JP2014233694A - SOLID ACID CATALYST, AND METHOD FOR PRODUCING α,β-UNSATURATED CARBOXYLIC ACID ESTER - Google Patents
SOLID ACID CATALYST, AND METHOD FOR PRODUCING α,β-UNSATURATED CARBOXYLIC ACID ESTER Download PDFInfo
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- JP2014233694A JP2014233694A JP2013118014A JP2013118014A JP2014233694A JP 2014233694 A JP2014233694 A JP 2014233694A JP 2013118014 A JP2013118014 A JP 2013118014A JP 2013118014 A JP2013118014 A JP 2013118014A JP 2014233694 A JP2014233694 A JP 2014233694A
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- acid
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- alcohol
- inorganic porous
- unsaturated carboxylic
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000011973 solid acid Substances 0.000 title claims abstract description 59
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 56
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- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 7
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000467 phytic acid Substances 0.000 claims abstract description 6
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 6
- 229940068041 phytic acid Drugs 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 42
- 239000011148 porous material Substances 0.000 claims description 40
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 239000012798 spherical particle Substances 0.000 claims 1
- -1 fluorinated alkyl sulfonic acid Chemical compound 0.000 abstract description 21
- 239000006227 byproduct Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract 1
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- 238000006116 polymerization reaction Methods 0.000 description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 14
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- 239000000203 mixture Substances 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 13
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- 238000001914 filtration Methods 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
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- 238000001816 cooling Methods 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
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- 125000001931 aliphatic group Chemical group 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
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- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 125000004414 alkyl thio group Chemical group 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
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- 125000005369 trialkoxysilyl group Chemical group 0.000 description 5
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 235000014380 magnesium carbonate Nutrition 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
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- 125000004434 sulfur atom Chemical group 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000013022 venting Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
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- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- HPQKGWKGZNXUEF-UHFFFAOYSA-N 1-nonylcyclohexan-1-ol Chemical compound CCCCCCCCCC1(O)CCCCC1 HPQKGWKGZNXUEF-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
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
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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)
Abstract
Description
本発明は、固体酸触媒及びα，β−不飽和カルボン酸エステルの製造方法に関する。更に詳しくは、α，β−不飽和カルボン酸エステルの製造に用いる固体酸触媒、及び該固体酸触媒を用いるα，β−不飽和カルボン酸エステルの製造方法に関する。 The present invention relates to a solid acid catalyst and a method for producing an α, β-unsaturated carboxylic acid ester. More specifically, the present invention relates to a solid acid catalyst used for producing an α, β-unsaturated carboxylic acid ester, and a method for producing an α, β-unsaturated carboxylic acid ester using the solid acid catalyst.
従来、種々の固体酸触媒を用いるα，β−不飽和カルボン酸エステルの製造方法が提案されている。これらは不均一系触媒である固体酸を用いることで容易に反応生成物と触媒が分離でき、酸触媒の中和、水洗等による廃棄物の発生を抑えるものである。
前記固体酸触媒としては、イオン交換樹脂（スチレン−ジビニルベンゼン共重合体のスルホン化物）を触媒とするもの（特許文献１、２）、スルホン酸含有フッ素樹脂（Ｄｕ−Ｐｏｎｔ社「ナフィオン」等）を触媒とするもの（特許文献３）、リンタングステン酸等の固体超強酸を触媒とするもの（特許文献４）、スルホン酸を担持させた固体酸を触媒とするもの（特許文献５）等が提案されている。
しかしながら、これら特許文献１〜４の固体酸触媒は、いずれもα，β−不飽和カルボン酸エステル合成のための触媒として触媒活性が満足できるものではなく、かつ副生成物が生成し易く、また触媒の分解によって溶出した硫黄酸化物等の酸成分が残存するため、得られたα，β−不飽和カルボン酸エステルの純度が低いという問題があった。
また、特許文献５のスルホン酸基担持固体酸には、繰り返し使用した場合、触媒活性が低下しやすいという問題があった。
Conventionally, methods for producing α, β-unsaturated carboxylic acid esters using various solid acid catalysts have been proposed. By using a solid acid that is a heterogeneous catalyst, the reaction product and the catalyst can be easily separated, and the generation of waste due to neutralization of the acid catalyst, washing with water, etc. is suppressed.
Examples of the solid acid catalyst include those using an ion exchange resin (sulfonated styrene-divinylbenzene copolymer) as a catalyst (Patent Documents 1 and 2), a sulfonic acid-containing fluororesin (Du-Pont "Nafion", etc.) (Patent document 3), a catalyst using a solid superacid such as phosphotungstic acid (patent document 4), a catalyst using a solid acid carrying sulfonic acid (patent document 5), etc. Proposed.
However, none of these solid acid catalysts of Patent Documents 1 to 4 have satisfactory catalytic activity as a catalyst for synthesizing α, β-unsaturated carboxylic acid esters, and byproducts are easily generated. Since acid components such as sulfur oxides eluted by decomposition of the catalyst remain, there is a problem that the purity of the obtained α, β-unsaturated carboxylic acid ester is low.
Further, the sulfonic acid group-supporting solid acid of Patent Document 5 has a problem that the catalyst activity tends to decrease when it is used repeatedly.
本発明の課題は、α，β−不飽和カルボン酸エステルの製造時の重合物が生成しにくく、繰り返し使用しても触媒活性が低下しにくい固体酸触媒、及び該固体酸触媒を用いるα，β−不飽和カルボン酸エステルの製造方法を提供することである。 An object of the present invention is to form a solid acid catalyst that is difficult to produce a polymer during the production of an α, β-unsaturated carboxylic acid ester, and whose catalytic activity does not decrease even when used repeatedly, and α, It is to provide a method for producing a β-unsaturated carboxylic acid ester.
本発明者は上記問題を解決するため鋭意検討し、本発明に到達した。すなわち本発明は、無機多孔体に、フッ素化アルキルスルホン酸、フィチン酸及びリン酸からなる群から選ばれる少なくとも１種を担持させた酸基担持無機多孔体（ａ）からなる固体酸触媒（Ａ）、並びに該固体酸触媒（Ａ）の存在下に、アルコール（Ｂ）とα，β−不飽和カルボン酸又はその低級アルキルエステル（Ｃ）とを反応させることを特徴とするα，β−不飽和カルボン酸エステル（Ｄ）の製造方法である。 The present inventor has intensively studied to solve the above problems and has reached the present invention. That is, the present invention provides a solid acid catalyst (A) comprising an acid group-supporting inorganic porous material (a) in which at least one selected from the group consisting of fluorinated alkylsulfonic acid, phytic acid and phosphoric acid is supported on an inorganic porous material. ), And the solid acid catalyst (A) in the presence of an α, β-unsaturated product, wherein the alcohol (B) is reacted with an α, β-unsaturated carboxylic acid or a lower alkyl ester thereof (C). It is a manufacturing method of saturated carboxylic acid ester (D).
本発明の固体酸触媒は、α，β−不飽和カルボン酸エステルの製造時の副生成物が生成しにくく、繰り返し使用しても触媒活性が低下しにくい、といった効果を奏する。 The solid acid catalyst of the present invention has an effect that a by-product during the production of an α, β-unsaturated carboxylic acid ester is difficult to be produced, and the catalytic activity is hardly lowered even when used repeatedly.
本発明の固体酸触媒（Ａ）は、無機多孔体にフッ素化アルキルスルホン酸、フィチン酸及びリン酸からなる群から選ばれる少なくとも１種を担持させた酸基担持無機多孔体（ａ）からなるものである。 The solid acid catalyst (A) of the present invention comprises an acid group-supporting inorganic porous material (a) in which at least one selected from the group consisting of fluorinated alkylsulfonic acid, phytic acid and phosphoric acid is supported on an inorganic porous material. Is.
無機多孔体としては、公知の無機多孔体が使用でき、例えば、シリカ、アルミナ、チタニア、マグネシア及びジルコニアからなる群から選ばれる少なくとも１種の無機多孔体が挙げられる。 As the inorganic porous material, known inorganic porous materials can be used, and examples thereof include at least one inorganic porous material selected from the group consisting of silica, alumina, titania, magnesia and zirconia.
前記シリカとしては、ガラス状シリカ、石英、珪藻土、無定型シリカ、シリカゲル、シリカ粉末、シリカゾルや、シリカ表面をアルミ等で被覆した各種被覆シリカ微粒子（ゼオライト等）、樹脂粒子や金属酸化物ゾル等の表面をシリカで被覆したシリカ被覆微粒子、球状シリカ微粒子、棒状シリカ微粒子及び球状シリカが連結したネックレス状シリカ微粒子等が挙げられる。 Examples of the silica include glassy silica, quartz, diatomaceous earth, amorphous silica, silica gel, silica powder, silica sol, various coated silica fine particles (zeolite, etc.) whose surface is coated with aluminum, resin particles, metal oxide sol, etc. Examples thereof include silica-coated fine particles whose surfaces are coated with silica, spherical silica fine particles, rod-like silica fine particles, and necklace-like silica fine particles linked with spherical silica.
前記アルミナとしては、様々な結晶構造を有する粒子が使用でき、例えば、α−アルミナ、ギブサイト、バイアライト、ベーマイト、β−アルミナ、γ−アルミナ、アモルファスアルミナ等が挙げられる。 As said alumina, the particle | grains which have various crystal structures can be used, For example, (alpha) -alumina, gibbsite, vialite, boehmite, (beta) -alumina, (gamma) -alumina, an amorphous alumina etc. are mentioned.
前記チタニアとしては、ルチル型チタニア及びアナターゼ型チタニア等が挙げられる。
これらは、例えば四塩化チタン、硫酸チタン等のチタンの無機塩の加水分解、脱水縮合、テトラエトキシチタン、テトライソプロポキシチタン、テトラ−ｎ−プロポキシチタン、テトラブトキシチタン、テトラメトキシチタン等の有機チタン化合物を酸存在下において加水分解及び脱水縮合を行い、次いで、４００℃〜５００℃における焼成によってアナターゼ型チタニアに変性し、６００℃〜７００℃の焼成によってルチル型チタニアに変性することができる。
Examples of the titania include rutile titania and anatase titania.
These include, for example, hydrolysis of titanium inorganic salts such as titanium tetrachloride and titanium sulfate, dehydration condensation, organic titanium such as tetraethoxy titanium, tetraisopropoxy titanium, tetra-n-propoxy titanium, tetrabutoxy titanium and tetramethoxy titanium. The compound can be hydrolyzed and dehydrated in the presence of an acid, then modified to anatase titania by calcination at 400 ° C. to 500 ° C., and modified to rutile type titania by calcination at 600 ° C. to 700 ° C.
前記マグネシアとしては、水酸化マグネシウムや天然鉱物としての炭酸マグネシウム（マグネサイト）又は海水より抽出した炭酸マグネシウムを溶融又は焼成した溶融マグネシア、焼結マグネシア、軽焼マグネシア及び仮焼マグネシア等が挙げられる。 Examples of the magnesia include magnesium hydroxide, magnesium carbonate (magnesite) as a natural mineral, or molten magnesia obtained by melting or firing magnesium carbonate extracted from seawater, sintered magnesia, light-burned magnesia, and calcined magnesia.
前記ジルコニアとしては、ＺｒＯ２を主成分とし、ＣａＯ、ＭｇＯ、Ｙ２Ｏ３等の安定化剤を１種以上含む部分安定化ジルコニア等が挙げられ、例えば、３〜９モル％のイットリア（Ｙ２Ｏ３）で部分安定化したジルコニア（ＺｒＯ２）や、９〜２６モル％のマグネシア（ＭｇＯ）で部分安定化したジルコニア（ＺｒＯ２）、８〜１２モル％のカルシア（ＣａＯ）で部分安定化したジルコニア（ＺｒＯ２）、８〜１６モル％のセリア（ＣｅＯ２）で部分安定化したジルコニア（ＺｒＯ２）等が挙げられる。 Examples of the zirconia include partially stabilized zirconia containing ZrO 2 as a main component and one or more stabilizers such as CaO, MgO, and Y 2 O 3 , for example, 3 to 9 mol% of yttria (Y 2 O 3 ) partially stabilized with zirconia (ZrO 2 ), 9 to 26 mol% magnesia (MgO) partially stabilized zirconia (ZrO 2 ), 8 to 12 mol% calcia (CaO) partially stabilized phased zirconia (ZrO 2), partially stabilized zirconia (ZrO 2), and the like at 8-16 mol% of ceria (CeO 2).
無機多孔体のうち、触媒活性の観点から好ましくは、シリカ及びアルミナであり、更に好ましくはシリカであり、特に好ましくはシリカゲル及びゼオライトである。 Of the inorganic porous materials, silica and alumina are preferable from the viewpoint of catalytic activity, silica is more preferable, and silica gel and zeolite are particularly preferable.
酸基担持無機多孔体（ａ）を得る方法としては、無機多孔体を酸基に変換可能な酸前駆体基含有化合物（ｓ）と反応させて酸前駆体基担持無機多孔体を得た後、酸前駆体基を酸基に変換する方法等が挙げられる。
前記（ｓ）としては、その分子中に、無機多孔体の表面に存在する官能基と反応する基及び酸基に変換可能な基を有する化合物である。無機多孔体の表面に存在する官能基としては水酸基、アミノ基及びカルボキシル基等が挙げられる。これらのうち、無機多孔体の表面を修飾し易いという観点から好ましくは水酸基である。
（ｓ）が含有する、無機多孔体の表面の官能基と反応する基としては、無機多孔体の表面に存在する官能基が水酸基又はアミノ基の場合は、トリアルコキシシリル基、グリシジル基及びカルボキシル基等が挙げられ、無機多孔体の表面に存在する官能基がカルボキシル基の場合は、トリアルコキシシリル基、グリシジル基及びアミノ基等が挙げられる。これらのうち、無機多孔体の表面に存在する官能基との反応が進行し易いという観点から好ましくは、トリアルコキシシリル基及びグリシジル基であり、更に好ましくはトリアルコキシシリル基である。
（ｓ）が含有する酸基に変換可能な酸前駆体基としては、フッ素化アルキルメルカプト基（酸化してフッ素化アルキルスルホン酸基に変換）、グリシジル基（フィチン酸、リン酸を反応させてそれぞれフィチン酸基、リン酸基に変換）等が挙げられる。
As a method for obtaining the acid group-supporting inorganic porous material (a), after reacting the inorganic porous material with an acid precursor group-containing compound (s) that can be converted into an acid group, an acid precursor group-supporting inorganic porous material is obtained. And a method of converting an acid precursor group into an acid group.
The (s) is a compound having in its molecule a group that reacts with a functional group present on the surface of the inorganic porous material and a group that can be converted into an acid group. Examples of the functional group present on the surface of the inorganic porous material include a hydroxyl group, an amino group, and a carboxyl group. Among these, a hydroxyl group is preferable from the viewpoint of easily modifying the surface of the inorganic porous material.
As the group which reacts with the functional group on the surface of the inorganic porous material contained in (s), when the functional group present on the surface of the inorganic porous material is a hydroxyl group or an amino group, a trialkoxysilyl group, a glycidyl group and a carboxyl group When the functional group present on the surface of the inorganic porous body is a carboxyl group, a trialkoxysilyl group, a glycidyl group, an amino group, and the like are included. Of these, a trialkoxysilyl group and a glycidyl group are preferable, and a trialkoxysilyl group is more preferable from the viewpoint that the reaction with the functional group present on the surface of the inorganic porous body easily proceeds.
Acid precursor groups that can be converted to acid groups contained in (s) include fluorinated alkyl mercapto groups (oxidized to convert to fluorinated alkyl sulfonic acid groups), glycidyl groups (phytic acid, phosphoric acid, and the like). Conversion to phytic acid groups and phosphoric acid groups).
（ｓ）の具体例としては、フッ素化アルキルメルカプト基含有シランカップリング剤（フッ素化アルキルメルカプトプロピルトリメトキシシラン及びフッ素化アルキルメルカプトプロピルトリエトキシシラン等）、グリシジル基含有シランカップリング剤（３−グリシジルオキシプロピルトリメトキシシラン及び３−グリシジルオキシプロピルトリエトキシシラン等）等が挙げられる。 Specific examples of (s) include fluorinated alkyl mercapto group-containing silane coupling agents (such as fluorinated alkyl mercaptopropyltrimethoxysilane and fluorinated alkylmercaptopropyltriethoxysilane), glycidyl group-containing silane coupling agents (3- Glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and the like).
（ｓ）と無機多孔体との反応は、種々の反応条件で行うことができる。例えば、（ｓ）を無機多孔体の重量に基づいて３０〜６０重量％の割合で仕込み、溶媒の存在下に加熱撹拌し、シランカップリング剤中のトリアルコキシシリル基と無機多孔体の表面に存在する官能基（水酸基、アミノ基及びカルボキシル基等）を反応させた後、精製して得ることができる。溶媒としては有機溶媒（トルエン、キシレン、酢酸エチル、メチルエチルケトン、アセトン及び／又は低級アルコール等）を使用することができ、水とこれらの有機溶媒との混合溶媒でもよい。水は無機多孔体表面に存在する官能基及び（ｓ）の活性を促進させるため少量使用するのが好ましく、水の割合は、（ｓ）１モルに対して３倍モル以下が好ましい。
溶媒の使用量は、無機多孔体の重量に基づいて、好ましくは８０〜３００重量％であり、更に好ましくは１００〜２５０重量％である。反応温度は、好ましくは６０〜１５０℃であり、（ｓ）がシランカップリング剤の場合は、無機多孔体との反応で副生するアルコキシ基由来物質（例えばメタノール及びエタノール等の低級アルコール）を除去しながら反応してもよい。
反応後は、粒状物をろ過又は遠心分離機等を用いて分離・回収し、未反応の（ｓ）を除去するために、前記有機溶剤で粒状物を数回洗浄した後、減圧乾燥（通常１００〜１２０℃、０．００１〜０．００３ＭＰａで３〜５時間）することができる。
Reaction of (s) and an inorganic porous body can be performed on various reaction conditions. For example, (s) is charged at a ratio of 30 to 60% by weight based on the weight of the inorganic porous material, and is heated and stirred in the presence of a solvent to form a trialkoxysilyl group in the silane coupling agent and the surface of the inorganic porous material. It can be obtained by purifying after reacting existing functional groups (hydroxyl group, amino group, carboxyl group, etc.). As the solvent, an organic solvent (toluene, xylene, ethyl acetate, methyl ethyl ketone, acetone, and / or lower alcohol, etc.) can be used, and a mixed solvent of water and these organic solvents may be used. Water is preferably used in a small amount in order to promote the activity of the functional group and (s) present on the surface of the inorganic porous body, and the proportion of water is preferably 3 times or less per 1 mol of (s).
The amount of the solvent used is preferably 80 to 300% by weight, more preferably 100 to 250% by weight, based on the weight of the inorganic porous material. The reaction temperature is preferably 60 to 150 ° C., and when (s) is a silane coupling agent, an alkoxy group-derived substance (for example, lower alcohol such as methanol and ethanol) produced as a by-product in the reaction with the inorganic porous material is used. You may react, removing.
After the reaction, the particulate matter is separated and collected by filtration or using a centrifuge, and the particulate matter is washed several times with the organic solvent to remove unreacted (s), and then dried under reduced pressure (usually 100 to 120 ° C. and 0.001 to 0.003 MPa for 3 to 5 hours).
無機多孔体に（ｓ）としてフッ素化アルキルメルカプト基含有シランカップリング剤を反応させた後、フッ素化アルキルメルカプト基をスルホン酸基に変換してフッ素化アルキルスルホン酸を担持させた酸基担持無機多孔体（ａ１）を得る方法としては、溶媒の存在下に酸化反応を行う方法が挙げられる。用いる酸化剤としては種々の酸化剤、例えば硝酸、過酸化水素、次亜塩素酸塩、過マンガン酸カリウム、クロム酸及び過酸化物等が挙げられ、これらのうち好ましくは過酸化水素である。溶媒としてはアセトン、低級アルコール、アセトニトリル、ピリジン、クロロホルム及び／又はジクロロメタン等が挙げられる。反応温度は通常０〜１００℃である。過酸化水素による酸化反応は、米国特許５９１２３８５号明細書記載の反応条件でも行うことができる。 An acid group-supporting inorganic material in which a fluorinated alkyl mercapto group-containing silane coupling agent is reacted as the inorganic porous material (s), and then the fluorinated alkyl mercapto group is converted into a sulfonic acid group to support a fluorinated alkyl sulfonic acid. Examples of the method for obtaining the porous body (a1) include a method in which an oxidation reaction is performed in the presence of a solvent. Examples of the oxidizing agent to be used include various oxidizing agents such as nitric acid, hydrogen peroxide, hypochlorite, potassium permanganate, chromic acid and peroxide. Among these, hydrogen peroxide is preferable. Examples of the solvent include acetone, lower alcohol, acetonitrile, pyridine, chloroform and / or dichloromethane. The reaction temperature is usually 0 to 100 ° C. The oxidation reaction with hydrogen peroxide can also be performed under the reaction conditions described in US Pat. No. 5,912,385.
フッ素化アルキルメルカプト基をフッ素化アルキルスルホン酸基に変換してフッ素化アルキルスルホン酸を担持させた酸基担持無機多孔体（ａ１）を得る方法の場合、反応後は（ａ１）をろ過又は遠心分離機等を用いて分離・回収し、前記有機溶媒で（ａ１）を数回洗浄した後、減圧乾燥（通常１００〜１２０℃、−０．０９９〜−０．０９７ＭＰａで３〜５時間）することができる。 In the method of obtaining an acid group-supporting inorganic porous material (a1) in which a fluorinated alkylmercapto group is converted to a fluorinated alkylsulfonic acid group and supporting the fluorinated alkylsulfonic acid, (a1) is filtered or centrifuged after the reaction. After separating and recovering using a separator, etc., (a1) is washed several times with the organic solvent, and then dried under reduced pressure (usually 100 to 120 ° C., −0.099 to −0.097 MPa for 3 to 5 hours). be able to.
本発明の固体酸触媒（Ａ）は、フッ素化アルキルスルホン酸を担持させた酸基担持無機多孔体（ａ１）を加熱処理することが、触媒活性及びα，β−不飽和カルボン酸エステルの製造時の副生成物が生成し難いという観点から好ましい。加熱処理の温度の好ましい範囲は、１５０〜２５０℃であり、更に好ましくは１６０〜２２０℃であり、特に好ましくは１８０〜２００℃である。加熱処理時間は、触媒活性及びα，β−不飽和カルボン酸エステルの製造時の副生成物が生成し難いという観点から好ましくは０．５〜４８時間であり、更に好ましくは１〜３５時間である。加熱処理は、空気又は窒素雰囲気下で行うのが好ましく、また、加熱媒体の存在下に行うことができ、加熱媒体としては有機溶媒（ｎ−オクタン、ｎ−ノナン、ｎ−デカン、ｎ−ウンデカン、ｎ−ドデカン、ｎ−トリデカン、トルエン、エチルベンゼン、キシレン、エチルトルエン及び１，２，４−トリメチルベンゼン等）、鉱物油（石油、鉱物油、パラフィン及びシリコンオイル等）及び合成油（ＰＡＯ油等）が挙げられる。加熱処理後は、粒状物をろ過又は遠心分離機等を用いて分離・回収し、前記有機溶媒で粒状物を数回洗浄した後、減圧乾燥（通常１００〜１２０℃、０．００１〜０．００３ＭＰａで３〜５時間）することができる。 In the solid acid catalyst (A) of the present invention, the heat treatment of the acid group-supporting inorganic porous material (a1) on which the fluorinated alkylsulfonic acid is supported is a catalyst activity and production of an α, β-unsaturated carboxylic acid ester. It is preferable from the viewpoint that a by-product is not easily generated. The preferable range of the temperature of the heat treatment is 150 to 250 ° C, more preferably 160 to 220 ° C, and particularly preferably 180 to 200 ° C. The heat treatment time is preferably 0.5 to 48 hours, more preferably 1 to 35 hours, from the viewpoint of catalytic activity and the difficulty of forming by-products during the production of the α, β-unsaturated carboxylic acid ester. is there. The heat treatment is preferably performed in an atmosphere of air or nitrogen, and can be performed in the presence of a heating medium. As the heating medium, an organic solvent (n-octane, n-nonane, n-decane, n-undecane) can be used. , N-dodecane, n-tridecane, toluene, ethylbenzene, xylene, ethyltoluene, 1,2,4-trimethylbenzene, etc.), mineral oil (petroleum, mineral oil, paraffin, silicone oil, etc.) and synthetic oil (PAO oil, etc.) ). After the heat treatment, the particulate matter is separated and recovered using filtration or a centrifuge, and the particulate matter is washed several times with the organic solvent, and then dried under reduced pressure (usually 100 to 120 ° C., 0.001 to 0.00. 3 to 5 hours at 003 MPa).
本発明の固体酸触媒（Ａ）の酸価は、好ましくは２０〜２００ｍｇＫＯＨ／ｇであり、更に好ましくは２０〜１５０ｍｇＫＯＨ／ｇ、特に好ましくは２０〜１００ｍｇＫＯＨ／ｇである。酸価が２０ｍｇＫＯＨ／ｇ以上であれば触媒活性が向上し、少量の触媒でエステル化反応が進行し易くなる。酸価が２００ｍｇＫＯＨ／ｇ以下であれば副反応が起こり難くなる。なお、（Ａ）の酸価は、イオン交換水に（Ａ）を浸し、過剰の水酸化ナトリウムを加えて撹拌し、０．１Ｎ塩酸水溶液で中和滴定するという方法で測定することができる。 The acid value of the solid acid catalyst (A) of the present invention is preferably 20 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g, and particularly preferably 20 to 100 mgKOH / g. When the acid value is 20 mgKOH / g or more, the catalytic activity is improved, and the esterification reaction easily proceeds with a small amount of catalyst. If the acid value is 200 mgKOH / g or less, side reactions are unlikely to occur. The acid value of (A) can be measured by a method in which (A) is immersed in ion-exchanged water, excess sodium hydroxide is added and stirred, and neutralization titration is performed with a 0.1N hydrochloric acid aqueous solution.
（Ａ）は、酸基を担持する前の無機多孔体と実質的に同じ形状であり、その平均粒子径、ＢＥＴ比表面積及びアスペクト比の好ましい範囲も同様である。 (A) has substantially the same shape as that of the inorganic porous material before supporting the acid group, and preferred ranges of the average particle diameter, the BET specific surface area, and the aspect ratio are the same.
（Ａ）の平均粒子径は、好ましくは１〜８,０００μｍであり、更に好ましくは１０〜６，０００μｍ、特に好ましくは４０〜５００μｍである。１μｍ以上であれば取り扱いが容易になり、８,０００μｍ以下であれば触媒活性の観点から好ましい。なお、（Ａ）の平均粒子径は、ＪＩＳ Ｋ１１５０の粒度分布測定法で測定することができる。 The average particle size of (A) is preferably 1 to 8,000 μm, more preferably 10 to 6,000 μm, and particularly preferably 40 to 500 μm. If it is 1 micrometer or more, handling will become easy, and if it is 8,000 micrometers or less, it is preferable from a viewpoint of catalyst activity. In addition, the average particle diameter of (A) can be measured by the particle size distribution measuring method of JIS K1150.
（Ａ）のＢＥＴ比表面積は、好ましくは３０〜１５００ｍ2／ｇであり、更に好ましくは５０〜１，５００ｍ2／ｇ、特に好ましくは１００〜８００ｍ2／ｇである。３０ｍ2／ｇ以上であれば、触媒活性が高くなりかつ副反応が少なくなる点で好ましい。なお、（Ａ）のＢＥＴ比表面積は、ＪＩＳ Ｋ１１５０の比表面積測定法で測定することができる。 BET specific surface area of (A) is preferably a 30~1500m 2 / g, more preferably 50~1,500m 2 / g, particularly preferably 100~800m 2 / g. If it is 30 m < 2 > / g or more, it is preferable at the point which a catalyst activity becomes high and a side reaction decreases. In addition, the BET specific surface area of (A) can be measured by the specific surface area measuring method of JIS K1150.
（Ａ）のアスペクト比は、好ましくは１．０〜１．２５であり、更に好ましくは１．０〜１．１８、特に好ましくは１．０〜１．１１である。アスペクト比が１．２５以下であれば、後述する流通法で反応させる際の圧力損失が小さい点で好ましい。なお、（Ａ）のアスペクト比は、（Ａ）の粒子１００個を顕微鏡観察し、最長直径と最短直径をそれぞれ計測し、以下の計算式から算出することができる。
アスペクト比＝［１００個の（Ａ）の最長直径の平均値／１００個の（Ａ）の最短直径の平均値］
The aspect ratio of (A) is preferably 1.0 to 1.25, more preferably 1.0 to 1.18, and particularly preferably 1.0 to 1.11. If the aspect ratio is 1.25 or less, it is preferable in that the pressure loss when the reaction is performed by a flow method described later is small. The aspect ratio of (A) can be calculated from the following formula by observing 100 particles of (A) under a microscope, measuring the longest diameter and the shortest diameter, respectively.
Aspect ratio = [average value of 100 (A) longest diameter / average value of 100 (A) shortest diameter]
（Ａ）の過酸化物価は、好ましくは０〜４０ｍｇ／ｋｇであり、更に好ましくは０〜１６ｍｇ／ｋｇである。４０ｍｇ／ｋｇ以下であれば重合物低減の観点から好ましい。なお、（Ａ）の過酸化物価は、ＪＩＳ Ｋ２２７６の過酸化物価測定法で測定することができる。 The peroxide value of (A) is preferably 0 to 40 mg / kg, more preferably 0 to 16 mg / kg. If it is 40 mg / kg or less, it is preferable from a viewpoint of polymer reduction. The peroxide value of (A) can be measured by the peroxide value measuring method of JIS K2276.
本発明の固体酸触媒（Ａ）は、繰り返し使用しても触媒活性が低下し難いため、再使用することができる。原料が同じ反応で再使用する際には洗浄等をせずそのまま使用することができるが、原料が異なる反応で再使用する際には、使用後の（Ａ）をろ過、デカンテーション又は遠心分離機等を用いて分離・回収し、前記有機溶媒で（Ａ）を数回洗浄した後、減圧乾燥（通常１００〜１２０℃、０．００１〜０．００３ＭＰａで３〜５時間）することが好ましい。 The solid acid catalyst (A) of the present invention can be reused because its catalytic activity is unlikely to decrease even when used repeatedly. When the raw material is reused in the same reaction, it can be used as it is without washing, but when it is reused in a different raw material reaction, (A) after use is filtered, decanted or centrifuged. It is preferable to separate and collect using a machine, etc., wash (A) several times with the organic solvent, and then dry under reduced pressure (usually 100 to 120 ° C., 0.001 to 0.003 MPa for 3 to 5 hours). .
本発明のα，β−不飽和カルボン酸エステル（Ｄ）の製造方法におけるアルコール（Ｂ）としては、１価アルコール（Ｂ１）及び２価以上の多価アルコール（Ｂ２）が挙げられる。 Examples of the alcohol (B) in the method for producing the α, β-unsaturated carboxylic acid ester (D) of the present invention include a monohydric alcohol (B1) and a dihydric or higher polyhydric alcohol (B2).
（Ｂ１）としては以下のものが挙げられる。
（Ｂ１１）飽和脂肪族１価アルコール［炭素数１〜３６の直鎖又は分岐のアルコール；例えばメチルアルコール、エチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコール、ブチルアルコール、２−エチルヘキシルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコール、ウンデシルアルコール、ドデシルアルコール、トリデシルアルコール、テトラデシルアルコール、ヘキサデシルアルコール、オクタデシルアルコール、ノナデシルアルコール、２−デシルテトラデシルアルコール及び２−テトラデシルオクタデシルアルコール等］；
（Ｂ１２）不飽和脂肪族１価アルコール［炭素数２〜３６の直鎖又は分岐のアルコール；例えばビニルアルコール、アリルアルコール、メタリルアルコール、オクテニルアルコール、デセニルアルコール、ドデセニルアルコール、トリデセニルアルコール、ペンタデセニルアルコール、オレイルアルコール、ガドレイルアルコール及びリノレイルアルコール等］；
（Ｂ１３）脂環式１価アルコール［脂環基を有する総炭素数６〜３６のアルコール；例えばエチルシクロヘキシルアルコール、プロピルシクロヘキシルアルコール、オクチルシクロヘキシルアルコール、ノニルシクロヘキシルアルコール及びアダマンチルアルコール等］；
（Ｂ１４）１価フェノール類［フェノール環を有する総炭素数６〜３６のフェノール類；例えばフェノール、クレゾール、ｔ−ブチルフェノール、スチレン化フェノール及びブロモフェノール等］；
（Ｂ１５）窒素原子、硫黄原子及び／又はハロゲン原子を有する１価アルコール［例えばジメチルアミノエタノール、ジエチルアミノエタノール、モルホリノエタノール及び２−クロロエタノール等］；
（Ｂ１６）前記アルコール（Ｂ１１）〜（Ｂ１５）のアルキレンオキサイド（以下、ＡＯと略記する。）［炭素数２〜８のＡＯ；例えばエチレンオキサイド（以下、ＥＯと略記する。）、１，２−プロピレンオキサイド（以下、ＰＯと略記する。）、１，２−又は２，３−ブチレンオキサイド、テトラヒドロフラン及びスチレンオキサイド等］
Examples of (B1) include the following.
(B11) Saturated aliphatic monohydric alcohol [C1-C36 linear or branched alcohol; for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, 2-ethylhexyl alcohol, octyl alcohol, nonyl Alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, 2-decyl tetradecyl alcohol and 2-tetradecyl octadecyl alcohol];
(B12) unsaturated aliphatic monohydric alcohol [C2-C36 linear or branched alcohol; for example, vinyl alcohol, allyl alcohol, methallyl alcohol, octenyl alcohol, decenyl alcohol, dodecenyl alcohol, Tridecenyl alcohol, pentadecenyl alcohol, oleyl alcohol, gadrelyl alcohol, linoleyl alcohol, etc.];
(B13) Alicyclic monohydric alcohol [alcohol having 6 to 36 carbon atoms having an alicyclic group; for example, ethylcyclohexyl alcohol, propylcyclohexyl alcohol, octylcyclohexyl alcohol, nonylcyclohexyl alcohol, adamantyl alcohol, etc.];
(B14) Monohydric phenols [phenols having a phenol ring and a total carbon number of 6 to 36; for example, phenol, cresol, t-butylphenol, styrenated phenol, bromophenol, etc.];
(B15) monohydric alcohols having a nitrogen atom, a sulfur atom and / or a halogen atom [for example, dimethylaminoethanol, diethylaminoethanol, morpholinoethanol, 2-chloroethanol and the like];
(B16) Alkylene oxide (hereinafter abbreviated as AO) of the alcohols (B11) to (B15) [AO having 2 to 8 carbon atoms; for example, ethylene oxide (hereinafter abbreviated as EO), 1,2- Propylene oxide (hereinafter abbreviated as PO), 1,2- or 2,3-butylene oxide, tetrahydrofuran, styrene oxide, etc.]
（Ｂ２）としては以下のものが挙げられる。
（Ｂ２１）２価アルコール［炭素数２〜１２のアルキレングリコール（エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，４−ブチレングリコール、１，６−ヘキサンジオール及び１，１２−ドデカメチレングリコール等）、重合度２〜１，０００のポリアルキレングリコール（ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール及びポリブチレングリコール等）、脂環式ジオール（脂環基を有する総炭素数６〜３６のジオール；例えば１，４−シクロヘキサンジメタノール及び水素添加ビスフェノールＡ等）、２価アルコールのＡＯ付加物（付加モル数１〜５０）及びビスフェノール類（ビスフェノールＡ、ビスフェノールＦ及びビスフェノールＳ等）のＡＯ付加物（付加モル数２〜３０）］；
（Ｂ２２）３〜８価又はそれ以上の脂肪族多価アルコール［アルカンポリオール及びその分子内又は分子間脱水物（グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、ソルビタン、ポリグリセリン及びジペンタエリスリトール等）、糖類及びその誘導体（蔗糖及びメチルグルコシド等）、及び前記脂肪族多価アルコールのＡＯ付加物（付加モル数１〜５０）］；
（Ｂ２３）３〜８価又はそれ以上の芳香環含有多価アルコール［トリスフェノール類（トリスフェノールＰＡ等）のＡＯ付加物（付加モル数２〜５０）、ノボラック樹脂（フェノールノボラック及びクレゾールノボラック等）のＡＯ付加物（付加モル数２〜５０）等］
Examples of (B2) include the following.
(B21) Dihydric alcohol [C2-C12 alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol and 1,12 -Dodecamethylene glycol, etc.), polyalkylene glycols with a polymerization degree of 2-1,000 (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.), alicyclic diols (with alicyclic groups) Diols having a total carbon number of 6 to 36, such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A, etc., AO adducts of dihydric alcohols (addition mole number of 1 to 50) and bisphenols (bisphenol A, bisphenol) Lumpur F and AO adducts of bisphenol S, etc.) (addition molar number 2 to 30)];
(B22) 3 to 8 or more aliphatic polyhydric alcohols [alkane polyol and intramolecular or intermolecular dehydrates thereof (glycerin, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, dipentaerythritol, etc.) , Sugars and derivatives thereof (such as sucrose and methyl glucoside), and AO adducts of the above aliphatic polyhydric alcohols (addition mole number 1 to 50)];
(B23) 3 to 8 or more aromatic ring-containing polyhydric alcohols [AO adducts (addition mole number 2 to 50) of trisphenols (trisphenol PA, etc.), novolac resins (phenol novolac, cresol novolac, etc.) AO adduct (number of added moles 2-50), etc.]
（Ｂ）のうち好ましくは、１価アルコール（Ｂ１）、２価アルコール（Ｂ２１）及びそれらのＡＯ付加物であり、更に好ましくは（Ｂ１）である。
（Ｂ１）のうち好ましくは、（Ｂ１１）、（Ｂ１２）、（Ｂ１５）それらのＡＯ付加物であり、更に好ましくは、高純度の生成物が得られ易いという観点から（Ｂ１１）のうちの炭素数８〜３２の飽和脂肪族１価アルコール及びそのＡＯ（特にＥＯ）付加物である。
（Ｂ）に含まれる水酸基としては１級水酸基及び２級水酸基が挙げられるが、好ましくは１級水酸基である。
Of these, (B) is preferably a monohydric alcohol (B1), a dihydric alcohol (B21), or an AO adduct thereof, more preferably (B1).
Among (B1), (B11), (B12), (B15) are those AO adducts, and more preferably, carbon in (B11) from the viewpoint that a highly pure product is easily obtained. A saturated aliphatic monohydric alcohol having a number of 8 to 32 and its AO (particularly EO) adduct.
Examples of the hydroxyl group contained in (B) include a primary hydroxyl group and a secondary hydroxyl group, with a primary hydroxyl group being preferred.
本発明におけるα，β−不飽和カルボン酸又はその低級アルキルエステル（Ｃ）としては、α，β−不飽和カルボン酸（Ｃ１）及びα，β−不飽和カルボン酸の低級アルキルエステル（Ｃ２）が挙げられる。 The α, β-unsaturated carboxylic acid or the lower alkyl ester (C) thereof in the present invention includes α, β-unsaturated carboxylic acid (C1) and α, β-unsaturated carboxylic acid lower alkyl ester (C2). Can be mentioned.
α，β−不飽和カルボン酸（Ｃ１）としては、脂肪族α，β−不飽和モノカルボン酸［アクリル酸、メタクリル酸及びクロトン酸等］及び脂肪族α，β−不飽和ジカルボン酸（マレイン酸、フマル酸、イタコン酸及びシトラコン酸等）が挙げられる。
α，β−不飽和カルボン酸の低級アルキルエステル（Ｃ２）としては、（Ｃ１）と炭素数１〜４のアルキル基を有するアルコールから得られるエステル（メチルエステル、エチルエステル、イソプロピルエステル及びｎ−ブチルエステル等）が挙げられる。
Examples of the α, β-unsaturated carboxylic acid (C1) include aliphatic α, β-unsaturated monocarboxylic acids [acrylic acid, methacrylic acid, crotonic acid and the like] and aliphatic α, β-unsaturated dicarboxylic acids (maleic acid). , Fumaric acid, itaconic acid and citraconic acid).
As the lower alkyl ester (C2) of α, β-unsaturated carboxylic acid, esters (methyl ester, ethyl ester, isopropyl ester and n-butyl) obtained from (C1) and an alcohol having an alkyl group having 1 to 4 carbon atoms Ester) and the like.
（Ｃ）のうち、純度の高いエステルが得られるという観点から好ましくは（Ｃ１）であり、更に好ましくは脂肪族α，β−不飽和モノカルボン酸であり、特に好ましくはアクリル酸及びメタクリル酸である。 Among (C), (C1) is preferable from the viewpoint of obtaining a highly pure ester, more preferably an aliphatic α, β-unsaturated monocarboxylic acid, particularly preferably acrylic acid and methacrylic acid. is there.
本発明の（Ｄ）の製造方法において、（Ｂ）と（Ｃ）の仕込み当量比は、好ましくは１：３〜３：１であり、更に好ましくは１：２〜２：１、特に好ましくは１：１.５〜１.５：１、最も好ましくは１：１.５〜１：１である。（Ｂ）又は（Ｃ）のうち除去が容易な方を過剰に用い、反応完了後、過剰の（Ｂ）又は（Ｃ）を除去するのが反応率向上の観点から好ましい。 In the production method of (D) of the present invention, the charge equivalent ratio of (B) and (C) is preferably 1: 3 to 3: 1, more preferably 1: 2 to 2: 1, particularly preferably. 1: 1.5 to 1.5: 1, most preferably 1: 1.5 to 1: 1. From the viewpoint of improving the reaction rate, it is preferable to use an excess of (B) or (C) which is easy to remove and to remove excess (B) or (C) after completion of the reaction.
本発明の（Ｄ）の製造方法において、不飽和基の重合を防止する目的で重合禁止剤を添加することもできる。重合禁止剤としては、フェノール系重合禁止剤（ハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、クレゾール、ジ−ｔ−ブチルクレゾール、ジ−ｔ−ブチルフェノール及びトリ−ｔ−ブチルフェノール等）、及びアミン系重合禁止剤（フェノチアジン、ジフェニルアミン及びアルキル化ジフェニルアミン等）等が挙げられる。これらのうち好ましくはフェノール系重合禁止剤である。重合禁止剤の添加量は、（Ｂ）及び（Ｃ）の総重量に基づいて、好ましくは０．００１〜２重量％であり、更に好ましくは０．０１〜１重量％、特に好ましくは０．０１〜０.５重量％、最も好ましくは０．０１〜０.２重量％である。 In the production method (D) of the present invention, a polymerization inhibitor may be added for the purpose of preventing polymerization of unsaturated groups. As polymerization inhibitors, phenol polymerization inhibitors (hydroquinone, hydroquinone monomethyl ether, catechol, cresol, di-t-butylcresol, di-t-butylphenol and tri-t-butylphenol), and amine polymerization inhibitors ( Phenothiazine, diphenylamine, alkylated diphenylamine, etc.). Of these, phenol-based polymerization inhibitors are preferred. The addition amount of the polymerization inhibitor is preferably 0.001 to 2% by weight, more preferably 0.01 to 1% by weight, particularly preferably 0. 0% based on the total weight of (B) and (C). It is 01 to 0.5% by weight, most preferably 0.01 to 0.2% by weight.
本発明の（Ａ）の使用量は、（Ｂ）及び（Ｃ）の総重量に基づいて、好ましくは０.１〜７０重量％であり、更に好ましくは１〜６０重量％、特に好ましくは２〜５０重量％、最も好ましくは３〜４０重量％である。０.１重量％以上用いることでエステル化反応が進行し易くなり、７０重量％以下であれば経済面から好ましい。
（Ａ）の使用量は、（Ｂ）の仕込み当量に対する（Ａ）中のスルホン酸基の当量の比が、好ましくは０．００５〜０．３、更に好ましくは０．０１〜０．２となる添加量である。０．００５以上であれば反応速度の観点から好ましく、０．３以下であれば副反応が抑制されるという観点から好ましい。
The amount of (A) used in the present invention is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, particularly preferably 2 based on the total weight of (B) and (C). -50% by weight, most preferably 3-40% by weight. The use of 0.1% by weight or more facilitates the esterification reaction, and 70% by weight or less is preferable from the economical aspect.
The amount of (A) used is such that the ratio of the equivalent amount of the sulfonic acid group in (A) to the charged equivalent of (B) is preferably 0.005 to 0.3, more preferably 0.01 to 0.2. The added amount becomes. If it is 0.005 or more, it is preferable from the viewpoint of the reaction rate, and if it is 0.3 or less, it is preferable from the viewpoint that side reactions are suppressed.
（Ｂ）と（Ｃ）とを反応させるときの反応の形態としては、バッチ法及び流通法等が挙げられる。 Examples of the reaction form when (B) and (C) are reacted include a batch method and a distribution method.
バッチ法の場合は、（Ａ）、（Ｂ）、（Ｃ）及び必要により反応溶媒を反応槽に仕込み、加熱撹拌し、生成する水又は低級アルコールを除去しながら反応を進行させる。反応完了後、生成した（Ｄ）と（Ａ）をデカンテーション、ろ過又は遠心分離等によって分離する。（Ｂ）又は（Ｃ）を過剰に用いた場合は、（Ａ）を分離する前又は分離後に過剰の原料を減圧留去することで（Ｄ）を得ることができる。 In the case of the batch method, (A), (B), (C) and, if necessary, a reaction solvent are charged into a reaction vessel, heated and stirred, and the reaction is allowed to proceed while removing generated water or lower alcohol. After completion of the reaction, the produced (D) and (A) are separated by decantation, filtration or centrifugation. When (B) or (C) is used excessively, (D) can be obtained by distilling off excess raw materials under reduced pressure before or after separating (A).
バッチ法における反応温度は、反応速度及び副反応を抑制するという観点から好ましくは６０〜１８０℃であり、更に好ましくは８０〜１６０℃、特に好ましくは１００〜１４０℃である。反応時間は、好ましくは１０分〜２４時間であり、更に好ましくは３０分〜１０時間、特に好ましくは１〜５時間である。
反応溶媒としては、炭化水素系溶媒（トルエン及びキシレン等の芳香族炭化水素等）、ケトン系溶媒（メチルエチルケトン及びメチルイソブチルケトン等）及びエーテル系溶媒（テトラヒドロフラン等）等が挙げられる。これらの反応溶媒のうち、反応生成水を分離して除去し易いという観点から好ましくは炭化水素系溶媒である。
（Ｂ）と（Ｃ）の反応で生成する水又は低級アルコールを除去する方法としては、常圧又は減圧下に留去させる方法、分液又は遠心分離する方法、モレキュラシーブス及び硫酸マグネシウム等の脱水剤と接触させる方法、水分離膜等の選択膜により膜分離する方法等が挙げられる。これらの方法のうち、バッチ法の場合は、常圧又は減圧下に水又は低級アルコールを留去させる方法が好ましい。
The reaction temperature in the batch method is preferably 60 to 180 ° C., more preferably 80 to 160 ° C., and particularly preferably 100 to 140 ° C. from the viewpoint of suppressing the reaction rate and side reaction. The reaction time is preferably 10 minutes to 24 hours, more preferably 30 minutes to 10 hours, and particularly preferably 1 to 5 hours.
Examples of the reaction solvent include hydrocarbon solvents (such as aromatic hydrocarbons such as toluene and xylene), ketone solvents (such as methyl ethyl ketone and methyl isobutyl ketone), and ether solvents (such as tetrahydrofuran). Of these reaction solvents, hydrocarbon solvents are preferred from the viewpoint that the reaction product water can be easily separated and removed.
As a method of removing water or lower alcohol produced by the reaction of (B) and (C), a method of distilling off under normal pressure or reduced pressure, a method of separating or centrifuging, dehydration of molecular sieves and magnesium sulfate, etc. Examples thereof include a method of contacting with an agent and a method of membrane separation using a selective membrane such as a water separation membrane. Among these methods, in the case of a batch method, a method of distilling off water or a lower alcohol under normal pressure or reduced pressure is preferable.
流通法の場合は、（Ａ）を充填したカラム、固定床又は流動床等に、所定の温度に温調した（Ｂ）と（Ｃ）の混合物を通液することで（Ｄ）を得ることができる。
（Ａ）に（Ｂ）と（Ｃ）の混合物を一回通液（１パス）した後、反応混合物を蒸留することにより（Ｄ）を得ることもできるが、反応率を高くすることができるという観点から、（Ａ）の存在下に（Ｂ）と（Ｃ）とを反応させる工程（１）と、（Ｂ）と（Ｃ）との反応によって生成した水又は低級アルコールを反応混合物から除去する工程（２）とからなる製造方法が好ましい。特に、工程（１）と工程（２）とを繰り返すことで反応率を更に高めることができる。 工程（１）において通液する（Ｂ）と（Ｃ）の温度は、好ましくは６０〜１８０℃であり、更に好ましくは８０〜１６０℃、特に好ましくは１００〜１４０℃である。６０℃以上であれば反応速度の観点から好ましく、１８０℃以下であれば副反応を抑制する観点から好ましい。
工程（１）における１パスあたりの平均通液時間［（Ａ）と、（Ｂ）及び（Ｃ）の平均接触時間］は、好ましくは０.１〜６０分であり、更に好ましくは０.２〜１０分、特に好ましくは０．５〜５分である。
工程（２）における水又は低級アルコールを除去する方法としては、連続式エバポレーターで留去する方法、コンデンサーを付した反応槽等を用いて常圧又は減圧下に留去させる方法、及び水分離膜、遠心分離又は脱水剤によって脱水する方法等が挙げられる。これらのうち、生産効率の観点から好ましくは、連続式エバポレーター、コンデンサーを付した反応槽及びそれらの併用である。
工程（１）と工程（２）の繰り返し回数は、好ましくは１〜５００回、更に好ましくは３〜２００回、特に好ましくは５〜１００回である。
In the case of the distribution method, (D) is obtained by passing a mixture of (B) and (C) that is temperature-controlled to a predetermined temperature through a column, fixed bed, or fluidized bed packed with (A). Can do.
(D) can be obtained by distilling the reaction mixture after passing the mixture of (B) and (C) through (A) once (1 pass), but the reaction rate can be increased. From the point of view, the step (1) of reacting (B) and (C) in the presence of (A), and removing water or lower alcohol produced by the reaction of (B) and (C) from the reaction mixture The manufacturing method which consists of the process (2) to perform is preferable. In particular, the reaction rate can be further increased by repeating step (1) and step (2). The temperature of (B) and (C) which let a liquid flow in a process (1) becomes like this. Preferably it is 60-180 degreeC, More preferably, it is 80-160 degreeC, Most preferably, it is 100-140 degreeC. If it is 60 degreeC or more, it is preferable from a viewpoint of reaction rate, and if it is 180 degrees C or less, it is preferable from a viewpoint which suppresses a side reaction.
The average liquid passing time per pass in the step (1) [average contact time of (A), (B) and (C)] is preferably 0.1 to 60 minutes, more preferably 0.2. -10 minutes, particularly preferably 0.5-5 minutes.
As a method of removing water or lower alcohol in the step (2), a method of distilling off with a continuous evaporator, a method of distilling off under normal pressure or reduced pressure using a reaction vessel equipped with a condenser, and a water separation membrane And a method of dehydrating by centrifugation or a dehydrating agent. Among these, from the viewpoint of production efficiency, a continuous evaporator, a reaction tank with a condenser, and a combination thereof are preferable.
The number of repetitions of step (1) and step (2) is preferably 1 to 500 times, more preferably 3 to 200 times, and particularly preferably 5 to 100 times.
本発明の製造方法において、（Ｃ）及び生成した（Ｄ）の重合を禁止する目的で、反応液中に酸素を溶存させることもできる。酸素の供給源としては、酸素ガス、空気及び空気と窒素の混合気［以下、「混合気」と略記する場合がある。］等が挙げられ、これらを反応液中に通気することで酸素を溶存させることができる。これらのうち、安全性の観点から好ましくは、空気及び混合気であり、更に好ましくは混合気である。 In the production method of the present invention, oxygen can be dissolved in the reaction solution for the purpose of prohibiting the polymerization of (C) and the produced (D). As an oxygen supply source, oxygen gas, air, and a mixture of air and nitrogen [hereinafter, abbreviated as “mixture” may be used in some cases. ], Etc., and oxygen can be dissolved by aeration of these into the reaction solution. Of these, air and air-fuel mixture are preferable from the viewpoint of safety, and air-fuel mixture is more preferable.
混合気中の空気と窒素の混合体積比率は、好ましくは１：９〜９：１であり、更に好ましくは１：９〜５：５、特に好ましくは２：８〜４：６である。空気の比率を高めることで重合禁止効果が高まり、窒素の比率を高めることで生成物の着色が少なくなる点で好ましい。
空気又は混合気の通気量は、（Ｂ）と（Ｃ）の総重量１ｋｇあたり、好ましくは１〜５，０００ｍＬ／分であり、更に好ましくは２０〜１，０００ｍＬ／分、特に好ましくは３０〜５００ｍＬ／分である。
空気又は混合気を通気する方法としては、バッチ法の場合は反応槽下部から反応中に常時通気する方法が挙げられる。
流通法の場合は、工程（１）、工程（２）又はそれらの途中の配管中に通気する方法が挙げられるが、工程（２）において通気することが反応速度と重合禁止の両立の観点から好ましい。
The mixing volume ratio of air and nitrogen in the mixture is preferably 1: 9 to 9: 1, more preferably 1: 9 to 5: 5, and particularly preferably 2: 8 to 4: 6. Increasing the ratio of air is preferable in that the effect of inhibiting polymerization is increased, and increasing the ratio of nitrogen is preferable in that coloring of the product is reduced.
The aeration amount of air or air-fuel mixture is preferably 1 to 5,000 mL / min, more preferably 20 to 1,000 mL / min, and particularly preferably 30 to 1 kg per kg of the total weight of (B) and (C). 500 mL / min.
As a method for ventilating air or a gas mixture, in the case of a batch method, a method of constantly venting from the lower part of the reaction tank during the reaction can be mentioned.
In the case of the flow method, there may be mentioned a method of venting into the step (1), the step (2) or the piping in the middle thereof, but the venting in the step (2) is from the viewpoint of coexistence of reaction rate and polymerization inhibition. preferable.
本発明の製造方法で得られた反応生成物（Ｘ）中の（Ｄ）の純度は、好ましくは９５モル％以上であり、更に好ましくは９８モル％以上である。（Ｘ）中の不純物としては、未反応の（Ｂ）、（Ｃ）及び（Ｄ）の重合物（以下、「重合物」と略記する。）、脱離反応生成物［１分子の（Ｂ）から水が脱離して生成するオレフィン等］、副生エーテル化合物［２分子の（Ｂ）から脱水縮合して生成するエーテル］、副生付加生成物［（Ｃ）が有するα，β−不飽和基にアルコールが付加して生成する付加物等］及び硫黄原子含有化合物［（Ａ）の分解によって溶出した硫黄酸化物等）等が挙げられる。また、不純物ではないが添加物としての重合禁止剤が含まれる。 The purity of (D) in the reaction product (X) obtained by the production method of the present invention is preferably 95 mol% or more, more preferably 98 mol% or more. As impurities in (X), unreacted polymers (B), (C) and (D) (hereinafter abbreviated as “polymer”), elimination reaction products [one molecule of (B Olefin etc. produced by desorption of water from)], by-product ether compound [ether produced by dehydration condensation from 2 molecules of (B)], and by-product addition product [α, β-depleted by (C) Adducts produced by addition of alcohol to saturated groups] and sulfur atom-containing compounds [sulfur oxides eluted by decomposition of (A), etc.], and the like. Moreover, although it is not an impurity, the polymerization inhibitor as an additive is contained.
（Ｘ）中の硫黄原子含有化合物の含有量は、（Ｘ）の重量に基づいて、硫黄原子含量（以下、Ｓ含量と略記する。）として、好ましくは５０ｐｐｍ以下であり、更に好ましくは２０ｐｐｍ（検出限界）以下である。 The content of the sulfur atom-containing compound in (X) is preferably 50 ppm or less, and more preferably 20 ppm (hereinafter, abbreviated as S content) based on the weight of (X). Detection limit) or less.
本発明の製造方法で得られた（Ｄ）の純度、（Ｘ）中の未反応の（Ｂ）、脱離反応生成物、副生エーテル化物及び副生付加生成物のそれぞれの含有率は、１Ｈ−ＮＭＲを測定して解析することにより定量できる。 The purity of (D) obtained by the production method of the present invention, the unreacted (B) in (X), the elimination reaction product, the by-product etherification product and the by-product addition product, It can be quantified by measuring and analyzing 1 H-NMR.
（Ｘ）中の重合物の含有率は、以下の方法で測定することができる。
＜α，β−不飽和カルボン酸エステル（Ｄ）の重合物含有率の測定方法＞
（Ｘ）１０ｇを冷却管つき三角フラスコに秤量し、メタノール１００ｇを加え、６０℃で３時間撹拌した。Ｎｏ．５のろ紙を敷いたガラスフィルターを秤量後、メタノール溶液を吸引ろ過し、更にガラスフィルター中のろ過残渣を新たなメタノール５０ｇで洗浄する。ろ過残渣の入ったガラスフィルターを８０℃の減圧乾燥器で３時間乾燥した後デシケーター中で冷却後秤量し、下記式から重合物（モル％）を算出する。
重合物（モル％）＝［（Ｗ１−Ｗ０）／Ｗｓ／Ｍ］×１００
Ｗ１：ろ過後のガラスフィルターの重量（ｇ）
Ｗ０：ろ過前のガラスフィルターの重量（ｇ）
ＷＳ：三角フラスコに秤量した（Ｘ）の重量（ｇ）
Ｍ：（Ｄ）の分子量
The content of the polymer in (X) can be measured by the following method.
<Method for Measuring Polymer Content of α, β-Unsaturated Carboxylic Acid Ester (D)>
(X) 10 g was weighed into an Erlenmeyer flask with a cooling tube, 100 g of methanol was added, and the mixture was stirred at 60 ° C. for 3 hours. No. After weighing the glass filter with 5 filter paper, the methanol solution is suction filtered and the filter residue in the glass filter is washed with 50 g of fresh methanol. The glass filter containing the filtration residue is dried in a vacuum dryer at 80 ° C. for 3 hours, cooled in a desiccator and weighed, and a polymer (mol%) is calculated from the following formula.
Polymer (mol%) = [(W 1 −W 0 ) / W s / M] × 100
W 1 : Weight of glass filter after filtration (g)
W 0 : Weight of glass filter before filtration (g)
W S : Weight of (X) weighed in an Erlenmeyer flask (g)
M: Molecular weight of (D)
（Ｘ）中のＳ含量は、誘導結合プラズマ発光分析装置「ＩＣＰＳ−８０００」［（株）島津製作所製］により定量できる。 The S content in (X) can be quantified with an inductively coupled plasma optical emission spectrometer “ICPS-8000” [manufactured by Shimadzu Corporation].
以下、実施例により本発明を詳細に説明するが、本発明はこれに限定されるものではな
い。以下において特に定めない限り、％は重量％、部は重量部を示す。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this. Unless otherwise specified, “%” means “% by weight” and “part” means “part by weight”.
＜実施例１＞ 固体酸触媒（Ａ−１）の製造；
撹拌装置、加熱冷却装置、温度計及び還流管を備えた反応容器に、あらかじめイオン交換水で洗浄後乾燥させたシリカゲル「ＣＡＲｉＡＣＴ Ｑ−６」［平均粒子径：７５〜５００μｍ、富士シリシア化学（株）製］２００部、溶媒としてのトルエン４００部及び水１０部を仕込んだ後、１００〜１１０℃に昇温した。次いで（３−メルカプトフッ素化プロピル）トリメトキシシラン（ｓ−１）１００部加え、環流下に８時間撹拌反応させた。その後更に水１５部を加えて８時間反応させた。反応混合物から固形分をろ別し、トルエン４００部で３回、イソプロピルアルコール４００部で３回の順で洗浄した後、１２０℃で５時間減圧（０．００３ＭＰａ）乾燥し、酸前駆体基担持無機多孔体２２０部を得た。
酸前駆体基担持無機多孔体１５０部、溶媒としての水４５０部及び３０％過酸化水素水１５０部を上記と同様の反応容器に仕込み、８０℃で８時間反応させた。反応混合物から固形分をろ別し、メタノール４００部で１回、０．１Ｎ−硫酸４００部で１回、イオン交換水４００部で３回の順で洗浄した後、１２０℃で５時間減圧乾燥し、フッ素化アルキルスルホン酸を担持させた酸基担持無機多孔体（ａ−１）を１４０部得た。
酸基担持無機多孔体（ａ−１）１００部を上記と同様の反応容器に仕込み、１８０℃で２４時間加熱処理した。室温まで冷却後トルエン３００部で３回、メタノール２５０部で３回洗浄し、１２０℃で３時間減圧（０．００３ＭＰａ）乾燥し、フッ素化アルキルスルホン酸を担持させた酸基担持無機多孔体からなる固体酸触媒（Ａ−１）１９０部を得た。
<Example 1> Production of solid acid catalyst (A-1);
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, and a reflux tube, silica gel “CariACT Q-6” [average particle size: 75 to 500 μm, Fuji Silysia Chemical Ltd. )] After charging 200 parts, 400 parts of toluene as a solvent and 10 parts of water, the temperature was raised to 100 to 110 ° C. Next, 100 parts of (3-mercaptofluorinated propyl) trimethoxysilane (s-1) was added, and the mixture was allowed to react with stirring for 8 hours under reflux. Thereafter, 15 parts of water was further added and reacted for 8 hours. The solid content was filtered off from the reaction mixture, washed with 400 parts of toluene three times and 400 parts of isopropyl alcohol three times in that order, and then dried under reduced pressure (0.003 MPa) at 120 ° C. for 5 hours to carry the acid precursor group. 220 parts of inorganic porous material were obtained.
150 parts of an acid precursor group-supported inorganic porous material, 450 parts of water as a solvent and 150 parts of 30% hydrogen peroxide water were charged in the same reaction vessel as described above, and reacted at 80 ° C. for 8 hours. The solid content was separated from the reaction mixture by filtration, washed once with 400 parts of methanol, once with 400 parts of 0.1N sulfuric acid and three times with 400 parts of ion-exchanged water, and then dried under reduced pressure at 120 ° C. for 5 hours. As a result, 140 parts of an acid group-supporting inorganic porous material (a-1) supporting fluorinated alkylsulfonic acid was obtained.
100 parts of the acid group-supporting inorganic porous material (a-1) was charged into the same reaction vessel as described above, and heat-treated at 180 ° C. for 24 hours. After cooling to room temperature, washing with 300 parts of toluene three times and 250 parts of methanol three times, drying under reduced pressure (0.003 MPa) at 120 ° C. for 3 hours, and from an acid group-supporting inorganic porous material supporting fluorinated alkylsulfonic acid 190 parts of a solid acid catalyst (A-1) was obtained.
＜実施例２＞ 固体酸触媒（Ａ−２）の製造；
撹拌装置、加熱冷却装置、温度計及び還流管を備えた反応容器に、３−グリシジルオキシプロピルトリエトキシシラン（ｓ−２）３０部をエタノールに溶かし、この溶液に、あらかじめイオン交換水で洗浄後乾燥させたシリカゲル「ＣＡＲｉＡＣＴ Ｑ−６」２００部を３０分間浸漬した。シリカゲルは濾過により取り出し、エタノールで洗浄後真空乾燥した。フィチン酸５０部の５０％水溶液を室温で真空乾燥し、Ｎ，Ｎ−ジメチルイミダゾリジノン１３０部に溶解した。この溶液に、先の表面修飾シリカゲルを入れ、５０〜６０℃で３０分間加温した。シリカゲルを濾別し、トルエン３００部で３回、メタノール２５０部で３回洗浄し、１２０℃で３時間減圧（０．００３ＭＰａ）乾燥し、フィチン酸を担持させた酸基担持無機多孔体（ａ−２）からなる固体酸触媒（Ａ−２）１５０部を得た。
<Example 2> Production of solid acid catalyst (A-2);
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, and a reflux tube, 30 parts of 3-glycidyloxypropyltriethoxysilane (s-2) is dissolved in ethanol, and this solution is washed with ion-exchanged water in advance. 200 parts of the dried silica gel “CARIACT Q-6” was immersed for 30 minutes. The silica gel was removed by filtration, washed with ethanol and dried in vacuo. A 50% aqueous solution of 50 parts of phytic acid was vacuum dried at room temperature and dissolved in 130 parts of N, N-dimethylimidazolidinone. The surface-modified silica gel was put into this solution and heated at 50 to 60 ° C. for 30 minutes. The silica gel was filtered off, washed three times with 300 parts of toluene and three times with 250 parts of methanol, dried under reduced pressure (0.003 MPa) at 120 ° C. for 3 hours, and supported with an acid group-supporting inorganic porous material (a -2), 150 parts of a solid acid catalyst (A-2) was obtained.
＜実施例３＞ 固体酸触媒（Ａ−３）の製造；
撹拌装置、加熱冷却装置、温度計及び還流管を備えた反応容器に、３−グリシジルオキシプロピルトリエトキシシラン（ｓ−２）３０部をエタノールに溶かし、この溶液に、あらかじめイオン交換水で洗浄後乾燥させたシリカゲル「ＣＡＲｉＡＣＴ Ｑ−６」２００部を３０分間浸漬した。シリカゲルは濾過により取り出し、エタノールで洗浄後真空乾燥した。リン酸８部の５０％水溶液を室温で真空乾燥し、Ｎ，Ｎ−ジメチルイミダゾリジノン１３０部に溶解した。この溶液に、先の表面修飾シリカゲルを入れ、５０〜６０℃で３０分間加温した。シリカゲルを濾別し、さらに水５０部とエタノール５０部で洗浄後、真空乾燥し、リン酸を担持させた酸基担持無機多孔体（ａ−３）からなる固体酸触媒（Ａ−３）１５０部を得た。
<Example 3> Production of solid acid catalyst (A-3);
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, and a reflux tube, 30 parts of 3-glycidyloxypropyltriethoxysilane (s-2) is dissolved in ethanol, and this solution is washed with ion-exchanged water in advance. 200 parts of the dried silica gel “CARIACT Q-6” was immersed for 30 minutes. The silica gel was removed by filtration, washed with ethanol and dried in vacuo. A 50% aqueous solution of 8 parts of phosphoric acid was vacuum dried at room temperature and dissolved in 130 parts of N, N-dimethylimidazolidinone. The surface-modified silica gel was put into this solution and heated at 50 to 60 ° C. for 30 minutes. The silica gel was filtered off, further washed with 50 parts of water and 50 parts of ethanol, vacuum-dried, and solid acid catalyst (A-3) 150 comprising an acid group-supporting inorganic porous material (a-3) supporting phosphoric acid. Got a part.
＜実施例４＞ 固体酸触媒（Ａ−４）の製造；
シリカゲル「ＣＡＲｉＡＣＴ Ｑ−６」２００部をアルミナ「活性アルミナ２００」［ナカライテスク（株）製］２００部に変更した以外は実施例１と同様にして、フッ素化アルキルスルホン酸を担持させた酸基担持無機多孔体（ａ−４）からなる固体酸触媒（Ａ−４）７０部を得た。
<Example 4> Production of solid acid catalyst (A-4);
Acid group carrying fluorinated alkylsulfonic acid in the same manner as in Example 1 except that 200 parts of silica gel “CALiACT Q-6” was changed to 200 parts of alumina “activated alumina 200” (manufactured by Nacalai Tesque). 70 parts of a solid acid catalyst (A-4) comprising the supported inorganic porous material (a-4) was obtained.
＜実施例５＞ 固体酸触媒（Ａ−５）の製造；
シリカゲル「ＣＡＲｉＡＣＴ Ｑ−６」２００部をシリカ−アルミナ系多孔体「キョーワード７００ＳＮ」［協和化学工業（株）製］２００部に変更した以外は実施例１と同様にして、フッ素化アルキルスルホン酸を担持させた酸基担持無機多孔体（ａ−５）からなる固体酸触媒（Ａ−５）１４０部を得た。
<Example 5> Production of solid acid catalyst (A-5);
Fluorinated alkyl sulfonic acid in the same manner as in Example 1, except that 200 parts of silica gel “CALiACT Q-6” was changed to 200 parts of silica-alumina porous material “KYOWARD 700SN” (manufactured by Kyowa Chemical Industry Co., Ltd.). There were obtained 140 parts of a solid acid catalyst (A-5) composed of an acid group-supporting inorganic porous material (a-5) on which was supported.
＜実施例６＞ 固体酸触媒（Ａ−６）の製造；
加熱処理温度を１５０℃に変更する以外は実施例１と同様にして、フッ素化アルキルスルホン酸を担持させた酸基担持無機多孔体（ａ−６）からなる固体酸触媒（Ａ−６）１４０部を得た。
<Example 6> Production of solid acid catalyst (A-6);
A solid acid catalyst (A-6) 140 composed of an acid group-supporting inorganic porous material (a-6) supporting a fluorinated alkylsulfonic acid in the same manner as in Example 1 except that the heat treatment temperature is changed to 150 ° C. Got a part.
＜実施例７＞ 固体酸触媒（Ａ−７）の製造；
加熱処理温度を２５０℃に変更する以外は実施例１と同様にして、フッ素化アルキルスルホン酸を担持させた酸基担持無機多孔体からなる固体酸触媒（Ａ−７）１４０部を得た。
<Example 7> Production of solid acid catalyst (A-7);
140 parts of solid acid catalyst (A-7) which consists of an acid group carrying | support inorganic porous body which carry | supported the fluorinated alkylsulfonic acid was obtained like Example 1 except changing heat processing temperature to 250 degreeC.
＜比較例１＞ 固体酸触媒（Ａ’−１）の製造；
撹拌装置、加熱冷却装置、温度計及び還流管を備えた反応容器に、あらかじめイオン交換水で洗浄後乾燥させたシリカゲル「ＣＡＲｉＡＣＴ Ｑ−６」２００部、溶媒としてのトルエン４００部及び水１０部を仕込んだ後、１００〜１１０℃に昇温した。次いで３−メルカプトプロピルトリメトキシシラン１００部加え、環流下に８時間撹拌反応させた。 その後更に水１５部を加えて８時間反応させた。反応混合物から固形分をろ別し、トルエン４００部で１回、イソプロピルアルコール４００部で１回の順で洗浄した後、１２０℃で５時間減圧（０．００３ＭＰａ）乾燥し、酸前駆体基担持無機多孔体２２０部を得た。
酸前駆体基担持無機多孔体１５０部、溶媒としての水４５０部及び３０％過酸化水素水１５０部を上記と同様の反応容器に仕込み、８０℃で８時間反応させた。反応混合物から固形分をろ別し、メタノール４００部で１回、０．１Ｎ−硫酸４００部で１回、イオン交換水４００部で１回の順で洗浄した後、１２０℃で５時間減圧乾燥し、スルホン酸を担持させた酸基担持無機多孔体（ａ’−１）を１４０部得た。
<Comparative Example 1> Production of solid acid catalyst (A'-1);
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, and a reflux tube, 200 parts of silica gel “CALiACT Q-6” previously washed with ion-exchanged water and dried, 400 parts of toluene as a solvent and 10 parts of water were added. After charging, the temperature was raised to 100 to 110 ° C. Next, 100 parts of 3-mercaptopropyltrimethoxysilane was added, and the mixture was stirred for 8 hours under reflux. Thereafter, 15 parts of water was further added and reacted for 8 hours. The solid content was filtered off from the reaction mixture, washed once with 400 parts of toluene and once with 400 parts of isopropyl alcohol, and then dried under reduced pressure (0.003 MPa) at 120 ° C. for 5 hours to carry the acid precursor group. 220 parts of inorganic porous material were obtained.
150 parts of an acid precursor group-supported inorganic porous material, 450 parts of water as a solvent and 150 parts of 30% hydrogen peroxide water were charged in the same reaction vessel as described above, and reacted at 80 ° C. for 8 hours. The solid content was separated from the reaction mixture by filtration, washed once with 400 parts of methanol, once with 400 parts of 0.1N sulfuric acid and once with 400 parts of ion-exchanged water, and then dried under reduced pressure at 120 ° C. for 5 hours. As a result, 140 parts of an acid group-supporting inorganic porous material (a′-1) supporting sulfonic acid was obtained.
実施例１〜７、比較例１で得られた固体酸触媒（Ａ−１）〜（Ａ−７）、（Ａ’−１）の平均粒子径、ＢＥＴ比表面積、酸価及びアスペクト比、過酸化物価を前記方法で測定した。結果を表１に示す。 The average particle diameter, BET specific surface area, acid value and aspect ratio of the solid acid catalysts (A-1) to (A-7) and (A′-1) obtained in Examples 1 to 7 and Comparative Example 1, The oxide value was measured by the above method. The results are shown in Table 1.
＜実施例８＞ α，β−不飽和カルボン酸エステル（Ｄ−１）の製造；
撹拌装置、加熱冷却装置、温度計及び分水管を備えた反応容器に、ラウリルアルコール１，８００部、メタクリル酸１，１００部を仕込み（モル比１：１．３）、これに固体酸触媒（Ａ−１）５８０部、重合禁止剤としてハイドロキノン０．３部を加えた。撹拌下、反応温度１１５〜１２５℃で生成水を分水管により連続的に系外へ除去しながら２時間エステル化反応させた。更に減圧下（０．０６１〜０．０６７ＭＰａ）、１１５〜１２５℃で１時間反応させ、次いで１２０〜１３０℃で過剰のメタクリル酸を減圧（０．００１〜０．００３ＭＰａ）留去した後室温まで冷却し、固体酸触媒（Ａ−１）をデカンテーションで除去することで、α，β−不飽和カルボン酸エステル（Ｄ−１）２，５００部を得た。
<Example 8> Production of α, β-unsaturated carboxylic acid ester (D-1);
A reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, and a water pipe is charged with 1,800 parts of lauryl alcohol and 1,100 parts of methacrylic acid (molar ratio 1: 1.3). A-1) 580 parts, hydroquinone 0.3 part was added as a polymerization inhibitor. Under stirring, the reaction was conducted at a reaction temperature of 115 to 125 ° C. for 2 hours while continuously removing the produced water out of the system through a water pipe. Further, the reaction was allowed to proceed at 115 to 125 ° C. for 1 hour under reduced pressure (0.061 to 0.067 MPa), and then excess methacrylic acid was distilled off at 120 to 130 ° C. under reduced pressure (0.001 to 0.003 MPa) until room temperature. By cooling and removing the solid acid catalyst (A-1) by decantation, 2,500 parts of an α, β-unsaturated carboxylic acid ester (D-1) was obtained.
＜実施例９〜１４、比較例２＞ α，β−不飽和カルボン酸エステル（Ｄ−２）〜（Ｄ−７）、（Ｄ’−１）の製造；
固体酸触媒（Ａ−１）５８０部を、それぞれ固体酸触媒（Ａ−２）〜（Ａ−７）、（Ａ’−１）に変更した以外は実施例８と同様にして、α，β−不飽和カルボン酸エステル（Ｄ−２）〜（Ｄ−７）、（Ｄ’−１）を製造した。
<Examples 9 to 14, Comparative Example 2> Production of α, β-unsaturated carboxylic acid esters (D-2) to (D-7) and (D'-1);
In the same manner as in Example 8 except that 580 parts of the solid acid catalyst (A-1) were changed to solid acid catalysts (A-2) to (A-7) and (A′-1), respectively, α, β -Unsaturated carboxylic acid ester (D-2)-(D-7), (D'-1) was manufactured.
＜実施例１５＞
実施例８で回収した固体酸触媒（Ａ−１）を再度実施例８の固体酸触媒（Ａ−１）として使用し、実施例８のエステル化反応を行い、（Ａ−１）を回収した。
上記操作を９回繰り返して行い、９回再使用した固体酸触媒（Ａ−１）５８０部を使用した以外は実施例８と同様にして、α，β−不飽和カルボン酸エステル（Ｄ−８）を製造した。
<Example 15>
The solid acid catalyst (A-1) recovered in Example 8 was used again as the solid acid catalyst (A-1) of Example 8, and the esterification reaction of Example 8 was performed to recover (A-1). .
The above operation was repeated 9 times, and the α, β-unsaturated carboxylic acid ester (D-8) was obtained in the same manner as in Example 8 except that 580 parts of the solid acid catalyst (A-1) reused 9 times was used. ) Was manufactured.
＜実施例１６〜２１、比較例３＞
固体酸触媒（Ａ−１）を、それぞれ固体酸触媒（Ａ−２）〜（Ａ−７）、（Ａ’−１）に変更した以外は実施例１５と同様にして、α，β−不飽和カルボン酸エステル（Ｄ−８）〜（Ｄ−１４）、（Ｄ’−２）を製造した。
<Examples 16 to 21, Comparative Example 3>
As in Example 15, except that the solid acid catalyst (A-1) was changed to solid acid catalysts (A-2) to (A-7) and (A′-1), respectively, α, β- Saturated carboxylic acid esters (D-8) to (D-14) and (D′-2) were produced.
＜実施例２２＞
撹拌装置、加熱冷却装置、温度計、気体吹き込み口、コンデンサー及びピットを付したステンレス製反応槽に、炭素数１２及び１３のアルキルアルコールの混合物「ドバノール２３」［三菱化学（株）製］５７００部、メタクリル酸３３００部（モル比１：１．３）、重合禁止剤としてハイドロキノン１部を仕込み、空気−窒素の混合気（１：２）を５００ｍｌ／分で通気した。１１５〜１２５℃まで昇温した後、ダイヤフラムポンプで反応槽内の反応液を、固体酸触媒（Ａ−１）１８００部を充填したステンレス製固定床へ流速１．１Ｌ／分で連続的に通液し、吐出液を元の反応槽へと循環させ、反応槽では、常圧下１１５〜１２５℃で脱水することで、反応工程と脱水工程を連続的に１時間繰り返した。その後、反応槽内を減圧（０．０６１〜０．０６７ＭＰａ）にして、更に２時間、反応工程と脱水工程を連続的に繰り返し、エステル化反応を完結させた。次いで、反応液の全量を反応槽に戻し、減圧下（０．００１〜０．００３ＭＰａ）、１２０〜１３０℃で過剰のメタクリル酸を留去し、α，β−不飽和カルボン酸エステル（Ｄ−１５）７７００部を得た。なお、固定床での１パスあたりの反応液の平均滞留時間は２．５分であった。また、エステル化反応における反応液全量の循環繰り返し回数は、固定床での流速から約１８回であった。
<Example 22>
5700 parts of a mixture of alkyl alcohols having 12 and 13 carbon atoms “Dovanol 23” [Mitsubishi Chemical Corporation] in a stainless steel reaction vessel equipped with a stirrer, heating / cooling device, thermometer, gas inlet, condenser and pit Then, 3300 parts of methacrylic acid (molar ratio 1: 1.3), 1 part of hydroquinone as a polymerization inhibitor were charged, and an air-nitrogen mixture (1: 2) was aerated at 500 ml / min. After raising the temperature to 115 to 125 ° C., the reaction solution in the reaction vessel was continuously passed by a diaphragm pump through a stainless steel fixed bed filled with 1800 parts of the solid acid catalyst (A-1) at a flow rate of 1.1 L / min. The reaction liquid and the discharge liquid were circulated to the original reaction tank, and dehydration was performed at 115 to 125 ° C. under normal pressure in the reaction tank, whereby the reaction process and the dehydration process were continuously repeated for 1 hour. Thereafter, the inside of the reaction vessel was depressurized (0.061 to 0.067 MPa), and the reaction step and the dehydration step were continuously repeated for another 2 hours to complete the esterification reaction. Next, the entire amount of the reaction solution was returned to the reaction vessel, and excess methacrylic acid was distilled off at 120 to 130 ° C. under reduced pressure (0.001 to 0.003 MPa) to obtain an α, β-unsaturated carboxylic acid ester (D- 15) 7700 parts were obtained. The average residence time of the reaction liquid per pass on the fixed bed was 2.5 minutes. Further, the number of circulation cycles of the total amount of the reaction solution in the esterification reaction was about 18 times from the flow rate in the fixed bed.
実施例８〜２２、比較例２、３で得られたα，β−不飽和カルボン酸エステル（Ｄ−１）〜（Ｄ−１５）、（Ｄ’−１）、（Ｄ’−２）の純度、未反応の（Ｂ）及び重合物の含有率を前記方法で測定した。結果を表２に示す。 Of the α, β-unsaturated carboxylic acid esters (D-1) to (D-15), (D′-1) and (D′-2) obtained in Examples 8 to 22 and Comparative Examples 2 and 3, Purity, unreacted (B) and polymer content were measured by the methods described above. The results are shown in Table 2.
表２から明らかなように、本発明の固体酸触媒（Ａ）を使用してα，β−不飽和カルボン酸エステル（Ｄ）を製造すると、得られた（Ｄ）の純度が高く、（Ｄ）中の重合物が少ない。また、本発明の（Ａ）は、繰り返し再使用しても触媒活性がほとんど低下しない。 一方、比較例の固体酸触媒を使用した場合には、得られたα，β−不飽和カルボン酸エステルの純度が低く、重合物が多い。また、比較例の固体酸触媒は、繰り返し再使用すると触媒活性が低下する。 As is apparent from Table 2, when the α, β-unsaturated carboxylic acid ester (D) is produced using the solid acid catalyst (A) of the present invention, the purity of the obtained (D) is high and (D ) There are few polymerization products in. Further, (A) of the present invention hardly reduces the catalytic activity even when it is repeatedly used. On the other hand, when the solid acid catalyst of the comparative example is used, the purity of the obtained α, β-unsaturated carboxylic acid ester is low and there are many polymers. Moreover, the catalytic activity of the solid acid catalyst of the comparative example decreases when it is repeatedly used.
本発明の固体酸触媒は、触媒活性が高く、繰り返し再使用しても触媒活性が低下し難いため、各種反応の酸触媒として有用である。特に、アルコールとα，β−不飽和カルボン酸又はその低級アルキルエステルとのエステル化反応の際に使用すると、得られたα，β−不飽和カルボン酸エステルの純度が高く、副生成物が少ないため、本発明の固体酸触媒を使用したα，β−不飽和カルボン酸エステルの製造方法は、高純度のα，β−不飽和カルボン酸エステルを得る方法として有用である。 The solid acid catalyst of the present invention is useful as an acid catalyst for various reactions because it has high catalytic activity and does not easily decrease even after repeated use. In particular, when used in the esterification reaction of an alcohol with an α, β-unsaturated carboxylic acid or a lower alkyl ester thereof, the purity of the obtained α, β-unsaturated carboxylic acid ester is high and there are few by-products. Therefore, the method for producing an α, β-unsaturated carboxylic acid ester using the solid acid catalyst of the present invention is useful as a method for obtaining a highly pure α, β-unsaturated carboxylic acid ester.
Claims (9)
アルキレンオキサイド付加物である請求項７記載の製造方法。 The production method according to claim 7, wherein the alcohol (B) is a monohydric alcohol, a divalent to octavalent polyhydric alcohol, or an alkylene oxide adduct thereof.
The method according to claim 7 or 8, wherein (C) is acrylic acid or methacrylic acid.
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| CN114426486B (en) * | 2020-09-23 | 2024-02-13 | 中国石油化工股份有限公司 | Method for preparing methyl methacrylate and supported catalyst |
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