WO2015016680A1 - 광반응성 화합물의 정제 방법 및 광반응성 화합물 - Google Patents
광반응성 화합물의 정제 방법 및 광반응성 화합물 Download PDFInfo
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- WO2015016680A1 WO2015016680A1 PCT/KR2014/007139 KR2014007139W WO2015016680A1 WO 2015016680 A1 WO2015016680 A1 WO 2015016680A1 KR 2014007139 W KR2014007139 W KR 2014007139W WO 2015016680 A1 WO2015016680 A1 WO 2015016680A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- the present invention relates to a method for purifying a photoreactive compound and a photoreactive compound. More specifically, the present invention relates to a method for purifying high-purity photoreactive compounds sensitive to light and heat by molecular distillation.
- TFT-LCDs which are driven by thin film transistors, independently drive individual pixels, and thus are able to realize high-quality moving images with excellent response speed of liquid crystals.
- the liquid crystal In order to use a liquid crystal as an optical switch in such a TFT-LCD, the liquid crystal must be initially oriented in a predetermined direction on a layer in which a thin film transistor is formed on the innermost side of a display cell.
- a method of aligning liquid crystals to date includes a rubbing process of rubbing and aligning an alignment film, a liquid crystal orientation (hereinafter referred to as photoalignment) process by light, and the like.
- Photo-alignment refers to a mechanism in which a photosensitive group bonded to a polymer by linearly polarized UV causes photoreaction, and in this process, the main chain of the polymer is aligned in a predetermined direction, thereby forming a photopolymerization type liquid crystal alignment layer in which the liquid crystal is oriented.
- Representative examples of such photoalignment include M. Schadt et al. (Jpn. J. Appl. Phys., VoBl A, 1992, 2155), Dae S. Kang et al. (US Pat. No. 5,464,669), Yuriy Reznikov (Jpn. J. Appl. Phys. Vol. 34, 1995, LI 000).
- polycinnamate-based polymers such as poly (vinyl cinnamate) (PVCN) and poly (vinyl methoxycinnamate (PVMC) are mainly used.
- PVN poly (vinyl cinnamate)
- PVMC poly (vinyl methoxycinnamate
- the double bond of cinnamate reacts with [2 + 2] cycloaddition to form cyclobutane by irradiated UV, resulting in anisotropic formation.
- the alignment of the liquid crystal molecules is induced by arranging the liquid crystal molecules in one direction.
- Exemplary photo-alignment polymers include a method for producing a polymeric alignment film having a side chain including photoreactive groups such as cinnamate groups in main chains of acrylates and methacrylates in JP-A-H11-181127 and the alignment films produced thereby Although it is disclosed, the thermal stability of the polymer backbone is poor and adversely affects the stability of the alignment layer. Also, it is not easy to control the photo reaction speed through the substituent of cinnamate.
- High purity photoreactive compounds are needed as monomers in order to produce high performance photo-aligned polymers.
- the photo-banung compounds are sensitive to light and heat and have high boiling point characteristics, making it difficult to purify them with high purity.
- an object of the present invention is to provide a method for purifying a photoreactive compound with high purity and a photoreactive compound.
- a crude product comprising any one or more photoreactors selected from Formula 2 to 4, and a photoreactive compound comprising a polymerizable unsaturated bond Preparing; Molecularly distilling the crude product comprising the photoreactive compound;
- It provides a method for purifying a photoreactive compound comprising the step of recovering the photo-banung compound.
- the step of molecular distillation of the crude product may be carried out at a temperature of 50 to 30 (TC and 0.01 to 100 mmbar)
- prior to the step of molecular distillation of the crude product may further comprise the step of preliminary distillation at a temperature of 20 to 200 ° C and a pressure of 0.01 to 100 mmbar.
- any one or more photoreactors selected from Formulas 2 to 4, and a polymerizable unsaturated bond and provides an optical semi-cyclic compound having an APHA value of less than 50.
- the photo-reflective compound can be purified with high purity, and the high-molecular weight photo-alignment polymer can be obtained using the purified photo-reflective compound in high yield.
- the photo-banung compound of the present invention includes any one or more photoreactors selected from Formulas 2 to 4, and a polymerizable unsaturated bond, and has an APHA value of less than 50.
- a high molecular weight photoalignment polymer can be obtained in high yield.
- a crude product including any one or more photo-reflective groups selected from the following Chemical Formulas 2 to 4, and an optically bin 1 reactive compound including a polymerizable unsaturated bond is prepared.
- A is a simple bond, substituted or unsubstituted CrC 20 alkylene, carbonyl, carboxy, substituted or unsubstituted C 6 -C 40 arylene and substituted or unsubstituted C 6 -C 40 heteroarylene Selected;
- B is a simple bond, oxygen, sulfur, or -NH-;
- X is oxygen or sulfur
- R 9 is a simple bond, substituted or unsubstituted C-C20 alkylene, substituted or unsubstituted c 2 -c 20 alkenylene, substituted or unsubstituted -cycloalkylene of- 2 , Substituted or unsubstituted c 6 -c 40 arylene, substituted or unsubstituted c 7 -c 15 aralkylene, and substituted or unsubstituted c 2 -c 20 alkynylene;
- Rio, Ru, R12, R 13 , and R 14 may be the same as or different from each other, and are each independently hydrogen, a hydroxy group, a halogen group, a substituted or unsubstituted aralkyl of 5 , a substituted or unsubstituted C 2 -C 20 Alkynyl, substituted or unsubstituted CrC 20 Alkyl, substituted or unsubstituted C, -C 20 Alkoxy, substituted or unsubstituted C 6 -C 30 Aryloxy, substituted or unsubstituted C 6 -C C 6 -C 40 hetero aryl containing 40 aryl, 14, 15, 16 heteroatoms, and substituted or unsubstituted C 6 -C 40 alkoxyaryl.
- the photo-banung compound may be a vinyl compound, a cycloolefin compound having a double bond or a (meth) acrylate compound.
- the photo-banung compounds may be represented by the formula (1).
- p is an integer from 0 to 4,
- At least one of R, R 2 , R 3 , and R 4 is a radical selected from the group consisting of the following Chemical Formulas 2, 3, and 4,
- the remains are each independently, hydrogen, halogen, substituted or unsubstituted - of C 20 alkyl, alkenyl substituted or unsubstituted C 2 -C 20, a substituted or unsubstituted C 3 - C 12 cyclo alkyl, substituted Or unsubstituted C 6 -C 40 aryl, substituted or unsubstituted -5 aralkyl;
- a polar functional group selected from the group consisting of substituted or unsubstituted C 2 -C 20 alkynyl and at least one non-hydrocarbonaceous polar group comprising at least one oxygen, nitrogen, phosphorus, sulfur, silicon, or boron ego,
- R, R 2 , R 3 , and R 4 are hydrogen, halogen, or a non-polar functional group, and Ri and R 2 , or R 3 and R 4 may be connected to each other to form an alkylidene group of d-do, or R, or R 2 is
- Chemical Formula 1 is a compound represented by Chemical Formula 2, and at least one of R 2 , R 3 , and R 4 may be selected from the group consisting of Chemical Formulas 2, 3, and 4 .
- the non-hydro carbonaceous polar group may include the following compound.
- It may include one or more selected from the group consisting of,
- Each R 5 in the functional group is substituted or unsubstituted -C 20 alkylene, Substituted or unsubstituted c 2 -c 20 alkenylene, substituted or unsubstituted 3 ⁇ 4- 2 cycloalkylene, substituted or unsubstituted c 6 -c 40 arylene, substituted or unsubstituted c 7 -c Aralkylene of 15 and substituted or unsubstituted alkynylene chain of c 2 -c 20 ,
- R 6 , R 7 , and R 8 are each independently hydrogen, halogen, substituted or unsubstituted CrC 20 alkyl, substituted or unsubstituted C 2 -C 20 alkenyl, substituted or unsubstituted C 3- for C 12 cyclo alkyl, a substituted or unsubstituted C 6 alkynyl can be selected from -C 40 aryl, substituted or unsubstituted C 7 -C 15 aralkyl and substituted or unsubstituted C 2 -C 20 of have.
- the heteroaryl group in the substituent of the C 6 -C 40 aryl, and Group 14, Group 15, or to a C 6 containing the interrogating element of Group 16 -C 40 is for containing the formula It may be.
- At least one of R ′ 10 to R ′ 18 in the formula is necessarily substituted or substituted alkoxy of -C 2 Q, or substituted or unsubstituted C 6 -C 30 aryloxy, and the rest are each independently substituted or unsubstituted.
- Alkyl means a straight or branched chain saturated monovalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms.
- the alkyl group is optionally substituted by one or more halogen substituents. Can be substituted.
- alkyl groups include methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, nucleus, dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, Dichloromethyl, trichloromethyl, iodomethyl, bromomethyl and the like.
- Alkenyl means a straight or branched chain monovalent hydrocarbon moiety of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms comprising at least one carbon-carbon backing bond. . Alkenyl groups may be bonded through a carbon atom comprising a carbon-carbon back bond or through a saturated carbon atom. Alkenyl groups may be optionally substituted by one or more halogen substituents. Examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-nucleenyl, dodecenyl, and the like.
- Cycloalkyl means a saturated or unsaturated non-aromatic monovalent monocyclic, bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons and may be optionally substituted by one or more halogen substituents. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclonuxyl, cyclonuxenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantyl, norbornyl (ie bicyclo [2,2, 1] hept-5-enyl).
- Aryl means a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 20, preferably 6 to 12 ring atoms, which may be optionally substituted by one or more halogen substituents or the like.
- Examples of the aryl group include phenyl, naphthalenyl, fluorenyl and the like.
- Alkoxyaryl means that at least one hydrogen atom of the aryl group as defined above is substituted with an alkoxy group.
- alkoxyaryl group examples include methoxyphenyl, ethoxyphenyl, propoxyphenyl, appendixylphenyl, phenoxyphenyl, nucleophenyl, Hepoxy, oxoxy, nanoxy, methoxy biphenyl, methoxy naphthalenyl, mesoxy fluorenyl, mesocyanracenyl, etc. are mentioned. '
- Alkyl means that at least one hydrogen atom of the alkyl group as defined above is substituted with an aryl group, and may be optionally substituted with one or more halogen substituents. For example, benzyl, benzhydryl, trityl, etc. are mentioned.
- Alkynyl means a monovalent hydrocarbon moiety of 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to 6, straight or branched chains containing at least one carbon-carbon triple bond. do. Alkynyl groups may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. Alkynyl groups may be optionally substituted by one or more halogen substituents. For example, ethynyl, propynyl, etc. are mentioned.
- Alkylene means a straight or branched chain saturated divalent hydrocarbon moiety of 1 to 20, preferably 1 to 10 , more preferably 1 to 6 carbon atoms. Alkylene groups may be optionally substituted by one or more halogen substituents. As an example of an alkyl group, methylene, ethylene, propylene, butylene, and nucleosilanes are mentioned.
- Alkenylene means a straight or branched chain divalent hydrocarbon moiety of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms comprising at least one carbon-carbon double bond. do. Alkenylene groups may be bonded through a carbon atom comprising a carbon-carbon back bond and / or through a saturated carbon atom. Alkenylene groups may be optionally substituted by one or more halogen substituents.
- Cycloalkylene means a saturated or unsaturated non-aromatic divalent monocyclic, bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons and may be optionally substituted by one or more halogen substituents. For example, cyclopropylene, cyclobutylene, etc. are mentioned.
- Arylene means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 20, preferably 6 to 12 ring atoms, which may be optionally substituted by one or more halogen substituents.
- the aromatic portion of an aryl group contains only carbon atoms. Phenylene as an example of arylene group Etc. can be mentioned.
- Alkylene means a divalent moiety wherein at least one hydrogen atom of the alkyl group as defined above is substituted with an aryl group, and may be optionally substituted by one or more halogen substituents. For example, benzylene etc. can be mentioned.
- Alkynylene 'is from 2 to 1 containing at least one carbon-carbon triple bond
- Alkynylene groups may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. Alkynylene groups may be optionally substituted by one or more halogen substituents. For example, ethynylene, propynylene, etc. are mentioned.
- the photoreactive compound represented by Formula 1 may be synthesized, for example, according to the method disclosed in Korean Patent Publication No. 2009-0047720.
- the crude product obtained according to the process contains not only the photoreactive compound but also impurities such as volatile compounds, or oligomers, including solvents and starting materials.
- molecular distillation is performed on the crude product containing the photoreactive compound.
- Alkenes, alkynes, alcohols, amines, thiols, phosphine compounds and other volatile compounds are very likely to act as substances which inhibit the polymerization activity by contaminating the catalyst during the polymerization reaction.
- the compounds may act as a chain transfer agent during the polymerization reaction to produce low molecular weight polymers smaller than the desired molecular weight. There is a need to remove various volatile compounds in order to prevent this problem.
- the oligomer remains in the final polymer to the end to inhibit thermal stability and to inhibit the optical and mechanical properties of the polymer.
- the oligomer itself may be an inhibitor to the polymerization reaction activity, which may ultimately be reduced yield.
- the photo-banung compound to be purified has a characteristic of being a high boiling point compound which is difficult to distill by a general distillation method.
- the boiling point of the photoreactive compound described above is about 180 ° C. or more, for example, in the range of about I SO to about 300 ° C., it is not easy to purify by conventional vacuum distillation methods.
- the molecular distillation (Short path distillation, Molecular distillation) is a distillation process performed under a nearly vacuum can be carried out at a relatively low temperature so that only the material required by distillation can be separated without colliding with other materials.
- the short distance between the evaporation zone and the expansion zone allows for mass evaporation and concentration in a short time while minimizing the destruction or damage of materials with low thermal stability.
- it may be suitable for the distillation of the high boiling point photoreactive compound that is the subject of purification of the present invention because it is carried out at a pressure much lower than the general vacuum distillation.
- the distillation apparatus used for the molecular distillation in the purification method of the present invention is, for example, MYERS-VACUUM, INCON, CHEMTECH SERVICE, Asahi, AULHI, ULVAC, Products from VTA or UIC are available, but are not necessarily limited to these facilities.
- the molecular distillation process of the crude product comprising the photoreactive compound may be carried out at a temperature of about 50 to about 3001, preferably about 90 to about 240 ° C. If the distillation silver is less than 50 ° C, the separation of impurities due to distillation may not occur effectively, and if it exceeds 300 ° C, there is a problem that the compound to be distilled due to heat is decomposed.
- the molecular distillation process of the crude product comprising the photo-banung compound is carried out under vacuum to almost vacuum conditions, for example from about 0.001 to about 100 mmbar, preferably from about 0.001 to Molecular distillation can be performed at a pressure of about 10 mmbar.
- the pressure is less than 0.001 mmbar, all impurities that need to be removed may be distilled, resulting in a drop in purity. If the pressure exceeds 100 mmbar, there is a problem that the efficiency of distillation is reduced because gasification is not easy.
- the distillation may be performed within a short time, for example for about 5 to 400 seconds, preferably for about 20 to about 300 seconds.
- the step of preliminary distillation before the distillation of the crude product, the step of preliminary distillation may be further performed.
- the preliminary distillation is for removing the solvent remaining in the crude product in the process of preparing the photo-banung compound can be carried out using the same or different equipment as the distillation apparatus used for the molecular distillation.
- the solvent remains in the crude product, the molecular weight of the polymer polymerized using the photoreactive compound may decrease, thereby deteriorating the physical properties of the polymer.
- the preliminary distillation may be carried out at a temperature lower than the molecular distillation conditions, for example, a temperature of about 20 to about 200 ° C and a pressure of about 0.01 to about 100 mmbar.
- the pressure is less than 0.001 mmbar, all solvents or impurities having a low boiling point to be removed may be distilled, resulting in a drop in purity. If the pressure exceeds 100 mmbar, the efficiency of distillation per hour may be lowered because the compound is not easily vaporized.
- the photoreactive compound is recovered from the crude product undergoing molecular distillation with or without the preliminary distillation.
- the purity of the photo semi-finished compound recovered through the purification method of the present invention may be about 90.0% or more, preferably about 90.0 to about 99.9%, more preferably about 95.0 to about 99.9%.
- the photoreactive compound obtained in high purity can be polymerized as a monomer.
- the photoreactive polymer is provided in Article 1 which provides a procatalyst comprising a transition metal of Group 10 and a Lewis base capable of weakly coordinating a photoreactive compound obtained according to the purification method of the present invention with a metal of Group 10.
- the photoreaction polymer may be polymerized at a temperature of about 10 to about 200 ° C. If the reaction temperature is lower than 10 ° C. is a problem that the polymerization activity is very low, and if it is higher than 200 ° C is a problem that the catalyst is decomposed, which is not preferable.
- the catalyst mixture comprises about 1 to about 1000 moles of a first cocatalyst which provides a Lewis base capable of weakly coordinating with the metal of the precatalyst relative to 1 mole of a procatalyst comprising a Group 10 transition metal, and optionally For example, it is preferable to include about 1 to about 1000 moles of the second cocatalyst which provides a compound containing a neutral group 15 electron donor ligand. If the content of the first and second cocatalysts is less than 1 mole, the catalyst There is a problem that the activation is not made, there is a problem that the catalytic activity is lowered if it is larger than 1000 moles is not preferable.
- the procatalyst comprising the Group 10 transition metal is easily separated by the System 1 co-catalyst providing Lewis acid, so that the central transition metal can be converted into a catalytically active species, thereby easily participating in the central acid-base reaction. It is possible to use compounds having Lewis base functional groups which break away from the metal.
- a transition metal produced in this way to provide a to-device base which can be weakly coordinated to the metal of the procatalyst
- a transition metal compound or a compound providing the same
- borate such as B (C 6 F 5 ) 3 or borate such as dimethylanilinium tetrakis (pentafluorophenyl) borate, methylaluminoxane (MAO) or A1 (C 2 H 5 ) there is a transition metal halide such as an alkyl aluminum, or AgSbF 6, such as 3.
- a compound which activates the catalyst by making the first and second cocatalysts into one salt may be used.
- alkyl phosphine and Compounds made by ion-bonding borane compounds may be used.
- the photoreactive compound obtained according to the purification method of the present invention is less than about 50, for example, about 0 to less than about 50, preferably about 0 to less than about 30, more preferably about 0 to less than about 20 It has a low APHA value and can exhibit excellent color characteristics.
- a photoreactive compound including any one or more photoreaction groups selected from Formulas 2 to 4, and a polymerizable unsaturated bond, and having an APHA value of less than 50 is provided.
- A is a simple bond, substituted or unsubstituted C r C 20 alkylene, carbonyl, carboxy, substituted or unsubstituted C 6 -C 40 arylene and substituted or unsubstituted-C 40 heteroarylene Is selected from;
- B is a simple bond, oxygen, sulfur, or -NH-;
- X is oxygen or sulfur
- R 9 is a simple bond, substituted or unsubstituted dC 20 alkylene, substituted or Unsubstituted c 2 -c 20 alkenylene, substituted or unsubstituted c 3 -c 12 cycloalkylene, substituted or unsubstituted C 6 -C 40 arylene, substituted or unsubstituted- 5 Aralkylene and substituted or unsubstituted C 2 -C 20 alkynylene;
- R 10 , R n , R 12 , R 13 , and R 14 may be the same as or different from each other, and each independently hydrogen, a hydroxyl group, a halogen group, a substituted or unsubstituted 15 aralkyl, substituted or unsubstituted C 2 ⁇ C 20 alkynyl, substituted or unsubstituted C ⁇ o alkyl, substituted or unsubstituted C!
- photo-banung compound More detailed description of the photo-banung compound and examples of specific compounds are as described in the method for purifying the photoreactive compound.
- the photo-banung compound has a low APHA value of less than about 50, for example, from about 0 to less than about 50, preferably from about 0 to less than about 30, more preferably from about 0 to about 20, resulting in excellent color properties. Can be.
- the APHA value may be a value measured by making the photoreactive compound into a solution of MC (methyl chloride) at a concentration of 10 wt%.
- the polymer polymerized using the photoreactive compound obtained in high purity according to the purification method of the present invention may have a high number average molecular weight and an extended average molecular weight.
- it may have a number average molecular weight of about 10,000 to about 500,000 g / mol, preferably about 20,000 to about 200,000 g / m. It may also have a weight average molecular weight of about 30,000 to about 1,000,000 g / mol, preferably about 60,000 to about 300,000 g / m.
- the photo-banung polymer in high yield when using the photo-banung compound obtained in high purity according to the purification method of the present invention. According to one embodiment of the invention it is possible to polymerize for example in a yield of about 70 to about 90%, preferably about 80 to about 98%.
- Magnesium sulfate (MgS0 4 ) was added to the separated organic solution to remove the remaining amount of water. After the water was removed, the magnesium sulfate was filtered and the solvent was blown off under reduced pressure.
- Feed speed 150ml /
- Feed part jacket temperature 100 ° C
- Residue discharge temperature 70 ° C
- Feed part jacket temperature 100 ° C
- Body main jacket temperature 160 ° C
- Residue discharge temperature 140 ° C
- Feeding part jacket temperature 90 ° C
- Feeding pump speed 0.72L / h
- Body main jacket silver 190 ° C
- Residue discharge temperature 140 ° C
- Feeding part Jacket Silver 90 ° C
- the alumina layering agent was dispersed in 2 L of luene and then slowly placed in a glass tube of 7 cm diameter and 30 cm length. Afterwards, the luluene was continually applied slowly, allowing the air bubbles to flow down so that no air bubbles remained between the aluminas in the glass tube. Thereafter, 100 g of the crude product including NB-Cin-OPr was dissolved in 200 g of toluene and poured slowly over the layered alumina. Then, while continuously adding toluenol, the purified NB-Cin-OPr solution was collected under a glass tube through alumina. The solvent was blown out of the purified NB-Cin-OPr solution to give a very light yellow NB-Cin-OPr solid. (64% yield, 97.6% purity)
- NB-Cin-OPr (5 g, recovered through the purification method according to Example 1 18.4 mmol) was dissolved in 15 mL of toluene, and stirred for 30 minutes while blowing nitrogen.
- Pd (acetate) 2 (4.13 mg, 18.4 ⁇ 1), tris (cyclonuclear chamber) hydrogen phosphino tetrakis (pentafluorobenz) borate dissolved in methylene chloride (ImL) at a temperature of 90 ° C (tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate) (37.2mg, 38,6 ⁇ ) 1) was added. Stir at 90 ° C for 15 h. After reaction, the temperature was lowered to room temperature, precipitated using ethane, and dried in a vacuum oven after the filter.
- NB-Cin-F (5g, 18.4mmol) recovered through the purification method according to Example 3 was dissolved in toluene (15ml), and stirred for 30 minutes while blowing nitrogen. Raise the silver to 90 ° C, Pd (acetate) 2 (4.13 mg, 18.4 ⁇ 1), tris (cyclonuclear) hydrogen phosphino tetrakis (pentafluorobenz) dissolved in methylene chloride (lmL) Borate (tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate) (37.2mg, 38.6 ⁇ ) 1) was added. Stir at 90 ° C for 15 h. After reaction, the temperature was lowered to room temperature, precipitated with ethane, filtered and dried in a vacuum oven.
- NB-Cin-OPr (5g, 18.4mmol) recovered through a purification method using an alumina column according to Comparative Example 1 was dissolved in toluene (15mL), and stirred for 30 minutes while blowing nitrogen.
- Tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate (37.2 mg, 38.6 ⁇ 1) was added.
- the yield and molecular weight of the obtained plymer are as follows.
- the APHA value was prepared by dissolving the sample in methyl chloride (MC) to prepare a solution having a concentration of 10 wt%, and then using the multifunctional spectrophotometer CM-5 of Konica Minolta Co., Ltd. in a cell for measuring the APHA value.
- MC methyl chloride
- Example 1 14 10wt% MC solution Crude monomer 140 10wt% MC solution Comparative example 1 52 10wt% MC solution
- the polymer was obtained in a high yield of 91% using the compound recovered through the purification method of the present invention. Moreover, the high number average molecular weight and the weight average molecular weight were shown about the case where the unrefined compound or the compound refine
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JP2016531536A JP6130601B2 (ja) | 2013-08-02 | 2014-08-01 | 光反応性化合物の精製方法および光反応性化合物 |
CN201480048675.1A CN105555751B (zh) | 2013-08-02 | 2014-08-01 | 光反应性化合物的纯化方法和光反应性化合物 |
US14/909,426 US9963418B2 (en) | 2013-08-02 | 2014-08-01 | Purification method of photoreactive compound and photoreactive compound |
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