KR101737171B1 - High refractive index acrylic compound and method for preparing the same - Google Patents
High refractive index acrylic compound and method for preparing the same Download PDFInfo
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- KR101737171B1 KR101737171B1 KR1020140076807A KR20140076807A KR101737171B1 KR 101737171 B1 KR101737171 B1 KR 101737171B1 KR 1020140076807 A KR1020140076807 A KR 1020140076807A KR 20140076807 A KR20140076807 A KR 20140076807A KR 101737171 B1 KR101737171 B1 KR 101737171B1
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- -1 acrylic compound Chemical class 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000000732 arylene group Chemical group 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 229940043279 diisopropylamine Drugs 0.000 claims description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 8
- 150000002367 halogens Chemical class 0.000 abstract description 8
- 125000002947 alkylene group Chemical group 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 235000019439 ethyl acetate Nutrition 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000012230 colorless oil Substances 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000005693 optoelectronics Effects 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- BXAVKNRWVKUTLY-UHFFFAOYSA-N 4-sulfanylphenol Chemical compound OC1=CC=C(S)C=C1 BXAVKNRWVKUTLY-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- SXIWNIQDOJKDGB-UHFFFAOYSA-N dichloro-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound ClP(Cl)(=S)C1=CC=CC=C1 SXIWNIQDOJKDGB-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical class CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LHWWETDBWVTKJO-UHFFFAOYSA-N et3n triethylamine Chemical compound CCN(CC)CC.CCN(CC)CC LHWWETDBWVTKJO-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
Abstract
본 발명의 아크릴계 화합물은 하기 화학식 1로 표시되는 것을 특징으로 한다. 상기 아크릴계 화합물은 할로겐 원소를 포함하지 않으며, 굴절률 1.65 이상의 고굴절률을 갖는다.
[화학식 1]
상기 화학식 1에서, R1 및 R2는 각각 독립적으로 탄소수 2 내지 10의 알킬렌기, 탄소수 6 내지 20의 아릴렌기, 탄소수 7 내지 20의 알킬아릴렌기 또는 아릴알킬렌기이고, Ar1은 탄소수 6 내지 10의 아릴기이고, X1 및 X2는 각각 독립적으로 -O- 또는 -S-이고, Y1 및 Y2는 각각 독립적으로 수소 원자, -OH, -NH2, 또는 
[Chemical Formula 1]
R 1 and R 2 are each independently an alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group or an arylalkylene group having 7 to 20 carbon atoms, Ar 1 is a group having 6 to 20 carbon atoms, X 1 and X 2 are each independently -O- or -S-, Y 1 and Y 2 are each independently a hydrogen atom, -OH, -NH 2 , or
Description
본 발명은 고굴절률 아크릴계 화합물 및 이의 제조방법에 관한 것이다. 보다 구체적으로 본 발명은 할로겐 원소를 포함하지 않는 굴절률 1.65 이상의 고굴절률 아크릴계 화합물 및 이의 제조방법에 관한 것이다.
The present invention relates to a high refractive index acrylic compound and a method for producing the same. More specifically, the present invention relates to a high refractive index acrylic compound having a refractive index of 1.65 or more that does not contain a halogen element, and a method for producing the same.
첨단 과학기기의 제조를 위한 기능성 소재들이 지속적으로 개발되고 있다. 특히, 고굴절률 고분자(Highly Refractive Index Polymers: HRIP)는 디스플레이 소자용 기판(substrate) 재료, OLED 소자용 광학접착제, 캡슐소자, 광학 기기용 반사방지 코팅용 재료, 광학 필름, 금속 산화막 반도체(CMOS) 이미지 센서(CIS) 등의 광전자 소재에서의 응용 가능성으로 인해 큰 주목을 받고 있다. 기존 고분자들의 굴절률(n)은 1.30 내지 1.60 범위 안에 있으나, CMOS 이미지 센서용 고분자 마이크로렌즈 등의 광전자 소재는 1.65 이상의 고굴절률이 요구되는 경우가 많다. 예를 들면, 고광도 LED의 경우, 반도체 다이(굴절률: 2.50 내지 3.50)와 통상의 고분자 캡슐소자(굴절률: 1.40 내지 1.60) 사이의 n값(굴절률) 격차는 특정 입사각에서 빛이 다이를 지나 캡슐소자를 투과할 때 내부 전반사를 유발하고, 이에 따라, 광추출 효율을 저하시킬 우려가 있다. 즉, 이러한 단점을 해결하기 위해서는, 굴절률 1.65 이상의 고굴절률 화합물을 캡슐소자에 적용하여, 캡슐소자와 반도체 다이와의 굴절률 격차를 줄여야 한다. 이와 같이, 많은 광전자 소재들이 고굴절률을 가지는 화합물의 적용을 요구하기 때문에, 새로운 고굴절률 화합물의 디자인과 합성기술이 매우 중요하다.Functional materials for the production of advanced scientific instruments are continuously being developed. In particular, HRED (Highly Refractive Index Polymers) (HRIP) is widely used as a substrate material for display devices, optical adhesives for OLED devices, encapsulants, antireflection coating materials for optical devices, optical films, metal oxide semiconductor (CMOS) Image sensors (CIS), and the like. The refractive index (n) of existing polymers is in the range of 1.30 to 1.60, but the optoelectronic materials such as polymer microlenses for CMOS image sensors often require a high refractive index of 1.65 or more. For example, in the case of a high brightness LED, the n value (refractive index) difference between a semiconductor die (refractive index: 2.50 to 3.50) and a conventional polymer encapsulating element (refractive index: 1.40 to 1.60) Thereby causing total internal reflection, which may lower the light extraction efficiency. That is, in order to solve such a disadvantage, it is necessary to apply a high-refractive index compound having a refractive index of 1.65 or more to the capsule element to reduce the refractive index difference between the capsule element and the semiconductor die. Thus, since many optoelectronic materials require the application of high refractive index compounds, the design and synthesis techniques of new high refractive index compounds are very important.
고굴절률 화합물을 합성하기 위한 방법으로, 화합물에 할로겐 원자를 도입하여 분자 내 분극률을 높이는 방법이 사용될 수 있다. 그러나, 할로겐 원자를 포함하는 고굴절률 화합물을 광전자 소재에 적용할 경우, 황변 등의 물성 저하, 환경 오염 등의 문제가 발생할 우려가 있다.As a method for synthesizing a high refractive index compound, a method of increasing the intramolecular polarization ratio by introducing a halogen atom into the compound may be used. However, when a high-refractive index compound containing a halogen atom is applied to an optoelectronic material, problems such as deterioration of physical properties such as yellowing and environmental pollution may occur.
따라서, 광전자 소재 등에 사용이 가능한 할로겐 원소를 포함하지 않는 굴절률 1.65 이상의 고굴절률 화합물의 개발이 필요한 실정이다.Therefore, it is necessary to develop a high-refractive index compound having a refractive index of 1.65 or more that does not contain a halogen element which can be used for optoelectronic materials and the like.
본 발명의 목적은 할로겐 원소를 포함하지 않는 굴절률 1.65 이상의 고굴절률 아크릴계 화합물 및 이의 제조방법을 제공하기 위한 것이다.It is an object of the present invention to provide a high refractive index acrylic compound having a refractive index of 1.65 or more that does not contain a halogen element and a method for producing the same.
본 발명의 상기 및 기타의 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.
The above and other objects of the present invention can be achieved by the present invention described below.
본 발명의 한 관점은 아크릴계 화합물에 관한 것이다. 상기 아크릴계 화합물은 하기 화학식 1로 표시되는 것을 특징으로 한다:One aspect of the present invention relates to acrylic compounds. The acrylic compound is represented by the following general formula (1)
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, R1 및 R2는 각각 독립적으로 탄소수 2 내지 10의 알킬렌기, 탄소수 6 내지 20의 아릴렌기, 탄소수 7 내지 20의 알킬아릴렌기 또는 아릴알킬렌기이고, Ar1은 탄소수 6 내지 10의 아릴기이고, X1 및 X2는 각각 독립적으로 -O- 또는 -S-이고, Y1 및 Y2는 각각 독립적으로 수소 원자, -OH, -NH2, 또는 
구체예에서, 상기 아크릴계 화합물은 하기 화학식 1a 내지 1f로 표시되는 화합물 중 1종 이상을 포함할 수 있다:In an embodiment, the acrylic compound may include at least one of the compounds represented by the following formulas (1a) to (1f):
[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)
상기 화학식 1a 내지 1f에서, R3, Ar1, X1, X2, X3, n1 및 n2는 상기 화학식 1에서 정의한 바와 같다.In the above formulas (1a) to (1f), R 3 , Ar 1 , X 1 , X 2 , X 3 , n 1 and n 2 are as defined in the above formula (1).
구체예에서, 상기 아크릴계 화합물은 굴절률이 1.65 내지 1.75일 수 있다.In an embodiment, the acrylic compound may have a refractive index of 1.65 to 1.75.
본 발명의 다른 관점은 상기 아크릴계 화합물의 제조방법에 관한 것이다. 상기 제조방법은 하기 화학식 2로 표시되는 황 함유 인계 화합물과 하기 화학식 3으로 표시되는 아크릴로일 할라이드 화합물을 반응시키는 단계를 포함하는 것을 특징으로 한다:Another aspect of the present invention relates to a method for producing the acrylic compound. The method comprises reacting a sulfur-containing phosphorus compound represented by the following formula (2) with an acryloyl halide compound represented by the following formula (3)
[화학식 2](2)
상기 화학식 2에서, R1, R2, Ar1, X1, X2, n1 및 n2는 상기 화학식 1에서 정의한 바와 같고, Z1 및 Z2는 각각 독립적으로 수소 원자, -OH 또는 -NH2이고, Z1 및 Z2 중 적어도 하나는 -OH 또는 -NH2이다;Wherein R 1 , R 2 , Ar 1 , X 1 , X 2 , n 1 and n 2 are as defined in Formula 1, Z 1 and Z 2 are each independently a hydrogen atom, NH 2 , and at least one of Z 1 and Z 2 is -OH or -NH 2 ;
[화학식 3](3)
상기 화학식 3에서, R3는 수소 원자 또는 메틸기이고, X는 할로겐 원자이다.In Formula 3, R 3 is a hydrogen atom or a methyl group, and X is a halogen atom.
구체예에서, 상기 반응은 염기성 촉매 존재 하에 -10 내지 10℃에서 수행될 수 있다.In embodiments, the reaction may be carried out at -10 to 10 < 0 > C in the presence of a basic catalyst.
구체예에서, 상기 염기성 촉매는 트리에틸아민, 트리부틸아민,디이소프로필아민, 테트라메틸에틸렌디아민, 피리딘, 수산화나트륨, 수산화칼륨, 탄산칼륨, 디부틸틴디라우레이트 및 아민 착화합물 중 1종 이상을 포함할 수 있다.In an embodiment, the basic catalyst comprises at least one of triethylamine, tributylamine, diisopropylamine, tetramethylethylenediamine, pyridine, sodium hydroxide, potassium hydroxide, potassium carbonate, dibutyltin dilaurate and amine complexes .
구체예에서, 상기 반응은 용매 중에서 수행되며, 상기 용매는 테트라히드로퓨란, 클로로포름, 디클로로메탄, N-메틸피롤리돈, 메틸설폭사이드, N,N-디메틸아세트아미드, 디옥산, 알코올, 벤젠, 톨루엔, 디메톡시에탄, 아세토니트릴 및 물 중 1종 이상을 포함할 수 있다.In an embodiment, the reaction is carried out in a solvent, wherein the solvent is selected from the group consisting of tetrahydrofuran, chloroform, dichloromethane, N-methylpyrrolidone, methylsulfoxide, N, N-dimethylacetamide, dioxane, Toluene, dimethoxyethane, acetonitrile, and water.
구체예에서, 상기 황 함유 인계 화합물은 하기 화학식 4로 표시되는 화합물과 하기 화학식 5a로 표시되는 화합물 및 하기 화학식 5b로 표시되는 화합물을 반응시켜 제조한 것일 수 있다: In an embodiment, the sulfur-containing phosphorus compound may be prepared by reacting a compound represented by the following formula (4) with a compound represented by the following formula (5a) and a compound represented by the following formula (5b)
[화학식 4][Chemical Formula 4]
상기 화학식 4에서, Ar1은 상기 화학식 1에서 정의한 바와 같고, X는 할로겐 원자이다;In Formula 4, Ar 1 is as defined in Formula 1, and X is a halogen atom;
[화학식 5a][Chemical Formula 5a]
[화학식 5b][Chemical Formula 5b]
상기 화학식 5a 및 5b에서, R1, R2, X1, X2, n1 및 n2는 상기 화학식 1에서 정의한 바와 같고, Z1 및 Z2는 수소원자, -OH 또는 -NH2이고, Z1 및 Z2 중 적어도 하나는 -OH 또는 -NH2이다.Wherein R 1 , R 2 , X 1 , X 2 , n 1 and n 2 are as defined in Formula 1, Z 1 and Z 2 are each a hydrogen atom, -OH or -NH 2 , At least one of Z 1 and Z 2 is -OH or -NH 2 .
구체예에서, 상기 반응은 염기성 촉매 존재 하에 -10 내지 50℃에서 수행될 수 있다.
In embodiments, the reaction may be carried out at -10 to 50 < 0 > C in the presence of a basic catalyst.
본 발명은 할로겐 원소를 포함하지 않으며, 굴절률이 1.65 이상인 신규한 구조의 고굴절률 아크릴계 화합물 및 이의 제조방법을 제공하는 발명의 효과를 가진다. 상기 아크릴계 화합물은 할로겐 원소에 의한 환경 오염, 물성 저하 등을 방지할 수 있고, 고굴절률을 가지므로, 광전자 소재로서 유용하다.
INDUSTRIAL APPLICABILITY The present invention has the effect of providing a high refractive index acrylic compound having a novel structure which does not contain a halogen element and has a refractive index of 1.65 or more and a method for producing the same. The acrylic compound can prevent environmental pollution and deterioration of properties due to a halogen element, and has high refractive index, so that it is useful as an optoelectronic material.
이하, 본 발명을 상세히 설명하면, 다음과 같다. Hereinafter, the present invention will be described in detail.
본 발명에 따른 아크릴계 화합물은 할로겐 원소를 포함하지 않으며, 굴절률이 1.65 이상인 신규한 구조의 고굴절률 화합물로서, 하기 화학식 1로 표시되는 것을 특징으로 한다.The acrylic compound according to the present invention is a high refractive index compound having a novel structure which does not contain a halogen element and has a refractive index of 1.65 or more, and is characterized by being represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, R1 및 R2는 각각 독립적으로 탄소수 2 내지 10의 알킬렌기, 탄소수 6 내지 20의 아릴렌기, 탄소수 7 내지 20의 알킬아릴렌기 또는 아릴알킬렌기이고, Ar1은 탄소수 6 내지 10의 아릴기이고, X1 및 X2는 각각 독립적으로 -O- 또는 -S-이고, Y1 및 Y2는 각각 독립적으로 수소 원자, -OH, -NH2, 또는 
구체예에서, 상기 아크릴계 화합물은 하기 화학식 1a 내지 1f로 표시되는 화합물 중 1종 이상을 포함할 수 있으나, 이에 제한되지 않는다. 이 중, 아크릴 기능기가 두 개인 화합물에 비하여, 아크릴 기능기가 하나인 화합물이 고굴절률을 발현하는데 유리할 수 있다.In an embodiment, the acrylic compound may include at least one compound represented by the following general formulas (1) to (1f), but is not limited thereto. Among them, a compound having one acrylic functional group as compared to a compound having two acrylic functional groups may be advantageous for expressing high refractive index.
[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)
상기 화학식 1a 내지 1f에서, R3, Ar1, X1, X2, X3, n1 및 n2는 상기 화학식 1에서 정의한 바와 같다.
In the above formulas (1a) to (1f), R 3 , Ar 1 , X 1 , X 2 , X 3 , n 1 and n 2 are as defined in the above formula (1).
구체예에서, 본 발명의 아크릴계 화합물은 굴절률(Refractive Index: RI)이 1.65 이상, 예를 들면 1.65 내지 1.75일 수 있다. 상기 범위에서 광전자 소재 등에 적용 시, 광추출 효율 등의 물성 저하, 황변 발생 등을 저감할 수 있다.
In an embodiment, the acrylic compound of the present invention may have a refractive index (RI) of 1.65 or more, for example, 1.65 to 1.75. When applied to an optoelectronic material or the like in the above range, deterioration of properties such as light extraction efficiency and yellowing can be reduced.
본 발명의 아크릴계 화합물은 예를 들면, 하기 화학식 2로 표시되는 황 함유 인계 화합물과 하기 화학식 3으로 표시되는 아크릴로일 할라이드 화합물을 반응시켜 제조할 수 있다.The acrylic compound of the present invention can be produced, for example, by reacting a sulfur-containing phosphorus compound represented by the following formula (2) with an acryloyl halide compound represented by the following formula (3).
[화학식 2](2)
상기 화학식 2에서, R1, R2, Ar1, X1, X2, n1 및 n2는 상기 화학식 1에서 정의한 바와 같고, Z1 및 Z2는 각각 독립적으로 수소 원자, -OH 또는 -NH2이고, Z1 및 Z2 중 적어도 하나는 -OH 또는 -NH2이다;Wherein R 1 , R 2 , Ar 1 , X 1 , X 2 , n 1 and n 2 are as defined in Formula 1, Z 1 and Z 2 are each independently a hydrogen atom, NH 2 , and at least one of Z 1 and Z 2 is -OH or -NH 2 ;
[화학식 3](3)
상기 화학식 3에서, R3는 수소 원자 또는 메틸기이고, X는 염소 원자(Cl), 브롬 원자(Br), 요오드 원자(I) 등의 할로겐 원자이다.In Formula 3, R 3 is a hydrogen atom or a methyl group, and X is a halogen atom such as a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I).
구체예에서, 상기 반응은 상기 황 함유 인계 화합물와 상기 아크릴로일 할라이드 화합물의 축합 반응으로서, 상기 황 함유 인계 화합물에서는 말단 -OH 또는 -NH2(Z1 및/또는 Z2)의 수소 원자가 상기 아크릴로일 할라이드 화합물에서는 할로겐 원자(X)가 떨어져 HX가 만들어지면서 상기 황 함유 인계 화합물와 상기 아크릴로일 할라이드 화합물이 에스테르 또는 아미드 결합을 형성하는 것이다. 상기 반응은 염기성 촉매 존재 하에 -10 내지 10℃, 예를 들면 -5 내지 5℃에서 30분 내지 20시간, 예를 들면 1시간 내지 10시간 동안 수행될 수 있다. 상기 범위에서 고수율로 아크릴계 화합물을 제조할 수 있다.In an embodiment, the reaction is a condensation reaction between the sulfur-containing phosphorus compound and the acryloyl halide compound. In the sulfur-containing phosphorus compound, hydrogen atoms of the terminal -OH or -NH 2 (Z 1 and / or Z 2 ) In the royl halide compound, the halogen atom (X) is reduced and HX is produced, so that the sulfur-containing phosphorus compound and the acryloyl halide compound form an ester or amide bond. The reaction may be carried out in the presence of a basic catalyst at -10 to 10 ° C, for example, at -5 to 5 ° C for 30 minutes to 20 hours, for example 1 hour to 10 hours. The acrylic compound can be produced in the above range at a high yield.
구체예에서, 상기 반응 시, 상기 황 함유 인계 화합물과 상기 아크릴로일 할라이드 화합물의 몰비(황 함유 인계 화합물:아크릴로일 할라이드 화합물)는 제조하고자 하는 아크릴계 화합물의 (메타)아크릴레이트기(
구체예에서, 상기 염기성 촉매는 트리에틸아민, 트리부틸아민, 디이소프로필아민, 테트라메틸에틸렌디아민, 피리딘, 수산화나트륨, 수산화칼륨, 탄산칼륨, 디부틸틴디라우레이트, 아민 착화합물, 이들의 혼합물 등을 포함할 수 있다.In an embodiment, the basic catalyst is selected from the group consisting of triethylamine, tributylamine, diisopropylamine, tetramethylethylenediamine, pyridine, sodium hydroxide, potassium hydroxide, potassium carbonate, dibutyltin dilaurate, amine complexes, . ≪ / RTI >
상기 염기성 촉매의 사용량은 상기 황 함유 인계 화합물 및 아크릴로일 할라이드 화합물 100 몰부에 대하여, 100 내지 220 몰부, 예를 들면 100 내지 150 몰부일 수 있다. 상기 범위에서 고수율로 아크릴계 화합물을 제조할 수 있다.The amount of the basic catalyst to be used may be 100 to 220 moles, for example, 100 to 150 moles per 100 moles of the sulfur-containing phosphorus compound and the acryloyl halide compound. The acrylic compound can be produced in the above range at a high yield.
구체예에서, 상기 반응은 용매 중에서 수행될 수 있으며, 상기 상기 용매는 테트라히드로퓨란, 클로로포름, 디클로로메탄, N-메틸피롤리돈, 메틸설폭사이드, N,N-디메틸아세트아미드, 디옥산, 알코올, 벤젠, 톨루엔, 디메톡시에탄, 아세토니트릴, 물, 이들의 혼합물 등을 포함할 수 있다.In an embodiment, the reaction may be carried out in a solvent, wherein the solvent is selected from the group consisting of tetrahydrofuran, chloroform, dichloromethane, N-methylpyrrolidone, methylsulfoxide, N, N-dimethylacetamide, dioxane, , Benzene, toluene, dimethoxyethane, acetonitrile, water, mixtures thereof, and the like.
상기 용매의 사용량은 상기 황 함유 인계 화합물 및 아크릴로일 할라이드 화합물 100 중량부에 대하여, 300 내지 800 중량부, 예를 들면 400 내지 500 중량부일 수 있다. 상기 범위에서 사용 용매 대비 높은 수율을 올릴 수 있다.The amount of the solvent to be used may be 300 to 800 parts by weight, for example, 400 to 500 parts by weight, based on 100 parts by weight of the sulfur-containing phosphorus compound and the acryloyl halide compound. Within this range, a higher yield relative to the solvent used can be obtained.
구체예에서, 상기 화학식 1로 표시되는 아크릴계 화합물의 
구체예에서, 상기 황 함유 인계 화합물은 하기 화학식 4로 표시되는 화합물과 하기 화학식 5a로 표시되는 화합물 및 하기 화학식 5b로 표시되는 화합물을 (축합) 반응시켜 제조한 것일 수 있다.In an embodiment, the sulfur-containing phosphorus compound may be prepared by condensing a compound represented by the following formula (4) with a compound represented by the following formula (5a) and a compound represented by the following formula (5b).
[화학식 4][Chemical Formula 4]
상기 화학식 4에서, Ar1은 상기 화학식 1에서 정의한 바와 같고, X는 염소 원자(Cl), 브롬 원자(Br), 요오드 원자(I) 등의 할로겐 원자이다;In the formula (4), Ar 1 is as defined in the above formula (1), and X is a halogen atom such as a chlorine atom (Cl), a bromine atom (Br) or an iodine atom (I);
[화학식 5a][Chemical Formula 5a]
[화학식 5b][Chemical Formula 5b]
상기 화학식 5a 및 5b에서, R1, R2, X1, X2, n1 및 n2는 상기 화학식 1에서 정의한 바와 같고, Z1 및 Z2는 수소원자, -OH 또는 -NH2이고, Z1 및 Z2 중 적어도 하나는 -OH 또는 -NH2이다.Wherein R 1 , R 2 , X 1 , X 2 , n 1 and n 2 are as defined in Formula 1, Z 1 and Z 2 are each a hydrogen atom, -OH or -NH 2 , At least one of Z 1 and Z 2 is -OH or -NH 2 .
상기 반응은 염기성 촉매 존재 하에 -10 내지 50℃, 예를 들면 -5 내지 30℃에서 30분 내지 20시간, 예를 들면 1시간 내지 10시간 동안 수행될 수 있다. 보다 구체적으로 상기 화학식 5a 내지 5b로 표시되는 화합물 투입 시 -10 내지 5℃에서 교반하다가 투입 완료 후, 5 내지 50℃, 예를 들면 10 내지 30℃의 온도로 조절하는 것일 수 있다. 상기 범위에서 보다 고수율로 상기 황 함유 인계 화합물을 제조할 수 있다.The reaction can be carried out in the presence of a basic catalyst at -10 to 50 ° C, for example, at -5 to 30 ° C for 30 minutes to 20 hours, for example 1 hour to 10 hours. More specifically, when the compound represented by the above general formulas (5a) to (5b) is added, the mixture is stirred at -10 to 5 ° C, and after the completion of the addition, the temperature is adjusted to 5 to 50 ° C, for example, 10 to 30 ° C. The sulfur-containing phosphorus compound can be produced at a higher yield in the above range.
구체예에서, 상기 반응 시, 상기 화학식 4로 표시되는 화합물과 상기 화학식 5a 및/또는 5b로 표시되는 화합물의 몰비(화학식 4:화학식 5a 및/또는 5b)는 1 : 2 내지 1 : 2.2일 수 있으나, 이에 제한되지 않는다.In an embodiment, the molar ratio of the compound represented by Formula 4 and the compound represented by Formula 5a and / or 5b (Formula 5a and / or 5b) may be 1: 2 to 1: 2.2 But is not limited thereto.
구체예에서, 상기 반응은 용매 중에서 수행될 수 있으며, 상기 염기성 촉매 및 용매로는 상기 황 함유 인계 화합물과 상기 아크릴로일 할라이드 화합물의 반응 시에 사용되는 염기성 촉매 및 용매가 사용될 수 있다.In an embodiment, the reaction may be performed in a solvent, and the basic catalyst and the solvent may be a basic catalyst and a solvent used in the reaction of the sulfur-containing phosphorus compound and the acryloyl halide compound.
상기 염기성 촉매의 사용량은 상기 반응물(화학식 4 및 화학식 5a 및/또는 5b의 화합물) 100 몰부에 대하여, 100 내지 200 몰부, 예를 들면 100 내지 150 몰부일 수 있다. 상기 범위에서 고수율로 상기 황 함유 인계 화합물을 제조할 수 있다.The amount of the basic catalyst to be used may be 100 to 200 moles, for example, 100 to 150 moles, per 100 moles of the reactants (the compounds of Chemical Formulas 4 and 5a and / or 5b). The sulfur-containing phosphorus compound can be produced in the above range at a high yield.
또한, 상기 용매의 사용량은 상기 반응물 100 중량부에 대하여, 300 내지 800 중량부, 예를 들면 400 내지 500 중량부일 수 있다. 상기 범위에서 사용 용매 대비 높은 수율을 올릴 수 있다.
The amount of the solvent may be 300 to 800 parts by weight, for example, 400 to 500 parts by weight based on 100 parts by weight of the reactant. Within this range, a higher yield relative to the solvent used can be obtained.
이하, 본 발명의 바람직한 실시예를 통해 본 발명의 구성 및 작용을 더욱 상세히 설명하기로 한다. 다만, 하기 실시예는 본 발명의 이해를 돕기 위한 것으로, 본 발명의 범위가 하기 실시예에 한정되지는 않는다. 여기에 기재되지 않은 내용은 이 기술 분야에서 숙련된 자이면 충분히 기술적으로 유추할 수 있는 것이므로 그 설명을 생략하기로 한다.
Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples. The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.
실시예 Example
제조예 1: 화학식 4-1로 표시되는 화합물의 제조Preparation Example 1: Preparation of the compound represented by the formula (4-1)
페닐렌티오포스포닉 디클로라이드(phenylthiophosphonic dichloride) 2.11 g(10 mmol)을 테트라히드로퓨란(THF) 30 mL로 희석한 용액을 얼음 배쓰(bath)를 이용하여 0℃로 냉각시킨 다음, 트리에틸아민(triethylamine) 1.14 g(11 mmol)을 첨가하였다. 다음으로, 티오페놀(thiophenol) 1.1 g(10 mmol)을 THF 10 mL에 희석한 용액을 적가 깔대기(dropping funnel)를 이용하여 상기 용액에 천천히 첨가하였다. 온도를 0℃로 유지한 채 트리에틸아민(triethylamine) 1.14 g, (11 mmol을 첨가하고, 4-아미노벤젠티올(4-aminobenzenthiol) 1.25 g(10 mmol)을 THF (6 mL)에 희석한 용액을 적가 깔대기(dropping funnel)를 이용하여 상기 용액에 천천히 첨가하였다. 첨가가 끝나면 얼음 배쓰를 제거하고, 2시간 정도 교반하여 반응시켰다. 반응 종결 후, 반응 용액을 필터(filter)하여 아민염(amine salts)을 제거하고, 감압증류하여 과량의 용매를 제거하였다. 농축된 유기물에 에틸아세테이트(EtOAC) 100 mL를 첨가하고 5% 염산(HCl) 80 mL와 수산화 나트륨 수용액(aq. NaOH, 2M) 100 mL로 씻어준 뒤, 유기층을 감압증류하였다. 다음으로, 칼럼크로마토그래피(SiO2, ethyl acetate : hexane = 1 : 2)를 이용하여 최종 화합물인 하기 화학식 4-1로 표시되는 화합물을 분리하였다{무색 오일(colorless oil), 수율: 85%, 굴절률(RI): 1.73, 1H-NMR (300 MHz, CDCl3) : δ 7.98-7.90 (m, 2H), 7.51-7.39 (m, 6H), 7.38-7.26 (m, 2H), 7.17-7.13 (m, 2H), 6.59-6.55 (m, 2H)}.A solution of phenylthiophosphonic dichloride (2.11 g, 10 mmol) in tetrahydrofuran (THF) (30 mL) was cooled to 0 ° C using an ice bath, and triethylamine triethylamine (1.14 g, 11 mmol). Next, a solution of 1.1 g (10 mmol) of thiophenol in 10 mL of THF was slowly added to the solution using a dropping funnel. A solution of 1.14 g (11 mmol) of triethylamine and 1.25 g (10 mmol) of 4-aminobenzenethiol in THF (6 mL) while maintaining the temperature at 0 ° C After completion of the reaction, the reaction solution was filtered to remove the amine salt (amine), and the reaction solution was added to the reaction solution, which was then added dropwise to the solution using a dropping funnel. 100 mL of ethyl acetate (EtOAc) was added to the concentrated organic material, and 80 mL of 5% hydrochloric acid (HCl) and 100 mL of an aqueous sodium hydroxide solution (aq. NaOH, 2M) were added to 100 mL of distilled water and distilled under reduced pressure to remove excess solvent. . after washed with mL, it was distilled under reduced pressure the organic layer was followed by column chromatography (SiO 2, ethyl acetate: hexane = 1: 2) using the following final compound was isolated compound represented by the formula {4-1 Colorless oil, yield: 85%, refractive index (RI): 1.73, 1 H-NMR (300 MHz, CDCl 3): δ 7.98-7.90 (m, 2H), 7.51-7.39 (m, 6H), 7.38-7.26 (m, 2H), 7.17-7.13 (m, 2H), 6.59-6.55 (m , 2H).
[화학식 4-1][Formula 4-1]
제조예 2: 화학식 4-2로 표시되는 화합물의 제조Production Example 2: Preparation of a compound represented by the formula (4-2)
상기 4-아미노벤젠티올 대신에 4-히드록시벤젠티올(4-hydroxybenzenethiol) 1.26 g(10 mmol)을 사용한 것을 제외하고는, 상기 제조예 1과 동일한 방법으로 하기 화학식 4-2로 표시되는 화합물을 제조하였다. 최종 화합물은 칼럼크로마토그래피(SiO2, ethyl acetate : hexane = 1/4)를 이용하여 분리하였다{무색 오일(colorless oil), 수율: 72%, 굴절률(RI): 1.69, 1H-NMR (300 MHz, CDCl3) : δ 7.99-7.91 (m, 2H), 7.52-7.35 (m, 6H), 7.31-7.23 (m, 5H), 6.74 (dd, J = 1.5, 6.6 Hz, 2H)}.4-2 was obtained in the same manner as in Preparation Example 1, except that 1.26 g (10 mmol) of 4-hydroxybenzenethiol was used in place of 4-aminobenzenethiol. . The final compound is purified by column chromatography (SiO 2, ethyl acetate: hexane = 1/4) were separated by using a {colorless oil (colorless oil), Yield: 72%, refractive index (RI): 1.69, 1 H -NMR (300 MHz, CDCl 3): δ 7.99-7.91 (m, 2H), 7.52-7.35 (m, 6H), 7.31-7.23 (m, 5H), 6.74 (dd, J = 1.5, 6.6 Hz, 2H)}.
[화학식 4-2][Formula 4-2]
실시예 1: 화학식 1-1로 표시되는 아크릴계 화합물의 제조Example 1: Preparation of acrylic compound represented by formula (1-1)
상기 화학식 4-1의 화합물 2.62 g(7.02 mmol)과 트리에틸아민(triethylamine) 0.71 g(7.02 mmol)을 THF 20 mL로 희석한 용액을 얼음 배쓰(bath)를 이용하여 0℃로 냉각시킨 다음, 아크릴로일 클로라이드(acroylyl chloride) 0.64 g(7.02 mmol)를 THF 8 mL로 희석한 용액을 천천히 첨가하고, 0℃에서 1 시간 동안 교반하여 반응시켰다. 반응 종결 후, 반응 용액을 필터(filter)하여 아민염(amine salts)을 제거하고, 감압증류하여 과량의 용매를 제거하였다. 농축된 유기물에 에틸아세테이트(EtOAC) 100 mL를 첨가하고 5% 염산(HCl) 80 mL와 수산화 나트륨 수용액(aq. NaOH, 2M) 100 mL로 씻어준 뒤, 유기층을 감압증류하였다. 다음으로, 칼럼크로마토그래피(SiO2, ethyl acetate : hexane = 1 : 2)를 이용하여 최종 화합물인 하기 화학식 1-1로 표시되는 화합물을 분리하였다{흰색 고체(white solid), 수율: 78%, 굴절률(RI): 1.72, 1H-NMR (300 MHz, CDCl3) : δ 7.98-7.93 (m, 2H), 7.53-7.51 (m, 3H), 7.45-7.39 (m, 5H), 7.38-7.25 (m, 5H), 6.42 (dd, J = 0.6, 10.2 Hz, 1H), 6.21 (dd, J = 6.3, 10.2 Hz, 1H), 5.77 (dd, J = 0.6, 6.3 Hz, 1H)}.A solution of 2.62 g (7.02 mmol) of the compound of Formula 4-1 and 0.71 g (7.02 mmol) of triethylamine in 20 mL of THF was cooled to 0 ° C using an ice bath, A solution of 0.64 g (7.02 mmol) of acryloyl chloride diluted with 8 mL of THF was added slowly, and the mixture was reacted at 0 DEG C for 1 hour with stirring. After completion of the reaction, the reaction solution was filtered to remove amine salts, and the excess solvent was removed by distillation under reduced pressure. To the concentrated organic material was added 100 mL of ethyl acetate (EtOAC), washed with 80 mL of 5% hydrochloric acid (HCl) and 100 mL of an aqueous sodium hydroxide solution (aq. NaOH, 2M), and then the organic layer was distilled off under reduced pressure. Next, the final compound, a compound represented by the following formula 1-1 was isolated using column chromatography (SiO 2 , ethyl acetate: hexane = 1: 2) (white solid, yield: 78% refractive index (RI): 1.72, 1 H -NMR (300 MHz, CDCl 3): δ 7.98-7.93 (m, 2H), 7.53-7.51 (m, 3H), 7.45-7.39 (m, 5H), 7.38-7.25 (m, 5H), 6.42 (dd, J = 0.6, 10.2 Hz, 1H), 6.21 (dd, J = 6.3, 10.2 Hz, 1H), 5.77 (dd, J = 0.6, 6.3 Hz, 1H).
[화학식 1-1][Formula 1-1]
실시예 2: 화학식 1-2로 표시되는 아크릴계 화합물의 제조Example 2: Preparation of acrylic compound represented by general formula (1-2)
상기 화학식 4-1의 화합물 대신에 상기 화학식 4-2의 화합물 2.19 g(5.8 mmol)을 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 하기 화학식 1-2로 표시되는 화합물을 제조하였다. 최종 화합물은 칼럼크로마토그래피(SiO2, ethyl acetate : hexane = 1/5)를 이용하여 분리하였다{무색 오일(colorless oil), 수율: 78%, 굴절률(RI): 1.685, 1H-NMR (300 MHz, CDCl3) : δ 8.00-7.92 (m, 2H), 7.53-7.32 (m, 10H), 7.09 (dd, J = 1.5, 6.6 Hz, 2H), 6.60 (dd, J = 1.2, 17.1 Hz, 1H), 6.29 (dd, J = 10.5, 17.4 Hz, 1H), 6.02 (dd, J = 1.2, 10.5 Hz, 1H)}.The compound represented by Formula 1-2 was prepared in the same manner as in Example 1 except that 2.19 g (5.8 mmol) of the compound of Formula 4-2 was used in place of the compound of Formula 4-1. The final compound is purified by column chromatography (SiO 2, ethyl acetate: hexane = 1/5) were separated by using a {colorless oil (colorless oil), Yield: 78%, refractive index (RI): 1.685, 1 H -NMR (300 MHz, CDCl 3): δ 8.00-7.92 (m, 2H), 7.53-7.32 (m, 10H), 7.09 (dd, J = 1.5, 6.6 Hz, 2H), 6.60 (dd, J = 1.2, 17.1 Hz, 1H), 6.29 (dd, J = 10.5, 17.4 Hz, 1H), 6.02 (dd, J = 1.2, 10.5 Hz, 1H).
[화학식 1-2][Formula 1-2]
실시예 3: 화학식 1-3으로 표시되는 아크릴계 화합물의 제조Example 3: Preparation of acrylic compound represented by formula 1-3
4-아미노벤젠티올(4-aminobenzenthiol) 25.04 g(200 mmol)을 THF 400 mL로 희석한 용액을 얼음 배쓰(bath)를 이용하여 0℃로 냉각시킨 다음, 트리에틸아민(triethylamine) 21.3 g(210 mmol)을 첨가하였다. 용액의 온도를 0℃로 유지한 채 페닐렌티오포스포닉 디클로라이드(phenylthiophosphonic dichloride) 21.1 g(100 mmol)를 THF 200 mL로 희석한 용액을 적가 깔대기(dropping funnel)를 이용하여 천천히 첨가하였다. 첨가가 끝나면 얼음 배쓰를 제거하고, 2시간 정도 교반하여 반응시켰다. 반응 종결 후, 반응 용액을 필터(filter)하여 아민염(amine salts)을 제거한 후, 0℃로 냉각시키고 트리에틸아민(triethylamine) 21.3 g(210 mmol)을 넣은 후, 아크릴로일 클로라이드(acroylyl chloride) 18.6 g(205 mmol)를 THF 100 mL로 희석한 용액을 천천히 첨가하고, 0℃에서 1 시간 동안 교반하여 반응시켰다. 반응 종결 후, 반응 용액을 필터(filter)하여 아민염(amine salts)을 제거하고, 감압증류하여 과량의 용매를 제거하였다. 농축된 유기물에 에틸아세테이트(EtOAC) 500 mL를 첨가하고 5% 염산(HCl) 200 mL와 수산화 나트륨 수용액(aq. NaOH, 2M) 300 mL로 씻어준 뒤, 유기층을 감압증류하였다. 다음으로, 칼럼크로마토그래피(SiO2, ethyl acetate : hexane = 2 : 1)를 이용하여 최종 화합물인 하기 화학식 1-3으로 표시되는 화합물을 분리하였다{흰색 고체(white solid), 수율: 64%, 굴절률(RI): 1.696, 1H-NMR (300 MHz, CDCl3) : δ 7.98-7.95 (m, 2H), 7.53-7.44 (m, 9H), 7.34-7.25 (m, 4H), 6.41 (dd, J = 0.9, 10.2 Hz, 1H), 6.23 (dd, J = 6.0, 9.9 Hz, 1H), 5.77 (dd, J = 0.6, 6.0 Hz, 1H)}.A solution of 25.04 g (200 mmol) of 4-aminobenzenethiol in 400 mL of THF was cooled to 0 ° C using an ice bath, and then 21.3 g (210 mmol) of triethylamine mmol). A solution of 21.1 g (100 mmol) of phenylthiophosphonic dichloride diluted with 200 mL of THF was added slowly using a dropping funnel while maintaining the temperature of the solution at 0 占 폚. When the addition was completed, the ice bath was removed, and the mixture was reacted by stirring for about 2 hours. After completion of the reaction, the reaction solution was filtered to remove amine salts, and the mixture was cooled to 0 ° C, and 21.3 g (210 mmol) of triethylamine was added thereto. Then, acroylyl chloride ) 18.6 g (205 mmol) in 100 mL of THF was added slowly, and the mixture was reacted at 0 DEG C for 1 hour with stirring. After completion of the reaction, the reaction solution was filtered to remove amine salts, and the excess solvent was removed by distillation under reduced pressure. To the concentrated organic material was added 500 mL of ethyl acetate (EtOAC), washed with 200 mL of 5% hydrochloric acid (HCl) and 300 mL of aqueous sodium hydroxide solution (aq. NaOH, 2M), and then the organic layer was distilled off under reduced pressure. Next, column chromatography (SiO 2, ethyl acetate: hexane = 2: 1) was the compound to the final separation of the compound represented by formula 1-3 using {white solid (white solid), yield: 64%, refractive index (RI): 1.696, 1 H -NMR (300 MHz, CDCl 3): δ 7.98-7.95 (m, 2H), 7.53-7.44 (m, 9H), 7.34-7.25 (m, 4H), 6.41 (dd , J = 0.9, 10.2 Hz, 1H), 6.23 (dd, J = 6.0, 9.9 Hz, 1H), 5.77 (dd, J = 0.6, 6.0 Hz, 1H).
[화학식 1-3][Formula 1-3]
실시예 4: 화학식 1-4로 표시되는 아크릴계 화합물의 제조Example 4: Preparation of acrylic compound represented by formula 1-4
상기 4-아미노벤젠티올 대신에 4-히드록시벤젠티올(4-hydroxybenzenethiol) 25.23 g(200 mmol)을 사용한 것을 제외하고는, 상기 실시예 3과 동일한 방법으로 하기 화학식 1-2로 표시되는 화합물을 제조하였다. 최종 화합물은 칼럼크로마토그래피(SiO2, ethyl acetate : hexane = 1/2)를 이용하여 분리하였다{무색 오일(colorless oil), 수율: 82%, 굴절률(RI): 1.657, 1H-NMR (300 MHz, CDCl3) : δ 7.95-7.93 (m, 2H), 7.53-7.51 (m, 1H), 7.47-7.40 (m, 6H), 7.10 dd, J = 1.8, 6.9 Hz, 4H), 6.59 (dd, J = 0.6, 10.2 Hz, 1H), 6.29 (dd, J = 6.3, 10.2 Hz, 1H), 6.01 (dd, J = 0.6, 6.0 Hz, 1H)}.(1-2) was obtained in the same manner as in Example 3, except that 25.23 g (200 mmol) of 4-hydroxybenzenethiol was used in place of 4-aminobenzenethiol. . The final compound is purified by column chromatography (SiO 2, ethyl acetate: hexane = 1/2) were separated by using a {colorless oil (colorless oil), Yield: 82%, refractive index (RI): 1.657, 1 H -NMR (300 MHz, CDCl 3): δ 7.95-7.93 (m, 2H), 7.53-7.51 (m, 1H), 7.47-7.40 (m, 6H), 7.10 dd, J = 1.8, 6.9 Hz, 4H), 6.59 (dd J = 0.6, 10.2 Hz, 1H), 6.29 (dd, J = 6.3, 10.2 Hz, 1H), 6.01 (dd, J = 0.6, 6.0 Hz, 1H).
[화학식 1-4][Formula 1-4]
실시예 5: 화학식 1-5로 표시되는 아크릴계 화합물의 제조Example 5: Preparation of acrylic compound represented by general formula (1-5)
상기 화학식 1-3의 아크릴계 화합물 0.18 g(0.37 mmol)을 디메틸포름아미드(Dimethylformamide: DMF)에 희석시킨 후, 0℃로 냉각하고 NaH 184 mg(1.6 mmol)를 첨가한 후, 30분간 교반하였다. 교반 후, 요오드화 메틸(methyl iodide) 227 mg(1.6 mmol)을 첨가하고, 상온에서 10시간 동안 교반하여 하기 화학식 1-5로 표시되는 아크릴계 화합물을 제조하였다. 최종 화합물은 칼럼크로마토그래피 (SiO2, ethyl acetate : hexane = 2 : 1)를 이용하여 분리하였다{흰색 고체(white solid), 수율: 82%, 굴절률(RI): 1.658, 1H-NMR (300 MHz, CDCl3) : δ 8.03-7.98 (m, 2H), 7.56-7.48 (m, 7H), 7.12-7.08 (m, 4H), 6.38 (dd, J = 0.9, 10.2 Hz, 1H), 6.03 (dd, J = 6.0, 9.9 Hz, 1H), 5.55 (dd, J = 0.6, 6.0 Hz, 1H), 3.34 (s, 6H)}.0.18 g (0.37 mmol) of the acrylic compound of Formula 1-3 was diluted with dimethylformamide (DMF), cooled to 0 캜, 184 mg (1.6 mmol) of NaH was added, and the mixture was stirred for 30 minutes. After stirring, 227 mg (1.6 mmol) of methyl iodide was added and stirred at room temperature for 10 hours to prepare an acrylic compound represented by the following Formula 1-5. The final compound is purified by column chromatography (SiO 2, ethyl acetate: hexane = 2: 1) were separated by using a {white solid (white solid), yield: 82%, refractive index (RI): 1.658, 1 H -NMR (300 MHz, CDCl 3): δ 8.03-7.98 (m, 2H), 7.56-7.48 (m, 7H), 7.12-7.08 (m, 4H), 6.38 (dd, J = 0.9, 10.2 Hz, 1H), 6.03 ( (dd, J = 6.0, 9.9 Hz, 1H), 5.55 (dd, J = 0.6, 6.0 Hz, 1H), 3.34 (s, 6H).
[화학식 1-5] [Formula 1-5]
실시예 6 내지 9: 화학식 1-6 내지 1-9로 표시되는 아크릴계 화합물의 제조Examples 6 to 9: Preparation of acrylic compounds represented by formulas 1-6 to 1-9
상기 실시예 1과 유사한 방법으로 하기 화학식 1-6, 1-7, 1-8 및 1-9로 표시되는 아크릴계 화합물이 제조됨을 확인하였으며, 각 화합물이 1.65 내지 1.75 범위의 굴절률을 가짐을 확인하였다.It was confirmed that acrylic compounds represented by the following Chemical Formulas 1-6, 1-7, 1-8 and 1-9 were prepared in a similar manner to Example 1, and that each compound had a refractive index in the range of 1.65 to 1.75 .
[화학식 1-6][Chemical Formula 1-6]
[화학식 1-7][Chemical Formula 1-7]
[화학식 1-8][Chemical Formula 1-8]
[화학식 1-9][Chemical Formula 1-9]
물성 측정 방법How to measure property
굴절률 측정: (1) 제조된 아크릴계 화합물이 액상일 경우, 유기 용매를 완벽히 제거한 다음, 그 자체를 굴절계(모델명: 3T, 제조사: 일본 ATAGO ABBE, 광원: 589.3 nm의 D광선 나트륨램프) 측정 표면에 얇게 펴 발라 측정하였다. Measurement of refractive index: (1) When the prepared acrylic compound is in a liquid state, the organic solvent is completely removed, and then the product itself is measured on a refractometer (model name: 3T, manufacturer: ATAGO ABBE, light source: 589.3 nm D- It was measured by spreading thinly.
(2) 제조된 아크릴계 화합물이 고체일 경우, 해당 고체가 용해될 수 있는 용매(DMSO(dimethyl sulfoxide), 굴절률: 1.479)에 희석하고, 그 자체를 굴절계(모델명: 3T, 제조사: 일본 ATAGO ABBE, 광원: 589.3 nm의 D광선 나트륨램프) 측정 표면에 얇게 펴 발라 측정하였다.
(2) When the prepared acrylic compound is a solid, it is diluted with a solvent (DMSO (dimethyl sulfoxide), refractive index: 1.479) in which the solid is dissolved, and the product is refracted by a refractometer (model: 3T, manufactured by ATAGO ABBE, Light source: 589.3 nm D-light sodium lamp) was measured by spreading thinly on the measurement surface.
상기 실시예의 결과로부터, 본원발명의 아크릴계 화합물은 할로겐 원소를 포함하지 않고도 굴절률 1.65 이상의 고굴절률을 얻을 수 있음을 알 수 있다.
From the results of the above example, it can be seen that the acrylic compound of the present invention can obtain a high refractive index with a refractive index of 1.65 or more without containing a halogen element.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
[화학식 1]
상기 화학식 1에서, R1 및 R2는 각각 독립적으로 탄소수 6 내지 20의 아릴렌기, 또는 탄소수 7 내지 20의 알킬아릴렌기 또는 아릴알킬렌기이고, Ar1은 탄소수 6 내지 10의 아릴기이고, X1 및 X2는 모두 -O- 또는 -S-이고, Y1 및 Y2는 각각 독립적으로 수소 원자, -OH, -NH2, 또는
An acrylic compound represented by the following formula (1) and having a refractive index of 1.65 to 1.75:
[Chemical Formula 1]
R 1 and R 2 are each independently an arylene group having 6 to 20 carbon atoms or an alkylarylene group or an arylalkylene group having 7 to 20 carbon atoms, Ar 1 is an aryl group having 6 to 10 carbon atoms, X 1 and X 2 are both -O- or -S-, Y 1 and Y 2 are each independently a hydrogen atom, -OH, -NH 2 , or
[화학식 1a]
[화학식 1b]
[화학식 1c]
상기 화학식 1a 내지 1c에서, R3, X1, X2, X3, n1 및 n2는 상기 화학식 1에서 정의한 바와 같다.
The acrylic compound according to claim 1, wherein the acrylic compound is one of compounds represented by the following formulas (1a) to (1c):
[Formula 1a]
[Chemical Formula 1b]
[Chemical Formula 1c]
Wherein R 3 , X 1 , X 2 , X 3 , n 1 and n 2 are the same as defined in the above formula (1).
[화학식 1]
상기 화학식 1에서, R1 및 R2는 각각 독립적으로 탄소수 6 내지 20의 아릴렌기, 또는 탄소수 7 내지 20의 알킬아릴렌기 또는 아릴알킬렌기이고, Ar1은 탄소수 6 내지 10의 아릴기이고, X1 및 X2는 모두 -O- 또는 -S-이고, Y1 및 Y2는 각각 독립적으로 수소 원자, -OH, -NH2, 또는
[화학식 2]
상기 화학식 2에서, R1, R2, Ar1, X1, X2, n1 및 n2는 상기 화학식 1에서 정의한 바와 같고, Z1 및 Z2는 각각 독립적으로 수소 원자, -OH 또는 -NH2이고, Z1 및 Z2 중 적어도 하나는 -OH 또는 -NH2이다;
[화학식 3]
상기 화학식 3에서, R3는 수소 원자 또는 메틸기이고, X는 할로겐 원자이다.
1. A method for producing an acrylic compound represented by the following formula (1), which comprises reacting a sulfur-containing phosphorus compound represented by the following formula (2) with an acryloyl halide compound represented by the following formula (3)
[Chemical Formula 1]
R 1 and R 2 are each independently an arylene group having 6 to 20 carbon atoms or an alkylarylene group or an arylalkylene group having 7 to 20 carbon atoms, Ar 1 is an aryl group having 6 to 10 carbon atoms, X 1 and X 2 are both -O- or -S-, Y 1 and Y 2 are each independently a hydrogen atom, -OH, -NH 2 , or
(2)
Wherein R 1 , R 2 , Ar 1 , X 1 , X 2 , n 1 and n 2 are as defined in Formula 1, Z 1 and Z 2 are each independently a hydrogen atom, NH 2 , and at least one of Z 1 and Z 2 is -OH or -NH 2 ;
(3)
In Formula 3, R 3 is a hydrogen atom or a methyl group, and X is a halogen atom.
5. The method of claim 4, wherein the reaction is carried out at -10 to 10 < 0 > C in the presence of a basic catalyst.
6. The process according to claim 5, wherein the basic catalyst comprises at least one of triethylamine, diisopropylamine, tetramethylethylenediamine, pyridine, sodium hydroxide, potassium hydroxide, potassium carbonate and dibutyltin dilaurate Of the acrylic compound.
5. The method of claim 4, wherein the reaction is carried out in a solvent, wherein the solvent is selected from the group consisting of tetrahydrofuran, chloroform, dichloromethane, N-methylpyrrolidone, methylsulfoxide, N, N-dimethylacetamide, dioxane, Benzene, dimethoxyethane, acetonitrile, and water. ≪ RTI ID = 0.0 > 11. < / RTI >
[화학식 4]
상기 화학식 4에서, Ar1은 상기 화학식 1에서 정의한 바와 같고, X는 할로겐 원자이다;
[화학식 5a]
[화학식 5b]
상기 화학식 5a 및 5b에서, R1, R2, X1, X2, n1 및 n2는 상기 화학식 1에서 정의한 바와 같고, Z1 및 Z2는 수소원자, -OH 또는 -NH2이고, Z1 및 Z2 중 적어도 하나는 -OH 또는 -NH2이다.
5. The process for preparing an acrylic compound according to claim 4, wherein the sulfur-containing phosphorus compound is prepared by reacting a compound represented by the following formula (4) with a compound represented by the following formula (5a) and a compound represented by the following formula (5b)
[Chemical Formula 4]
In Formula 4, Ar 1 is as defined in Formula 1, and X is a halogen atom;
[Chemical Formula 5a]
[Chemical Formula 5b]
Wherein R 1 , R 2 , X 1 , X 2 , n 1 and n 2 are as defined in Formula 1, Z 1 and Z 2 are each a hydrogen atom, -OH or -NH 2 , At least one of Z 1 and Z 2 is -OH or -NH 2 .
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| TW104119906A TWI632154B (en) | 2014-06-23 | 2015-06-22 | Acrylic compound, method for preparing the same, composition for optical patterns and optical sheet |
| US14/748,010 US20150368280A1 (en) | 2014-06-23 | 2015-06-23 | High refractive index acrylic compound and method for preparing the same |
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