KR101911131B1 - Method for the production process of methacryl acid ester - Google Patents
Method for the production process of methacryl acid ester Download PDFInfo
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- KR101911131B1 KR101911131B1 KR1020150069390A KR20150069390A KR101911131B1 KR 101911131 B1 KR101911131 B1 KR 101911131B1 KR 1020150069390 A KR1020150069390 A KR 1020150069390A KR 20150069390 A KR20150069390 A KR 20150069390A KR 101911131 B1 KR101911131 B1 KR 101911131B1
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- Prior art keywords
- alcohol
- acid ester
- methacrylic acid
- buo
- ester
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 150000002148 esters Chemical class 0.000 title claims description 4
- 238000004519 manufacturing process Methods 0.000 title abstract description 15
- 239000002253 acid Substances 0.000 title 1
- 125000005641 methacryl group Chemical group 0.000 title 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- -1 alkyl methacrylate ester Chemical class 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000007664 blowing Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 53
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 31
- 235000019441 ethanol Nutrition 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 3
- 229960005235 piperonyl butoxide Drugs 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 claims description 2
- 229940061334 2-phenylphenol Drugs 0.000 claims description 2
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 claims description 2
- VTDOEFXTVHCAAM-UHFFFAOYSA-N 4-methylpent-3-ene-1,2,3-triol Chemical compound CC(C)=C(O)C(O)CO VTDOEFXTVHCAAM-UHFFFAOYSA-N 0.000 claims description 2
- LUMNWCHHXDUKFI-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethanol Chemical compound C1C2C(CO)CC1C=C2 LUMNWCHHXDUKFI-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 2
- 235000010292 orthophenyl phenol Nutrition 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 claims 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 claims 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims 1
- CWRHALJWSFHEIE-UHFFFAOYSA-N [4-(hydroxymethyl)-4-methylcyclohexyl]methanol Chemical compound OCC1(C)CCC(CO)CC1 CWRHALJWSFHEIE-UHFFFAOYSA-N 0.000 claims 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 20
- 239000003112 inhibitor Substances 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- 125000004185 ester group Chemical group 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- 150000003609 titanium compounds Chemical class 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGQLBLGDIQNGSB-UHFFFAOYSA-N benzene-1,4-diol;methoxymethane Chemical compound COC.OC1=CC=C(O)C=C1 KGQLBLGDIQNGSB-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- YVZMWNWBUNPSDM-UHFFFAOYSA-N non-1-ene-1,9-diol Chemical compound OCCCCCCCC=CO YVZMWNWBUNPSDM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 하기 화학식 1로 표시되는 촉매 하에서, 알킬 메타크릴산 에스터와 알코올을 공기 주입(Air Blowing)하면서 에스터 교환 반응하여 메타크릴산 에스터를 생성하는 메타크릴산 에스터의 제조방법에 관한 것이다.
[화학식 1]
Ti(BuO)nㆍ(HQ)4-n (n=1, 2, 3)
본 발명의 메타크릴산 에스터의 제조방법은 별도의 중합방지제를 사용하지 않고도, 메타크릴산 에스터의 제조시에 폴리머의 생성을 방지할 수 있으며, 수율도 증가시킬 수 있다.The present invention relates to a process for producing a methacrylic acid ester in which a methacrylic acid ester is produced by an ester exchange reaction while air-blowing an alkyl methacrylate ester and an alcohol under a catalyst represented by the following formula (1).
[Chemical Formula 1]
Ti (BuO) n (HQ) 4-n (n = 1, 2, 3)
The production method of the methacrylic acid ester of the present invention can prevent the formation of polymer in the production of the methacrylic acid ester and increase the yield without using a separate polymerization inhibitor.
Description
본 발명은 메타크릴산 에스터의 제조방법에 관한 것으로서, 보다 상세하게는 중합방지제를 사용하지 않고도 수율 및 전환률을 획기적으로 높일 수 있는 메타크릴산 에스터의 제조방법에 관한 것이다.The present invention relates to a methacrylic acid ester, and more particularly, to a method for producing methacrylic acid ester, which can dramatically increase the yield and conversion rate without using a polymerization inhibitor.
메타크릴산 에스터를 제조하기 위해 종래부터 사용되는 방법은 하기 반응식 1과 같이 알킬 메타크릴산 에스터에 알코올을 첨가한 후, 여기에 촉매와 함께 중합방지제를 별도로 첨가하는 것이다. A method conventionally used for producing a methacrylic acid ester is a method in which an alcohol is added to an alkyl methacrylate ester as shown in
[반응식 1][Reaction Scheme 1]
이러한 종래의 제조방법에서는, 형성된 메타크릴산 에스터 간의 중합이 일어나는 것을 방지하기 위하여, PT(phenothiazine), HQ(hydroquinone), MEHQ(mono-methyl ether hydroquinone) 등과 같은 중합방지제를 사용하고 있다. In such a conventional production method, a polymerization inhibitor such as phenothiazine (PT), hydroquinone (HQ), mono-methyl ether hydroquinone (MEHQ) or the like is used to prevent polymerization between the formed methacrylic acid esters.
하지만, 중합방지제의 사용에 따라서, 불순물이 생성되어, 수율 및 전환율이 저하되는 문제가 있는바, 상기 중합방지제를 사용하지 않고도 수율 및 전환율을 향상시키기 위한 개선이 필요한 실정이다.However, in accordance with the use of the polymerization inhibitor, there is a problem that impurities are generated and the yield and the conversion ratio are lowered. Therefore, there is a need to improve the yield and conversion ratio without using the polymerization inhibitor.
상기와 같은 종래기술의 문제점을 해결하고자, In order to solve the above problems of the prior art,
본 발명은 별도의 중합방지제를 사용하지 않더라도, 중합 반응을 방지할 수 있으며, 수율도 향상시킬 수 있는 새로운 메타크릴산 에스터의 제조방법을 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a process for producing a novel methacrylic acid ester which can prevent the polymerization reaction and improve the yield without using a separate polymerization inhibitor.
상기의 목적을 달성하기 위하여, In order to achieve the above object,
본 발명은 하기 화학식 1로 표시되는 촉매 하에서, 알킬 메타크릴산 에스터와 알코올을 에스터 교환 반응하여 메타크릴산 에스터를 생성하는 메타크릴산 에스터의 제조방법을 제공한다.The present invention provides a process for producing a methacrylic ester in which a methacrylic acid ester is produced by subjecting an alkyl methacrylate ester and an alcohol to an ester exchange reaction under a catalyst represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
Ti(BuO)nㆍ(HQ)4-n (n=1, 2, 3) Ti (BuO) n (HQ) 4-n (n = 1, 2, 3)
(상기 식에서, BuO는 butoxide anion을 나타내고, HQ은 hydroquinone을 나타낸다.)(Wherein BuO represents butoxide anion and HQ represents hydroquinone).
본 발명의 메타크릴산 에스터의 제조방법에 따르면, According to the method for producing methacrylic acid ester of the present invention,
별도의 중합방지제를 사용하지 않더라도, 중합 반응을 방지할 수 있을 뿐만 아니라, 중합방지제를 사용하지 않기 때문에 중합방지제의 사용에 따른 불용성 고체의 형성도 방지하여 수율 및 전환율을 향상시킬 수 있으며, 또한 별도의 중합방지제의 첨가 공정이 없기 때문에 제조 공정이 기존에 비하여 단순해지기 때문에, 전체적인 공정 시간 및 공정 비용을 절감할 수 있다는 장점이 있다.It is possible not only to prevent the polymerization reaction but also to prevent the formation of an insoluble solid due to the use of the polymerization inhibitor because the polymerization inhibitor is not used and the yield and conversion rate can be improved There is no addition step of the polymerization inhibitor, so that the manufacturing process is simpler than that of the prior art, thereby reducing the overall process time and process cost.
도 1은 HQ(hydroquinone)의 피크를 나타낸 13C NMR 그래프이다.
도 2는 타이타늄 부톡사이드(Titanium Buotoxide)의 피크를 나타낸 13C NMR 그래프이다.
도 3은 부탄올(Butanol)의 피크를 나타낸 13C NMR 그래프이다.
도 4는 본 발명 실시예에서 사용한 촉매 화합물의 피크를 나타낸 13C NMR 그래프이다.1 is a 13 C NMR graph showing the peak of HQ (hydroquinone).
Figure 2 is a 13 C NMR graph showing the peak of Titanium Buotoxide.
3 is a 13 C NMR graph showing the peak of butanol.
4 is a 13 C NMR graph showing the peaks of the catalyst compounds used in the examples of the present invention.
이하 본 발명의 메타크릴산 에스터의 제조방법에 대하여 상세하게 설명한다.
Hereinafter, a method for producing the methacrylic acid ester of the present invention will be described in detail.
본 발명은 종래의 발명과 같이 HQ(hydroquinone)과 같은 중합방지제를 촉매와 별도로 알킬 메타크릴산 에스터와 알코올의 반응에 첨가하는 것이 아니라, 중합방지의 기능을 하는 촉매를 사용하여, 중합방지제를 추가하는 공정 없이 메타크릴산 에스터를 제조하는 방법에 관한 것이다.
The present invention is not limited to adding a polymerization inhibitor such as HQ (hydroquinone) to the reaction of an alkyl methacrylate ester and an alcohol separately from a catalyst as in the case of the conventional invention, but by adding a polymerization inhibitor To a methacrylic acid ester.
이를 위하여, 본 발명의 메타크릴산 에스터의 제조방법은 하기의 화학식 1로 표시되는 촉매 하에서 알킬 메타크릴산 에스터와 알코올의 혼합물을 반응시킨다.To this end, the methacrylic acid ester of the present invention is produced by reacting a mixture of an alkyl methacrylate ester and an alcohol under a catalyst represented by the following formula (1).
[화학식 1][Chemical Formula 1]
Ti(BuO)nㆍ(HQ)4-n (n=1, 2, 3) Ti (BuO) n (HQ) 4-n (n = 1, 2, 3)
(상기 식에서, BuO는 butoxide anion을 나타내고, HQ은 hydroquinone을 나타낸다.)
(Wherein BuO represents butoxide anion and HQ represents hydroquinone).
상기 화학식 1의 화합물은 Ti(BuO)4와 HQ을 반응시켜 제조되는 것으로서, The compound of Formula 1 is prepared by reacting Ti (BuO) 4 with HQ,
하기의 단계를 포함하는 제조방법에 의하여 제조될 수 있다.Can be prepared by a process comprising the following steps.
a) Ti(BuO)4와 HQ를 상온에서 0.5 내지 24 시간 동안 교반하는 단계;a) stirring Ti (BuO) 4 and HQ at room temperature for 0.5 to 24 hours;
b) 상기 a) 단계의 교반 후, Methylene chloride를 2 내지 50 중량비 투입한 후, 30분 내지 2시간 동안 교반하는 단계;b) stirring the mixture in the step a), adding 2 to 50 parts by weight of methylene chloride, and stirring the mixture for 30 minutes to 2 hours;
c) 상기 b) 단계의 교반 후, 아세톤(acetone)을 투입한 후 교반하여 여과하는 단계; 및 c) stirring the mixture in step b), adding acetone, stirring the mixture, and filtering the mixture; And
d) 상기 c) 단계의 여과 후, 세척한 후 건조하는 단계
d) filtering, washing, and then drying in step c)
상기 제조단계에 있어서, Ti(BuO)4와 HQ은 1:0.1 내지 1:20의 몰비로 반응시켜 제조할 수 있다. 상기 Ti(BuO)4와 HQ의 반응 몰비가 1:0.1보다 작으면 수율이 낮아지고 1:20 보다 크면 미반응 HQ가 많아져 경제성이 없다는 단점이 있다.
In the preparation step, Ti (BuO) 4 and HQ may be reacted at a molar ratio of 1: 0.1 to 1:20. If the reaction molar ratio of Ti (BuO) 4 and HQ is less than 1: 0.1, the yield is lowered. If the molar ratio is higher than 1:20, unreacted HQ is increased, which is not economical.
본 발명의 메타크릴산 에스터의 제조방법에 있어서, 상기 알킬 메타크릴산 에스터로는 메틸 메타아크릴레이트, 에틸 메타아크릴레이트, 프로필 메타아크릴레이트, 부틸 메타아크릴레이트 등으로 이루어지는 군에서 선택되는 어느 하나 이상을 사용할 수 있으며, 가장 바람직하게는 메틸 메타아크릴레이트를 사용할 수 있다.
In the method for producing a methacrylic acid ester of the present invention, the alkyl methacrylic acid ester may be at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like And most preferably methyl methacrylate can be used.
본 발명의 메타크릴산 에스터의 제조방법에 있어서, 상기 알코올은 목적으로 하는 메타크릴산 에스터에 따라 적절히 정할 수 있으나, 바람직하게는 메탄올, 에탄올, n-프로판올, i-프로판올, n-부탄올, i-부탄올, t-부탄올, n-펜탄올, t-아밀알콜, n-헥산올, n-헵탄올, n-옥탄올, 2-에틸헥실알콜, n-노난올, n-데칸올, n-운데칸올, n-도데칸올, 라우릴 알콜, 스테아릴 알콜, 에틸렌 글라이콜, 1,3-프로페인다이올, 1,2-프로페인다이올, 1,4-부테인다이올, 1,5-펜테인다이올, 1,6-헥세인다이올, 1,8-옥테인다이올, 1,9-노네인다이올, 1,10-데케인다이올, 1,12-도데케인다이올, 글라이세롤 등의 지방족 포화 알콜; 알릴 알콜, 1,1-다이메틸 알릴 알콜, 프레놀, 이소프레놀 등의 지방족 불포화 알콜; 사이클로헥산올, 메틸사이클로헥산올, 사이클로헥세인-1,4-다이메탄올, 노보네인-2-메탄올, 5-노보넨-2-메탄올, 1-아다만탄올, 2-메틸-2-아다만탄올 등의 지방족 환상 알콜; 글라이시돌, 아이소프로필리덴 글라이세롤, 글라이세린 카보네이트 등의 작용기 함유 알콜; 페놀, 2-페닐페놀 등의 페놀류; 벤질 알콜, 1-페닐 에틸 알콜, 2-페닐에틸 알콜 등의 아릴기 함유 알콜 등으로 이루어지는 군에서 선택되는 어느 하나 이상을 사용할 수 있으며, 가장 바람직하게는 n-부탄올을 사용할 수 있다.
In the method for producing a methacrylic acid ester of the present invention, the alcohol may be appropriately determined according to the objective methacrylic acid ester, but is preferably selected from methanol, ethanol, n-propanol, i-propanol, n-butanol, i Butanol, t-butanol, n-pentanol, t-amyl alcohol, n-hexanol, n-heptanol, n-octanol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,4-butanediol, 1,4-butanediol, 5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonene diol, 1,10-decane diol, 1,12-dodecane di Aliphatic saturated alcohols such as oligo, glycerol and the like; Aliphatic unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol, prenol, and isoprenol; Cyclohexane-1,4-dimethanol, norbornene-2-methanol, 5-norbornene-2-methanol, 1-adamantanol, 2-methyl- Aliphatic cyclic alcohols such as ethanol; Functional alcohols such as glycidol, isopropylidene glycerol, and glycerin carbonate; Phenols such as phenol and 2-phenylphenol; And allyl group-containing alcohols such as benzyl alcohol, 1-phenylethyl alcohol and 2-phenylethyl alcohol, and most preferably n-butanol can be used.
또한, 본 발명의 메타크릴산 에스터의 제조방법은, 상기 알킬 메타크릴산 에스터와 알코올의 혼합물의 반응 시에 공기 주입(Air Blowing)하는 것이 바람직하다. 공기 중의 산소와 HQ가 반응하여 라디칼을 생성할 수 있으며, 이렇게 생성된 라디칼은 반응기 내에 존재하는 라디칼과 반응하여 안정한 화합물을 만들어 후속반응의 진행을 막을 수 있다는 장점이 있다.
In addition, the methacrylic acid ester of the present invention may preferably be subjected to air blowing during the reaction of the alkyl methacrylate ester and the alcohol. Oxygen in the air reacts with HQ to generate radicals. The radicals thus generated react with radicals present in the reactor to form stable compounds, thereby preventing the subsequent reaction from proceeding.
또한, 본 발명의 메타크릴산 에스터의 제조방법은, 상기 알킬 메타크릴산 에스터와 알코올의 반응 몰비가 1:1 내지 5:1 인 것이 바람직하다. 상기 알킬 메타크릴산 에스터와 알코올의 반응 몰비가 1:1 미만이면 수율이 떨어지고, 5:1 초과이면 미반응 알킬 메타크릴산 에스터가 많아져 경제성이 없다는 단점이 있다.
In the method for producing a methacrylic acid ester of the present invention, the molar ratio of the alkyl methacrylate ester to the alcohol is preferably 1: 1 to 5: 1. If the molar ratio of the alkyl methacrylate ester to the alcohol is less than 1: 1, the yield decreases. If the molar ratio exceeds 5: 1, unreacted alkyl methacrylate esters increase, resulting in poor economical efficiency.
또한, 본 발명의 메타크릴산 에스터의 제조방법에 있어서, 상기 알킬 메타크릴산 에스터와 알코올의 반응 온도는 80 내지 150℃인 것이 바람직하다. 상기 알킬 메타크릴산 에스터와 알코올의 반응 온도가 80℃ 미만이면 수율이 감소하고 150℃ 초과이면 고분자가 생성될 위험이 커지고 미반응물의 기화로 전환율이 떨어진다는 단점이 있다.
In the method for producing a methacrylic acid ester of the present invention, the reaction temperature of the alkyl methacrylate ester and the alcohol is preferably 80 to 150 ° C. If the reaction temperature of the alkyl methacrylic acid ester and the alcohol is lower than 80 ° C, the yield decreases. If the reaction temperature exceeds 150 ° C, the risk of polymer formation increases and the conversion rate to the vaporization of unreacted materials decreases.
본 발명의 제조방법에 의하여 제조된 메타크릴산 에스터의 수율은 65% 이상이다.
The yield of methacrylic acid ester prepared by the production method of the present invention is 65% or more.
본 발명의 메타크릴산 에스터의 제조방법에 있어서, 상기 알킬 메타크릴산 에스터와 알코올은 통상의 구입 가능한 것을 특별한 제한 없이 사용할 수 있으며, 바람직하게는 순도 60 내지 99.5%의 것을 사용할 수 있다.
In the process for producing a methacrylic acid ester of the present invention, the alkyl methacrylate ester and the alcohol can be used without any particular limitation, and those having a purity of 60 to 99.5% can be used.
이하 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변경 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.
실시예Example
촉매 화합물의 제조 Preparation of Catalyst Compounds
[합성예 1] [Synthesis Example 1]
Ti(BuO)4 1.5g과 HQ(Hydroquinone) 0.5g을 상온에서 15시간 동안 교반한 후, methylene chloride 20g 투입한 후, 1시간 동안 교반하였다. 이 후, acetone을 투입하여 3시간 동안 교반하고 여과한 후, 다시 acetone으로 세척 한 후 100℃ 진공 오븐(vacuum oven)에서 15시간 동안 건조하여 타이타늄 화합물을 제조하였다.
After 1.5 g of Ti (BuO) 4 and 0.5 g of HQ (hydroquinone) were stirred at room temperature for 15 hours, 20 g of methylene chloride was added and the mixture was stirred for 1 hour. After that, acetone was added, and the mixture was stirred for 3 hours, filtered, washed again with acetone, and dried in a vacuum oven at 100 ° C for 15 hours to prepare a titanium compound.
메타크릴산 에스터의 제조Preparation of methacrylic acid ester
[실시예 1][Example 1]
상기 합성예 1에서 제조된 타이타늄 화합물 2000ppm을 촉매로 투입하여, 메틸 메타아크릴레이트와 n-부탄올이 1.5: 1의 비율로 혼합된 혼합액을 115℃에서 공기 주입(Air Blowing)하면서, 1시간 동안 반응시켜 메타크릴산 에스터를 제조하였다.2000 ppm of the titanium compound prepared in Synthesis Example 1 was added as a catalyst to prepare a mixed solution of methyl methacrylate and n-butanol in a ratio of 1.5: 1, followed by air blowing at 115 ° C for 1 hour To prepare a methacrylic acid ester.
[실시예 2][Example 2]
n-부탄올 대신 터르트-부탄올을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 반응시켜 메타크릴산 에스터를 제조하였다.butyric acid was used in place of n-butanol, methacrylic acid ester was prepared.
[실시예 3][Example 3]
메틸 메타아크릴레이트 대신 메타아크릴 산을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 반응시켜 메타크릴산 에스터를 제조하였다.A methacrylic acid ester was prepared by reacting in the same manner as in Example 1 except that methacrylic acid was used instead of methylmethacrylate.
[비교예 1][Comparative Example 1]
촉매로 Ti(BuO)4 2000ppm을 투입하고, 중합방지제로 HQ(Hydroquinone)을 10,000ppm 투입한 후, 메틸 메타아크릴레이트와 n-부탄올이 1.5: 1의 비율로 혼합된 혼합액을 115℃에서 공기 주입(Air Blowing) 없이, 1시간 동안 반응시켜 메타크릴산 에스터를 제조하였다.2000 ppm of Ti (BuO) 4 as a catalyst, 10,000 ppm of HQ (Hydroquinone) as a polymerization inhibitor, and a mixed solution of methyl methacrylate and n-butanol in a ratio of 1.5: (Air blowing) for 1 hour to prepare a methacrylic acid ester.
[비교예 2][Comparative Example 2]
공기 주입(Air Blowing) 없이 반응을 진행한 것을 제외하고는 실시예 1과 동일한 방법으로 반응시켜 메타크릴산 에스터를 제조하였다.The reaction was carried out in the same manner as in Example 1 except that the reaction was carried out without air blowing, thereby preparing a methacrylic acid ester.
[비교예 3][Comparative Example 3]
촉매로 Ti(BuO)4 1000ppm을 투입하고, 중합방지제로 HQ(Hydroquinone)을 1,000ppm 투입한 후, 메틸 메타아크릴레이트와 n-부탄올이 1.5: 1의 비율로 혼합된 혼합액을 115℃에서 공기 주입(Air Blowing)하면서, 1시간 동안 반응시켜 메타크릴산 에스터를 제조하였다.1000 ppm of Ti (BuO) 4 was added as a catalyst, 1,000 ppm of HQ (Hydroquinone) was added as a polymerization inhibitor, and a mixed solution of methyl methacrylate and n-butanol in a ratio of 1.5: (Air blowing), and reacted for 1 hour to prepare a methacrylic acid ester.
[비교예 4][Comparative Example 4]
메틸 메타아크릴레이트와 n-부탄올이 0.5: 1의 비율로 혼합된 혼합액을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 반응시켜 메타크릴산 에스터를 제조하였다.Methyl methacrylate and n-butanol in a ratio of 0.5: 1 was used in place of the methacrylic acid ester.
[비교예 5][Comparative Example 5]
메틸 메타아크릴레이트와 n-부탄올이 7.0: 1의 비율로 혼합된 혼합액을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 반응시켜 메타크릴산 에스터를 제조하였다.Methyl methacrylate and n-butanol in a ratio of 7.0: 1 was used in place of the methacrylic acid ester.
[비교예 6][Comparative Example 6]
메틸 메타아크릴레이트와 n-부탄올의 혼합액을 70℃에서 공기 주입(Air Blowing)하면서 반응시킨 것을 제외하고는 실시예 1과 동일한 방법으로 반응시켜 메타크릴산 에스터를 제조하였다.Methacrylic acid ester was prepared by reacting a mixture of methyl methacrylate and n-butanol in the same manner as in Example 1, except that the mixture was reacted at 70 ° C with air blowing.
[비교예 7][Comparative Example 7]
메틸 메타아크릴레이트와 n-부탄올의 혼합액을 180℃에서 공기 주입(Air Blowing)하면서 반응시킨 것을 제외하고는 실시예 1과 동일한 방법으로 반응시켜 메타크릴산 에스터를 제조하였다.
Methacrylic acid ester was prepared by reacting a mixture of methyl methacrylate and n-butanol in the same manner as in Example 1, except that the mixture was reacted while air-blowing at 180 ° C.
실험예Experimental Example 1 One
상기 제조된 타이타늄 화합물의 구조를 알아보기 위하여, 하기와 같은 분광기를 이용하여 각 화합물의 13C NMR 피크를 확인하였다. In order to examine the structure of the prepared titanium compound, 13 C NMR peak of each compound was confirmed using the following spectrometer.
Varian 400 MHz SSNMR/ 4 mm MAS probeVarian 400 MHz SSNMR / 4 mm MAS probe
- 13C MAS NMR (Static)- 13 C MAS NMR (Static)
- 13C MAS NMR (Spinning rate = 10 kHz)
- 13 C MAS NMR (Spinning rate = 10 kHz)
먼저, HQ(hydroquinone)에 대한 13C NMR 피크는, 115.29(ppm), 121.40(ppm), 153.23(ppm)에서 나타났으며, 이에 대한 13C NMR 그래프를 도 1에 나타내었다.First, 13 C NMR peaks for HQ (hydroquinone) were found at 115.29 (ppm), 121.40 (ppm) and 153.23 (ppm), and a 13 C NMR graph thereof was shown in Fig.
타이타늄 부톡사이드(Titanium Buotoxide)에 대한 13C NMR 피크는, 18.65(ppm), 23.96(ppm), 40.49(ppm), 79.36(ppm)에서 나타났으며, 이에 대한 13C NMR 그래프를 도 2에 나타내었다. 13 C NMR peaks for titanium butoxide (Titanium Buotoxide) has, 18.65 (ppm), 23.96 ( ppm), 40.49 (ppm), were found at 79.36 (ppm), also indicated in the 2 to 13 C NMR graph for this .
부탄올(Butanol)에 대한 13C NMR 피크는, 18.65(ppm), 23.60(ppm), 39.36(ppm), 66.02(ppm)에서 나타났으며, 이에 대한 13C NMR 그래프를 도 3에 나타내었다. 13 C NMR peaks for butanol were found at 18.65 (ppm), 23.60 (ppm), 39.36 (ppm) and 66.02 (ppm), and a 13 C NMR graph thereof was shown in Fig.
마지막으로 타이타늄 화합물의 피크는, 82.52(ppm), 115.28(ppm), 120.91(ppm), 153.71(ppm), 164.89(ppm)에서 나타났으며, 이에 대한 13C NMR 그래프를 도 4에 나타내었다.Finally the titanium compound peaks, 82.52 (ppm), 115.28 ( ppm), 120.91 (ppm), 153.71 (ppm), were found in 164.89 (ppm), it shows a 13 C NMR graph for it in Fig.
도 1 내지 도 4의 결과를 통하여, 실시예에서 제조된 타이타늄 화합물이 Ti(BuO)3ㆍ(HQ) 인 것을 확인할 수 있었다.
1 to 4, it was confirmed that the titanium compound prepared in the examples was Ti (BuO) 3 (HQ).
실험예Experimental Example 2 2
상기 실시예 1 내지 3 및 비교예 1 내지 7에서 제조된 메타크릴산 에스터를 MeOH에 침지시킨 후, 가스 크로마토그래피(GC 6890N, agilent)를 이용하여, 정량하여 BuOH 전환율 및 메타크릴산 에스터의 수율을 측정하였으며, 폴리머의 생성여부를 육안으로 확인하였다.The methacrylic acid esters prepared in Examples 1 to 3 and Comparative Examples 1 to 7 were immersed in MeOH and quantified using gas chromatography (GC 6890N, agilent) to determine the conversion of BuOH and the yield of methacrylic acid ester And the formation of polymer was visually confirmed.
상기 표 1에서 나타낸 바와 같이, 본 발명의 메타크릴산 에스터의 제조방법에 의하여 제조한 실시예 1의 경우, 수율은 71.03%로 종래의 방법에 비하여, 10% 이상 높게 나타났으며, 폴리머의 생성도 나타나지 않았다. 또한, 터르트-부탄올을 사용한 실시예 2나, 메타아크릴 산을 사용한 실시예 3 역시 수율이 10~30% 가까이 높게 나타났으며, 폴리머의 생성도 없었다. 이에 비하여, 비교예 1 내지 7은 수율이 낮을 뿐만 아니라, 비교예 1 내지 3, 5 및 7의 경우에는 폴리머의 생성이 관찰되어 중합방지의 효과가 충분하지 않은 것을 알 수 있었다. 따라서, 실시예 1 내지 3에 따른 메타크릴산 에스터의 제조 방법에 의하면, 종래의 중합방지제를 사용하는 경우에 비하여, 중합방지효과를 확실하게 나타내면서도, 수율도 향상시킬 수 있다는 것을 확인할 수 있었다.
As shown in Table 1, the yield of the Example 1 prepared by the methacrylic acid ester producing method of the present invention was 71.03%, which was higher than that of the conventional method by more than 10% Did not appear. In addition, the yield of the Example 2 using the but-butanol and the methacrylic acid was also as high as 10-30%, and no polymer was produced. On the other hand, in Comparative Examples 1 to 3, 5 and 7, the production of polymer was observed, and the effect of preventing polymerization was not sufficient. Therefore, it was confirmed that the methacrylic acid ester production methods according to Examples 1 to 3 can improve the yield while showing the polymerization inhibiting effect, as compared with the case of using the conventional polymerization inhibitor.
Claims (10)
상기 알킬 메타크릴산 에스터와 알코올의 반응 몰비가 1:1 내지 5:1이며,
상기 알킬 메타크릴산 에스터와 알코올의 반응 온도는 80 내지 150℃인 것을 특징으로 하는 메타크릴산 에스터의 제조방법.
[화학식 1]
Ti(BuO)nㆍ(HQ)4-n (n=1, 2, 3)
(상기 식에서, BuO는 부톡사이드 음이온[butoxide anion]을 나타내고, HQ은 하이드로퀴논[hydroquinone]을 나타낸다.)Under the presence of a catalyst represented by the following general formula (1), an alkylmethacrylate ester and an alcohol are subjected to ester exchange reaction by air blowing to produce methacrylic acid ester,
Wherein the reaction molar ratio of the alkyl methacrylate ester to the alcohol is from 1: 1 to 5: 1,
Wherein the reaction temperature of the alkyl methacrylate ester with the alcohol is 80 to 150 ° C.
[Chemical Formula 1]
Ti (BuO) n (HQ) 4-n (n = 1, 2, 3)
(Wherein BuO represents a butoxide anion, and HQ represents hydroquinone).
상기 화학식 1의 화합물은 Ti(BuO)4와 HQ을 반응시켜 제조되는 것을 특징으로 하는 메타크릴산 에스터의 제조방법.The method according to claim 1,
Wherein the compound of Formula 1 is prepared by reacting Ti (BuO) 4 with HQ.
상기 화학식 1의 화합물은 하기 단계들을 포함하는 제조방법에 의하여 제조되는 것을 특징으로 하는 메타크릴산 에스터의 제조방법.
a) Ti(BuO)4와 HQ를 상온에서 0.5 내지 24 시간 동안 교반하는 단계;
b) 상기 a) 단계의 교반 후, 메틸렌 클로라이드(Methylene chloride)를 상기 Ti(BuO)4와 HQ의 혼합물 1 중량부에 대하여 2 내지 50 중량비 투입한 후, 30분 내지 2시간 동안 교반하는 단계;
c) 상기 b) 단계의 교반 후, 아세톤(acetone)을 투입한 후 교반하여 여과하는 단계; 및
d) 상기 c) 단계의 여과 후, 세척한 후 건조하는 단계The method of claim 2,
Wherein the compound of Formula 1 is prepared by a process comprising the steps of:
a) stirring Ti (BuO) 4 and HQ at room temperature for 0.5 to 24 hours;
b) adding 2 to 50 parts by weight of methylene chloride to 1 part by weight of the mixture of Ti (BuO) 4 and HQ, followed by stirring for 30 minutes to 2 hours;
c) stirring the mixture in step b), adding acetone, stirring the mixture, and filtering the mixture; And
d) filtering, washing, and then drying in step c)
상기 Ti(BuO)4와 HQ을 1:0.1 내지 1:20의 몰비로 반응시키는 것을 특징으로 하는 메타크릴산 에스터의 제조방법.The method of claim 2,
And reacting the Ti (BuO) 4 with HQ in a molar ratio of 1: 0.1 to 1:20.
상기 메타크릴산 에스터의 수율이 65% 이상인 것을 특징으로 하는 메타크릴산 에스터의 제조방법.The method according to claim 1,
Wherein the yield of the methacrylic acid ester is 65% or more.
상기 알킬 메타크릴산 에스터는 메틸 메타아크릴레이트, 에틸 메타아크릴레이트, 프로필 메타아크릴레이트, 부틸 메타아크릴레이트로 이루어지는 군에서 선택되는 어느 하나 이상인 것을 특징으로 하는 메타크릴산 에스터의 제조 방법.The method according to claim 1,
Wherein the alkyl methacrylate ester is at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate.
상기 알코올은 메탄올, 에탄올, n-프로판올, i-프로판올, n-부탄올, i-부탄올, t-부탄올, n-펜탄올, t-아밀알콜, n-헥산올, n-헵탄올, n-옥탄올, 2-에틸헥실알콜, n-노난올, n-데칸올, n-운데칸올, n-도데칸올, 라우릴 알콜, 스테아릴 알콜, 에틸렌 글라이콜, 1,3-프로페인다이올, 1,2-프로페인다이올, 1,4-부테인다이올, 1,5-펜테인다이올, 1,6-헥세인다이올, 1,8-옥테인다이올, 1,9-노네인다이올, 1,10-데케인다이올, 1,12-도데케인다이올, 글라이세롤, 알릴 알콜, 1,1-다이메틸 알릴 알콜, 프레놀, 이소프레놀, 사이클로헥산올, 메틸사이클로헥산올, 사이클로헥세인-1,4-다이메탄올, 노보네인-2-메탄올, 5-노보넨-2-메탄올, 1-아다만탄올, 2-메틸-2-아다만탄올, 글라이시돌, 아이소프로필리덴 글라이세롤, 글라이세린 카보네이트, 페놀, 2-페닐페놀, 벤질 알콜, 1-페닐 에틸 알코올 및 2-페닐에틸 알콜로 이루어지는 군에서 선택되는 어느 하나 이상인 것을 특징으로 하는 메타크릴산 에스터의 제조 방법.The method according to claim 1,
The alcohol may be at least one selected from the group consisting of methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, N-decanol, n-undecanol, n-dodecanol, lauryl alcohol, stearyl alcohol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, Indole, 1,10-decane diol, 1,12-dodecane diol, glycerol, allyl alcohol, 1,1-dimethylallyl alcohol, prenol, isoprenol, cyclohexanol, methyl Cyclohexane-1,4-dimethanol, norbornene-2-methanol, 5-norbornene-2-methanol, 1-adamantanol, 2- , Isopropylidene glycerol, glycerin carbonate, phenol, 2-phenylphenol, benzyl alcohol, 1-phenylethyl alcohol and 2- One method of producing a methacrylic acid ester, characterized in that at least selected from the group consisting of carbonyl ethyl alcohol.
상기 알코올은 n-부탄올인 것을 특징으로 하는 메타크릴산 에스터의 제조 방법.The method of claim 9,
Wherein the alcohol is n-butanol.
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