタクリル酸エステルの製造方法に関する。
更に詳しく述べると、本発明はイソブチレン、ターシャ
リーブタノール、メタクロレインまたはイソブチルアル
デヒドを接触気相酸化して得られたメタクリル酸をアル
コールと反応させることからなるメタクリル酸エステル
の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a methacrylic acid ester.
More specifically, the present invention relates to a method for producing a methacrylic acid ester, which comprises reacting methacrylic acid obtained by catalytic gas phase oxidation of isobutylene, tert-butanol, methacrolein or isobutyraldehyde with alcohol.
［従来の技術及び問題点］ イソブチレン、ターシャリーブタノール、メタクロレイ
ンまたはイソブチルアルデヒドを接触気相酸化するメタ
クリルの製造法はよく知られている。該接触気相酸化反
応においては、メタクリル酸が主生成物として得られる
が、その他に数多くの副生物が生成する。これらの副成
分はメタクリル酸の分離精製工程において不都合を生ず
るのみならず、メタクリル酸をメタクリル酸エステル製
造用原料として用いた場合には、メタクリル酸エステル
化工程において、あるいはメタクリル酸エステル製品の
品質においてトラブルの原因となる。例えば、接触気相
酸化法で得られたメタクリル酸を陽イオン交換樹脂の存
在下にアルコールとエステル化反応させてメタクリル酸
エステルを製造する場合には、陽イオン交換樹脂の接触
性能が低下したり、得られたメタクリル酸エステル製
品、更には該メタクリル酸エステルを原料として用いて
得られるエマルジョン等の製品の色相安定性等の品質が
悪化したりするが、その主要な要因はメタクリル酸中に
含まれてくる該副生物にある。このため、例えば特開昭
60−252446号、同59−44338号、同59−44337号各公報な
どのような様々な改善策が提案されている。これらの方
法ではいずれも、接触気相酸化反応によって生成したガ
スを冷却し、水で捕集してメタクリル酸水溶液を得、こ
れから軽沸点物を除去した後、重亜硫酸塩を添加してキ
シレン、トルエン等の如き芳香族炭化水素等を溶媒とし
て用いてメタクリル酸を抽出し、更に溶剤分離、軽沸点
物分離、高沸点物分離および蒸留精製などの如き多数の
複雑な工程を順次経ることによって高品質のメタクリル
酸を製造している。しかしながらこれらの方法は多数の
複雑の工程および装置を必要とする。更に、該接触気相
酸化法ではテレフタル酸、安息香酸等の如き高沸点カル
ボン酸やタール状物質等の如き比較的高沸点の副生物が
生成する。これらの副生物は、高沸点物分離工程におい
てメタクリル酸が留出されるにつれて塔底に析出し操作
を困難ならしめるため、ここでの濃縮は高沸点物が析出
しない程度に制限される。従って高沸点物分離工程での
廃液として塔底から放出される高沸点物中には実質的な
量のメタクリル酸が残存しており、収率の低下および廃
液処理の負荷の増大をもよぎなくされる。[Prior Art and Problems] A method for producing methacryl by catalytic gas phase oxidation of isobutylene, tert-butanol, methacrolein or isobutyraldehyde is well known. In the catalytic gas-phase oxidation reaction, methacrylic acid is obtained as a main product, but many other by-products are produced. These subcomponents not only cause inconvenience in the separation and purification process of methacrylic acid, but also when methacrylic acid is used as a raw material for the production of methacrylic acid ester, in the methacrylic acid esterification process or in the quality of methacrylic acid ester product. It causes trouble. For example, when the methacrylic acid obtained by the catalytic gas phase oxidation method is subjected to an esterification reaction with an alcohol in the presence of a cation exchange resin to produce a methacrylic acid ester, the contact performance of the cation exchange resin decreases. , The quality such as hue stability of the obtained methacrylic acid ester product, and further the product such as an emulsion obtained by using the methacrylic acid ester as a raw material may be deteriorated. It is in the by-product coming. Therefore, for example,
Various improvement measures such as 60-252446, 59-44338, and 59-44337 have been proposed. In any of these methods, the gas generated by the catalytic gas-phase oxidation reaction is cooled, and methacrylic acid aqueous solution is obtained by collecting with water, and after removing the light-boiling substance from this, bisulfite is added to xylene, Methacrylic acid is extracted using an aromatic hydrocarbon such as toluene as a solvent, and then a high number of complicated steps such as solvent separation, light-boiling point separation, high-boiling point separation, and distillation purification are sequentially performed to improve the methacrylic acid. Manufactures quality methacrylic acid. However, these methods require a large number of complicated steps and equipment. Further, in the catalytic gas phase oxidation method, high boiling carboxylic acids such as terephthalic acid and benzoic acid, and relatively high boiling by-products such as tar-like substances are produced. These by-products deposit on the bottom of the column as methacrylic acid is distilled off in the high-boiling point separation step and make the operation difficult, so the concentration here is limited to the extent that high-boiling points do not deposit. Therefore, a substantial amount of methacrylic acid remains in the high-boiling substance discharged from the bottom of the column as waste liquid in the high-boiling substance separation step, which may reduce the yield and increase the load of waste liquid treatment. To be done.
一方、メタクリル酸を陽イオン交換樹脂の存在下にアル
コールと反応させてメタクリル酸エステルを製造する方
法も公知である（特公昭48−1369号公報、特開昭55−12
2740号公報、特開昭58−159442号公報参照）。通常かか
る方法では、メタクリル酸を陽イオン交換樹脂の存在下
にアルコールと反応させた後、エステル化反応生成物を
蒸留し、未反応メタクリル酸を塔底から抜出してエステ
ル化反応器に戻すとともに、メタクリル酸エステル、ア
ルコールおよび水の混合物を留出させ、留出液を抽出や
蒸留等の工程にかけてメタクリル酸エステル製品を得、
アルコールを回収し再利用する。しかし、前述したよう
に原料メタクリル酸中に含まれる副生物やメタクリル酸
の重合物あるいはメタクリル酸エステルの重合物等が蓄
積すると陽イオン交換樹脂層の閉塞や触媒性能低下等の
支障が生じたりする。このため前述したような複雑な工
程および装置を経て精製したメタクリル酸をエステル化
反応原料として使用する必要があるうえに、エステル化
反応後に回収した未反応メタクリル酸をエステル化反応
器に戻す前に薄層蒸発器等で処理し高沸点不純物や重合
物を除去することも必要である。しかしこの場合、薄層
蒸発器等の処理装置に重合物や不純物が徐々に固型物と
なって析出するため、時々装置を停止し析出物を除去し
なければならない。On the other hand, a method for producing a methacrylic acid ester by reacting methacrylic acid with alcohol in the presence of a cation exchange resin is also known (Japanese Patent Publication No. 48-1369 and Japanese Patent Laid-Open No. 55-12).
2740, JP-A-58-159442). Usually in such a method, after reacting methacrylic acid with alcohol in the presence of a cation exchange resin, the esterification reaction product is distilled, unreacted methacrylic acid is withdrawn from the bottom of the column and returned to the esterification reactor, A mixture of methacrylic acid ester, alcohol and water is distilled out, and the distillate is subjected to steps such as extraction and distillation to obtain a methacrylic acid ester product,
Recover alcohol for reuse. However, as described above, accumulation of by-products contained in the raw material methacrylic acid, a polymer of methacrylic acid, a polymer of methacrylic acid ester, or the like may cause problems such as clogging of the cation exchange resin layer and deterioration of catalytic performance. . For this reason, it is necessary to use methacrylic acid purified through the complicated steps and devices as described above as a raw material for the esterification reaction, and before returning the unreacted methacrylic acid recovered after the esterification reaction to the esterification reactor. It is also necessary to remove the high boiling impurities and the polymer by treating with a thin layer evaporator or the like. However, in this case, the polymer and impurities gradually precipitate as a solid substance in the processing apparatus such as a thin-layer evaporator, and therefore the apparatus must be stopped occasionally to remove the precipitate.
このような従来の多数の複雑の工程および装置を経て得
た高品質のメタクリル酸を原料とするメタクリル酸エス
テルの製造法に対し、メタクリル酸水溶液から炭素数５
〜17の各種炭化水素を抽出溶剤として用いてメタクリル
酸を含む溶剤相を得、この溶剤相をエステル化用触媒存
在下にアルコールと反応させ、エステル化反応生成物を
水または食塩水で洗浄して不純物を除去した後、蒸留精
製するメタクリル酸エステルの製造法も示されている
（特開昭49−45020号公報）。この方法では、エステル
化反応原料のメタクリル酸を得るまでの工程は簡略化さ
れており、しかも接触気相酸化反応によって生成したメ
タクリル酸は全量エステル化反応工程に供給されるので
ここまでにはメタクリル酸の損失もない。しかし、エス
テル化反応後、反応生成物を炭酸ナトリウム水溶液で中
和処理するので、アルコールは回収されるものの未反応
のメタクリル酸は廃棄されてしまい、メタクリル酸を損
失するのみならず廃液処理の面でも問題である。また、
多量の溶剤を含んだ状態でメタクリル酸がエステル化反
応工程に供給されるので、エステル化反応器は生産量に
比べて大きくなり、単位エステル化触媒量当りの処理液
量も多くなって効率が悪い。In contrast to a method for producing a methacrylic acid ester using high-quality methacrylic acid as a raw material obtained through many conventional complicated steps and devices as described above, a methacrylic acid aqueous solution has 5 carbon atoms.
~ 17 various hydrocarbons are used as extraction solvent to obtain a solvent phase containing methacrylic acid, this solvent phase is reacted with alcohol in the presence of an esterification catalyst, and the esterification reaction product is washed with water or saline. A method for producing a methacrylic acid ester, in which impurities are removed by distillation and then purification by distillation is also disclosed (JP-A-49-45020). In this method, the process up to obtaining methacrylic acid as the esterification reaction raw material is simplified, and moreover, the whole amount of methacrylic acid produced by the catalytic gas phase oxidation reaction is supplied to the esterification reaction process, so that the methacrylic acid has not been processed so far. There is no loss of acid. However, after the esterification reaction, the reaction product is neutralized with an aqueous solution of sodium carbonate, so that alcohol is recovered but unreacted methacrylic acid is discarded, which not only causes loss of methacrylic acid but also waste liquid treatment. But it's a problem. Also,
Since methacrylic acid is supplied to the esterification reaction step while containing a large amount of solvent, the esterification reactor becomes larger than the production amount, and the treatment liquid amount per unit esterification catalyst amount also increases, resulting in higher efficiency. bad.
更には本発明者等の知見によれば、長期間連続運転する
につれて触媒性能が低下し支障をきたすことがわかっ
た。Further, according to the knowledge of the present inventors, it was found that the catalyst performance deteriorates and the trouble occurs when the catalyst is continuously operated for a long period of time.
また更に本発明者等は、接触気相酸化反応により得られ
たメタクリル酸中に微量の副生アセトニルアセトンが含
まれており、これが該エステル化反応において縮合環化
してジメチルフランになり、これがメタクリル酸エステ
ル製品に含まれると該製品や該製品を用いて得られるエ
マルジョン等の二次製品の色相に悪影響を及ぼすことを
見出だした。アセトニルアセトンがジメチルフランへの
転化率はさほど大きくないが、未反応メタクリル酸を回
収再使用する際にアセトニルアセトンも同伴して系内に
蓄積し、それにつれてジメチルフランの発生量も多くな
る。しかもジメチルフランは特にメタクリル酸メチル等
の如き低級メタクリル酸エステルとの比揮発度が小さい
ため、分離するのが難しい。前述の公報等にはこのよう
なことは記載されておらず、これを考慮した有効な方策
も開示されていない。Further, the present inventors have found that methacrylic acid obtained by the catalytic gas phase oxidation reaction contains a small amount of by-product acetonylacetone, which is condensed and cyclized into dimethylfuran in the esterification reaction. It has been found that inclusion in a methacrylic acid ester product adversely affects the hue of the product or a secondary product such as an emulsion obtained using the product. The conversion rate of acetonylacetone to dimethylfuran is not so great, but when unreacted methacrylic acid is recovered and reused, acetonylacetone accompanies and accumulates in the system, and the amount of dimethylfuran generated increases accordingly. . Moreover, dimethyl furan is difficult to separate because it has a low relative volatility with lower methacrylic acid esters such as methyl methacrylate. The above-mentioned publications and the like do not describe such a thing, nor an effective measure in consideration of this.
従って本発明の目的は、このような従来法の欠点を改善
すること、即ち工程および装置を簡略化し、廃液量を削
減し、長期間の連続運転を可能にし、かつ効率よく高品
質のメタクリル酸エステルを得ることができるようなメ
タクリル酸エステルの製造法を提供することにある。Therefore, an object of the present invention is to improve the drawbacks of the conventional method, that is, to simplify the process and apparatus, reduce the amount of waste liquid, enable long-term continuous operation, and efficiently produce high-quality methacrylic acid. It is an object of the present invention to provide a method for producing a methacrylic acid ester that can obtain an ester.
［問題点を解決する為の手段］ 本発明者等は鋭意検討の結果、メタクリル酸水溶液から
メタクリル酸を抽出する工程において使用する抽出溶剤
として炭素数６〜９の脂肪族鎖状飽和炭化水素を用い、
エステル化工程においてエステル化用触媒として多孔質
の強酸性陽イオン交換樹脂を用いることにより、前記本
発明の目的を達成できることを見出した。かくして本発
明によれば、イソブチレン、ターシャリーブタノール、
メタクロレインまたはイソブチルアルデヒドを接触気相
酸化し、得られた反応生成物から軽沸点物質を蒸留また
は放射操作によって除去し、得られたメタクリル酸水溶
液から炭素数６〜９の脂肪族鎖状飽和炭化水素を溶剤と
して用いてメタクリル酸を抽出し、得られたメタクリル
酸溶剤溶液から溶剤を回収し、得られたアセトニルアセ
トンを含有する粗製メタクリル酸をエステル化用触媒と
して架橋度２〜16％、比表面積0.2〜50m2/g、ポロシテ
ィ０〜1.0ml/g、平均細孔径100〜600Åである多孔質の
強酸性陽イオン交換樹脂を用いて炭素数１〜12の低級脂
肪族アルコールまたは低級脂環式アルコールと反応させ
ることによってエステル化し、ジメチルフラン含有量の
低減されたエステル化反応生成物を得、ここに得られた
該エステル化反応生成物を精製工程に付することを特徴
とする高純度メタクリル酸エステルの製造方法が提供さ
れる。[Means for Solving Problems] As a result of earnest studies by the present inventors, an aliphatic chain saturated hydrocarbon having 6 to 9 carbon atoms was used as an extraction solvent used in the step of extracting methacrylic acid from an aqueous methacrylic acid solution. Used,
It has been found that the object of the present invention can be achieved by using a porous strongly acidic cation exchange resin as the esterification catalyst in the esterification step. Thus, according to the present invention, isobutylene, tertiary butanol,
Catalytic gas phase oxidation of methacrolein or isobutyraldehyde, light boiling point substances are removed from the obtained reaction product by distillation or radiative operation, and saturated aliphatic carbon chain having 6 to 9 carbon atoms is obtained from the obtained aqueous solution of methacrylic acid. Methacrylic acid was extracted using hydrogen as a solvent, the solvent was recovered from the obtained methacrylic acid solvent solution, and the crude methacrylic acid containing the obtained acetonylacetone was used as a catalyst for esterification and the degree of crosslinking was 2 to 16%. Using a porous strongly acidic cation exchange resin having a specific surface area of 0.2 to 50 m 2 / g, porosity of 0 to 1.0 ml / g, and an average pore size of 100 to 600 Å, a lower aliphatic alcohol or lower fat having 1 to 12 carbon atoms The esterification reaction product having a reduced dimethylfuran content is obtained by esterification by reacting with a cyclic alcohol, and the esterification reaction product obtained here is purified. Provided is a method for producing a high-purity methacrylic acid ester, which is characterized by being subjected to a production process.
本発明においては、まず従来方法の通り、イソブチレ
ン、ターシャリーブタノール、メタクロレインまたはイ
ソブチルアルデヒドを接触気相酸化し、得られた反応生
成ガスを冷却して水で捕集し、得られた水溶液を蒸留ま
たは放散工程にかけて該水溶液中の若干量のメタクロレ
イン、アセトン等の如き軽沸点物質を除去する。In the present invention, first, as in the conventional method, isobutylene, tert-butanol, methacrolein or isobutyraldehyde is subjected to catalytic gas phase oxidation, and the obtained reaction product gas is cooled and collected with water to obtain an aqueous solution. A small amount of light boiling substances such as methacrolein, acetone and the like in the aqueous solution are removed by a distillation or stripping process.
次いで該メタクリル酸水溶液を溶剤抽出工程に送り、こ
こでメタクリル酸を含む溶剤相と水相とに分離する。そ
の際、抽出溶剤として炭素数６〜９の脂肪族鎖状飽和炭
化水素を用いる。キシレン、トルエンなどの如き芳香族
炭化水素を用いた場合は、抽出後の溶剤相中におけるメ
タクリル酸濃度に対する高沸点不純物濃度の比率が高
く、前記の高沸点不純物に起因すると考えられる固型物
の析出やエステル化触媒の触媒性能低下の問題を起こ
し、またアセトニルアセトンの比率が高くなることから
前述したごとく製品々質面でも問題を起こす。しかし本
発明に従い、炭素数６〜９の脂肪族鎖状飽和炭化水素を
用いる場合には、抽出後の溶剤相中におけるメタクリル
酸濃度に対する高沸点不純物濃度の比率が低くなり、後
述するごとくエステル化用触媒として多孔質の強酸性陽
イオン交換樹脂を組合せて用いる結果として、前記従来
方法に認められた工程および装置の複雑化についての問
題点は解決されるに至る。Then, the methacrylic acid aqueous solution is sent to a solvent extraction step, where it is separated into a solvent phase containing methacrylic acid and an aqueous phase. At that time, an aliphatic chain saturated hydrocarbon having 6 to 9 carbon atoms is used as the extraction solvent. When an aromatic hydrocarbon such as xylene or toluene is used, the ratio of the high boiling point impurity concentration to the methacrylic acid concentration in the solvent phase after extraction is high, and solid substances considered to be caused by the high boiling point impurities are This causes problems such as precipitation and deterioration of catalytic performance of the esterification catalyst, and also causes a problem in product quality as described above due to the high proportion of acetonylacetone. However, according to the present invention, when the aliphatic chain saturated hydrocarbon having 6 to 9 carbon atoms is used, the ratio of the high-boiling point impurity concentration to the methacrylic acid concentration in the solvent phase after extraction becomes low, and the esterification as described later. As a result of using a combination of a porous strong acid cation exchange resin as a catalyst for use, the problems of the complicated process and apparatus recognized in the conventional method can be solved.
炭素数６〜９の脂肪族鎖状飽和炭化水素とは具体的には
ヘキサン、ヘプタン、オクタン、ノナンであり、これら
は直鎖状のものであっても分岐を有するものであっても
よく、またこれらの混合物であってもよい。しかし、炭
素数６〜９の脂肪族鎖状飽和炭化水素を抽出溶剤として
用いると、メタクリル酸の抽出率がやや低いため抽出溶
剤量が多めになる。従って、抽出溶剤量を節減するた
め、炭素数６〜９の脂肪族鎖状飽和炭化水素に他の溶
剤、例えばメタクリル酸エステルやキシレン、トルエン
などの如き芳香族炭化水素を混合したものを抽出溶剤と
して用いることも有効な方法である。この場合の混合比
率としては炭素数６〜９の脂肪族鎖状飽和炭化水素を50
重量％以上含有していることが好ましい。The aliphatic chain saturated hydrocarbon having 6 to 9 carbon atoms is specifically hexane, heptane, octane, or nonane, which may be linear or branched. It may also be a mixture of these. However, when an aliphatic chain saturated hydrocarbon having 6 to 9 carbon atoms is used as the extraction solvent, the extraction rate of methacrylic acid is rather low and the extraction solvent amount becomes large. Therefore, in order to reduce the amount of the extraction solvent, a mixture of an aliphatic chain saturated hydrocarbon having 6 to 9 carbon atoms with another solvent, for example, an aromatic hydrocarbon such as methacrylic acid ester, xylene, or toluene is used as the extraction solvent. Is also an effective method. The mixing ratio in this case is 50% of the aliphatic chain saturated hydrocarbon having 6 to 9 carbon atoms.
It is preferable that the content is at least wt%.
抽出装置、抽出条件などに関しては通常行なわれている
ものでよい。例えば、通常の向流接触装置を用い、常温
〜70℃の温度範囲及びメタクリル酸水溶液に対する抽出
溶剤の重量比0.5〜1.5の範囲で操作すれば良好な抽出結
果が得られる。The extraction device, the extraction conditions and the like may be those normally used. For example, good extraction results can be obtained by using an ordinary countercurrent contact device and operating in a temperature range of room temperature to 70 ° C. and a weight ratio of the extraction solvent to the aqueous methacrylic acid solution of 0.5 to 1.5.
従来は前記特開昭60−252446号公報などにみられるよう
に、メタクリル酸を含む溶剤相を溶剤分離装置、軽沸点
物分離工程、高沸点物分離工程および蒸留精製工程など
多数の複雑な工程に付して高品質のメタクリル酸を取得
し、それをエステル化反応用原料として用いていた。し
かし本発明においては、溶剤抽出工程を出たメタクリル
酸を含む溶剤相を蒸留等からなる簡単な溶剤分離工程に
送って粗製メタクリル酸と溶剤とに分け、溶剤を回収し
て循環使用する一方、粗製メタクリル酸をエステル化工
程に送り、触媒の存在下でメタクリル酸を炭素数１〜12
の低級脂肪族アルコールと反応させてメタクリル酸エス
テルを製造するという簡単な工程だけですむ。Conventionally, as seen in JP-A-60-252446, a solvent phase containing methacrylic acid is subjected to a number of complicated steps such as a solvent separation device, a light-boiling point separation step, a high-boiling point separation step and a distillation purification step. Then, high quality methacrylic acid was obtained and used as a raw material for the esterification reaction. However, in the present invention, the solvent phase containing methacrylic acid that has exited the solvent extraction step is sent to a simple solvent separation step consisting of distillation or the like to separate the crude methacrylic acid and the solvent, while the solvent is recovered and recycled, Crude methacrylic acid is sent to the esterification process, and methacrylic acid has 1 to 12 carbon atoms in the presence of a catalyst.
It only requires a simple process of producing a methacrylic acid ester by reacting with the lower aliphatic alcohol of.
エステル化工程における原料メタクリル酸としては前記
粗製メタクリル酸に後の工程からくる回収メタクリル酸
を混合して用いてもよい。前記粗製メタクリル酸は少量
のテレフタル酸、安息香酸等の如き高沸点カルボン酸を
含んでいる。しかし、これら高沸点カルボン酸はエステ
ル化され、メタクリル酸エステル中での溶解度がカルボ
ン酸の状態である場合に比べて増加するので、これらの
析出は起らず、エステル化工程においてエステル化触媒
層の閉塞が避けられる。As the raw material methacrylic acid in the esterification step, the crude methacrylic acid may be mixed with the recovered methacrylic acid from the subsequent step. The crude methacrylic acid contains a small amount of high boiling carboxylic acids such as terephthalic acid and benzoic acid. However, these high-boiling carboxylic acids are esterified, and the solubility in the methacrylic acid ester is higher than that in the case of the carboxylic acid state. The blockage of can be avoided.
エステル化工程で使用する炭素数１〜12の低級脂肪族ア
ルコールの具体例としてはメタノール、エタノール、プ
ロパノール、ブタノール、２−エチル−ヘキサノール、
シクロヘキサン等が挙げられ、これらは直鎖状のもので
あっても分岐を有するものであっても良い。Specific examples of the lower aliphatic alcohol having 1 to 12 carbon atoms used in the esterification step include methanol, ethanol, propanol, butanol, 2-ethyl-hexanol,
Examples thereof include cyclohexane and the like, which may be linear or branched.
本発明ではエステル化工程における触媒として前記した
様な特定物性を満足する多孔質の強酸性陽イオン交換樹
脂を用いる。該触媒は向上した耐有機汚染性を示し、十
分な触媒性能を持続するが、他の強酸性陽イオン交換樹
脂は使用時間が経過するにつれて触媒性性能が低下し長
期間の連続運転に支障をきたす。また、前述したごと
く、本発明者等は接触気相酸化反応で副生したアセトニ
ルアセトンが該エステル化反応において縮合環化してジ
メチルフランになりこれがメタクリル酸エステル製品に
含まれると該製品や該製品を用いて得られるエマルジョ
ン等の二次製品の色相に悪影響を及ぼすことを見出だし
たが、更に、該エステル化反応において前記した多孔質
の強酸性陽イオン交換樹脂を用いた場合にはゲル型の陽
イオン交換樹脂を用いた場合に比べてジメチルフランの
生成が少なくなることも見出だした。In the present invention, a porous strongly acidic cation exchange resin satisfying the above-mentioned specific physical properties is used as a catalyst in the esterification step. The catalyst exhibits improved resistance to organic pollution and maintains sufficient catalytic performance, but other strong acid cation exchange resins have a decline in catalytic performance over the use time, which hinders long-term continuous operation. Come here. Further, as described above, the present inventors have confirmed that when acetonylacetone produced as a by-product in the catalytic gas-phase oxidation reaction is condensed and cyclized into dimethylfuran in the esterification reaction and is included in the methacrylic acid ester product, It was found that the hue of a secondary product such as an emulsion obtained by using the product is adversely affected. Furthermore, when the above-mentioned porous strong acid cation exchange resin is used in the esterification reaction, gel is obtained. It was also found that the production of dimethylfuran was reduced as compared with the case of using the cation exchange resin of the type.
多孔質の強酸性陽イオン交換樹脂としては架橋度２〜16
％、比表面積0.2〜50m2/g、ポロシティ０〜1.0mol/g、
平均細孔径100〜600Åのものが使用されるべきである。
多孔質の強酸性陽イオン交換樹脂の具体例としては、デ
ュオライトES−26（住友化学社製）、PK−208、PK−21
6、PK−228（三菱化成社製）、MSC−１、88（ダウ社
製）、アンバーリスト16（ロームアンドハース社製）な
どが挙げられる。As a porous strong acid cation exchange resin, the degree of crosslinking is 2 to 16
%, Specific surface area 0.2 to 50 m 2 / g, porosity 0 to 1.0 mol / g,
Those with an average pore size of 100-600Å should be used.
Specific examples of the porous strongly acidic cation exchange resin include Duolite ES-26 (Sumitomo Chemical Co., Ltd.), PK-208, and PK-21.
6, PK-228 (manufactured by Mitsubishi Kasei), MSC-1, 88 (manufactured by Dow), Amberlist 16 (manufactured by Rohm and Haas), and the like.
エステル化反応は液相において50〜110℃の温度条件下
に懸濁床または固定床型式で行われる。また通常行なわ
れているように、本発明方法においても重合禁止剤を用
いることができる。使用される重合禁止剤としては例え
ばハイドロキノン、メトキシハイドロキノン、メチレン
ブルーあるいはフェノチアジンなどが挙げられる。な
お、反応を分子状酸素の存在下に行うと重合禁止剤の効
果を更に高めることができる。The esterification reaction is carried out in the liquid phase under the temperature condition of 50 to 110 ° C. in the suspension bed or fixed bed type. A polymerization inhibitor can also be used in the method of the present invention, as is usually done. Examples of the polymerization inhibitor used include hydroquinone, methoxyhydroquinone, methylene blue and phenothiazine. The effect of the polymerization inhibitor can be further enhanced by carrying out the reaction in the presence of molecular oxygen.
このようにして得られたエステル化反応生成物は通常行
なわれているような方法で処理し、メタクリル酸および
アルコールは回収、再利用するとともに、メタクリル酸
エステル製品を得ることができる。しかも前述しごと
く、溶剤抽出工程から供給されるメタクリル酸中に含ま
れている高沸点カルボン酸はエステル化反応工程におい
てエステル化されて溶解度がカルボン酸の状態である場
合に比べて増加するので、真空蒸発器等を用いてメタク
リル酸中の重合物や不純物を除去する際にこれらが固型
物となって析出することがないかまたは軽減され、従っ
て長期間の連続運転が可能となる。The esterification reaction product thus obtained can be treated by a conventional method to recover and reuse methacrylic acid and alcohol, and a methacrylic acid ester product can be obtained. Moreover, as described above, since the high boiling point carboxylic acid contained in the methacrylic acid supplied from the solvent extraction step is esterified in the esterification reaction step and the solubility increases as compared with the case where the solubility is in the carboxylic acid state, When the polymer and impurities in methacrylic acid are removed using a vacuum evaporator or the like, these do not precipitate or become a solid substance and are reduced, so that long-term continuous operation becomes possible.
また、特にエステル化反応工程で使用するアルコールが
炭素数１〜４の低級脂肪族アルコールである場合には、
精製工程において、エステル化反応生成物を蒸発器にて
蒸留し、蒸発器の缶出液をエステル化反応工程に還流さ
せる一方、蒸発器の留出液を冷却して油相と水相とに分
離させ、水相からアルコールを蒸留分離してエステル化
反応工程に還流し、油相からメタクリル酸エステルを蒸
留精製することが有効である。この場合、エステル化反
応生成物は蒸発器に送られ、メタクリル酸を主成分とす
る缶出液と反応により生成したメタクリル酸エステル、
水およびアルコールを主成分とする留出液とに分離す
る。缶出液は回収し、エステル化反応工程に還流させ
る。好ましくは還流させる途中、缶出液の一部または全
部を蒸留してメタクリル酸中の重合物や不純物を除去
し、これらが系内に蓄積するのを防ぐ。こうすることに
より、エステル化触媒層の閉塞等の障害が避けられる。
また、特に高沸点不純物を除去することにより、エステ
ル化反応におけるジメチルフランの発生源となるアセト
ニルアセトンの蓄積を防ぐことができ、より色相安定性
のよい製品あるいは該製品を原料とする二次製品を得る
ことができる。Further, particularly when the alcohol used in the esterification reaction step is a lower aliphatic alcohol having 1 to 4 carbon atoms,
In the purification process, the esterification reaction product is distilled in an evaporator, and the bottom liquid of the evaporator is refluxed to the esterification reaction process, while the distillate of the evaporator is cooled to an oil phase and an aqueous phase. It is effective to separate and distill the alcohol from the aqueous phase and then reflux to the esterification reaction step to distill and purify the methacrylic acid ester from the oil phase. In this case, the esterification reaction product is sent to the evaporator, the methacrylic acid ester produced by the reaction with the bottoms liquid containing methacrylic acid as a main component,
Separate into water and distillate containing alcohol as the main component. The bottoms are collected and refluxed in the esterification reaction step. Preferably, during the reflux, a part or all of the bottoms is distilled to remove the polymer and impurities in methacrylic acid and prevent them from accumulating in the system. By doing so, obstacles such as clogging of the esterification catalyst layer can be avoided.
In addition, especially by removing high-boiling point impurities, it is possible to prevent the accumulation of acetonylacetone, which is a source of dimethylfuran in the esterification reaction, and to obtain a product having better hue stability or a secondary product using the product as a raw material. You can get the product.
一方、蒸発器からの留出液は冷却して油相と水相とに分
離させ、水相からアルコールを蒸留分離してエステル化
反応工程に還流し、油相からメタクリル酸エステルを蒸
留精製して製品を得る。この際蒸発器からの留出液中に
同伴するメタクリル酸の量は極めて僅かであるからメタ
クリル酸収率上問題にならないが、前述した油相からメ
タクリル酸エステルを蒸留精製する工程で回収できるの
でこれをエステル化反応工程に還流させてもよい。ま
た、蒸発器の代わりに精留塔を用いることにより、留出
液中に同伴されるメタクリル酸の量を痕跡程度にまで減
少させることも可能である。On the other hand, the distillate from the evaporator is cooled and separated into an oil phase and an aqueous phase, alcohol is distilled off from the aqueous phase and refluxed to the esterification reaction step, and the methacrylic acid ester is distilled and purified from the oil phase. To get the product. At this time, since the amount of methacrylic acid entrained in the distillate from the evaporator is extremely small, there is no problem in the yield of methacrylic acid, but it can be recovered in the step of distilling and refining the methacrylic acid ester from the oil phase described above. This may be refluxed in the esterification reaction step. It is also possible to reduce the amount of methacrylic acid entrained in the distillate to a trace level by using a rectification column instead of the evaporator.
一方、エステル化反応工程で使用するアルコールが炭素
数５以上の低級脂肪族アルコールである場合には、エス
テル化反応で生成するエステルの沸点がメタクリル酸お
よびアルコールの沸点よりも高くなり、このような場合
には、反応蒸留法が好ましく用いられる。この場合、エ
ステル化反応によって生成する水を反応器に併設した蒸
留塔から留出させ、系外に除去して反応を進行させる。
この際、メタクリル酸が留出するのを防ぐために一部の
アルコールを蒸留塔の塔頂より供給することが好まし
い。反応器の缶出液は軽沸点物分離塔に供給し、未反応
のアルコールとメタクリル酸を留去させ、エステル化反
応工程に還流させる。軽沸点物分離塔の缶出液は高沸点
物理塔に供給し、塔頂から精製メタクリル酸エステルを
得る。高沸点物分離塔の缶出液は回収し、その一部また
は全部を薄層蒸留器等に送って重合物等の不純物を除去
し、これらが系内に蓄積するのを防ぐ。On the other hand, when the alcohol used in the esterification reaction step is a lower aliphatic alcohol having 5 or more carbon atoms, the boiling point of the ester produced in the esterification reaction becomes higher than the boiling points of methacrylic acid and alcohol, In this case, the reactive distillation method is preferably used. In this case, the water produced by the esterification reaction is distilled from the distillation column attached to the reactor and removed outside the system to allow the reaction to proceed.
At this time, it is preferable to supply a part of the alcohol from the top of the distillation column in order to prevent methacrylic acid from distilling. The bottoms of the reactor are supplied to a light-boiling point separation column to distill off unreacted alcohol and methacrylic acid, and then reflux the esterification reaction step. The bottoms of the light-boiling substance separation column are supplied to a high-boiling point physical column, and purified methacrylic acid ester is obtained from the top of the column. The bottoms of the high-boiling-point separation column is recovered, and a part or all of the bottoms is sent to a thin-layer distillation apparatus or the like to remove impurities such as polymerized products and prevent these from accumulating in the system.
次に、第１図に従って本発明を更に詳しく説明する。第
１図は炭素数１〜４の低級脂肪族アルコールを使用する
場合の本発明の好適な実施態様を例示するフローシート
である。Next, the present invention will be described in more detail with reference to FIG. FIG. 1 is a flow sheet illustrating a preferred embodiment of the present invention when a lower aliphatic alcohol having 1 to 4 carbon atoms is used.
イソブチレン、ターシャリーブタノール、メタクロレイ
ンまたはイソブチルアルデヒドの接触気相酸化反応工程
で得られたメタクリル酸水溶液をライン１を経てメタク
リル酸抽出塔に供給する。一方、ライン２より抽出溶
剤をメタクリル酸抽出塔に供給し、メタクリル酸水溶
液と向流接触させ、メタクリル酸を溶剤相に抽出する。
水相はライン３より抜出され適宜処理される。メタクリ
ル酸を含む溶剤相をライン４より溶剤分離塔に供給す
る。ここで溶剤は蒸留々分として回収され、ライン２よ
りメタクリル酸抽出塔に戻される。一方、溶剤分離塔
の塔底から粗製メタクリル酸を抜出しライン６を経
て、ライン12より供給される回収メタクリル酸とともに
エステル化反応器に供給する。エステル化反応器に
は多孔質の強酸性陽イオン交換樹脂が充填されており、
ここでメタクリル酸はライン７より供給されるアルコー
ルとエステル化反応する。メタクリル酸、メタクリル酸
エステル、アルコールおよび水からなるエステル化反応
生成物はライン８より蒸発器に供給され、蒸留され
る。未反応メタクリル酸および重合物や原料メタクリル
酸に同伴してきた高沸点不純物は蒸発器の塔底から抜
出され、その一部あるいは全部はライン10より薄層蒸発
器を併設した蒸留塔へ送られ、重合物や高沸点不純
物が薄層蒸発器の底部から抜出されてライン11を経て
系外に除去される。蒸留塔の塔頂から留出したメタク
リル酸はライン12を経てエステル化反応器に循環さ
れ、再度エステル化原料として利用される。また、蒸発
器の塔頂からはメタクリル酸エステル、アルコールお
よび水が留出し、ライン９を経て油水分離器に送られ
る。アルコールを含む水相はライン13よりアルコール回
収塔に供給して蒸留し、アルコールをライン15より回
収しエステル化反応器へ循環する。アルコール回収塔
の塔底からは水を抜出し、ライン16より廃水として系
外へ除去する。油水分離器で分離したメタクリル酸エ
ステルを含む油相はライン17より軽沸物分離塔に供給
し蒸留する。ライン18より留出した軽沸留分は水相と油
相とに分離させ、油相は軽沸物分離塔に還流し、水相
は19よりアルコール回収塔に循環する。軽沸物分離塔
の留分の水相と油相との分離が不完全な場合は、アル
コール回収塔の缶出液の一部を添加するか、蒸発器の留
分９と混合して油水相分離させるのが望ましい。軽沸物
分離塔の塔底からはメタクリル酸エステルが抜出さ
れ、ライン20を経て高沸物分離塔へ供給される。ここ
でメタクリル酸エステルは精留され、ライン21よりメタ
クリル酸エステル製品を得る。高沸物分離塔の塔底か
ら取り出された高沸点物はライン22を経て抜出される。
高沸点物中に未反応メタクリル酸が含まれる場合には、
回収してエステル化反応器へ循環される。The methacrylic acid aqueous solution obtained in the catalytic gas phase oxidation reaction step of isobutylene, tertiary butanol, methacrolein or isobutyraldehyde is supplied to the methacrylic acid extraction column via line 1. On the other hand, the extraction solvent is supplied from the line 2 to the methacrylic acid extraction column and is brought into countercurrent contact with the methacrylic acid aqueous solution to extract methacrylic acid into the solvent phase.
The aqueous phase is extracted from line 3 and treated as appropriate. The solvent phase containing methacrylic acid is supplied to the solvent separation column through line 4. Here, the solvent is recovered as distilled fractions and returned to the methacrylic acid extraction column through line 2. On the other hand, crude methacrylic acid is withdrawn from the bottom of the solvent separation column and is supplied to the esterification reactor through a line 6 together with the recovered methacrylic acid supplied from a line 12. The esterification reactor is filled with porous strong acid cation exchange resin,
Here, methacrylic acid undergoes an esterification reaction with the alcohol supplied from the line 7. The esterification reaction product consisting of methacrylic acid, methacrylic acid ester, alcohol and water is supplied to the evaporator through line 8 and distilled. Unreacted methacrylic acid and high boiling impurities that accompany the polymer and raw material methacrylic acid are extracted from the bottom of the evaporator, and part or all of them are sent to the distillation column equipped with a thin layer evaporator from line 10. Polymers and high-boiling-point impurities are extracted from the bottom of the thin-layer evaporator and removed to the outside of the system via line 11. Methacrylic acid distilled from the top of the distillation column is circulated to the esterification reactor via line 12 and used again as an esterification raw material. Further, methacrylic acid ester, alcohol and water are distilled out from the top of the evaporator and sent to the oil / water separator via line 9. The aqueous phase containing alcohol is supplied to the alcohol recovery column through line 13 and distilled, and the alcohol is recovered through line 15 and circulated to the esterification reactor. Water is withdrawn from the bottom of the alcohol recovery tower and removed from the system as waste water through line 16. The oil phase containing the methacrylic acid ester separated by the oil-water separator is supplied from line 17 to the light-boiling substance separation column for distillation. The light-boiling fraction distilled from the line 18 is separated into a water phase and an oil phase, the oil phase is refluxed to the light-boiling separation column, and the water phase is circulated from 19 to the alcohol recovery tower. When the separation of the water phase and the oil phase of the fraction of the light-boiling substance separation column is incomplete, a part of the bottom liquid of the alcohol recovery column is added or mixed with the fraction 9 of the evaporator to obtain an oil-water mixture. It is desirable to phase separate. The methacrylic acid ester is extracted from the bottom of the light-boiling substance separating column and is supplied to the high-boiling substance separating column via line 20. Here, the methacrylic acid ester is rectified to obtain a methacrylic acid ester product from line 21. The high-boiling substance taken out from the bottom of the high-boiling substance separation column is withdrawn via the line 22.
When unreacted methacrylic acid is contained in the high-boiling substance,
It is recovered and recycled to the esterification reactor.
［実施例］ 更に、本発明を以下の実施例によって詳しく説明する。[Examples] Further, the present invention will be described in detail by the following examples.
実施例１ モリブデン系触媒を用いてイソブチレンを水蒸気の存在
下に空気による接触気相酸化反応させ、反応生成ガスを
冷却凝縮させ、メタクロレインなどの軽沸点物質を蒸留
除去してメタクリル酸35重量％、酢酸5.3重量％、フタ
ル酸類（ｏ−、ｍ−、ｐ−）2.0重量％、マレイン酸1.2
重量％及びタール状物質1.5重量％を含むメタクリル酸
水溶液12.5Kg/時を得た。Example 1 Using a molybdenum-based catalyst, isobutylene was subjected to a catalytic gas-phase oxidation reaction with air in the presence of water vapor, the reaction product gas was cooled and condensed, and light boiling substances such as methacrolein were distilled off to remove 35% by weight of methacrylic acid. , Acetic acid 5.3% by weight, phthalic acids (o-, m-, p-) 2.0% by weight, maleic acid 1.2
A methacrylic acid aqueous solution of 12.5 Kg / hr containing 1% by weight and a tar-like substance of 1.5% by weight was obtained.
内径700mm、全高1800mmの回転円板塔からなる抽出塔
の上部から該メタクリル酸水溶液を、抽出塔下部からｎ
−ヘプタン16.4Kg/時をそれぞれ供給し、連続的に向流
抽出を行なった。抽出操作は常温常圧にて行ない。十分
に抽出平衡に達せしめたのち、抽出塔上部よりメタクリ
ル酸を含むｎ−ヘプタン相20.8Kg/時および抽出塔下部
より水相8.1Kg/時をそれぞれ得た。抽出塔の二層界面で
のスカムの発生は認められなかった。得られたｎ−ヘプ
タン相を溶剤分離塔（内径６インチ、シーブトレー30
段、SUS304製）の15段目に供給し、塔頂圧105mmHg、還
流比1.0で蒸留した。塔頂より留出したｎ−ヘプタンは
抽出塔に循環、再使用した。溶剤分離塔の塔底部から9
9.7重量％メタクリル酸を4.35Kg/時で得た。The methacrylic acid aqueous solution is introduced from the upper part of the extraction column consisting of a rotating disk column having an inner diameter of 700 mm and a total height of 1800 mm, and n
-Heptane (16.4 Kg / hr) was supplied to carry out continuous countercurrent extraction. The extraction operation is performed at normal temperature and pressure. After the extraction equilibrium was sufficiently reached, an n-heptane phase containing methacrylic acid of 20.8 kg / hr was obtained from the upper part of the extraction column and an aqueous phase of 8.1 kg / hr was obtained from the lower part of the extraction column. No scum was observed at the two-layer interface of the extraction tower. The obtained n-heptane phase was added to a solvent separation column (inner diameter: 6 inches, sieve tray: 30).
The column top pressure was 105 mmHg and the reflux ratio was 1.0. The n-heptane distilled from the top of the column was recycled to the extraction column and reused. 9 from the bottom of the solvent separation tower
9.7 wt% methacrylic acid was obtained at 4.35 Kg / h.
架橋度８％、比表面積4m2/g（BET法）、ポロシティ0.1m
l/g、平均細孔径300Åの多孔質の強酸性陽イオン交換樹
脂20.6（乾燥型）を充填したエステル化反応器へ、
該メタクリル酸、後述の回収メタクリル酸、新規メタノ
ールおよび後述の回収メタノールからなる原料（成分組
成：メタクリル酸44.65、メタノール8.90、メタクリル
酸メチル43.17、水1.64、その他1.65の各重量％、アセ
トニトリル225ppm）を26.65Kg/時で供給し、90℃でエス
テル化反応を行ない、エステル化反応生成物（成分組
成：メタクリル酸28.44、メタノール2.84、メタクリル
酸メチル61.93、水5.01、その他1.79各重量％、アセト
ニルアセトン221ppm、ジメチルフラン4ppm）を得た。Crosslinking degree 8%, specific surface area 4m 2 / g (BET method), porosity 0.1m
To the esterification reactor filled with porous strong acid cation exchange resin 20.6 (dry type) with l / g and average pore diameter 300Å,
A raw material consisting of the methacrylic acid, the recovered methacrylic acid described below, new methanol and the recovered methanol described below (component composition: methacrylic acid 44.65, methanol 8.90, methyl methacrylate 43.17, water 1.64, each weight% of other 1.65, acetonitrile 225 ppm). Supplied at 26.65 Kg / hr, esterification reaction at 90 ℃, esterification reaction product (component composition: methacrylic acid 28.44, methanol 2.84, methyl methacrylate 61.93, water 5.01, other 1.79 each wt%, acetonylacetone 221 ppm, dimethyl furan 4 ppm) was obtained.
該エステル化反応生成物を蒸発器に供給して常圧蒸留
し、留分を6.68Kg/時で得た。蒸発器の底部から抜き
出した缶出液の一部を1.50Kg/時で薄層蒸発器を併設
した蒸留塔に供給し、薄層蒸発器の底部から廃油0.06
Kg/時を抜き出し廃棄した。蒸発器の残りの缶出液と
蒸留塔の留分を混合した回収メタクリル酸19.91Kg/時
をエステル化反応器の入口へ循環した。The esterification reaction product was fed to an evaporator and distilled under atmospheric pressure to obtain a fraction at 6.68 Kg / hour. A portion of the bottoms extracted from the bottom of the evaporator was supplied at 1.50 Kg / hr to a distillation column equipped with a thin-layer evaporator, and waste oil 0.06 was supplied from the bottom of the thin-layer evaporator.
Kg / hour was extracted and discarded. The recovered methacrylic acid (19.91 Kg / hr) obtained by mixing the bottoms of the evaporator and the fraction of the distillation column was circulated to the inlet of the esterification reactor.
蒸発器の留出液は油水分離器において油相と水相と
を形成した。油相の組成はメタクリル酸1.15、メタノー
ル4.00、メタクリル酸メチル92.40、水2.45各重量％で
あり、水相の組成はメタクリル酸0.16、メタノール27.5
3、メタクリル酸メチル5.23、水67.09各重量％であっ
た。The evaporator distillate formed an oil phase and an aqueous phase in the oil-water separator. The composition of the oil phase is methacrylic acid 1.15, methanol 4.00, methyl methacrylate 92.40, water 2.45 each weight%, the composition of the aqueous phase is methacrylic acid 0.16, methanol 27.5
3, methyl methacrylate 5.23, water 67.09 was each weight%.
次にこの油相5.54Kg/時を軽沸物分離塔（塔径7.5cm、
段数20段のガラス製オルダーショウ型蒸留塔）に供給
し、塔頂圧力300mmHg、塔頂温度52℃で蒸留を行ない、
缶出液5.13Kg/時を得た。留出分のうち油相は再度軽沸
物分離塔の塔頂へ還流し、水相0.41Kg/時をアルコール
回収塔へ供給した。またこの時、缶出液にメタノー
ル、水、アクリル酸メチルは検出されなかった。Next, this oil phase 5.54 Kg / hour is a light boiling material separation column (column diameter 7.5 cm,
It is supplied to a glass Oldershaw type distillation column with 20 stages, and distillation is performed at a column top pressure of 300 mmHg and a column top temperature of 52 ° C.
A bottom liquor of 5.13 Kg / hour was obtained. The oil phase in the distillate was refluxed again to the top of the light-boiling substance separation column, and 0.41 Kg / hour of the aqueous phase was supplied to the alcohol recovery column. At this time, neither methanol, water nor methyl acrylate was detected in the bottoms.
さらに軽沸物分離塔の缶出液を高沸物分離塔（塔径
10cm、段数15段のガラス製オルダーショウ型蒸留塔）に
供給した。供給段10段、塔頂圧力100mmHg、塔頂温度46
℃、塔底温度66℃で蒸留を行ない、塔頂より精製メタク
リル酸メチルを5.00Kg/時、塔底より缶出液を0.13Kg/時
でそれぞれ得た。得られた精製メタクリル酸メチルの純
度は99.99重量％であった。この精製メタクリル酸メチ
ルを用いて乳化重合させて得たエマルジョンの色相安定
性は良好であった。Further, the bottoms of the light-boiling substance separation tower are separated from the high-boiling substance separation tower (tower diameter
It was supplied to a glass Oldershaw type distillation column with 10 cm and 15 plates. Supply stage 10 stages, tower top pressure 100 mmHg, tower top temperature 46
Distillation was carried out at a temperature of 66 ° C and a bottom temperature of 66 ° C. Purified methyl methacrylate was obtained from the top of the column at 5.00 Kg / hr, and the bottom liquid was obtained from the bottom of the column at 0.13 Kg / hr. The purity of the obtained purified methyl methacrylate was 99.99% by weight. The emulsion obtained by emulsion polymerization using this purified methyl methacrylate had good hue stability.
一方、蒸発器および軽沸物分離塔の各留出液の水相
は1.55Kg/時でアルコール回収塔（塔径5.0cm、段数20
段のガラス製オルダーショウ型蒸留塔）に供給した。供
給段10段、常圧、塔頂温度66℃、塔底温度103℃で蒸留
を行ない、留出液0.65Kg/時、缶出液0.90Kg/時を得た。
缶出液には0.2重量％のメタクリル酸を含む以外はメタ
ノール、メタクリル酸メチルは検出されなかった。On the other hand, the water phase of each distillate of the evaporator and the light-boiling separation column was 1.55 Kg / hr, and the alcohol recovery column (column diameter 5.0 cm, plate number 20
It was supplied to a glass-made Oldershaw type distillation column). Distillation was carried out at a feed stage of 10 stages, normal pressure, a tower top temperature of 66 ° C. and a tower bottom temperature of 103 ° C. to obtain a distillate solution of 0.65 Kg / hour and a bottom solution of 0.90 Kg / hour.
Neither methanol nor methyl methacrylate was detected in the bottoms except that it contained 0.2% by weight of methacrylic acid.
60日間の連続運転中、上述したエステル化反応器、精留
塔、その他の装置はいずれも重合物などによるトラブル
はなく、エステル化反応用触媒である陽イオン交換樹脂
の性能についても、運転前後のメタクリル酸の転化率に
変化はなく、イオン交換容量の低下は3.0％に過ぎなか
った。これらの結果は本発明の方法が長期間の運転に充
分に耐えられることを示している。During the 60-day continuous operation, the esterification reactor, rectification column, and other equipment described above did not have any troubles due to polymerized products, etc., and the performance of the cation exchange resin, which is the esterification reaction catalyst, was also measured before and after operation. There was no change in the conversion rate of methacrylic acid and the decrease in ion exchange capacity was only 3.0%. These results show that the method of the present invention is well tolerated for long term operation.
実施例２ 抽出溶剤としてｎ−ヘプタンの代りにｎ−ヘキサンを用
いた他は実施例１と同様にしてエステル化反応、精製を
実施した。得られた精製メタクリル酸メチルの純度は9
9.99重量％であった。更に、この精製メタクリル酸メチ
ルを乳化重合させて得たエマルジョンの色相安定性は良
好であった。Example 2 The esterification reaction and purification were carried out in the same manner as in Example 1 except that n-hexane was used as the extraction solvent instead of n-heptane. The purity of the obtained purified methyl methacrylate is 9
It was 9.99% by weight. Further, the emulsion obtained by emulsion polymerization of this purified methyl methacrylate had good hue stability.
60日間の連続運転中、上述したエステル化反応器、精留
塔、その他の装置はいずれも重合物などによるトラブル
はなく、エステル化反応用触媒である陽イオン交換樹脂
の性能についても、運転前後のメタクリル酸の転化率に
変化はなく、イオン交換容量の低下も3.5％に過ぎなか
った。これらの結果は本発明の方法が長期間の運転に充
分に耐えられることを示している。During the 60-day continuous operation, the esterification reactor, rectification column, and other equipment described above did not have any troubles due to polymerized products, etc., and the performance of the cation exchange resin, which is the esterification reaction catalyst, was also measured before and after operation. There was no change in the conversion rate of methacrylic acid and the decrease in ion exchange capacity was only 3.5%. These results show that the method of the present invention is well tolerated for long term operation.
実施例３ 抽出溶剤としてｎ−ヘプタンの代りにｎ−オクタンを用
いた他は実施例１と同様にしてエステル化反応、精製を
実施した。得られた精製メタクリル酸メチルの純度は9
9.99重量％であった。更に、この精製メタクリル酸メチ
ルを乳化重合させて得たエマルジョンの色相安定性は良
好であった。Example 3 The esterification reaction and purification were carried out in the same manner as in Example 1 except that n-octane was used instead of n-heptane as the extraction solvent. The purity of the obtained purified methyl methacrylate is 9
It was 9.99% by weight. Further, the emulsion obtained by emulsion polymerization of this purified methyl methacrylate had good hue stability.
60日間の連続運転中、上述したエステル化反応器、精留
塔、その他の装置はいずれも重合物などによるトラブル
はなく、エステル化反応用触媒である陽イオン交換樹脂
の性能についても、運転前後のメタクリル酸の転化率に
変化はなく、イオン交換容量の低下も3.3％に過ぎなか
った。これらの結果は本発明の方法が長期間の運転に充
分に耐えられことを示している。During the 60-day continuous operation, the esterification reactor, rectification column, and other equipment described above did not have any troubles due to polymerized products, etc., and the performance of the cation exchange resin, which is the esterification reaction catalyst, was also measured before and after operation. There was no change in the conversion of methacrylic acid and the decrease in ion exchange capacity was only 3.3%. These results show that the method of the present invention is well tolerated for long term operation.
実施例４ メタノールの代わりにブタノールを用い、反応温度を90
℃から100℃とした他は実施例１と同様にしてエステル
化反応、精製を実施した。得られた精製メタクリル酸ブ
チルの純度は99.90重量％であった。Example 4 Butanol was used instead of methanol and the reaction temperature was 90%.
The esterification reaction and purification were carried out in the same manner as in Example 1 except that the temperature was changed from 100 ° C to 100 ° C. The purity of the obtained purified butyl methacrylate was 99.90% by weight.
60日間の連続運転中、上述したエステル化反応器、精留
塔、その他の装置はいずれも重合物などによるトラブル
はなく、エステル化反応用触媒である陽イオン交換樹脂
の性能についても、運転前後のメタクリル酸の転化率に
変化はなく、イオン交換容量の低下も3.5％に過ぎなか
った。これらの結果は本発明の方法が長期間の運転に充
分に耐えられることを示している。During the 60-day continuous operation, the esterification reactor, rectification column, and other equipment described above did not have any troubles due to polymerized products, etc., and the performance of the cation exchange resin, which is the esterification reaction catalyst, was also measured before and after operation. There was no change in the conversion rate of methacrylic acid and the decrease in ion exchange capacity was only 3.5%. These results show that the method of the present invention is well tolerated for long term operation.
実施例５ 抽出溶剤としてｎ−ヘプタン16.4Kg/時の代りにｎ−ヘ
プタン：メタクリル酸メチル混合溶剤（重量比率60:4
0）10Kg/時を抽出塔下部から供給した他は実施例１と同
様にしてエステル化反応、精製を実施した。得られた精
製メタクリル酸メチルの純度は99.99重量％であった。
更に、この精製メタクリル酸メチルを乳化重合させて得
たエマルジョンの色相安定性は良好であった。Example 5 Instead of 16.4 kg / h of n-heptane as an extraction solvent, a mixed solvent of n-heptane: methyl methacrylate (weight ratio 60: 4) was used.
0) The esterification reaction and purification were carried out in the same manner as in Example 1 except that 10 Kg / hour was supplied from the lower part of the extraction column. The purity of the obtained purified methyl methacrylate was 99.99% by weight.
Further, the emulsion obtained by emulsion polymerization of this purified methyl methacrylate had good hue stability.
60日間の連続運転中、上述したエステル化反応器、精留
塔、その他の装置はいずれも重合物などによるトラブル
はなく、エステル化反応用触媒である陽イオン交換樹脂
の性能についても、運転前後のメタクリル酸の転化率に
変化はなく、イオン交換容量の低下も3.2％に過ぎなか
った。これらの結果は本発明の方法が長期間の運転に充
分に耐えられることを示している。During the 60-day continuous operation, the esterification reactor, rectification column, and other equipment described above did not have any troubles due to polymerized products, etc., and the performance of the cation exchange resin, which is the esterification reaction catalyst, was also measured before and after operation. There was no change in the conversion rate of methacrylic acid and the decrease in ion exchange capacity was only 3.2%. These results show that the method of the present invention is well tolerated for long term operation.
実施例６ 蒸発器の代りに塔径10cm、段数15段のガラス製オルダ
ーショウ型蒸留塔を用いることによって該蒸留塔の留分
中にメタクリル酸が混入しないようにした以外は実施例
１と同様にしてエステル化反応、精製を実施した。得ら
れた精製メタクリル酸メチルの純度は99.99重量％であ
った。更に、この精製メタクリル酸メチルを乳化重合さ
せて得たエマルジョンの色相安定性は良好であった。Example 6 The same as Example 1 except that a methacrylic acid was not mixed into the fraction of the distillation column by using a glass Oldershaw type distillation column having a column diameter of 10 cm and 15 plates in place of the evaporator. Esterification reaction and purification were carried out. The purity of the obtained purified methyl methacrylate was 99.99% by weight. Further, the emulsion obtained by emulsion polymerization of this purified methyl methacrylate had good hue stability.
60日間の連続運転中、上述したエステル化反応器、精留
塔、その他の装置はいずれも重合物などによるトラブル
はなく、エステル化反応用触媒である陽イオン交換樹脂
の性能についても、運転前後のメタクリル酸の転化率に
変化はなく、イオン交換容量の低下も3.3％に過ぎなか
った。これらの結果は本発明の方法が長期間の運転に充
分に耐えられることを示している。During the 60-day continuous operation, the esterification reactor, rectification column, and other equipment described above did not have any troubles due to polymerized products, etc., and the performance of the cation exchange resin, which is the esterification reaction catalyst, was also measured before and after operation. There was no change in the conversion of methacrylic acid and the decrease in ion exchange capacity was only 3.3%. These results show that the method of the present invention is well tolerated for long term operation.
実施例７ 内部にバッフル、底部に反応液抜出し管、上部に原料供
給管、蒸留塔、攪拌機を有するステンレス製100のエ
ステル化反応器に実施例１と同じイオン交換樹脂18を
充填し、実施例１と同様の操作で得られたメタクリル
酸、後述の回収メタクリル酸、新規２−エチルヘキサノ
ールおよび後述の回収２−エチルヘキサノールからなる
原料（成分組成：メタクリル酸36.52、２−エチルヘキ
サノール49.69、メタクリル酸２−エチルヘキシル11.8
0、水0.69各重量％）を70仕込み、反応器内の圧力70m
mHg、温度90℃でエステル化反応を開始した。Example 7 A 100-ester stainless steel esterification reactor having a baffle inside, a reaction liquid extraction tube at the bottom, a raw material supply tube at the top, a distillation column, and a stirrer was filled with the same ion exchange resin 18 as in Example 1, A raw material composed of methacrylic acid obtained by the same operation as that of No. 1, recovered methacrylic acid described later, novel 2-ethylhexanol and recovered 2-ethylhexanol (component composition: methacrylic acid 36.52, 2-ethylhexanol 49.69, methacrylic acid 2-ethylhexyl 11.8
0, water 0.69 each% by weight) 70, pressure in the reactor 70m
The esterification reaction was started at mHg and a temperature of 90 ° C.
エステル化反応は、反応器上部の原料供給管から原料液
を36.60Kg/時で供給し、蒸留塔の塔頂部より２−エチル
ヘキサノールを18.05Kg/時で供給した。エステル化反応
器上部に設けられた蒸留塔の塔頂部から留出する液を油
相（0.28Kg/時）と水相（2.45Kg/時）とに分離し、油相
は還流してエステル化反応系に戻し、水相は系外に除去
した。一方、反応のあいだ反応器内の液量を70に保つ
ようにエステル化反応器底部からエステル化反応生成物
（成分組成：メタクリル酸6.46、２−エチルヘキサノー
ル40.45、メタクリル酸２−エチルヘキシル52.37、水0.
71各重量％）を連続的に抜出した。メタクリル酸転化率
74.8％、２−エチルヘキサノール転化率41.7％であり、
系外に除去した水相中のメタクリル酸は痕跡程度であっ
た。In the esterification reaction, the raw material liquid was supplied from the raw material supply pipe in the upper part of the reactor at 36.60 Kg / hour, and 2-ethylhexanol was supplied from the top of the distillation column at 18.05 Kg / hour. The liquid distilled from the top of the distillation column installed at the upper part of the esterification reactor is separated into an oil phase (0.28 Kg / hour) and an aqueous phase (2.45 Kg / hour), and the oil phase is refluxed for esterification. After returning to the reaction system, the aqueous phase was removed outside the system. On the other hand, the esterification reaction product (component composition: 6.46 methacrylate, 2-ethylhexanol 40.45, 2-ethylhexyl methacrylate 52.37, water, from the bottom of the esterification reactor so as to maintain the liquid amount in the reactor at 70 during the reaction. 0.
71% by weight) were continuously extracted. Methacrylic acid conversion rate
74.8%, 2-ethylhexanol conversion 41.7%,
The amount of methacrylic acid in the aqueous phase removed outside the system was in traces.
ついで該エステル化反応生成物を軽沸点物分離塔に供給
して蒸留し、塔頂より未反応メタクリル酸、２−エチル
ヘキサノール等からなる留分（成分組成：メタクリル酸
12.66、２−エチルヘキサノール79.28、メタクリル酸２
−エチルヘキシル6.67、水1.39各重量％）26.63Kg/時を
回収し、エステル化反応器に戻した。Then, the esterification reaction product is fed to a light-boiling substance separation column for distillation, and a fraction containing unreacted methacrylic acid, 2-ethylhexanol and the like (component composition: methacrylic acid is supplied from the top of the column.
12.66, 2-ethylhexanol 79.28, methacrylic acid 2
-Ethylhexyl 6.67, water 1.39 each wt%) 26.63 Kg / hr were recovered and returned to the esterification reactor.
更に軽沸点物分離塔の缶出液を25.56Kg/時で高沸点物分
離塔に供給し、塔頂より22.63Kg/時で純度99.0重量％の
精製メタクリル酸２−エチルヘキシルを得た。高沸点物
分離塔の缶出液を2.93Kg/時で抜出し、一部を薄層蒸発
器に供給し、薄層蒸発器の底部から廃油を0.49Kg/時で
抜き出し廃棄した。Further, the bottoms of the light-boiling substance separation column was supplied to the high-boiling substance separation column at 25.56 Kg / hr, and purified 2-ethylhexyl methacrylate having a purity of 99.0% by weight was obtained from the top of the column at 22.63 Kg / hr. The bottoms of the high-boiling-point separation column was withdrawn at 2.93 Kg / hr, a part was supplied to the thin-layer evaporator, and the waste oil was withdrawn from the bottom of the thin-layer evaporator at 0.49 Kg / hr and discarded.
60日間の連続運転中、上述したエステル化反応器、精留
塔、その他の装置はいずれも重合物などによるトラブル
はなく、エステル化反応用触媒である陽イオン交換樹脂
の性能についても、運転前後のメタクリル酸の転化率に
変化はなく、イオン交換容量の低下も3.0％に過ぎなか
った。これらの結果は本発明の方法が長期間の運転に充
分に耐えられることを示している。During the 60-day continuous operation, the esterification reactor, rectification column, and other equipment described above did not have any troubles due to polymerized products, etc., and the performance of the cation exchange resin, which is the esterification reaction catalyst, was also measured before and after operation. There was no change in the conversion rate of methacrylic acid and the decrease in ion exchange capacity was only 3.0%. These results show that the method of the present invention is well tolerated for long term operation.
比較例１ 触媒としてゲル型の強酸性陽イオン交換樹脂（架橋度８
％、比表面積0.1m2/g以下、ポロシティ0ml/g、細孔径０
Å）を全交換容量が等しくなる様に充填した他は実施例
１と同様にしてエステル化反応、精製を実施した。得ら
れた精製メタクリル酸メチルの純度は99.99重量％であ
った。ところが、この精製メタクリル酸メチルを乳化重
合させて得たエマルジョンの色相安定性は実施例１〜３
のものの色相安定性に比べて明らかに劣った。更に、エ
ステル化反応器でのメタクリル酸の転化率が徐々に低下
し、２週間で連続運転を停止せざるをえなかった。運転
終了後、陽イオン交換樹脂の全交換容量を測定したとこ
ろ、運転前に比べて55％低下していた（このようなイオ
ン交換樹脂はもはや使用できないことが明らかであ
る）。Comparative Example 1 As a catalyst, a gel-type strongly acidic cation exchange resin (with a crosslinking degree of 8
%, Specific surface area 0.1 m 2 / g or less, porosity 0 ml / g, pore size 0
Esterification reaction and purification were carried out in the same manner as in Example 1 except that Å) was charged so that the total exchange capacity became equal. The purity of the obtained purified methyl methacrylate was 99.99% by weight. However, the hue stability of the emulsion obtained by emulsion-polymerizing this purified methyl methacrylate is as shown in Examples 1-3.
It was clearly inferior to the hue stability of the product. Furthermore, the conversion rate of methacrylic acid in the esterification reactor gradually decreased, and the continuous operation had to be stopped in two weeks. After the end of the operation, the total exchange capacity of the cation exchange resin was measured and found to be 55% lower than before the operation (it is clear that such an ion exchange resin can no longer be used).
比較例２ 実施例１で用いたメタクリル酸のかわりに、溶剤分離塔
の缶出液として抜き出したメタクリル酸をさらに高沸物
分離塔にて精製したメタクリル酸を用い、また多孔質の
強酸性陽イオン交換樹脂のかわりにゲル型の強酸性陽イ
オン交換樹脂を全交換容量が等しくなる様に充填した以
外は実施例１と同様にしてエステル化反応、精製を実施
した。得られた精製メタクリル酸メチルは純度99.99重
量％であった。この精製メタクリル酸メチルを乳化重合
させて得たエマルジョンの色相安定性は実施例１〜３の
ものの色相安定性に比べて明らかに劣った。Comparative Example 2 Instead of the methacrylic acid used in Example 1, methacrylic acid obtained by further refining methacrylic acid extracted as a bottom liquid of the solvent separation column in a high boiling point separation column was used, and a porous strongly acidic positive electrode was used. The esterification reaction and purification were carried out in the same manner as in Example 1 except that a gel-type strongly acidic cation exchange resin was charged in place of the ion exchange resin so that the total exchange capacity was equal. The obtained purified methyl methacrylate had a purity of 99.99% by weight. The hue stability of the emulsions obtained by emulsion polymerization of this purified methyl methacrylate was clearly inferior to that of Examples 1 to 3.
60日間の連続運転中、上述したエステル化反応器、精留
塔、その他の装置はいずれも重合物などによるトラブル
はなかったが、エステル化反応用触媒である陽イオン交
換樹脂の性能には問題があり、メタクリル酸の転化率が
徐々に低下して運転終了時には運転前に比べて16％低下
した。During 60 days of continuous operation, there was no trouble with the esterification reactor, rectification column, and other equipment due to polymerized products, etc., but there was a problem with the performance of the cation exchange resin, which is the catalyst for the esterification reaction. However, the conversion rate of methacrylic acid gradually decreased, and at the end of the operation, it decreased by 16% compared to that before the operation.
比較例３ 抽出工程に供給するメタクリル酸水溶液に30重量％重亜
硫酸ナトリウム水溶液0.34Kg/時を添加し、抽出溶媒と
してトルエン12.5Kg/時を用いた以外は実施例１と同様
にしてエステル化反応、精製を実施した。得られた精製
メタクリル酸メチルは純度99.99重量％であった。この
精製メタクリル酸メチルを重合させて得たエマルジョン
の色相安定性は実施例１〜３のものの色相安定性に比べ
て明らかに劣った。Comparative Example 3 Esterification reaction was carried out in the same manner as in Example 1 except that 0.34 Kg / hour of 30 wt% sodium bisulfite aqueous solution was added to the methacrylic acid aqueous solution supplied to the extraction step and toluene 12.5 Kg / hour was used as the extraction solvent. , Purification was performed. The obtained purified methyl methacrylate had a purity of 99.99% by weight. The hue stability of the emulsions obtained by polymerizing this purified methyl methacrylate was clearly inferior to that of Examples 1 to 3.
60日間の連続運転中、上述したエステル化反応器、精留
塔、その他の装置にはいずれかも重合物などによるトラ
ブルはなかったが、エステル化反応応用触媒である陽イ
オン交換樹脂の性能には問題があり、メタクリル酸の転
化率が徐々に低下して運転終了時には運転前に比べて9.
1％低下した。During the 60-day continuous operation, there was no trouble with the esterification reactor, rectification tower, and other equipment due to polymerized products, but the performance of the cation exchange resin, which is the esterification reaction application catalyst, There was a problem, the conversion rate of methacrylic acid gradually decreased, and at the end of operation compared to before operation 9.
It fell by 1%.
比較例４、実施例１で用いた架橋度８％の多孔質陽イオ
ン交換樹脂の代わりに、架橋度20％のアンバーリスト15
（ロール・アンド・ハース社製）を全交換容量が等しく
なる様に充填した他は、実施例１と同様にしてエステル
化反応、精製を実施した。得られた精製メタクリル酸メ
チルの純度は99.9％であった。30日間の連続運転中、エ
ステル化反応器でのメタクリル酸の転化率が徐々に低下
し、運転終了時には運転開始時に比べて８％低下した。
これは実用上問題である。Instead of the porous cation exchange resin having a crosslinking degree of 8% used in Comparative Example 4 and Example 1, an amberlyst 15 having a crosslinking degree of 20% was used.
Esterification reaction and purification were carried out in the same manner as in Example 1 except that (Roll and Haas Co., Ltd.) was charged so that the total exchange capacity was the same. The purity of the obtained purified methyl methacrylate was 99.9%. During continuous operation for 30 days, the conversion rate of methacrylic acid in the esterification reactor gradually decreased, and at the end of the operation, it decreased by 8% compared to the start of the operation.
This is a practical problem.
実施例１〜６及び比較例１〜３で得れたメタクリル酸メ
チル中のジメチルフラン量と、このメタクリル酸メチル
を乳化重合させて得られたエマルジョンの色相について
の測定結果を一括して示すと第１表の通りである。When the amount of dimethylfuran in methyl methacrylate obtained in Examples 1 to 6 and Comparative Examples 1 to 3 and the measurement results of the hue of emulsions obtained by emulsion polymerization of this methyl methacrylate are collectively shown. It is as shown in Table 1.
第１図は本発明の一実施態様を表わすフローシート図で
ある。 ……メタクリル酸抽出塔、……溶剤分離塔 ……エステル化反応器、……蒸発器 ……蒸留塔、……薄層蒸発器 ……油水分離器、……アルコール回収塔 ……軽沸物分離塔、……高沸物分離塔 １……メタクリル酸水溶液供給ライン ２……抽出溶剤供給ライン ３……水相抜出しライン ４……溶剤相供給ライン ５……溶剤留分ライン ６……精製メタクリル酸供給ライン ７……アルコール供給ライン ８……エステル化反応生成物供給ライン ９……留分ライン 10……高沸点物供給ライン 11……高沸点不純物抜出しライン 12……回収メタクリル酸供給ライン 13……アルコール含有水相供給ライン 14……軽沸留分ライン 15……回収アルコール抜出しライン 16……廃水抜出しライン 17……メタクリル酸エステル含有油相供給ライン 18……軽沸留分ライン 19……アルコール含有水相抜出しライン 20……メタクリル酸エステル供給ライン 21……メタクリル酸エステル製品抜出しライン 22……高沸物抜出しラインFIG. 1 is a flow sheet diagram showing an embodiment of the present invention. ...... Methacrylic acid extraction tower ...... Solvent separation tower ...... Esterification reactor ...... Evaporator ...... Distillation tower ...... Thin layer evaporator ...... Oil water separator ...... Alcohol recovery tower ...... Light boiling material Separation tower …… High boiling material separation tower 1 …… Methacrylic acid aqueous solution supply line 2 …… Extraction solvent supply line 3 …… Aqueous phase extraction line 4 …… Solvent phase supply line 5 …… Solvent fraction line 6 …… Refining Methacrylic acid supply line 7 …… Alcohol supply line 8 …… Esterification reaction product supply line 9 …… Distillation line 10 …… High boiling point material supply line 11 …… High boiling point impurity extraction line 12 …… Recovered methacrylic acid supply line 13 …… Alcohol-containing water phase supply line 14 …… Light boiling fractionation line 15 …… Recovered alcohol extraction line 16 …… Wastewater extraction line 17 …… Methacrylic acid ester-containing oil phase supply line 18 …… Light boiling fractionation line 19 …… Alcohol-containing aqueous phase extraction line 20 …… Methacrylic acid ester supply line 21 …… Methacrylic acid ester product extraction line 22 …… High boiling substance extraction line
フロントページの続き (72)発明者 吉田 紘 兵庫県姫路市網干区興浜字西沖992―１ 日本触媒化学工業株式会社姫路製造所内 (72)発明者 馬場 将夫 兵庫県姫路市網干区興浜字西沖992―１ 日本触媒化学工業株式会社姫路製造所内 (56)参考文献 特開 昭49−45020（ＪＰ，Ａ) 特開 昭58−192851（ＪＰ，Ａ) 特開 昭49−100016（ＪＰ，Ａ) 特開 昭55−31046（ＪＰ，Ａ) 特開 昭55−62047（ＪＰ，Ａ) 特開 昭58−77845（ＪＰ，Ａ) 特開 昭58−159442（ＪＰ，Ａ) 特公 昭44−31329（ＪＰ，Ｂ１) 特公 昭46−27726（ＪＰ，Ｂ１) 特公 昭48−1369（ＪＰ，Ｂ１)Front page continuation (72) Inventor Hiro Yoshida, 992-1 Nishioki, Okihama, Aboshi-ku, Himeji-shi, Hyogo Inside Himeji Works, Nippon Catalytic Chemical Co., Ltd. (72) Masao Baba, 92-1 Nishioki, Nishihama, Aboshi-ku, Himeji-shi, Hyogo (56) Reference JP 49-45020 (JP, A) JP 58-192851 (JP, A) JP 49-100016 (JP, A) JP 55- 31046 (JP, A) JP-A-55-62047 (JP, A) JP-A-58-77845 (JP, A) JP-A-58-159442 (JP, A) JP-B-44-31329 (JP, B1) JP-B-46-27726 (JP, B1) JP-B-48-1369 (JP, B1)
Claims (2)
メタクロレインまたはイソブチルアルデヒドを接触気相
酸化し、得られた反応生成物から軽沸点物質を蒸留また
は拡散によって除去し、得られたメタクリル酸水溶液か
ら炭素数６〜９の脂肪族鎖状飽和炭化水素を溶剤として
用いてメタクリル酸を抽出し、得られたメタクリル酸溶
剤溶液から溶剤を回収し、得られたアセトニルアセトン
を含有する粗製メタクリル酸を、エステル化用触媒とし
て架橋度２〜16％、比表面積0.2〜50m2/g,ポロシティ０
〜1.0ml/g,平均細孔径100〜600Åである多孔質の強酸性
陽イオン交換樹脂を用いて炭素数１〜12の低級脂肪族ア
ルコールまたは低級脂環式アルコールと反応させること
によってエステル化し、ジメチルフラン含有量の低減さ
れたエステル化反応生成物を得、ここに得られた該エス
テル化反応生成物を精製工程に付することを特徴とする
高純度メタクリル酸エステルの製造方法。1. Isobutylene, tertiary butanol,
Catalytic gas phase oxidation of methacrolein or isobutyraldehyde, light boiling point substances are removed from the obtained reaction product by distillation or diffusion, and aliphatic chain saturated hydrocarbon having 6 to 9 carbon atoms from the obtained aqueous solution of methacrylic acid. Methacrylic acid is extracted by using as a solvent, the solvent is recovered from the obtained methacrylic acid solvent solution, the crude methacrylic acid containing the obtained acetonylacetone, the degree of crosslinking of 2 to 16% as a catalyst for esterification, Specific surface area 0.2 to 50m 2 / g, porosity 0
~ 1.0 ml / g, using a porous strong acid cation exchange resin having an average pore size of 100 ~ 600 Å by esterification by reacting with a lower aliphatic alcohol or a lower alicyclic alcohol having 1 to 12 carbon atoms, A process for producing a high-purity methacrylic acid ester, which comprises obtaining an esterification reaction product having a reduced dimethylfuran content, and subjecting the esterification reaction product obtained here to a purification step.
ルコールである請求項１に記載の製造方法。2. The method according to claim 1, wherein the alcohol is a lower aliphatic alcohol having 1 to 4 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63074602A JPH0764787B2 (en) | 1987-04-16 | 1988-03-30 | Method for producing high-purity methacrylic acid ester |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9193287 | 1987-04-16 | ||
| JP19534787 | 1987-08-06 | ||
| JP62-195347 | 1987-08-06 | ||
| JP62-91932 | 1987-08-06 | ||
| JP63074602A JPH0764787B2 (en) | 1987-04-16 | 1988-03-30 | Method for producing high-purity methacrylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01139547A JPH01139547A (en) | 1989-06-01 |
| JPH0764787B2 true JPH0764787B2 (en) | 1995-07-12 |
Family
ID=27301558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63074602A Expired - Lifetime JPH0764787B2 (en) | 1987-04-16 | 1988-03-30 | Method for producing high-purity methacrylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764787B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110133620A (en) * | 2009-03-27 | 2011-12-13 | 루사이트 인터내셔널 유케이 리미티드 | Treatment method of ion exchange resin |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2509049B2 (en) * | 1991-07-09 | 1996-06-19 | 株式会社日本触媒 | Method for producing methacrylic acid |
| JP2001131116A (en) * | 1999-11-08 | 2001-05-15 | Nippon Shokubai Co Ltd | Method of distillation for liquid including material liable to polymerize |
| DE102006001771A1 (en) * | 2006-01-12 | 2007-07-19 | Röhm Gmbh | Process for the purification of (meth) acrylates |
| JP2009062289A (en) * | 2007-09-04 | 2009-03-26 | Nippon Shokubai Co Ltd | Method for producing acrylic acid and (meth) acrylic acid ester |
| JP2010241765A (en) * | 2009-04-09 | 2010-10-28 | Daicel Chem Ind Ltd | Method for producing carboxylic acid ester |
| FR3024143B1 (en) * | 2014-07-28 | 2016-07-15 | Arkema France | IMPROVED METHOD OF MANUFACTURING ALKYL (METH) ACRYLATES |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5238535B2 (en) * | 1972-09-08 | 1977-09-29 | ||
| JPS49100016A (en) * | 1973-02-03 | 1974-09-20 | ||
| JPS5531046A (en) * | 1978-08-28 | 1980-03-05 | Mitsubishi Chem Ind Ltd | Preparation of acrylic or methacrylic ester |
| JPS5562047A (en) * | 1978-10-31 | 1980-05-10 | Mitsubishi Rayon Co Ltd | Preparation of methacrylic acid ester |
| JPS5877845A (en) * | 1981-11-02 | 1983-05-11 | Nippon Shokubai Kagaku Kogyo Co Ltd | Preparation of acrylic acid ester or methacrylic acid ester |
| JPS58159442A (en) * | 1982-03-17 | 1983-09-21 | Nippon Kayaku Co Ltd | Preparation of acrylic or methacrylic ester |
| JPS58192851A (en) * | 1982-05-04 | 1983-11-10 | Nippon Shokubai Kagaku Kogyo Co Ltd | Preparation of higher alcoholic ester from acrylic or methacrylic acid |
-
1988
- 1988-03-30 JP JP63074602A patent/JPH0764787B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110133620A (en) * | 2009-03-27 | 2011-12-13 | 루사이트 인터내셔널 유케이 리미티드 | Treatment method of ion exchange resin |
| US9821304B2 (en) | 2009-03-27 | 2017-11-21 | Lucite International Uk Limited | Process for the treatment of an ion exchange resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01139547A (en) | 1989-06-01 |
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