KR980001982A - 에스테르화 공정 - Google Patents
에스테르화 공정 Download PDFInfo
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- KR980001982A KR980001982A KR1019970024054A KR19970024054A KR980001982A KR 980001982 A KR980001982 A KR 980001982A KR 1019970024054 A KR1019970024054 A KR 1019970024054A KR 19970024054 A KR19970024054 A KR 19970024054A KR 980001982 A KR980001982 A KR 980001982A
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- South Korea
- Prior art keywords
- acid
- process according
- reaction
- zirconium
- titanium
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- 238000000034 method Methods 0.000 title claims abstract 21
- 238000005886 esterification reaction Methods 0.000 title claims abstract 14
- 230000032050 esterification Effects 0.000 title abstract 4
- 239000003054 catalyst Substances 0.000 claims abstract 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract 9
- 239000010936 titanium Substances 0.000 claims abstract 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract 9
- 150000002148 esters Chemical class 0.000 claims abstract 8
- 238000006243 chemical reaction Methods 0.000 claims abstract 7
- 150000002905 orthoesters Chemical class 0.000 claims abstract 7
- 238000004519 manufacturing process Methods 0.000 claims abstract 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract 3
- 239000007795 chemical reaction product Substances 0.000 claims abstract 2
- 229920000728 polyester Polymers 0.000 claims abstract 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 235000015165 citric acid Nutrition 0.000 claims 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 claims 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 2
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 claims 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000005711 Benzoic acid Substances 0.000 claims 1
- 239000004135 Bone phosphate Substances 0.000 claims 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- 239000005642 Oleic acid Substances 0.000 claims 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims 1
- 235000021314 Palmitic acid Nutrition 0.000 claims 1
- 235000021319 Palmitoleic acid Nutrition 0.000 claims 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 1
- 235000021355 Stearic acid Nutrition 0.000 claims 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 239000001361 adipic acid Substances 0.000 claims 1
- 235000011037 adipic acid Nutrition 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 239000001530 fumaric acid Substances 0.000 claims 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims 1
- 239000004310 lactic acid Substances 0.000 claims 1
- 235000014655 lactic acid Nutrition 0.000 claims 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims 1
- 239000000347 magnesium hydroxide Substances 0.000 claims 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- 239000001630 malic acid Substances 0.000 claims 1
- 235000011090 malic acid Nutrition 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 1
- 235000021313 oleic acid Nutrition 0.000 claims 1
- WLJNZVDCPSBLRP-UHFFFAOYSA-N pamoic acid Chemical compound C1=CC=C2C(CC=3C4=CC=CC=C4C=C(C=3O)C(=O)O)=C(O)C(C(O)=O)=CC2=C1 WLJNZVDCPSBLRP-UHFFFAOYSA-N 0.000 claims 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229960004889 salicylic acid Drugs 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 239000008117 stearic acid Substances 0.000 claims 1
- 239000011975 tartaric acid Substances 0.000 claims 1
- 235000002906 tartaric acid Nutrition 0.000 claims 1
- 150000003628 tricarboxylic acids Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000005809 transesterification reaction Methods 0.000 abstract 1
- 238000004383 yellowing Methods 0.000 abstract 1
Classifications
-
- 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
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/80—Phthalic acid esters
- C07C69/82—Terephthalic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
1. 청구범위에 기제된 발명이 속한 기술분야
본 발명은 에스테르화 공정에 관한 것으로서, 특히 신규한 유기티타늄 또는 유기지르코늄 촉매를 사용하는 에스테르화 공정에 관한 것이다.
2. 발명이 해결하려고 하는 기술적 과제
본 발명에 따른 촉매는 최종 생성물내에 흐림(탁함)이 없는 에스테르를 효과적으로 제조할 수 있으며, 공지된 촉매와 비교하여 볼때 폴리에스테르가 황색화되는 량이 감소된다.
3. 발명의 해결방법의 요지
티타늄 또는 지르코늄의 오르토에스테르 또는 축합 오르토에스테르, 적어도 2개의 히드록실기를 함유하는 알코올, 2-히드록시 카복실산, 및 염기의 반응생성물을 함유하는 촉매의 존재하에서 에스테르화 반응을 수행시키는 공정을 포함하는 에스테르의 제조방법을 제공한다. 본 발명의 제조방법은 직접 에스테르화 반응 또는 트랜스에스테르화 반응일 수 있으며 폴리에스테르화 반응일 수 있다.
4. 발명의 중요한 용도
본 발명은 에스테르화 공정시 사용된다.
Description
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
Claims (20)
- 촉매의 존재하에서 에스테르화 반응을 수행시키는 공정을 포함하는 에스테르의 제조방법에 있어서, 상기 촉매는 티타늄 또는 지르코늄의 오르토에스테르 또는 축합 오르토에스테르, 적어도 2개의 히드록실기를 함유하는 알코올, 2-히드록시 카복실산, 및 염기의 반응생성물을 함유하는 것을 특징으로 하는 에스테르의 제조방법.
- 제1항에 있어서, 오로토에스테르는 일반식 M(OR)4을 가지며, 여기서 온 티타늄 또는 지르코늄이고, R은 1-6의 탄소원자를 함유하는 알킬기인 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 축합된 오르토에스테르는 일반식R1O[M(OR1)2O]nR|1을 가지며, 여기서 R1은 1-6의 탄소원자를 함유하는 알킬기이고 M은 티타늄 또는 지르코늄인 것을 특징으로 하는 제조방법.
- 제3항에 있어서, n은 10이하인 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 적어도 2개의 히드록실기를 함유하는 알코올은 디히드릭 알코올인 것을 특징으로 하는 제조방법.
- 제5항에 있어서, 촉매는 티타늄 또는 지르코늄의 몰당 디히드릭 알코올을 2-12몰 함유하는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 2-히드록시산은 유산, 구연산, 사과산 및 주석산으로 구성된 군으로부터 선택되는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 촉매는 티타늄 또는 지르코늄의 몰당 2-히드록시산을 1-4몰 함유하는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 염기는 수산화나트륨, 수산화캄륨, 수산화암모늄, 탄산나트륨, 수산화마그네슘 및 암모니아로 구성된 군으로부터 선택되는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 촉매는 일염기 2-히드록시산으로부터 제조되며, 염기의 량은 2-히드록시 카복실산의 몰당 염기 0.8-1.2몰의 범위내에서 사용되는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 촉매는 삼염기 2-히드록시 카복실산으로부터 제조되며, 염기량은 2-히드록시 카복실산의 몰당 염기 1-3몰의 범위내에서 사용되는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 촉매는 티타늄 혹은 지르코늄의 몰당 염기 1-12몰을 함유하는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 촉매는 물을 함유하며 6-8 범위의 pH를 갖는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 에스테르화 반응은 스테아르산, 이소스테아르산, 카프리산, 카프로산, 팔미트산, 올레산, 팔미톨레산, 트리아콘타노산, 벤조산, 메틸 벤조산, 살리실산, 프탈산, 이소프탈산, 테레프탈산, 세박산, 아디프산, 아젤라산, 숙신산, 푸마르산, 말레산, 나프탈렌 디카복실산, 파모산 트리멜리트산, 시트르산, 트리메스산, 및 피로멜리트산으로 구성된 순으로부터 선택된 산과 알코올의 반응을 포함하는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 에스테르화 반응은 디카복실산 또는 트리카복실산의 무수물과 알코올의 반응을 포함하는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 에스테르화 반응은 아크릴산 및 메타크릴산으로 구성된 군으로부터 선택된 산의 메틸 에스테르, 에틸 에스테르, 및 프로필 에스테르로 구성된 군으로부터 선택된 에스테르와 알코올의 반응을 포함하는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 에스테르화 반응은 알콕시기를 교환시킴에 의하여 2개의 다른 에스테르를 생성하도록 2개의 에스테르간의 반응을 포함하는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 에스테르화 반응은 1,2-에탄디올, 1,4-부탄디올, 2,3-프로판디올, 1,6-헥산디올, 트리메틸올프로판, 및 펜타에리스리톨로 구성된 군으로부터 선택된 알코올과 함께 테레프탈산 및 디메틸 테레프탈레이트로 구성된 군으로부터 선택된 산의 반응을 포함하는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 촉매는 생성 에스테르의 중량에 관하여 티타늄 또는 지르코늄의 중량부로서 계산된 백만당 30-1000부의 범위내의 량으로 함유되는 것을 특징으로 하는 제조방법.
- 제1항에 있어서, 에스테르화 반응은 폴리에스테르화 반응이며 촉매는 생성 폴리에스테르의 중량에 관하여 티타늄 또는 지르코늄의 중량부로서 계산된 백만당 5-500부의 범위내의 량으로 함유되는 것을 특징으로 하는 제조방법.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9612161.1A GB9612161D0 (en) | 1996-06-11 | 1996-06-11 | Esterification process |
| GB9612161.1 | 1996-06-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR980001982A true KR980001982A (ko) | 1998-03-30 |
| KR100567476B1 KR100567476B1 (ko) | 2006-12-01 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019970024054A KR100567476B1 (ko) | 1996-06-11 | 1997-06-11 | 에스테르의 제조방법 및 그 반응에 이용되는 촉매 조성물 |
Country Status (25)
| Country | Link |
|---|---|
| US (1) | US5866710A (ko) |
| EP (2) | EP1120392B1 (ko) |
| JP (1) | JP4354541B2 (ko) |
| KR (1) | KR100567476B1 (ko) |
| CN (1) | CN1068864C (ko) |
| AR (1) | AR007540A1 (ko) |
| AT (2) | ATE207866T1 (ko) |
| AU (1) | AU730131B2 (ko) |
| BR (1) | BR9703577A (ko) |
| CA (1) | CA2207111A1 (ko) |
| CO (1) | CO4810331A1 (ko) |
| CZ (1) | CZ176297A3 (ko) |
| DE (2) | DE69707757T2 (ko) |
| DK (1) | DK0812818T3 (ko) |
| ES (2) | ES2166505T3 (ko) |
| GB (1) | GB9612161D0 (ko) |
| HU (1) | HU218143B (ko) |
| MX (1) | MX9704069A (ko) |
| MY (1) | MY115541A (ko) |
| NO (1) | NO307961B1 (ko) |
| PL (1) | PL194313B1 (ko) |
| PT (2) | PT1120392E (ko) |
| RU (1) | RU2178783C2 (ko) |
| TR (1) | TR199700487A3 (ko) |
| TW (1) | TW349937B (ko) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000059815A (ko) * | 1999-03-09 | 2000-10-05 | 한형수 | 지방족 폴리에스테르 제조방법 |
| KR20030084183A (ko) * | 2002-04-25 | 2003-11-01 | 켐엔텍 주식회사 | 폴리에스테르의 제조방법 |
Families Citing this family (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6255441B1 (en) | 1998-04-17 | 2001-07-03 | E. I. Du Pont De Nemours And Company | Titanium-containing catalyst composition and processes therefor and therewith |
| DE19825350A1 (de) * | 1998-06-05 | 1999-12-09 | Basf Ag | Thermoplastische Polyesterformmasse mit verbesserter Stabilität |
| US6130191A (en) * | 1998-09-29 | 2000-10-10 | Henkel Corporation | Process for the preparation of trimethylolpropane caprylate/caprate |
| US6664413B1 (en) * | 1998-11-19 | 2003-12-16 | A. E. Staley Manufacturing Co. | Process for production of esters |
| US6075115A (en) * | 1999-10-19 | 2000-06-13 | E. I. Du Pont De Nemours And Company | Process for the production of 5-sulfo isophthalate bis-glycolate ester metal salts and oxysulfonated polyesters made therefrom |
| US6166170A (en) | 1999-12-02 | 2000-12-26 | E. I. Du Pont De Nemours And Company | Esterification catalysts and processes therefor and therewith |
| ES2237478T3 (es) | 1999-12-10 | 2005-08-01 | Equipolymers Gmbh | Sistemas cataliticos para reacciones de policondensacion. |
| US6372879B1 (en) | 2000-01-07 | 2002-04-16 | Atofina Chemicals, Inc. | Polyester polycondensation with catalyst and a catalyst enhancer |
| US6355817B1 (en) * | 2000-07-15 | 2002-03-12 | Exxonmobil Chemical Patents Inc. | Optimized catalyst addition to enhance esterification catalyst performance |
| US6303738B1 (en) | 2000-08-04 | 2001-10-16 | E. I. Du Pont De Nemours And Company | Esterification process |
| BR0115879A (pt) * | 2000-11-21 | 2005-02-01 | Ici Plc | Catalisador de esterificação, processo de poliéster e artigo de poliéster |
| DE10059612A1 (de) | 2000-12-01 | 2002-06-20 | Bayer Ag | Titan-/Zirkonium-Katalysatoren sowie deren Verwendung zur Herstellung von Estern oder Polyestern |
| US6914107B2 (en) | 2001-01-24 | 2005-07-05 | E. I. Du Pont De Nemours And Company | Catalyst composition and process therewith |
| US6489433B2 (en) | 2001-02-23 | 2002-12-03 | E. I. Du Pont De Nemours And Company | Metal-containing composition and process therewith |
| US6855797B2 (en) | 2002-04-25 | 2005-02-15 | E. I. Du Pont De Nemours And Company | Stable aqueous solutions comprising titanium and zinc and process therewith |
| US20030203811A1 (en) * | 2002-04-25 | 2003-10-30 | Putzig Donald Edward | Stable aqueous solutions comprising titanium and zinc and process therewith |
| US6841505B2 (en) * | 2002-07-26 | 2005-01-11 | E..I. Du Pont De Nemours And Company | Titanium-zirconium catalyst compositions and use thereof |
| AU2003285547A1 (en) * | 2002-12-04 | 2004-06-23 | Johnson Matthey Plc | Organometallic catalyst composition and process for polyurethane manufacture using said catalyst |
| GB0228267D0 (en) * | 2002-12-04 | 2003-01-08 | Johnson Matthey Plc | Catalyst and process |
| JP4529485B2 (ja) * | 2003-03-07 | 2010-08-25 | 三菱化学株式会社 | ポリエステル重合触媒、その製造方法、及びそれを用いたポリエステルの製造方法 |
| WO2004111105A1 (ja) * | 2003-06-17 | 2004-12-23 | Mitsui Chemicals, Inc. | チタン含有溶液、ポリエステル製造用触媒、ポリエステル樹脂の製造方法およびポリエステルからなる中空成形体 |
| DE10336883A1 (de) * | 2003-08-08 | 2005-03-10 | Basf Ag | Kunststoff, insbesondere Polyurethan enthaltend ein sterisch gehindertes, verestertes Amin |
| GB0323386D0 (en) * | 2003-10-07 | 2003-11-05 | Johnson Matthey Plc | Catalyst for manufacture of esters |
| KR100760027B1 (ko) | 2006-09-22 | 2007-09-18 | 이수화학 주식회사 | 고정층형 반응기를 이용한 바이오디젤의 연속식 제조방법 |
| KR100849206B1 (ko) * | 2006-12-21 | 2008-07-31 | 주식회사 자연사랑 | 무독성 생분해성 수용성 폴리에스테르 수지 제조 방법 |
| US8344174B2 (en) * | 2007-03-13 | 2013-01-01 | Exxonmobil Chemical Patents Inc. | Batch esterification |
| DE102007031474A1 (de) * | 2007-07-05 | 2009-01-08 | Evonik Röhm Gmbh | Verfahren zur Herstellung von Butandioldimethacrylaten |
| KR101044393B1 (ko) * | 2007-12-27 | 2011-06-27 | 주식회사 엘지화학 | 지르코늄 화합물을 포함하는 에스테르화 촉매 조성물 및이를 이용한 에스테르 화합물의 제조방법 |
| DE102008040221A1 (de) * | 2008-07-07 | 2010-01-14 | Evonik Röhm Gmbh | Verfahren zur Herstellung von (Meth)acrylsäureestern |
| JP5326741B2 (ja) * | 2008-09-29 | 2013-10-30 | 東レ株式会社 | ポリエステル重合触媒およびそれを用いるポリエステルの製造方法 |
| EP2287225A1 (en) | 2009-08-20 | 2011-02-23 | Saudi Basic Industries Corporation | Process for making polyethylene terephthalate |
| US8933162B2 (en) | 2011-07-15 | 2015-01-13 | Saudi Basic Industries Corporation | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
| US8877862B2 (en) | 2011-07-15 | 2014-11-04 | Saudi Basic Industries Corporation | Method for color stabilization of poly(butylene-co-adipate terephthalate |
| US9334360B2 (en) | 2011-07-15 | 2016-05-10 | Sabic Global Technologies B.V. | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
| US8946345B2 (en) | 2011-08-30 | 2015-02-03 | Saudi Basic Industries Corporation | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst |
| US8969506B2 (en) | 2012-02-15 | 2015-03-03 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
| US8889820B2 (en) | 2012-02-15 | 2014-11-18 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
| US8901273B2 (en) | 2012-02-15 | 2014-12-02 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
| US9034983B2 (en) | 2012-03-01 | 2015-05-19 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof |
| US8895660B2 (en) | 2012-03-01 | 2014-11-25 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture, and uses thereof |
| US8901243B2 (en) | 2012-03-30 | 2014-12-02 | Saudi Basic Industries Corporation | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
| EP2725048B1 (de) * | 2012-10-29 | 2016-07-20 | Uhde Inventa-Fischer GmbH | Verfahren zur Herstellung eines hochmolekularen Polyesters oder Copolyesters sowie diese enthaltende Polymerblends |
| LT2765149T (lt) * | 2013-02-06 | 2019-03-12 | Uhde Inventa-Fischer Gmbh | Katalizatoriaus, kurio sudėtyje yra titano, gamybos būdas, katalizatorius, kurio sudėtyje yra titano, poliesterio gamybos būdas ir poliesteris |
| TWI466863B (zh) * | 2013-03-21 | 2015-01-01 | Chang Chun Plastics Co Ltd | 對苯二甲酸二（２－乙基己酯）之製造方法 |
| CN105237393B (zh) * | 2015-09-06 | 2017-06-30 | 浙江皇马科技股份有限公司 | 一种癸二酸脂肪醇酯的制备方法 |
| PL3687969T3 (pl) * | 2017-09-26 | 2024-03-25 | Public Joint Stock Company "Sibur Holding" | Sposób wytwarzania estrów kwasu tereftalowego |
| TWI670291B (zh) * | 2018-08-02 | 2019-09-01 | 遠東新世紀股份有限公司 | 低黏度聚酯多元醇的製法 |
| CN111087583B (zh) * | 2018-10-23 | 2022-11-04 | 中国石油化工股份有限公司 | 低端羧基pbt树脂的制备方法 |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3056818A (en) * | 1955-10-13 | 1962-10-02 | Goodrich Co B F | Titanium and zirconium esterification catalysts |
| GB811425A (en) * | 1955-10-31 | 1959-04-08 | Nat Lead Co | Organic titanium complex and method of making same |
| US3047515A (en) * | 1956-07-09 | 1962-07-31 | Goodyear Tire & Rubber | Preparation of polyesters using titanium-containing catalysts |
| DE1142868B (de) * | 1960-08-23 | 1963-01-31 | Wachker Chemie G M B H | Verfahren zur diskontinuierlichen oder kontinuierlichen Herstellung von Carbonsaeureestern |
| CH398538A (de) * | 1960-08-23 | 1966-03-15 | Wacker Chemie Gmbh | Verfahren zur Herstellung von Estern |
| GB991020A (en) * | 1960-11-29 | 1965-05-05 | Martin Marietta Corp | Esterification of iso- and terephthalic acids |
| GB970431A (ko) * | 1961-02-04 | 1900-01-01 | ||
| JPS5133890B2 (ko) * | 1971-09-10 | 1976-09-22 | ||
| GB1514361A (en) * | 1976-03-13 | 1978-06-14 | Tioxide Group Ltd | Titanium chelates |
| JPS5398393A (en) * | 1977-02-09 | 1978-08-28 | Teijin Ltd | Production of polyester |
| DD144674A1 (de) * | 1979-06-28 | 1980-10-29 | Rema S Barshtein | Verfahren zur herstellung der polyestern |
| JPS59157058A (ja) * | 1983-02-28 | 1984-09-06 | Ueno Seiyaku Oyo Kenkyusho:Kk | 芳香族ヒドロキシカルボン酸ベンジルエステル類の製造法 |
| US4452969A (en) * | 1983-06-09 | 1984-06-05 | General Electric Company | Poly(alkylene dicarboxylate) process and catalysts for use therein |
| US4780527A (en) * | 1987-05-06 | 1988-10-25 | Industrial Technology Research Institute | Preparation of polyesters from terephthalic acid |
| GB8717667D0 (en) * | 1987-07-25 | 1987-09-03 | Tioxide Group Plc | Titanium compounds |
| DE3850672T2 (de) * | 1987-09-29 | 1995-03-02 | John Wentworth Bucknell | Krafterzeuger. |
| JP3341430B2 (ja) * | 1994-01-07 | 2002-11-05 | 三菱化学株式会社 | チタン触媒組成液 |
-
1996
- 1996-06-11 GB GBGB9612161.1A patent/GB9612161D0/en active Pending
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1997
- 1997-05-27 AU AU23635/97A patent/AU730131B2/en not_active Ceased
- 1997-06-02 MX MX9704069A patent/MX9704069A/es unknown
- 1997-06-03 DK DK97303744T patent/DK0812818T3/da active
- 1997-06-03 DE DE69707757T patent/DE69707757T2/de not_active Expired - Lifetime
- 1997-06-03 AT AT97303744T patent/ATE207866T1/de not_active IP Right Cessation
- 1997-06-03 ES ES97303744T patent/ES2166505T3/es not_active Expired - Lifetime
- 1997-06-03 EP EP01105564A patent/EP1120392B1/en not_active Expired - Lifetime
- 1997-06-03 PT PT01105564T patent/PT1120392E/pt unknown
- 1997-06-03 DE DE69726200T patent/DE69726200T2/de not_active Expired - Lifetime
- 1997-06-03 EP EP97303744A patent/EP0812818B1/en not_active Expired - Lifetime
- 1997-06-03 PT PT97303744T patent/PT812818E/pt unknown
- 1997-06-03 AT AT01105564T patent/ATE254096T1/de not_active IP Right Cessation
- 1997-06-03 ES ES01105564T patent/ES2211678T3/es not_active Expired - Lifetime
- 1997-06-05 US US08/869,629 patent/US5866710A/en not_active Expired - Lifetime
- 1997-06-06 CA CA002207111A patent/CA2207111A1/en not_active Abandoned
- 1997-06-09 HU HU9701024A patent/HU218143B/hu not_active IP Right Cessation
- 1997-06-09 NO NO972645A patent/NO307961B1/no unknown
- 1997-06-09 MY MYPI97002555A patent/MY115541A/en unknown
- 1997-06-09 CZ CZ971762A patent/CZ176297A3/cs unknown
- 1997-06-10 AR ARP970102514A patent/AR007540A1/es active IP Right Grant
- 1997-06-10 CN CN97113609A patent/CN1068864C/zh not_active Expired - Lifetime
- 1997-06-10 JP JP15229797A patent/JP4354541B2/ja not_active Expired - Lifetime
- 1997-06-10 CO CO97031854A patent/CO4810331A1/es unknown
- 1997-06-10 BR BR9703577A patent/BR9703577A/pt not_active IP Right Cessation
- 1997-06-10 RU RU97109363/04A patent/RU2178783C2/ru not_active IP Right Cessation
- 1997-06-10 PL PL320469A patent/PL194313B1/pl unknown
- 1997-06-11 KR KR1019970024054A patent/KR100567476B1/ko not_active IP Right Cessation
- 1997-06-11 TR TR97/00487A patent/TR199700487A3/tr unknown
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000059815A (ko) * | 1999-03-09 | 2000-10-05 | 한형수 | 지방족 폴리에스테르 제조방법 |
| KR20030084183A (ko) * | 2002-04-25 | 2003-11-01 | 켐엔텍 주식회사 | 폴리에스테르의 제조방법 |
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