KR20150032017A - Dimeric complex comprising rare earth metal and method for manufacturing the same - Google Patents
Dimeric complex comprising rare earth metal and method for manufacturing the same Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 46
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 69
- 239000000126 substance Substances 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- 230000000737 periodic effect Effects 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 20
- -1 Metal complex compound Chemical class 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- 239000012454 non-polar solvent Substances 0.000 claims description 11
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- DUHQIGLHYXLKAE-UHFFFAOYSA-N 3,3-dimethylglutaric acid Chemical compound OC(=O)CC(C)(C)CC(O)=O DUHQIGLHYXLKAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- CVKMFSAVYPAZTQ-UHFFFAOYSA-N 2-methylhexanoic acid Chemical compound CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 claims 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 229920002857 polybutadiene Polymers 0.000 abstract description 15
- 239000005062 Polybutadiene Substances 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000010992 reflux Methods 0.000 description 23
- NKBWMBRPILTCRD-UHFFFAOYSA-N 2-Methylheptanoic acid Chemical compound CCCCCC(C)C(O)=O NKBWMBRPILTCRD-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 12
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 150000002798 neodymium compounds Chemical class 0.000 description 2
- 238000010092 rubber production Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000004810 2-methylpropylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:2])C([H])([H])[*:1] 0.000 description 1
- IHYIHDYFVDIKID-UHFFFAOYSA-N C(CC1=[O][IH]O1)CC1=[O]CCO1 Chemical compound C(CC1=[O][IH]O1)CC1=[O]CCO1 IHYIHDYFVDIKID-UHFFFAOYSA-N 0.000 description 1
- JTOYPFXHZZJVPF-UHFFFAOYSA-N CCCCCC(C)C(O1)=[Cl]C2C1[O]=C(C(C)CCCCC)OC2 Chemical compound CCCCCC(C)C(O1)=[Cl]C2C1[O]=C(C(C)CCCCC)OC2 JTOYPFXHZZJVPF-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- RBBOWEDMXHTEPA-UHFFFAOYSA-N hexane;toluene Chemical compound CCCCCC.CC1=CC=CC=C1 RBBOWEDMXHTEPA-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
본 발명은 부타디엔 고무 중합에 촉매제로 사용 가능한 희토류 금속 (rare earth metal)을 함유하는 이분자계 착화합물 (dimeric complex) 및 이의 제조 방법에 관한 것이다.The present invention relates to a dimeric complex containing a rare earth metal which can be used as a catalyst for butadiene rubber polymerization and a process for preparing the same.
타이어, 내충격 폴리스티렌, 구두 밑창, 및 골프공 등 여러 가지 제조 분야에서 고무 혼합물의 수요가 점차 증가함에 따라, 생산량이 부족한 천연고무의 대체 물질로서 석유화학 제품의 중간체인 부타디엔 고무의 가치가 높아지고 있다. The demand for rubber mixtures in various manufacturing sectors such as tires, impact resistant polystyrene, shoe soles, and golf balls is increasing, and the value of butadiene rubber, an intermediate in petrochemical products, is increasing as a substitute for natural rubber, which lacks production.
하지만, 최근 고유가 상황으로 인한 부타디엔 고무의 주원료의 가격이 상승하면서, 부타디엔 고무의 가격이 동반 상승하여 합성고무의 원가 상승에 대한 부담이 가중되고 있다.However, as prices of butadiene rubbers have risen due to the recent high oil prices, prices of butadiene rubbers have risen along with the burden of rising costs for synthetic rubbers.
이에, 부타디엔 고무의 공급량을 향상시키기 위한 부타디엔 고무 생산 공장의 증설과 함께 부타디엔 고무의 생산원가 절감을 위한 공정 개발이 요구되고 있다.Accordingly, it is required to expand the butadiene rubber production plant to improve the supply of butadiene rubber, and to develop a process for reducing the production cost of butadiene rubber.
상기 부타디엔 고무는 희토류 금속 함유 촉매를 이용한 중합 시스템에 의해 제조되는 것으로 알려져 있다. 특히, 상기 희토류계 금속 함유 촉매 중에서도 촉매 활성도가 보다 높은 Nd(OOCR)3 (이때, R=알킬기), NdCl3, NdCl3·xTHF (x는 1~6의 정수; THF는 테트라하이드로퓨란) 또는 NdCl3·yTBP (y는 1~6의 정수; TBP는 트리부틸포스핀) 등의 화학식으로 표기되는 네오디뮴 화합물이 특히 효과적인 것으로 입증되고 있다 (EP 1 055 659 참조).The butadiene rubber is known to be produced by a polymerization system using a rare earth metal containing catalyst. Among these rare earth metal-containing catalysts, Nd (OOCR) 3 (where R = alkyl group), NdCl 3 , NdCl 3 .xTHF (x is an integer of 1 to 6; THF is tetrahydrofuran) or NdCl 3 .yTBP (y is an integer of 1 to 6; TBP is tributylphosphine), etc. have been proved to be particularly effective (see EP 1 055 659).
상기 네오디뮴 화합물은 일반적으로 극성용매인 테트라하이드로퓨란, 에틸알코올 및 이소프로필알코올 등을 용매 및 배위화합물로 이용하여 네오디뮴할로겐과 반응시켜 제조하는 것으로 알려져 있다. 이렇게 얻어진 네오디뮴할로겐 화합물은 비극성 용매 하에서 알킬알루미늄과의 반응을 통해 촉매활성을 갖게 되어 부타디엔 고무 중합에 이용할 수 있게 된다. 한편, 상기 비극성 용매에 대한 네오디뮴 화합물의 용해도가 낮은 경우, 촉매 활동도가 낮기 때문에 부타디엔 고무 생산 효율 개선에 어려움이 있다.The neodymium compound is generally known to be prepared by reacting a polar solvent such as tetrahydrofuran, ethyl alcohol and isopropyl alcohol with a neodymium halogen as a solvent and a coordination compound. The neodymium halogen compound thus obtained is catalytically active through reaction with an alkylaluminum in a nonpolar solvent and can be used for butadiene rubber polymerization. On the other hand, when the solubility of the neodymium compound in the nonpolar solvent is low, it is difficult to improve the butadiene rubber production efficiency because the activity of the catalyst is low.
본 발명에서는 부타디엔 고무 중합 제조시 수율 향상 효과를 얻기 위하여, 촉매 성분으로 이용 가능한 희토류 금속을 함유하는 이분자계 착화합물을 제공한다. The present invention provides a bimetallic complex compound containing a rare earth metal which can be used as a catalyst component in order to obtain a yield improving effect in the production of butadiene rubber polymerization.
또한, 본 발명에서는 상기 희토류 금속을 함유하는 이분자계 착화합물의 제조 방법을 제공한다.In addition, the present invention provides a method for producing a bimolecular complex compound containing the rare earth metal.
구체적으로, 본 발명에서는 Specifically, in the present invention,
하기 화학식 1로 표시되는 희토류 금속을 함유하는 이분자계 착화합물을 제공한다. There is provided a bimolecular complex compound containing a rare earth metal represented by the following formula (1).
[화학식 1][Chemical Formula 1]
(상기 화학식 1에서,(In the formula 1,
M은 주기율표 3B족 원소를 나타내며, E는 C3 내지 C30의 선형 또는 분지형 알킬렌기 또는 C6 내지 C20의 아릴기이고, R1은 C3 내지 C30의 선형 또는 분지형 알킬기이다.)M represents a Group 3B element of the periodic table, E is a C 3 to C 30 linear or branched alkylene group or a C 6 to C 20 aryl group, and R 1 is a C 3 to C 30 linear or branched alkyl group. )
또한, 본 발명에서는 In the present invention,
하기 화학식 3으로 표시되는 희토류 금속 카르복실레이트 화합물과 이가 산 (di-acid) 화합물을 반응시켜 하기 화학식 4로 표시되는 희토류 금속 함유 이분자계 화합물을 합성하는 단계(S1); 및 상기 희토류 금속 함유 이분자계 화합물과 일가 산 (mono-acid)화합물을 반응시켜 상기 화학식 1로 표시되는 희토류 금속 함유 이분자계 착화합물을 합성하는 단계(S2)를 포함하는 희토류 금속 함유 이분자계 착화합물의 제조 방법을 제공한다.(S1) of reacting a rare earth metal carboxylate compound represented by the following formula (3) with a di-acid compound to synthesize a rare earth metal-containing bicyclic compound represented by the following formula (4); And a step (S2) of reacting the rare earth metal-containing bimetallic compound with a mono-acid compound to synthesize a rare-earth metal-containing bimetallic complex compound represented by the general formula (1) ≪ / RTI >
[화학식 3](3)
M(OAc)3·xH2OM (OAc) 3 .xH 2 O
[화학식 4][Chemical Formula 4]
(상기 화학식 3 및 4에서,(In the above formulas 3 and 4,
M은 주기율표 3B족 원소를 나타내며, Ac는 아세테이트기이고, E는 C3 내지 C30의 선형 또는 분지형 알킬렌기 또는 C6 내지 C20의 아릴기이다.)M represents a Group 3B element of the periodic table, Ac represents an acetate group, and E represents a linear or branched alkylene group of C 3 to C 30 or a C 6 to C 20 aryl group.)
이상에서 설명한 바와 같이, 본 발명에 따라 제조된 희토류 금속 함유 착화합물을 비극성 용매에 대한 용해도가 우수하기 때문에, 이를 부타디엔 고무 중합 시에 촉매로 이용하여 부타디엔 고무의 생산 효율을 향상시킬 수 있다.As described above, since the rare earth metal-containing complex produced according to the present invention has excellent solubility in a non-polar solvent, it is possible to improve the production efficiency of butadiene rubber by using it as a catalyst in polymerization of butadiene rubber.
본 명세서에 첨부되는 다음의 도면은 본 발명의 바람직한 실시예를 예시하는 것이며, 전술한 발명의 내용과 함께 본 발명의 기술 사상을 더욱 이해시키는 역할을 하는 것이므로, 본 발명은 그러한 도면에 기재된 사항에만 한정되어 해석되어서는 아니다.
도 1은 본 발명의 실시예에 의해 제조된 화학식 1a로 나타내는 희토류 금속 함유 이분자계 착화합물에 대한 분석 결과 그래프이다.BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate preferred embodiments of the invention and together with the description of the invention serve to further the understanding of the technical idea of the invention, It is not limited.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the results of analysis of a rare earth metal-containing bimetallic complex compound represented by Formula 1a prepared according to an embodiment of the present invention. FIG.
이하, 본 발명에 대한 이해를 돕기 위해 본 발명을 더욱 상세하게 설명한다. 이때, 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.
Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention. Herein, terms and words used in the present specification and claims should not be construed to be limited to ordinary or dictionary meanings, and the inventor may appropriately define the concept of the term to describe its own invention in the best way. It should be construed as meaning and concept consistent with the technical idea of the present invention.
구체적으로, 본 발명에서는 하기 화학식 1로 표시되는 희토류 금속을 함유하는 이분자계 착화합물을 제공한다. Specifically, the present invention provides a bimetallic complex compound containing a rare earth metal represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서,In Formula 1,
M은 주기율표 3B족 원소를 나타내며, E는 C3 내지 C30의 선형 또는 분지형 알킬렌기 또는 C6 내지 C20의 아릴기이고, R1은 C3 내지 C30의 선형 또는 분지형 알킬기이다.M represents a Group 3B element of the periodic table, E is a C 3 to C 30 linear or branched alkylene group or a C 6 to C 20 aryl group, and R 1 is a C 3 to C 30 linear or branched alkyl group.
상기 화학식 1로 표시되는 희토류 금속을 함유하는 이분자계 착화합물에 있어서, 상기 M은 특별히 제한하지 않지만, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y 및 Sc로 이루어진 군으로부터 선택된 적어도 하나 이상의 희토류 금속을 들 수 있으며, 구체적으로 Ce, La, Nd 및 Gd인 경우 촉매활성이 보다 우수한 것으로 알려져 있으며, 특히 M이 Nd인 경우 촉매 활성이 가장 우수한 것으로 알려져 있다.In the bimetallic complex containing the rare earth metal represented by the above formula 1, M is not particularly limited, but La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm At least one rare earth metal selected from the group consisting of Yb, Lu, Y and Sc. Specifically, it is known that Ce, La, Nd and Gd are superior in catalytic activity. Especially, when M is Nd, Activity is known to be the most excellent.
또한, 상기 화학식 1의 희토류 금속을 함유하는 이분자계 착화합물에 있어서, 가교 결합 단위인 E의 대표적인 예로는 프로필렌기, 부틸렌기, 펜틸렌기, 헥실렌기, 헵틸렌기, 페닐렌기, 옥틸렌기 및 2,2-메틸-프로필렌기로 이루어진 군으로부터 선택된 적어도 하나의 선형 또는 분지형 알킬렌기를 들 수 있다.In the bicyclic complex containing the rare earth metal of Formula 1, typical examples of the crosslinking unit E include a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, a phenylene group, Methyl-propylene group, and a 2-methyl-propylene group.
상기 화학식 1의 희토류 금속을 함유하는 이분자계 착화합물에 있어서, R1으로 나타내는 리간드의 예로는 1-메틸-펜틸기, 1-메틸-헥실기, 2-메틸-헥실기 및 노닐기로 이루어진 군으로부터 선택된 적어도 하나의 선형 또는 분지형 알킬기를 들 수 있다.Examples of the ligand represented by R 1 in the bicyclic complex containing the rare earth metal of the above formula (1) are selected from the group consisting of a 1-methyl-pentyl group, a 1-methyl-hexyl group, a 2-methyl- At least one linear or branched alkyl group.
또한, 비극성 용매에 대한 상기 화학식 1로 표시되는 희토류 금속을 함유하는 이분자계 착화합물의 용해도는 50 이상 인 것이 바람직하다.In addition, the solubility of the bifunctional complex compound containing a rare earth metal represented by the general formula (1) in the nonpolar solvent is preferably 50 or more.
또한, 본 발명에 있어서, 상기 화학식 1로 표시되는 희토류 금속을 함유하는 이분자계 착화합물의 예로는 하기 화학식 1a 내지 화학식 1i로 표시되는 화합물을 포함할 수 있다.Further, in the present invention, examples of the bimetallic complex compound containing the rare earth metal represented by the general formula (1) may include compounds represented by the following general formulas (1a) to (1i).
[화학식 1a][Formula 1a]
[화학식 1b][Chemical Formula 1b]
[화학식 1c][Chemical Formula 1c]
[화학식 1d]≪ RTI ID = 0.0 &
[화학식 1e][Formula 1e]
[화학식 1f](1f)
[화학식 1g][Formula 1g]
[화학식 1h][Chemical Formula 1h]
[화학식 1i][Formula 1i]
종래 올레핀 중합 반응에 사용되던 네오디뮴 촉매는 하기 화학식 2로 표시되는 바와 같이 카르복실레이트를 리간드로 함유하고, 전이금속 또는 희토류 금속을 중심 금속으로 함유하는 단분자 형태(monomeric)의 화합물인 반면에, 본 발명에서는 상기 화학식 1로 나타낸 바와 같이 희토류 금속 원자를 2개 이상 함유하는 이분자계 착화합물을 제공하여 비극성 유기 용매에 대한 용해도 향상 효과를 얻을 수 있다. The neodymium catalyst used in conventional olefin polymerization is a monomeric compound containing a carboxylate as a ligand and containing a transition metal or a rare earth metal as a central metal, In the present invention, it is possible to obtain a solubility-enhancing effect in a non-polar organic solvent by providing a bimetallic complex compound containing at least two rare earth metal atoms as shown in the formula (1).
[화학식 2](2)
(상기 식에서, (Wherein,
M은 주기율표 3B족 원소를 나타내며, R1은 C6 내지 C30의 선형 또는 분지형 알킬기이다.)
M represents a Group 3B element of the periodic table, and R 1 is a linear or branched alkyl group of C 6 to C 30. )
또한, 본 발명에서는 In the present invention,
하기 화학식 3으로 표시되는 희토류 금속 함유 카르복실레이트 화합물과 이가 산 (di-acid) 화합물을 반응시켜 하기 화학식 4로 표시되는 희토류 금속 함유 이분자계 화합물을 합성하는 단계 (S1); 및(S1) of reacting a rare earth metal-containing carboxylate compound represented by the following formula (3) with a di-acid compound to synthesize a rare earth metal-containing bicyclic compound represented by the following formula (4); And
상기 합성된 희토류 금속 함유 이분자계 화합물과 일가 산 (mono-acid)화합물을 반응시켜 상기 화학식 1로 표시되는 희토류 금속 함유 이분자계 착화합물을 합성하는 단계(S2)를 포함하는 희토류 금속 함유 이분자계 착화합물의 제조 방법을 제공한다.And (S2) reacting the synthesized rare earth metal-containing bimetallic compound with a mono-acid compound to synthesize a rare-earth metal-containing bimetallic complex compound represented by the general formula (1) And a manufacturing method thereof.
[반응식 1][Reaction Scheme 1]
(상기 반응식 1에서, (In the above Reaction Scheme 1,
M은 주기율표 3B족 원소를 나타내며, Ac는 아세테이트기이고, E는 C3 내지 C30의 선형 또는 분지형 알킬렌기 또는 C3 내지 C20의 아릴기이고, R1은 C3 내지 C30의 선형 또는 분지형 알킬기이다.)M is a Group 3B element of the periodic table, Ac is an acetate group, E is a C 3 to C 30 linear or branched alkylene group or a C 3 to C 20 aryl group, R 1 is a C 3 to C 30 linear Or branched alkyl group.)
이때, 상기 본 발명의 방법에 있어서, 상기 이가 산 화합물 (di-acid)의 예로는 아디프산 (adipic acid), 글루타르산 (Glutaric acid), 피멜산 (Pimelic acid), 수베르산 (Suberic acid), 아젤라산 (Azelaic acid), 세바스산 (Sebacic acid), 테레프탈산 (Terephthalic acid) 및 3,3-디메틸글루타르산 (3,3-Dimethylglutaric acid)으로 이루어진 군으로부터 선택된 적어도 하나 이상의 화합물을 들 수 있으며, 이들로 한정되는 것은 아니다.At this time, in the method of the present invention, examples of the di-acid include adipic acid, glutaric acid, pimelic acid, suberic acid, at least one compound selected from the group consisting of acetic acid, azelaic acid, sebacic acid, terephthalic acid and 3,3-dimethylglutaric acid, But are not limited to these.
이때, 상기 희토류 금속 함유 카르복실레이트 화합물 : 상기 이가 산 화합물의 혼합비(몰비)는 2 내지 6:1일 수 있다. 만약, 상기 희토류 금속 함유 카르복실레이트 화합물의 함량이 6을 초과하거나, 2 미만인 경우 이가 산 화합물에 희토류 금속 카르복실레이트 2개가 결합된 구조의 화합물을 얻을 수 없다.At this time, the mixing ratio (molar ratio) of the rare earth metal-containing carboxylate compound: the diacid compound may be 2 to 6: 1. If the content of the rare earth metal-containing carboxylate compound is more than 6 or less than 2, it is impossible to obtain a compound having a structure in which two rare earth metal carboxylates are bonded to the bivalent acid compound.
또한, 본 발명의 방법에 있어서, 상기 일가 산 화합물의 예로는 피로피온산(Propionic acid), 부티르산(n-Butyric acid), 2메탈헥사노익산(2-Methylhexanoic acid), 데칸산 (decanoic acid) 를 들 수 있으며, 이들로 한정되는 것은 아니다.In the method of the present invention, examples of the monovalent acid compound include propionic acid, n-butyric acid, 2-methylhexanoic acid, decanoic acid, But are not limited thereto.
이때, 상기 희토류 금속 함유 이분자계 화합물 : 일가 산 화합물의 혼합비(몰비)는 1:4 내지 10, 구체적으로 1:5일 수 있다. 만약, 상기 일가 산 화합물의 10을 초과하거나, 4 미만인 경우 Ac기가 모두 원하는 일가 산 화합물로 치환되지 않는 문제가 있다.At this time, the mixing ratio ( molar ratio) of the rare earth metal-containing bicomponent compound: monovalent acid compound may be 1: 4 to 10, specifically 1: 5. If the amount of the monovalent acid compound is more than 10 or less than 4, there is a problem that the Ac group is not substituted with the desired monovalent acid compound.
또한, 상기 방법에 있어서, (S1) 및 (S2) 단계에 있어서, 반응 용매는 클로로벤젠, 톨루엔 및 자일렌 등의 비극성 용매를 사용할 수 있으며, 이들 비극성 용매는 반응물 전체 100 중량부에 대하여 50 내지 90 중량부로 사용할 수 있다.In the above method, non-polar solvents such as chlorobenzene, toluene and xylene may be used as the reaction solvent in steps (S1) and (S2). These non-polar solvents may be used in an amount of 50 to 100 parts by weight, 90 parts by weight.
또한, 상기 방법의 각 단계는 환류 냉각기를 이용한 교반 반응을 실시하는 것이 바람직하다.
In addition, it is preferable that each step of the above method is carried out by a stirring reaction using a reflux condenser.
또한, 본 발명에서는 상기 희토류 금속을 함유하는 이분자계 착화합물을 이용하는 방법에 의해 제조된 부타디엔 고무를 제공할 수 있다.
Further, in the present invention, it is possible to provide the butadiene rubber produced by the method using the bifunctional complex compound containing the rare earth metal.
이하, 실시예 및 비교예를 통하여 본 발명을 더욱 상세하게 설명한다. 단, 실시예는 본 발명을 예시하기 위한 것이지 이들 만으로 본 발명의 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. It should be noted, however, that the examples are for illustrative purposes only and are not intended to limit the scope of the invention.
실시예Example
(실시예 1)(Example 1)
(S1 단계)(Step S1)
250㎖ 라운드 플라스크에 Nd(OAc)3·xH2O (1.0m㏖, 0.32g)과 아디프산 (0.5m㏖, 0.036g)을 넣고, 클로로벤젠 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 밝은 하늘색 파우더 형태의 하기 화학식 5의 화합물 (0.32g, 수율 96%)를 얻었다.Nd (OAc) 3 xH 2 O (1.0 mmol, 0.32 g) and adipic acid (0.5 mmol, 0.036 g) were placed in a 250 ml round-bottomed flask, and 20 ml of chlorobenzene was added thereto. - Stark condenser was connected and reflux stirring reaction was performed for 24 hours. After completion of the reaction, all of the solvent was removed under a reduced pressure to remove the solvent to obtain 0.32 g (yield 96%) of a compound of the following formula (5) in the form of a light-blue powder.
[화학식 5][Chemical Formula 5]
(S2 단계)(Step S2)
250㎖ 라운드 플라스크에 상기 화학식 5의 화합물 (0.30m㏖, 0.20g)과 2-메틸 헵타논산 (1.5m㏖, 0.22g)을 넣고, 톨루엔 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 밝은 하늘색 겔 형태의 상기 화학식 1a의 화합물 (0.29g, 수율 96%)를 얻었다(도 1 참조). The compound of formula 5 (0.30 mmol, 0.20 g) and 2-methylheptanoic acid (1.5 mmol, 0.22 g) were placed in a 250 ml round-bottomed flask, and 20 ml of toluene was added thereto. And the mixture was stirred under reflux for 24 hours. After completion of the reaction, all of the solvent was removed under a reduced pressure to obtain a compound of the above formula (1a) (0.29 g, yield: 96%) in the form of a light blue gel (see FIG.
FT-IR (cm-1): 2958.4, 2925.6, 2857.9, 1709.9, 1516.7, 1465.3, 1419.0, 1376.4, 1259.8, 1200.1, 1017.5, 865.4, 797.7, 724.8, 659.6, 552.0, 501.5
FT-IR (cm -1 ): 2958.4, 2925.6, 2857.9, 1709.9, 1516.7, 1465.3, 1419.0, 1376.4, 1259.8, 1200.1, 1017.5, 865.4, 797.7, 724.8, 659.6, 552.0, 501.5
(실시예 2)(Example 2)
(S1 단계)(Step S1)
250㎖ 라운드 플라스크에 Nd(OAc)3·xH2O (1.0m㏖, 0.32g)과 글루타르산 (0.5m㏖, 0.66g)을 넣고, 클로로벤젠 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 밝은 하늘색 파우더 형태의 하기 화학식 6의 화합물 (0.32g, 수율 96%)를 얻었다.Nd (OAc) 3 xH 2 O (1.0 mmol, 0.32 g) and glutaric acid (0.5 mmol, 0.66 g) were placed in a 250 ml round-bottom flask, and 20 ml of chlorobenzene was added thereto. - Stark condenser was connected and reflux stirring reaction was performed for 24 hours. After completion of the reaction, all of the solvent was removed under a reduced pressure to obtain a compound of the following formula (6) (0.32 g, yield 96%) in the form of a light blue powder.
[화학식 6][Chemical Formula 6]
(S2 단계) (Step S2)
250㎖ 라운드 플라스크에 상기 화학식 6의 화합물 (0.30m㏖, 0.2g)과 2-메틸 헵타논산 (1.5m㏖, 0.22g)을 넣고, 톨루엔 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 밝은 하늘색 겔 형태의 상기 화학식 1b의 화합물 (0.29g, 수율 96%)를 얻었다. (0.30 mmol, 0.2 g) and 2-methylheptanoic acid (1.5 mmol, 0.22 g) were placed in a 250 mL round-bottomed flask, and 20 mL of toluene was added thereto. Then, a reflux condenser was charged with a Dean- And the mixture was stirred under reflux for 24 hours. After completion of the reaction, all of the solvent was removed under reduced pressure to remove the solvent to obtain the compound of Formula 1b (0.29 g, yield: 96%) in the form of a light blue gel.
FT-IR (cm-1): 2955.7, 2926.6, 2858.2, 1706.2, 1523.9, 1464.6, 1417.9, 1376.8, 1294.8, 1227.9, 1197.4, 1154.4, 1101.7, 928.7, 782.7, 725.3, 643.9, 552.0
FT-IR (cm -1 ): 2955.7, 2926.6, 2858.2, 1706.2, 1523.9, 1464.6, 1417.9, 1376.8, 1294.8, 1227.9, 1197.4, 1154.4, 1101.7, 928.7, 782.7, 725.3, 643.9, 552.0
(실시예 3)(Example 3)
(S1 단계)(Step S1)
250㎖ 라운드 플라스크에 Nd(OAc)3·xH2O (1.0m㏖, 0.32g)과 피멜산 (0.5m㏖, 0.08g)을 넣고, 클로로벤젠 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 밝은 하늘색 파우더 형태의 하기 화학식 7의 화합물 (0.32g, 수율 95%)를 얻었다.Nd (OAc) 3 xH 2 O (1.0 mmol, 0.32 g) and pimelic acid (0.5 mmol, 0.08 g) were placed in a 250 ml round-bottomed flask, and 20 ml of chlorobenzene was added thereto. Followed by reflux stirring for 24 hours. After completion of the reaction, all of the solvent was removed under a reduced pressure to obtain a compound of the following formula (7) (0.32 g, yield 95%) in the form of a light-blue powder.
[화학식 7](7)
(S2 단계)(Step S2)
250㎖ 라운드 플라스크에 상기 화학식 7의 화합물 (0.30m㏖, 0.20g)과 2-메틸 헵타논산 (1.5m㏖, 0.22g)을 넣고, 톨루엔 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 밝은 하늘색 겔 형태의 상기 화학식 1c의 화합물 (0.28g, 수율 90%)를 얻었다. (0.30 mmol, 0.20 g) and 2-methylheptanoic acid (1.5 mmol, 0.22 g) were placed in a 250 ml round-bottomed flask, and 20 ml of toluene was added thereto. And the mixture was stirred under reflux for 24 hours. After completion of the reaction, all of the solvent was removed under a reduced pressure to obtain a compound of the above formula (Ic) (0.28 g, yield 90%) in the form of a light blue gel.
FT-IR (cm-1): 2956.0, 2927.5, 2958.5, 1706.3, 1521.9, 1464.8, 1418.5, 1376.8, 1294.2, 1227.9, 1194.9, 1152.1, 1120.9, 1101.6, 1042.4, 929.7, 844.6, 782.0, 725.6, 551.4
FT-IR (cm -1 ): 2956.0, 2927.5, 2958.5, 1706.3, 1521.9, 1464.8, 1418.5, 1376.8, 1294.2, 1227.9, 1194.9, 1152.1, 1120.9, 1101.6, 1042.4, 929.7, 844.6, 782.0,
(실시예 4)(Example 4)
(S1 단계)(Step S1)
250㎖ 라운드 플라스크에 Nd(OAc)3·xH2O (1.0m㏖, 0.32g)과 수베르산 (0.5m㏖, 0.087g)을 넣고, 클로로벤젠 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 밝은 하늘색 파우더 형태의 하기 화학식 8의 화합물 (0.33g, 수율 95%)를 얻었다.Nd (OAc) 3 xH 2 O (1.0 mmol, 0.32 g) and suberic acid (0.5 mmol, 0.087 g) were placed in a 250 ml round-bottomed flask, and 20 ml of chlorobenzene was added thereto. - Stark condenser was connected and reflux stirring reaction was performed for 24 hours. After completion of the reaction, all of the solvent was removed under a reduced pressure to obtain a compound of the following formula (8) (0.33 g, yield 95%) in the form of a light-blue powder.
[화학식 8][Chemical Formula 8]
(S2 단계)(Step S2)
250㎖ 라운드 플라스크에 상기 화학식 8의 화합물 (0.30m㏖, 0.21g)과 2-메틸 헵타논산 (1.5m㏖, 0.22g)을 넣고, 톨루엔 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 연한 하늘색 끈적한 겔 형태의 상기 화학식 1d의 화합물 (0.30g, 수율 96%)를 얻었다. (0.30 mmol, 0.21 g) and 2-methylheptanoic acid (1.5 mmol, 0.22 g) were placed in a 250 ml round-bottomed flask, and 20 ml of toluene was added thereto. And the mixture was stirred under reflux for 24 hours. After completion of the reaction, the solvent was removed under a reduced pressure to remove the solvent to obtain the compound of the above formula (1d) (0.30 g, yield 96%) in the form of a light-blue sticky gel.
FT-IR (cm-1): 2955.7, 2929.2, 2858.3, 1706.8, 1518.9, 1464.7, 1418.8, 1376.5, 1294.7, 1227.6, 1195.0, 1152.9, 1120.9, 1042.5, 929.9, 782.5, 647.6, 552.2
FT-IR (cm -1 ): 2955.7, 2929.2, 2858.3, 1706.8, 1518.9, 1464.7, 1418.8, 1376.5, 1294.7, 1227.6, 1195.0, 1152.9, 1120.9, 1042.5, 929.9, 782.5, 647.6, 552.2
(실시예 5)(Example 5)
(S1 단계)(Step S1)
250㎖ 라운드 플라스크에 Nd(OAc)3·xH2O (1.0m㏖, 0.32g)과 아젤라산 (0.5m㏖, 0.094g)을 넣고, 클로로벤젠 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 밝은 하늘색 파우더 형태의 하기 화학식 9의 화합물 (0.34g, 수율 95%)를 얻었다.Nd (OAc) 3 xH 2 O (1.0 mmol, 0.32 g) and azelaic acid (0.5 mmol, 0.094 g) were placed in a 250 ml round-bottomed flask, and 20 ml of chlorobenzene was added. Followed by reflux stirring for 24 hours. After completion of the reaction, all of the solvent was removed under a reduced pressure to obtain a compound of the following formula (9) (0.34 g, yield 95%) in the form of a light blue powder.
[화학식 9][Chemical Formula 9]
(S2 단계)(Step S2)
250㎖ 라운드 플라스크에 상기 화학식 9의 화합물 (0.30m㏖, 0.21g)과 2-메틸 헵타논산 (1.5m㏖, 0.22g)을 넣고, 톨루엔 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 밝은 하늘색 겔 형태의 상기 화학식 1e의 화합물 (0.29g, 수율 92%)를 얻었다. (0.30 mmol, 0.21 g) and 2-methylheptanoic acid (1.5 mmol, 0.22 g) were placed in a 250 ml round-bottomed flask, and 20 ml of toluene was added thereto. And the mixture was stirred under reflux for 24 hours. After completion of the reaction, the solvent was removed under a reduced pressure to remove the solvent to obtain the compound of the formula (1e) (0.29 g, yield 92%) in the form of a light blue gel.
FT-IR (cm-1): 2955.7, 2926.9, 2858.2, 1706.7, 1521.4, 1464.7, 1418.5, 1376.7, 1294.4, 1277.3, 1227.7, 1195.7, 1153.1, 1120.9, 1101.2, 1044.0, 928.8, 782.1, 551.5
FT-IR (cm -1 ): 2955.7, 2926.9, 2858.2, 1706.7, 1521.4, 1464.7, 1418.5, 1376.7, 1294.4, 1277.3, 1227.7, 1195.7, 1153.1, 1120.9, 1101.2, 1044.0, 928.8, 782.1, 551.5
(실시예 6)(Example 6)
(S1 단계)(Step S1)
250㎖ 라운드 플라스크에 Nd(OAc)3·xH2O (1.0m㏖, 0.32g)과 테레프탈산 (0.5m㏖, 0.083g)을 넣고, 클로로벤젠 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 밝은 하늘색 파우더 형태의 하기 화학식 10의 화합물 (0.31g, 수율 91%)를 얻었다. Nd (OAc) 3 · xH 2 O (1.0m㏖, 0.32g) and terephthalic acid (0.5m㏖, 0.083g) and the mixture, which turned the chlorobenzene 20㎖ Next, the reflux condenser to the flask, a Dean 250㎖ round-Stark The condenser was connected to perform a reflux stirring reaction for 24 hours. After completion of the reaction, all of the solvent was removed under reduced pressure to remove the solvent to obtain a compound of the following formula (10) (0.31 g, yield 91%) in the form of a light blue powder.
[화학식 10][Chemical formula 10]
(S2 단계)(Step S2)
250㎖ 라운드 플라스크에 상기 화학식 10의 화합물 (0.30m㏖)과 2-메틸 헵타논산 (1.5m㏖, 0.22g)을 넣고, 톨루엔 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 밝은 하늘색 겔 형태의 상기 화학식 1f의 화합물 (0.29g, 수율 93%)를 얻었다. The compound of formula (10) (0.30 mmol) and 2-methylheptanoic acid (1.5 mmol, 0.22 g) were placed in a 250 ml round-bottomed flask, 20 ml of toluene was added thereto, and a dean- Followed by reflux stirring for 24 hours. After completion of the reaction, the solvent was removed under a reduced pressure to remove the solvent to obtain the compound of the above formula (1f) (0.29 g, yield 93%) in the form of a light-blue gel.
FT-IR (cm-1): 2928.4, 1668.9, 1523.6, 1465.6, 1420.4, 1400.4, 1295.9, 1102.2, 1051.1, 1018.0, 932.1, 839.8, 751.5, 726.3, 669.7, 553.1, 517.6, 477.1
FT-IR (cm -1 ): 2928.4, 1668.9, 1523.6, 1465.6, 1420.4, 1400.4, 1295.9, 1102.2, 1051.1, 1018.0, 932.1, 839.8, 751.5, 726.3, 669.7, 553.1, 517.6, 477.1
(실시예 7)(Example 7)
(S1 단계)(Step S1)
250㎖ 라운드 플라스크에 상기 실시예 1의 화학식 1의 화합물 (0.30m㏖, 0.20g)과 데칸산 (1.5m㏖, 0.26g)을 넣고, 톨루엔 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 밝은 하늘색 파우더 형태의 상기 화학식 1g의 화합물 (0.32g, 수율 94%)를 얻었다. The compound of formula 1 (0.30 mmol, 0.20 g) and decanoic acid (1.5 mmol, 0.26 g) were added to a 250 ml round-bottomed flask, and 20 ml of toluene was added thereto. The condenser was connected to perform a reflux stirring reaction for 24 hours. After completion of the reaction, all of the solvent was removed under a reduced pressure to remove the solvent to obtain the compound of the formula (1g) (0.32 g, yield 94%) in the form of a light-blue powder.
FT-IR (cm-1): 2954.4, 2917.6, 2849.2, 1694.4, 1536.9, 1421.7, 1416.1, 1335.8, 1306.2, 1265.6, 1200.9, 1109.4, 1073.6, 939.9, 791.6, 720.2, 661.6, 590.7
FT-IR (cm -1 ): 2954.4, 2917.6, 2849.2, 1694.4, 1536.9, 1421.7, 1416.1, 1335.8, 1306.2, 1265.6, 1200.9, 1109.4, 1073.6, 939.9, 791.6, 720.2, 661.6, 590.7
(실시예 8)(Example 8)
(S1 단계)(Step S1)
250㎖ 라운드 플라스크에 Nd(OAc)3·xH2O (1.0m㏖, 0.32g)과 세바스산 (0.5m㏖, 0.10g)을 넣고, 클로로벤젠 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 밝은 하늘색 파우더 형태의 하기 화학식 11의 화합물 (0.35g, 수율 97%)를 얻었다.250㎖ a put Nd (OAc) 3 · xH 2 O (1.0m㏖, 0.32g) and sebacic acid (0.5m㏖, 0.10g) in a flask round chlorobenzene 20㎖ In the following, a reflux device, Dean- Followed by reflux stirring for 24 hours. After completion of the reaction, all of the solvent was removed under a reduced pressure to remove the solvent to obtain a compound of the following formula (11) (0.35 g, yield 97%) in the form of a light blue powder.
[화학식 11](11)
(S2 단계)(Step S2)
250㎖ 라운드 플라스크에 상기 화학식 11의 화합물 (0.30m㏖, 0.22g)과 2-메틸 헵타논산 (1.5m㏖, 0.22g)을 넣고, 톨루엔 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 투명한 하늘색 끈적한 겔 형태의 상기 화학식 1 h의 화합물 (0.29g, 수율 91%)를 얻었다. The compound of formula 11 (0.30 mmol, 0.22 g) and 2-methylheptanoic acid (1.5 mmol, 0.22 g) were placed in a 250 ml round-bottomed flask, and 20 ml of toluene was added thereto. And the mixture was stirred under reflux for 24 hours. After completion of the reaction, all of the solvent was removed under a reduced pressure to remove the solvent to obtain a compound of the above formula (1h) (0.29 g, yield 91%) in the form of a clear, light-colored sticky gel.
FT-IR (cm-1): 2956.1, 2928.3, 2858.6, 1705.9, 1530.4, 1464.7, 1415.4, 1377.6, 1293.8, 1245.2, 1228.7, 1194.5, 1150.7, 1120.7, 1101.7, 928.3, 841.4, 782.4, 669.9
FT-IR (cm -1 ): 2956.1, 2928.3, 2858.6, 1705.9, 1530.4, 1464.7, 1415.4, 1377.6, 1293.8, 1245.2, 1228.7, 1194.5, 1150.7, 1120.7, 1101.7, 928.3, 841.4, 782.4, 669.9
(실시예 9)(Example 9)
(S1 단계)(Step S1)
250㎖ 라운드 플라스크에 Nd(OAc)3·xH2O (1.0m㏖, 0.32g)과 3,3-디메틸글루타르산 (0.5m㏖, 0.080g)을 넣고, 클로로벤젠 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 파우더 형태의 하기 화학식 12의 화합물 (0.32g, 수율 93%)를 얻었다.Nd (OAc) 3 xH 2 O (1.0 mmol, 0.32 g) and 3,3- dimethylglutaric acid (0.5 mmol, 0.080 g) were placed in a 250 ml round-bottomed flask, and 20 ml of chlorobenzene was added , A reflux condenser was connected to the reflux condenser, and a reflux stirring reaction was performed for 24 hours. After completion of the reaction, all of the solvent was removed under a reduced pressure to remove the solvent to obtain 0.32 g (yield 93%) of a compound of the following formula (12) in powder form.
[화학식 12][Chemical Formula 12]
(S2 단계)(Step S2)
250㎖ 라운드 플라스크에 상기 제조된 화학식 12의 화합물 (0.30m㏖, 0.20g)과 2-메틸 헵타논산 (1.5m㏖, 0.22g)을 넣고, 톨루엔 20㎖를 투입한 다음, 환류 장치에 딘-스탁 콘덴서를 연결하여 24hr 동안 환류 교반 반응을 실시하였다. 반응 완료 후, 감압 중류하에 용매를 모두 제거하여 투명한 옅은 하늘색 끈적한 겔 형태의 상기 화학식 1 i의 화합물 (0.28g, 수율 90%)를 얻었다.(0.30 mmol, 0.20 g) and 2-methylheptanoic acid (1.5 mmol, 0.22 g) were put in a 250 ml round-bottomed flask, and 20 ml of toluene was added thereto. Followed by reflux stirring for 24 hours. After completion of the reaction, the solvent was removed under a reduced pressure to remove the solvent to obtain the compound of the above formula (1) (0.28 g, yield 90%) in the form of a pale, light-colored sticky gel.
FT-IR (cm-1): 2956.1, 2926.7, 2858.4, 1705.9, 1525.5, 1464.8, 1416.1, 1377.3, 1306.0, 1294.7, 1246.5, 1225.4, 1194.0, 1150.5, 1120.6, 929.1, 841.2, 782.4, 725.4
FT-IR (cm -1 ): 2956.1, 2926.7, 2858.4, 1705.9, 1525.5, 1464.8, 1416.1, 1377.3, 1306.0, 1294.7, 1246.5, 1225.4, 1194.0, 1150.5, 1120.6, 929.1, 841.2, 782.4, 725.4
(실험예 1)(Experimental Example 1)
상기 실시예 1 내지 5에서 제조된 화학식 1a 내지 1e의 화합물의 비극성 용매에 대한 용해도 값을 측정하고, 그 결과를 하기 표 1에 나타내었다.The solubility values of the compounds of formulas (1a) to (1e) prepared in Examples 1 to 5 in non-polar solvents were measured, and the results are shown in Table 1 below.
이때, 용해도 측정 방법은 동일한 온도 조건하에서 각각의 해당하는 용매 100g 당 하기 화합물이 얼마나 녹는지 확인하는 방법으로 수행할 수 있다. 이때, 50g 이상 녹는 경우를 ○으로 표기하였다.At this time, the solubility measurement method can be performed by determining how much the following compounds are dissolved per 100 g of the corresponding solvent under the same temperature condition. In this case, the case where 50 g or more was melted was marked with a circle.
상기 표 1에 나타낸 바와 같이, 본 발명의 화학식 1a 내지 1e의 희토류 금속 함유 이분자계 착화합물은 비극성 용매에 대한 용해도가 높은 것을 확인할 수 있었다.As shown in Table 1, it was confirmed that the rare earth metal-containing bicyclic complexes of the general formulas (1a) to (1e) of the present invention had a high solubility in a non-polar solvent.
Claims (13)
[화학식 1]
(상기 화학식 1에서,
M은 주기율표 3B족 원소를 나타내며, E는 C3 내지 C30의 선형 또는 분지형 알킬렌기 또는 C6 내지 C20의 아릴기이고, R1은 C3 내지 C30의 선형 또는 분지형 알킬기이다.)A bicomponent complex compound containing a rare earth metal represented by the following formula (1).
[Chemical Formula 1]
(In the formula 1,
M represents a Group 3B element of the periodic table, E is a C 3 to C 30 linear or branched alkylene group or a C 6 to C 20 aryl group, and R 1 is a C 3 to C 30 linear or branched alkyl group. )
상기 화학식 1의 착화합물에서 M은 La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y 및 Sc로 이루어진 군으로부터 선택된 적어도 하나 이상의 희토류 금속인 것을 특징으로 하는 희토류 금속을 함유하는 이분자계 착화합물. The method according to claim 1,
In the complex of Formula 1, M is at least one rare earth element selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Metal complex compound containing a rare earth metal.
상기 M은 Nd인 것을 특징으로 하는 희토류 금속을 함유하는 이분자계 착화합물. The method of claim 2,
Wherein M is Nd. ≪ RTI ID = 0.0 > 11. < / RTI >
상기 E는 프로필렌기, 부틸렌기, 펜틸렌기, 헥실렌기, 헵틸렌기, 페닐렌기, 옥틸렌기 및 2,2-메틸-프로필렌기로 이루어진 군으로부터 선택된 적어도 하나의 선형 또는 분지형 알킬렌기인 것을 특징으로 하는 희토류 금속을 함유하는 이분자계 착화합물. The method according to claim 1,
Wherein E is at least one linear or branched alkylene group selected from the group consisting of a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, a phenylene group, an octylene group and a 2,2- Based rare earth metals.
상기 R1는 1-메틸-펜틸기, 1-메틸-헥실기, 2-메틸-헥실기 및 노닐기로 이루어진 군으로부터 선택된 적어도 하나의 선형 또는 분지형 알킬기인 것을 특징으로 하는 희토류 금속을 함유하는 이분자계 착화합물. The method according to claim 1,
Wherein R 1 is at least one linear or branched alkyl group selected from the group consisting of a 1-methyl-pentyl group, a 1-methyl-hexyl group, a 2-methyl-hexyl group, and a nonyl group. Complex compounds.
상기 화학식 1로 표시되는 희토류 금속을 함유하는 이분자계 착화합물은 하기 화학식 1a 내지 화학식 1i로 표시되는 것을 특징으로 하는 희토류 금속을 함유하는 이분자계 착화합물:
[화학식 1a]
[화학식 1b]
[화학식 1c]
[화학식 1d]
[화학식 1e]
[화학식 1f]
[화학식 1g]
[화학식 1h]
[화학식 1i]
The bimetallic complex compound containing a rare earth metal represented by the general formula (1) is represented by the following general formulas (1a) to (1i):
[Formula 1a]
[Chemical Formula 1b]
[Chemical Formula 1c]
≪ RTI ID = 0.0 &
[Formula 1e]
(1f)
[Formula 1g]
[Chemical Formula 1h]
[Formula 1i]
상기 합성된 희토류 금속 함유 이분자계 화합물과 일가 산 (mono-acid)화합물을 반응시켜 상기 화학식 1로 표시되는 희토류 금속 함유 이분자계 착화합물을 합성하는 단계(S2)를 포함하는 청구항 1 기재의 희토류 금속 함유 이분자계 착화합물의 제조 방법:
[화학식 3]
M(OAc)3·xH2O
[화학식 4]
(상기 화학식 1에서,
M은 주기율표 3B족 원소를 나타내며, E는 C3 내지 C30의 선형 또는 분지형 알킬렌기 또는 C6 내지 C20의 아릴기이다.).(S1) of reacting a rare earth metal-containing carboxylate compound represented by the following formula (3) with a di-acid compound to synthesize a rare earth metal-containing bicyclic compound represented by the following formula (4); And
(2) reacting the synthesized rare earth metal-containing bimetallic compound with a mono-acid compound to synthesize a rare earth metal-containing bimetallic complex compound represented by the general formula (1) Preparation method of bimolecular complex:
(3)
M (OAc) 3 .xH 2 O
[Chemical Formula 4]
(In the formula 1,
M represents a Group 3B element of the periodic table and E is a linear or branched alkylene group of C 3 to C 30 or a C 6 to C 20 aryl group.
상기 이가 산 화합물은 아디프산, 글루타르산, 피멜산, 수베르산, 아젤라산, 세바스산, 테레프탈산 및 3,3-디메틸글루타르산으로 이루어진 군으로부터 선택된 적어도 하나 이상의 산 화합물인 것을 특징으로 하는 희토류 금속 함유 이분자계 착화합물의 제조 방법. The method of claim 7,
Wherein the divalent acid compound is at least one acid compound selected from the group consisting of adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid and 3,3-dimethylglutaric acid Wherein the rare-earth metal-containing bimolecular complex compound is a rare earth metal.
상기 희토류 금속 함유 카르복실레이트 화합물 : 상기 이가 산 화합물의 혼합비(몰비)는 2 내지 5:1인 것을 특징으로 하는 희토류 금속 함유 이분자계 착화합물의 제조 방법. The method of claim 7,
Wherein the mixing ratio (molar ratio) of the rare earth metal-containing carboxylate compound to the diacid compound is 2 to 5: 1.
상기 일가 산 화합물은 피로피온산, 부티르산, 2-메탈헥사노익산 및 데칸산으로 이루어진 군으로부터 선택된 적어도 하나 이상의 산 화합물인 것을 특징으로 하는 희토류 금속 함유 이분자계 착화합물의 제조 방법. The method of claim 7,
Wherein the monovalent acid compound is at least one acid compound selected from the group consisting of pyrophosphonic acid, butyric acid, 2-methylhexanoic acid, and decanoic acid.
상기 희토류 금속 함유 이분자계 화합물 : 일가 산 화합물의 혼합비(몰비)는 1:4 내지 10인 것을 특징으로 하는 희토류 금속 함유 이분자계 착화합물의 제조 방법. The method of claim 7,
Wherein the mixing ratio (molar ratio) of the rare-earth metal-containing bicomponent compound: monovalent acid compound is 1: 4 to 10. The method for producing a rare-earth metal-containing bicomponent complex compound according to claim 1,
상기 (S1) 및 (S2) 단계의 반응 용매는 클로로벤젠, 톨루엔 및 자일렌으로 이루어진 군으로부터 선택된 적어도 하나의 비극성 용매를 포함하는 것을 특징으로 하는 희토류 금속 함유 이분자계 착화합물의 제조 방법. The method of claim 7,
Wherein the reaction solvent in steps (S1) and (S2) comprises at least one non-polar solvent selected from the group consisting of chlorobenzene, toluene and xylene.
상기 비극성 용매는 반응물 전체 100 중량부에 대하여 50 내지 90 중량부로 포함되는 것을 특징으로 하는 희토류 금속 함유 이분자계 착화합물의 제조 방법. The method of claim 12,
Wherein the non-polar solvent is contained in an amount of 50 to 90 parts by weight based on 100 parts by weight of the total reactants.
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