TWI747343B - Synthesis method of monomolecular benzophenone derivative photoinitiator with visible light waveband absorption - Google Patents
Synthesis method of monomolecular benzophenone derivative photoinitiator with visible light waveband absorption Download PDFInfo
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Abstract
本發明單分子型二苯甲酮衍生物涉及用於可見光波段吸收之光起始劑，其具有一氫受體、一氫予體及一共軛片，藉由不同共軛片段具可見光吸收波段致使有不同之光反應速度，其特徵為單分子型二苯甲酮衍生物於光起始劑之用途，可避免分散不均及增加分子內質子或電子轉移效率，此寬廣吸收波段亦可滿足不同曝光光源之需求，更進一步亦可應用於光吸收劑之用途。 The monomolecular benzophenone derivative of the present invention relates to a photoinitiator for absorption in the visible light band, which has a hydrogen acceptor, a hydrogen precursor and a conjugate sheet, and different conjugated fragments have visible light absorption bands. There are different photoreaction speeds, which are characterized by the use of monomolecular benzophenone derivatives as photoinitiators, which can avoid uneven dispersion and increase the efficiency of intramolecular proton or electron transfer. This wide absorption band can also meet different requirements. The demand for exposure light sources can be further applied to the use of light absorbers.
Description
本發明單分子型二苯甲酮衍生物涉及用於可見光波段吸收之光起始劑，其具有一氫受體、一氫予體及一共軛片，藉由不同共軛片段具可見光吸收波段致使有不同之光反應速度，其特徵為單分子型二苯甲酮衍生物於光起始劑之用途，可避免分散不均及增加分子內質子或電子轉移效率，此寬廣吸收波段亦可滿足不同曝光光源之需求，更進一步亦可應用於光吸收劑之用途。 The monomolecular benzophenone derivative of the present invention relates to a photoinitiator for absorption in the visible light band, which has a hydrogen acceptor, a hydrogen precursor and a conjugate sheet, and different conjugated fragments have visible light absorption bands. There are different photoreaction speeds, which are characterized by the use of monomolecular benzophenone derivatives as photoinitiators, which can avoid uneven dispersion and increase the efficiency of intramolecular proton or electron transfer. This wide absorption band can also meet different requirements. The demand for exposure light sources can be further applied to the use of light absorbers.
光固化技術通常是指在紫外光、可見光下或在電子束等照射下，所產生的能量會使得不飽和單體由液態轉換成固態的情形，此技術已被廣泛的應用在非成相系統如塗料、黏著劑、牙科補強材料等以及成相系統的3D列印、半導體、印刷電路板製程等電子元件。光源為光固化系統中之重要因子，是指光起始劑接受到光的能量之後轉變成活性自由基進行後續連鎖反應，因此光起始劑的選擇與光源的搭配對於光固化效率具有一決定性影響，近年來業者以持朝向將傳統UV汞燈轉換為較為環保之LED燈源或是可具有底部穿透效果之可見 光波長光源等。因此如何設計新穎光起始劑以符合適當光源之需求已刻不容緩。 Light curing technology usually refers to the situation in which the energy generated under ultraviolet light, visible light or electron beam irradiation will cause the unsaturated monomer to be converted from liquid to solid. This technology has been widely used in non-phase systems. Such as coatings, adhesives, dental reinforcement materials, etc., as well as electronic components such as 3D printing of phase systems, semiconductors, and printed circuit board manufacturing processes. The light source is an important factor in the light curing system. It means that the photoinitiator receives the energy of the light and transforms into active free radicals for subsequent chain reactions. Therefore, the choice of the photoinitiator and the combination of the light source are decisive for the efficiency of light curing. In recent years, the industry has changed the traditional UV mercury lamp into a more environmentally friendly LED lamp source or can have a visible bottom penetrating effect. Light wavelength light source, etc. Therefore, how to design novel photoinitiators to meet the needs of appropriate light sources is of urgency.
光固化系統依應用可分成不同組成如寡聚物、反應性單體、光起始劑及添加劑等。而通常光起始劑之含量約佔整體配方的1-5wt%，雖其量不多但卻有反應速率的決定步驟。其反應機制為光起始劑捕捉光輻射能量，藉由能量產生反應性片段並將能量傳遞給寡聚物及反應性單體，產生反應固化的相變化過程，並可因應需求添加相對應之添加劑，使該系統符合需求。一般光起始劑需要具備：(1)能吸收光輻射能，使單體產生聚合反應；(2)且有良好的熱穩定性等。光起始劑因結構、能量傳遞的方式不同，可分為陽離子型(Cationic polymerization,CP)與自由基型(Free radical polymerization,FRP)光固化系統，其中自由基光起始劑目前被廣泛的應用於業界，因為其具有固化速率快、成本低廉、無後固化等優點。自由基型反應機制區又可分為Type I(直接裂解型)與Type II(雙分子型)兩類，其反應機制如下：Type I光起始劑反應機制如圖一，並以市售之TPO為例。當光照射Type I光起始劑時，分子中碳-磷鍵產生斷鍵，生成自由基引發寡聚物與反應性單體進行交聯聚合反應，此外下圖為市面上常見的Type I光起始劑。 The light curing system can be divided into different components such as oligomers, reactive monomers, photoinitiators and additives according to the application. Generally, the content of the photoinitiator is about 1-5% by weight of the overall formula. Although the amount is not large, there is a step in determining the reaction rate. The reaction mechanism is that the photoinitiator captures the light radiation energy, and the reactive fragments are generated by the energy and the energy is transferred to the oligomers and reactive monomers, resulting in a phase change process of reaction curing, and the corresponding ones can be added according to the demand. Additives to make the system meet the demand. Generally, the photoinitiator needs to have: (1) It can absorb light radiation energy to cause the monomer to polymerize; (2) It has good thermal stability and so on. Photoinitiators can be divided into cationic (CP) and free radical polymerization (FRP) photocuring systems due to their different structures and energy transfer methods. Among them, free radical photoinitiators are currently widely used. Used in the industry because of its advantages such as fast curing rate, low cost, and no post-curing. The free radical type reaction mechanism zone can be divided into Type I (direct cleavage type) and Type II (bimolecular type). The reaction mechanism is as follows: The reaction mechanism of Type I photoinitiator is shown in Figure 1, and is commercially available. Take TPO as an example. When the Type I photoinitiator is irradiated with light, the carbon-phosphorus bond in the molecule is broken, and free radicals are generated to initiate cross-linking polymerization of oligomers and reactive monomers. In addition, the following picture shows the common Type I light on the market. Initiator.
Type II系統則是由光起始劑(PI，又稱為氫受體Hydrogen acceptor)、共起始劑(Co-initiator，又稱氫予體Hydrogen donor，DH)雙成分所組成，其反應機制如圖二所示，由光起始劑吸收光子並斷鍵成為氫原子的被攻擊者(P˙)，氫原子予體(DH)進行給予氫原子之動作，產生自由基(D˙)，並生成自由基引發寡聚物與反應性單體進行交聯聚合反應。常見的Type II中hydrogen acceptor結構如Benzophenone(BP)、Thioxanthones(TX)、Acridine、Ocl-HABI、Camphorqinone(CQ)等結構，不同的hydrogen acceptor具有不同感光度與吸光範圍並已經被廣泛的應用於電子業、黏著劑、牙科材料與印刷等產業。以BP為氫受體(hydrogen acceptor)，TEA(Triethylamine，三乙胺)為氫予體(hydrogen donor)之Type II工作機制如圖二所示，藉由hydrogen acceptor照光後產生之電子轉移至hydrogen donor分子而誘使單體進行光聚合動作。當BP在適當的光源照射下，藉由激發產生三重態與TEA作用，並進行電子轉移形成二苯甲醇負離子與胺正離子，爾後二苯甲醇負離子從胺正離子奪取氫生成無引發活性之二苯甲醇自由基(Ketyl radical)和活性很高的胺基自由基，胺基自由基可與具有不飽和官能基之單體或寡聚進行聚合反應。 Type II system is composed of two components: photoinitiator (PI, also known as Hydrogen acceptor) and co-initiator (co-initiator, also known as Hydrogen donor, DH). Its reaction mechanism As shown in Figure 2, the attacked person (P˙) who absorbs the photon by the photoinitiator and breaks the bond to become a hydrogen atom, the hydrogen atom precursor (DH) performs the action of donating hydrogen atoms to generate free radicals (D˙), And generate free radicals to initiate cross-linking polymerization of oligomers and reactive monomers. Common hydrogen acceptor structures in Type II such as Benzophenone (BP), Thioxanthones (TX), Acridine, Ocl-HABI, Camphorqinone (CQ) and other structures. Different hydrogen acceptors have different sensitivity and light absorption ranges and have been widely used. Electronics, adhesives, dental materials and printing industries. The Type II working mechanism with BP as the hydrogen acceptor and TEA (Triethylamine) as the hydrogen donor is shown in Figure 2. The electrons generated by the hydrogen acceptor are transferred to hydrogen. The donor molecule induces the monomer to undergo photopolymerization. When BP is irradiated by a suitable light source, it generates a triplet state and TEA through excitation, and transfers electrons to form benzyl alcohol anions and amine cations, and then benzyl alcohol anions abstract hydrogen from the amine cations to produce no initiating activity. Benzyl alcohol radicals (Ketyl radicals) and highly active amine radicals, which can polymerize with monomers or oligomers with unsaturated functional groups.
常見單分子型二苯甲酮系之BP-Ph(4-phenyl-benzophenone，4-苯基二苯甲酮)、BPN(4-(diethylamino)-benzophenone,4-(二乙氨基)二苯甲酮)、EMK(4,4'-Bis(diethylamino)benzophenone,4,4'-雙(二乙氨基)二苯甲酮)如第1圖所示，其想法是將hydrogen acceptor與hydrogen donor利用共價鍵結方式形成單分子結構，此方式可避免雙分子型光起始劑系統分散不均之風險。 Common single-molecule benzophenone series of BP-Ph (4-phenyl-benzophenone, 4-phenyl benzophenone), BPN (4-(diethylamino)-benzophenone, 4-(diethylamino) benzophenone) Ketone), EMK (4,4'-Bis(diethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone) as shown in Figure 1. The idea is to use a hydrogen acceptor and a hydrogen donor together. The valence bonding method forms a single molecular structure, which can avoid the risk of uneven dispersion of the bimolecular photoinitiator system.
本發明以BPN為起始單體進行延伸共軛長度之合成，製備出單分子型二苯甲酮衍生物(BPNs)：BPN-D(4-N,N-二乙基胺基-4'-N,N-二苯基胺基二苯甲酮，4-N,N-diethylamino-4'-N,N-diphenylamino benzophenone)、BPN-Ph(4-N,N-二乙基胺基-4'-苯基二苯甲酮，4-N,N-diethylamino-4'-phenyl benzophenone)、BPN-N(4-N,N-二乙基胺基-4'-萘基二苯甲酮，4-N,N-diethylamino-4'-naphthalene benzophenone)、BPN-An(4-N,N-二乙基胺基-4'-蒽基二苯甲酮，
4-N,N-diethylamino-4'-anthracene benzophenone)及BPN-Py(4-N,N-二乙基胺基-4'-芘基二苯甲酮，4-N,N-diethylamino-4'-pyrene benzophenone)(如第2圖)，除了比較其光反應特性外，亦評估可見光波長單分子二苯甲酮之可行性。此外非單分子型光起始劑(BP-Ph)(如第1圖)亦使用並比較其光反應特性。本發明乃是一種可見光波段吸收之單分子型二苯甲酮衍生物光起始劑合成方法，其單分子型二苯甲酮衍生具有以下通式(I)：
第1圖係顯示習知BP-Ph、BPN、EMK結構示意圖。 Figure 1 is a schematic diagram showing the structure of the conventional BP-Ph, BPN, and EMK.
第2圖係顯示本發明BPN-D、BPN-Ph、BPN-N、BPN-An及BPN-Py結構示意圖。 Figure 2 is a schematic diagram showing the structure of BPN-D, BPN-Ph, BPN-N, BPN-An and BPN-Py of the present invention.
第3圖係顯示本發明BPN反應流程圖。 Figure 3 shows a flow chart of the BPN reaction of the present invention.
第4圖係顯示本發明BPN-Br反應流程圖。 Figure 4 shows a flow chart of the BPN-Br reaction of the present invention.
第5圖係顯示本發明BPNs衍生物反應流程圖。 Figure 5 shows the reaction scheme of the BPNs derivatives of the present invention.
第6圖係顯示本發明溶解度測試中TMPTMA(Trihydroxymethylpropyl trimethylacrylate)之結構示意圖。 Figure 6 is a schematic diagram showing the structure of TMPTMA (Trihydroxymethylpropyl trimethylacrylate) in the solubility test of the present invention.
第7圖係顯示本發明BP衍生物之UV/Vis吸收光譜圖。 Figure 7 shows the UV/Vis absorption spectrum of the BP derivative of the present invention.
第8圖係顯示本發明BPN、EMK與BPNs光起始劑及TMPTMA為單體之Photo-DSC圖(a)Heat flow(b)Double bond conversion efficiency。 Figure 8 shows the Photo-DSC diagram of the BPN, EMK and BPNs photoinitiators of the present invention and TMPTMA as monomers (a) Heat flow (b) Double bond conversion efficiency.
以下係藉由特定的具體實施例說明本創作之實施方式，熟習此技藝之人士可由本說明書所揭示之內容輕易地了解本創作之其他優點與功效。本創作亦可藉由其他不同的具體實施例加以施行或應用，本說明書中的各項細節亦可基於不同觀點與應用，在不悖離本創作之精神下進行各種修飾與變更。 The following is a specific embodiment to illustrate the implementation of this creation. Those who are familiar with this technique can easily understand the other advantages and effects of this creation from the content disclosed in this manual. This creation can also be implemented or applied by other different specific embodiments, and various details in this specification can also be based on different viewpoints and applications, and various modifications and changes can be made without departing from the spirit of this creation.
本發明乃是一種可見光波段吸收之單分子型二苯甲酮衍生物光起始劑合成方法，其單分子型二苯甲酮衍生具有以下通式(I)：
欲合成BPNs須先合成BPN-Br(4-N,N-二乙基胺基-4'-氯二苯甲酮，4-N,N-diethylamino-4'-chlorobenzophenone)，將中間體BPN-Br(第4圖)利用C-N coupling reaction或鈀Suszki cross-coupling reaction與不同結構進行共軛片段之連結(第5圖)。其BPN-Br之合成乃是使用傅里德-克拉夫茨反應(Friedel craft)以 四-氯化苯甲醯氯及與苯基二乙胺合成中間體BPN-Br，將4-bromobenzoyl chloride(2.450g,11.36mmol)、N,N-diethylaniline(2.04g,13.67mmol)、AlCl3(1.82g,13.65mmol)及DCM(dichloromethane，二氯甲烷)作為溶劑回流反應12h後，反應結束冷卻後加入HCl(aq)(1N)終止反應，並使用DCM(dichloromethane，二氯甲烷)/水與氯化銨水溶液進行萃取，收集有機層，經無水硫酸鎂除水後，粗產物以管柱層析純化，(n-Hexane(正己烷)：DCM=3：1)，得白色固體1.86g(45.4%)。1H-NMR(氫-核磁共振光譜)(CDCl3(氘代氯仿)，400MHz)：δ(ppm)=1.20-1.26(6H,Ar-H),3.41-3.47(4H,Ar-H),6.63-6.66(2H,Ar-H),7.59-7.60(4H,Ar-H),7.72-7.75(2H,Ar-H)。 To synthesize BPNs, BPN-Br (4-N,N-diethylamino-4'-chlorobenzophenone, 4-N,N-diethylamino-4'-chlorobenzophenone) must be synthesized first, and the intermediate BPN- Br (Figure 4) uses CN coupling reaction or Palladium Suszki cross-coupling reaction to link conjugated fragments with different structures (Figure 5). The synthesis of BPN-Br is the use of Friedel craft reaction (Friedel craft) to synthesize intermediate BPN-Br with tetrachlorobenzyl chloride and phenyldiethylamine, and 4-bromobenzoyl chloride (2.450g ,11.36mmol), N,N-diethylaniline (2.04g, 13.67mmol), AlCl3 (1.82g, 13.65mmol) and DCM (dichloromethane, dichloromethane) as a solvent and refluxed for 12h. After the reaction was cooled, HCl (aq ) (1N) Terminate the reaction, and use DCM (dichloromethane, dichloromethane)/water and ammonium chloride aqueous solution to extract, collect the organic layer, after removing water with anhydrous magnesium sulfate, the crude product is purified by column chromatography, (n -Hexane (n-hexane): DCM=3:1) to obtain 1.86 g (45.4%) of a white solid. 1 H-NMR (hydrogen-nuclear magnetic resonance spectrum) (CDCl 3 (deuterochloroform), 400MHz): δ (ppm) = 1.20-1.26 (6H, Ar-H), 3.41-3.47 (4H, Ar-H), 6.63-6.66 (2H, Ar-H), 7.59-7.60 (4H, Ar-H), 7.72-7.75 (2H, Ar-H).
BPN-D(4-N,N-二乙基胺基-4'-N,N-二苯基胺基二苯甲酮，4-N,N-diethylamino-4'-N,N-diphenylamino benzophenone)單分子型二苯甲酮衍生物之合成乃是將BPN-Br(4-N,N-二乙基胺基-4'-氯二苯甲酮，4-N,N-diethylamino-4'-chlorobenzophenone)(2.356g,6.54mmol)、diphenylamine(二苯胺)(1.217g,7.192mmol)、Pd2(dba)3(三(二亞苄基丙酮)二鈀)(0.1197g,0.131mmol)和NaOtBu(叔丁醇鈉)(0.943g,9.81mmol)置於圓底燒瓶內，抽灌氮氣數次後打入P(tBu)3(叔丁醇鈉)(0.5ml,0.5M)及toluene(甲苯)(20ml)為溶劑加熱至95℃反應12h。反應結束後將溶劑移除，並使用DCM(dichloromethane，二氯甲烷)/水與氯化銨水溶液進行萃取，收集有機層，經無水硫酸鎂除水後，粗產物以管柱層析純化(n-Hexane(正己烷)：DCM=1：1)，得鵝黃色固體產率32.68%(0.913g)。1H-NMR(氫-核磁共振光譜)(CDCl3(氘代氯仿)，400MHz)：δ(ppm)=1.19-1.24(6H,CH3),3.40-3.46(4H,CH2),6.63-6.70(2H,Ar-H),7.02-7.18 (8H,Ar-H),7.28-7.33(4H,Ar-H),7.63-7.67(2H,Ar-H),7.77-7.81(2H,Ar-H).FT-Mass(傅立葉轉換質譜)：m/z=421.22744(M-H+)。 BPN-D(4-N,N-diethylamino-4'-N,N-diphenylamino benzophenone, 4-N,N-diethylamino-4'-N,N-diphenylamino benzophenone ) The synthesis of monomolecular benzophenone derivatives is to combine BPN-Br(4-N,N-diethylamino-4'-chlorobenzophenone, 4-N,N-diethylamino-4' -chlorobenzophenone) (2.356g, 6.54mmol), diphenylamine (1.217g, 7.192mmol), Pd 2 (dba) 3 (tris(dibenzylideneacetone) dipalladium) (0.1197g, 0.131mmol) and NaOtBu (sodium tert-butoxide) (0.943g, 9.81mmol) was placed in a round-bottomed flask, and nitrogen was pumped several times and then filled with P( t Bu) 3 (sodium tert-butoxide) (0.5ml, 0.5M) and toluene (Toluene) (20ml) as the solvent was heated to 95°C and reacted for 12h. After the reaction, the solvent was removed, and DCM (dichloromethane)/water and ammonium chloride aqueous solution were used for extraction, and the organic layer was collected. After the water was removed by anhydrous magnesium sulfate, the crude product was purified by column chromatography (n -Hexane (n-hexane): DCM=1:1), the yield of goose yellow solid is 32.68% (0.913g). 1 H-NMR (hydrogen-nuclear magnetic resonance spectrum) (CDCl 3 (deuterochloroform), 400MHz): δ (ppm)=1.19-1.24 (6H, CH 3 ), 3.40-3.46 (4H, CH 2 ), 6.63 6.70(2H,Ar-H),7.02-7.18 (8H,Ar-H),7.28-7.33(4H,Ar-H),7.63-7.67(2H,Ar-H),7.77-7.81(2H,Ar- H). FT-Mass (Fourier Transform Mass Spectrometry): m/z=421.22744 (MH + ).
BPN-Ph(4-N,N-二乙基胺基-4'-苯基二苯甲酮，4-N,N-diethylamino-4'-phenyl benzophenone)單分子型二苯甲酮衍生物之合成乃是將反應瓶抽灌氮氣數次後打入dry THF(乾燥四氫呋喃)(20ml)為溶劑，並降溫至-78℃後，加入bromobenzene(溴苯)(3ml)緩慢滴入n-BuLi(正丁基鋰)(6.5ml)(維持低溫反應)反應1h，再加入B(OMe)3(硼酸三甲酯)(1.17ml)後，回溫至室溫攪拌過夜後，加入鹽酸(aq)(2N)攪拌1h，使用DCM(dichloromethane，二氯甲烷)/水與鹽酸水溶液進行萃取，收集有機層經無水硫酸鎂除水後粗產物Ph-B(OH)2(苯基硼酸)。將BPN-Br(4-N,N-二乙基胺基-4'-氯二苯甲酮，4-N,N-diethylamino-4'-chlorobenzophenone)(3.012g,8.36mmol)、Ph-B(OH)2(苯基硼酸)(1.120g,9.20mmol)、Pd(PPh3)4(四(三苯基膦)鈀)(0.193g,0.167mmol)置入圓底燒瓶內抽灌氮氣數次，打入K2CO3(碳酸鉀)(2M)(12.50ml)、toluene(甲苯)為溶劑(15ml)加熱至95℃反應12h。反應結束後將溶劑移除，使用DCM(dichloromethane，二氯甲烷)/水與氯化銨水溶液進行萃取，收集有機層經無水硫酸鎂除水後粗產物以管柱層析純化(n-Hexane(正己烷)：DCM=5：2)純化得黃色固體，產率32.68%(0.805g)。1H-NMR(氫-核磁共振光譜)(CDCl3(氘代氯仿)，400MHz)：δ(ppm)=1.21-1.25(6H,CH3),3.42-3.48(4H,CH2),6.65-6.69(2H,Ar-H),7.37-7.42(1H,Ar-H),7.45-7.50(2H,Ar-H),7.63-7.70(4H,Ar-H),7.80-7.84(4H,Ar-H).FT-Mass(傅立葉轉換質譜)：m/z=329.17747(M-H+)。 BPN-Ph (4-N,N-diethylamino-4'-phenyl benzophenone, 4-N,N-diethylamino-4'-phenyl benzophenone) one of the monomolecular benzophenone derivatives The synthesis is to pump nitrogen into the reaction flask several times, then pour dry THF (dry tetrahydrofuran) (20ml) as the solvent, and after cooling to -78℃, add bromobenzene (3ml) and slowly drip into n-BuLi( N-Butyllithium) (6.5ml) (reaction maintained at low temperature) react for 1h, then add B(OMe) 3 (trimethyl borate) (1.17ml), warm to room temperature and stir overnight, then add hydrochloric acid (aq) (2N) Stir for 1h, use DCM (dichloromethane, dichloromethane)/water and aqueous hydrochloric acid to extract, collect the crude product Ph-B(OH) 2 (phenylboronic acid) after removing water from the organic layer with anhydrous magnesium sulfate. BPN-Br (4-N,N-diethylamino-4'-chlorobenzophenone, 4-N,N-diethylamino-4'-chlorobenzophenone) (3.012g, 8.36mmol), Ph-B (OH) 2 (phenylboronic acid) (1.120g, 9.20mmol), Pd(PPh 3 ) 4 (tetrakis (triphenylphosphine) palladium) (0.193g, 0.167mmol) put into the round bottom flask and pump nitrogen K 2 CO 3 (potassium carbonate) (2M) (12.50ml), toluene (toluene) as the solvent (15ml) was added, and heated to 95°C for 12h. After the reaction, the solvent was removed, and DCM (dichloromethane)/water and ammonium chloride aqueous solution were used for extraction. The organic layer was collected and the crude product was purified by column chromatography (n-Hexane (n-Hexane( N-hexane):DCM=5:2) Purified to obtain a yellow solid with a yield of 32.68% (0.805g). 1 H-NMR (hydrogen nuclear magnetic resonance spectrum) (CDCl 3 (deuterochloroform), 400MHz): δ (ppm)=1.21-1.25 (6H, CH 3 ), 3.42-3.48 (4H, CH 2 ), 6.65 6.69 (2H, Ar-H), 7.37-7.42 (1H, Ar-H), 7.45-7.50 (2H, Ar-H), 7.63-7.70 (4H, Ar-H), 7.80-7.84 (4H, Ar- H). FT-Mass (Fourier Transform Mass Spectrometry): m/z=329.17747 (MH + ).
BPN-N(4-N,N-二乙基胺基-4'-萘基二苯甲酮，4-N,N-diethylamino-4'-naphthalene benzophenone)單分子型二苯甲酮衍生物之合成乃是將反應瓶抽灌氮氣數次後打入dry THF(乾燥四氫呋喃)(20ml)為溶劑，並降溫至-78℃後，加入1-bromonaphthalene(1-溴萘)(3ml)緩慢滴入n-BuLi(正丁基鋰)(6.24ml)並維持低溫反應1h，再加入B(OMe)3(硼酸三甲酯)(1.11ml)後，回溫至室溫攪拌隔夜後，加入鹽酸(aq)(2N)攪拌1h，使用DCM(dichloromethane，二氯甲烷)/水與鹽酸水溶液進行萃取，收集有機層經無水硫酸鎂除水後粗產物N-B(OH)2(萘基硼酸)。將BPN-Br(4-N,N-二乙基胺基-4'-氯二苯甲酮，4-N,N-diethylamino-4'-chlorobenzophenone)(1.0363g,2.88mmol)、N-B(OH)2(萘基硼酸)(0.5445g,3.16mmol)、Pd(PPh3)4(四(三苯基膦)鈀)(0.066g,0.0571mmol)置入圓底燒瓶內抽灌氮氣數次，打入K2CO3(碳酸鉀)(2M)(4.30ml)、toluene(甲苯)(20ml)為溶劑加熱反應95℃反應24h。反應結束後將溶劑移除，使用DCM(dichloromethane，二氯甲烷)/水與氯化銨水溶液進行萃取，收集有機層經無水硫酸鎂除水後粗產物以管柱層析純化(n-Hexane(正己烷)：EA(乙酸乙酯)=10：1)純化得黃色固體，產率35%(0.382g)。1H-NMR(氫-核磁共振光譜)(CDCl3(氘代氯仿)，400MHz)：δ(ppm)=1.22-1.26(6H,CH3),3.43-3.49(4H,CH2),6.68-6.72(2H,Ar-H),7.44-7.77(6H,Ar-H),7.85-7.89(2H,Ar-H),7.89-7.95(5H,Ar-H).FT-Mass(傅立葉轉換質譜)：m/z=380.20066(M-H+)。 BPN-N (4-N,N-diethylamino-4'-naphthalene benzophenone, 4-N,N-diethylamino-4'-naphthalene benzophenone) one of the monomolecular benzophenone derivatives The synthesis is to pump nitrogen into the reaction flask several times and then pour into dry THF (dry tetrahydrofuran) (20ml) as the solvent, and after cooling to -78℃, add 1-bromonaphthalene (1-bromonaphthalene) (3ml) and slowly drip into it. n-BuLi (n-butyllithium) (6.24ml) and keep the reaction at low temperature for 1h, then add B(OMe) 3 (trimethyl borate) (1.11ml), warm to room temperature and stir overnight, add hydrochloric acid ( aq) (2N) Stir for 1 h, extract with DCM (dichloromethane)/water and aqueous hydrochloric acid solution, collect the organic layer and remove the water with anhydrous magnesium sulfate, the crude product NB(OH) 2 (naphthylboronic acid). BPN-Br (4-N, N-diethylamino-4'-chlorobenzophenone, 4-N, N-diethylamino-4'-chlorobenzophenone) (1.0363g, 2.88mmol), NB (OH ) 2 (naphthyl boronic acid) (0.5445g, 3.16mmol), Pd(PPh 3 ) 4 (tetrakis(triphenylphosphine) palladium) (0.066g, 0.0571mmol) were put into a round bottom flask and pumped with nitrogen several times, Add K 2 CO 3 (potassium carbonate) (2M) (4.30ml) and toluene (toluene) (20ml) as the solvent and heat the reaction at 95°C for 24h. After the reaction, the solvent was removed, and DCM (dichloromethane)/water and ammonium chloride aqueous solution were used for extraction. The organic layer was collected and the crude product was purified by column chromatography (n-Hexane (n-Hexane( N-hexane): EA (ethyl acetate) = 10:1) purified to obtain a yellow solid with a yield of 35% (0.382g). 1 H-NMR (hydrogen-nuclear magnetic resonance spectrum) (CDCl 3 (deuterochloroform), 400MHz): δ (ppm) = 1.22-1.26 (6H, CH 3 ), 3.43-3.49 (4H, CH 2 ), 6.68- 6.72(2H,Ar-H),7.44-7.77(6H,Ar-H),7.85-7.89(2H,Ar-H),7.89-7.95(5H,Ar-H).FT-Mass (Fourier Transform Mass Spectrometry) : M/z=380.20066 (MH + ).
BPN-An(4-N,N-二乙基胺基-4'-蒽基二苯甲酮，4-N,N-diethylamino-4'-anthracene benzophenone)單分子型二苯甲酮衍生物之合成乃是將9-bromoanthracene(9-溴蒽)(2.497g,9.71mmol)置入圓底燒瓶抽灌氮 氣數次後打入dry THF(乾燥四氫呋喃)(20ml)為溶劑，並降溫至-78℃後緩慢滴入n-BuLi(正丁基鋰)(6.7ml)並維持低溫反應1h，再加入B(OMe)3(硼酸三甲酯)(1.2ml)後，回溫至室溫攪拌隔夜後，加入鹽酸(aq)(2N)攪拌1h，使用DCM(dichloromethane，二氯甲烷)/水與鹽酸水溶液進行萃取，收集有機層經無水硫酸鎂除水後粗產物An-B(OH)2(蒽基硼酸)。將BPN-Br(4-N,N-二乙基胺基-4'-氯二苯甲酮，4-N,N-diethylamino-4'-chlorobenzophenone)(2.346g,6.51mmol)、An-B(OH)2(蒽基硼酸)(1.591g,7.162mmol)、Pd(PPh3)4(四(三苯基膦)鈀)(0.131g,0.114mmol)置入圓底燒瓶內抽灌氮氣數次，打入K2CO3(碳酸鉀)(2M)(9ml)、toluene(甲苯)(20ml)為溶劑加熱反應95℃反應24h。反應結束後將溶劑移除，使用DCM(dichloromethane，二氯甲烷)/水與氯化銨水溶液進行萃取，收集有機層經無水硫酸鎂除水後粗產物以管柱層析純化(n-Hexane(正己烷)：EA(乙酸乙酯)=10：1)純化得黃色固體，產率8.18%(0.229g)。1H-NMR(氫-核磁共振光譜)(CDCl3(氘代氯仿)，400MHz)：δ(ppm)=1.12-1.27(6H,CH3),3.45-3.51(4H,CH2),6.72-6.75(2H,Ar-H),7.36-7.51(4H,Ar-H),7.52-7.55(2H,Ar-H),7.68-7.71(2H,Ar-H),7.93-7.97(4H,Ar-H),8.06-8.08(2H,Ar-H),8.53(1H,Ar-H).FT-Mass(傅立葉轉換質譜)：m/z=430.21653(M-H+)。 BPN-An (4-N,N-diethylamino-4'-anthracene benzophenone, 4-N,N-diethylamino-4'-anthracene benzophenone) one of the monomolecular benzophenone derivatives The synthesis is to put 9-bromoanthracene (9-bromoanthracene) (2.497g, 9.71mmol) into a round-bottomed flask and pump nitrogen several times, then add dry THF (dry tetrahydrofuran) (20ml) as the solvent, and cool to -78 Slowly drop n-BuLi (n-butyllithium) (6.7ml) after temperature temperature and keep the reaction at low temperature for 1h, then add B(OMe) 3 (trimethyl borate) (1.2ml), warm to room temperature and stir overnight Then, hydrochloric acid (aq) (2N) was added and stirred for 1 h, and extracted with DCM (dichloromethane)/water and aqueous hydrochloric acid solution. The organic layer was collected and the crude product An-B(OH) 2 ( Anthryl boronic acid). Combine BPN-Br (4-N,N-diethylamino-4'-chlorobenzophenone, 4-N,N-diethylamino-4'-chlorobenzophenone) (2.346g, 6.51mmol), An-B (OH) 2 (anthryl boronic acid) (1.591g, 7.162mmol), Pd(PPh 3 ) 4 (tetrakis (triphenylphosphine) palladium) (0.131g, 0.114mmol) put into a round bottom flask and pump nitrogen Next, add K 2 CO 3 (potassium carbonate) (2M) (9ml) and toluene (toluene) (20ml) as the solvent and heat the reaction at 95°C for 24h. After the reaction, the solvent was removed, and DCM (dichloromethane)/water and ammonium chloride aqueous solution were used for extraction. The organic layer was collected and the crude product was purified by column chromatography (n-Hexane (n-Hexane( N-hexane): EA (ethyl acetate) = 10:1) purified to obtain a yellow solid, the yield was 8.18% (0.229 g). 1 H-NMR (hydrogen-nuclear magnetic resonance spectrum) (CDCl 3 (deuterochloroform), 400MHz): δ (ppm) = 1.12-1.27 (6H, CH 3 ), 3.45-3.51 (4H, CH 2 ), 6.72 6.75(2H,Ar-H),7.36-7.51(4H,Ar-H),7.52-7.55(2H,Ar-H),7.68-7.71(2H,Ar-H),7.93-7.97(4H,Ar- H), 8.06-8.08 (2H, Ar-H), 8.53 (1H, Ar-H). FT-Mass (Fourier transform mass spectrum): m/z=430.21653 (MH + ).
BPN-Py(4-N,N-二乙基胺基-4'-芘基二苯甲酮，4-N,N-diethylamino-4'-pyrene benzophenone)單分子型二苯甲酮衍生物之合成乃是將1-bromopyrene(1-溴芘)(2.825g,10.09mmol)置入圓底燒瓶抽灌氮氣數次後打入dry THF(乾燥四氫呋喃)(20ml)為溶劑，並降溫至-78℃後，緩慢滴入n-BuLi(正丁基鋰)(6.93ml)並維持低溫反應1h，再加入B(OMe)3(硼酸三甲酯)(0.7ml) 後，回溫至室溫攪拌隔夜後，加入鹽酸(aq)(2N)攪拌1h，使用DCM(dichloromethane，二氯甲烷)/水與鹽酸水溶液進行萃取，收集有機層經無水硫酸鎂除水後粗產物Py-B(OH)2(芘基硼酸)。將BPN-Br(4-N,N-二乙基胺基-4'-氯二苯甲酮，4-N,N-diethylamino-4'-chlorobenzophenone)(1.344g,3.730mmol)、Py-B(OH)2(芘基硼酸)(1.009g,4.100mmol)、Pd(PPh3)4(四(三苯基膦)鈀)(0.086g,0.074mmol)置入圓底燒瓶內抽灌氮氣數次，打入K2CO3(碳酸鉀)(2M)(9ml)、toluene(甲苯)為溶劑(20ml)加熱反應95℃反應72h。反應結束後將溶劑移除，使用DCM(dichloromethane，二氯甲烷)/水與氯化銨水溶液進行萃取，收集有機層經無水硫酸鎂除水後粗產物以管柱層析純化(n-Hexane(正己烷)：EA(乙酸乙酯)=10：1)純化得黃色固體，產率42.45%(0.723g)。1H-NMR(氫-核磁共振光譜)(CDCl3(氘代氯仿)，400MHz)：δ(ppm)=1.23-1.27(6H,CH3),3.44-3.51(4H,CH2),6.70-6.74(2H,Ar-H),7.71-7.75,(2H,Ar-H),7.90-7.94(2H,Ar-H),7.93-7.96(2H,Ar-H),8.012-8.27(9H,Ar-H).FT-Mass(傅立葉轉換質譜)：m/z=454.21663(M-H+)。 BPN-Py (4-N,N-diethylamino-4'-pyrene benzophenone, 4-N,N-diethylamino-4'-pyrene benzophenone) one of the monomolecular benzophenone derivatives The synthesis is to place 1-bromopyrene (1-bromopyrene) (2.825g, 10.09mmol) in a round bottom flask with nitrogen for several times, then add dry THF (dry tetrahydrofuran) (20ml) as the solvent, and cool to -78 After temperature, slowly drop n-BuLi (n-butyllithium) (6.93ml) and keep the reaction at low temperature for 1h, then add B(OMe) 3 (trimethyl borate) (0.7ml), warm to room temperature and stir Overnight, hydrochloric acid (aq) (2N) was added and stirred for 1 h, and extracted with DCM (dichloromethane)/water and aqueous hydrochloric acid solution. The organic layer was collected and the crude product Py-B(OH) 2 was removed by anhydrous magnesium sulfate. (Pyrenyl boronic acid). Combine BPN-Br (4-N,N-diethylamino-4'-chlorobenzophenone, 4-N,N-diethylamino-4'-chlorobenzophenone) (1.344g, 3.730mmol), Py-B (OH) 2 (pyrenyl boronic acid) (1.009g, 4.100mmol), Pd(PPh 3 ) 4 (tetrakis(triphenylphosphine) palladium) (0.086g, 0.074mmol) into the round-bottomed flask to pump nitrogen Next, add K 2 CO 3 (potassium carbonate) (2M) (9ml) and toluene (toluene) as the solvent (20ml) and heat the reaction at 95°C for 72 hours. After the reaction, the solvent was removed, and DCM (dichloromethane)/water and ammonium chloride aqueous solution were used for extraction. The organic layer was collected and the crude product was purified by column chromatography (n-Hexane (n-Hexane( N-hexane): EA (ethyl acetate) = 10:1) purified to obtain a yellow solid with a yield of 42.45% (0.723 g). 1 H-NMR (hydrogen-nuclear magnetic resonance spectrum) (CDCl 3 (deuterochloroform), 400MHz): δ (ppm) = 1.23-1.27 (6H, CH 3 ), 3.44-3.51 (4H, CH 2 ), 6.70- 6.74(2H,Ar-H),7.71-7.75,(2H,Ar-H),7.90-7.94(2H,Ar-H),7.93-7.96(2H,Ar-H),8.012-8.27(9H,Ar -H).FT-Mass (Fourier Transform Mass Spectrometry): m/z=454.21663 (MH + ).
溶解度測試目的是探討光起始劑在不同的工業上常用有機溶劑下之溶解度，藉以了解光起始劑的溶劑選擇性，避免在光固化體系中發生無法溶解的現象；此外本發明亦使用單體TMPTMA(第6圖)來檢測其與光起始劑之互溶性，以確保配方在混合時無沉澱物產生，另外當光起始劑在室溫下無法溶於溶劑時，透過加溫方式，提升光起始劑在該溶劑的溶解度。 The purpose of the solubility test is to investigate the solubility of the photoinitiator in different industrially used organic solvents, so as to understand the solvent selectivity of the photoinitiator and avoid the phenomenon of insoluble in the photocuring system; in addition, the present invention also uses a single TMPTMA (Figure 6) is used to test its miscibility with the photoinitiator to ensure that no precipitation occurs when the formula is mixed. In addition, when the photoinitiator cannot be dissolved in the solvent at room temperature, use heating , To improve the solubility of the photoinitiator in the solvent.
測試結果如第1表所示，將BPN、EMK、BPN-D、BPN-Ph、BPN-N、BPN-An、BPN-Py進行比較，發現新合成光起始劑可溶解於Acetone、DCM、THF及DMF中，在MeOH中的結果則需經加熱狀態方可溶解，這是因為雖有導入具有碳鏈結構之酯肪族胺類，但由於多苯環結構導致。此外於TMPTMA單體下，具有萘環與蒽環之BPN-N與BPN-An因其結構較為平面性導致其溶解度較差，相對的，含芘環之BPN-Py由於立體障礙的關係而會破壞分子結構堆疊因此有不錯之溶解度。 The test results are shown in Table 1. Comparing BPN, EMK, BPN-D, BPN-Ph, BPN-N, BPN-An, BPN-Py, it is found that the new synthetic photoinitiator can be dissolved in Acetone, DCM, In THF and DMF, the results in MeOH need to be heated before they can be dissolved. This is because although aliphatic amines with carbon chain structure are introduced, they are caused by the polyphenyl ring structure. In addition, under the TMPTMA monomer, BPN-N and BPN-An with naphthalene ring and anthracene ring have poor solubility due to their relatively flat structure. In contrast, BPN-Py with pyrene ring will be destroyed due to steric barriers. The molecular structure stack therefore has good solubility.
UV/Vis測試是將BPN、EMK與BPNs以DCM作為溶劑，濃度為10-5M下進行UV/Vis之量測，其UV/Vis圖如第7圖所示，且其結果整理於第2表中。在第7圖中可得知導入二乙胺推電子結構之BPN-D因其二苯胺為電子豐盈結構，
使最大吸收波長最為往紅光波長移動，並從390-400nm延伸至410nm左右之位置，且也有較好的消光係數；另外將二苯胺結構以苯、萘、蒽、芘等不同苯環數據之BPNs可調整其吸收波長的位置與莫耳消光係數；BPN-An及BPN-Py因為接枝蒽與芘環的分子結構導致其較具有不錯之莫耳消光係數。
The UV/Vis test uses DCM as the solvent to measure UV/Vis at a concentration of 10 -5 M. The UV/Vis diagram is shown in Figure 7, and the results are summarized in
光聚合特性分析，由於BPNs本身就具有氫予體功用(二乙胺)，因此不需要添加氫予體就可以產生光聚合反應，並進一步測試其光固化轉化率，使用Photo-DSC進行光固化之量測。當光固化反應發生時，會釋放反應熱，並藉由公式C=△Ht/Htheor來計算光固化轉化率，其中C為光固化轉化率，△Ht為t時間下的反應熱，而Htheor反應性單體的理論放熱值。在光聚合反應中，採用 TMPTMA作為反應性單體其理論放熱值為86KJ/mol，以UV光源100W/m2照射光固化配方，配方為TMPTMA為98wt%、光起始劑BPNs為2wt%，實驗結果如第8圖所示且數據整理於第3表中，可以觀察到BPN-Ph具有最大的放熱峰值(Hmax)，其值為48.69mW/mg，其最大放熱時間(Tmax)分別為76s(秒)，所有之轉化率順序為BPN-Ph(56.61%)>BPN(46.84%)>EMK(40.59%)>BPN-An(39.69%)>BPN-Py(34.67%)>BPN-D(32.50%)>BPN-N(25.74%)，將結果歸納為以下幾點原因： Analysis of photopolymerization characteristics, because BPNs itself has the function of hydrogen precursor (diethylamine), it can produce photopolymerization without adding hydrogen precursor, and further test its photocuring conversion rate, and use Photo-DSC for photocuring The measurement. When the light curing reaction occurs, the heat of reaction will be released, and the light curing conversion rate is calculated by the formula C=△H t /H theor , where C is the light curing conversion rate and △H t is the heat of reaction at time t, And the theoretical exothermic value of H theor reactive monomer. In the photopolymerization reaction, using TMPTMA as the reactive monomer, the theoretical exothermic value is 86KJ/mol, and the UV light source 100W/m 2 is used to irradiate the light curing formula. The formula is 98wt% TMPTMA and 2wt% photoinitiator BPNs. The experimental results are shown in Figure 8 and the data are sorted out in Table 3. It can be observed that BPN-Ph has the largest exothermic peak (H max ), its value is 48.69mW/mg, and its maximum exothermic time (T max ) is respectively 76s (seconds), the order of all conversion rates is BPN-Ph(56.61%)>BPN(46.84%)>EMK(40.59%)>BPN-An(39.69%)>BPN-Py(34.67%)>BPN- D(32.50%)>BPN-N(25.74%), summarize the results into the following reasons:
(1)所合成出的BPNs因添加了二乙胺及共軛片段可有效改善光收成效果，反應出較好的莫耳消光係數。 (1) The synthesized BPNs can effectively improve the light yield effect due to the addition of diethylamine and conjugated fragments, reflecting a better molar extinction coefficient.
(2)所合成出單分子型BPNs可以改善Type II光起始劑在氫予體與氫受體共混上的均勻性的疑慮，將其配方從原本的雙光子系統進一步的變成單成分系統，且相較於市面上常見的光敏劑有較好的效率。 (2) The synthesized single-molecule BPNs can improve the uniformity of the Type II photoinitiator in the blending of hydrogen precursors and hydrogen acceptors, and change its formula from the original two-photon system to a single-component system , And has better efficiency than the common photosensitizers on the market.
(3)接枝苯環之BPN-Ph得最佳轉化率至約56%位置且具有快的反應速率，可以嘗試將BPN-Ph導入現在的光固化配方中，不但可以解決現今Type II雙光子配方混摻時會發現的聚集問題，也能考慮將其導入現今市售的配方中，以改善現今的光固化配方。 (3) The best conversion rate of BPN-Ph grafted with benzene ring is about 56% and it has a fast reaction rate. You can try to introduce BPN-Ph into the current light curing formula, which can not only solve the current Type II two-photon The problem of aggregation found when the formula is mixed can also be considered to be introduced into the current commercially available formula to improve the current light-curing formula.
另外比較例中，本發明亦取非單分子型光起始劑BP-Ph與TMPTMA於同比例下進行Photo-DSC之量測，可發現BP-Ph因無氫予體的存在導致此系統無光反應之結果。 In addition, in the comparative example, the present invention also takes the non-single-molecule photoinitiator BP-Ph and TMPTMA in the same ratio to carry out the Photo-DSC measurement. The result of light reaction.
本發明乃是一種單分子型二苯甲酮衍生物涉及用於可見光波段吸收之光起始劑，其具有一氫受體、一氫予體及一共軛片，藉由不同共軛片段具可見光吸收波段致使有不同之光反應速度，其特徵為單分子型二苯甲酮衍生物於光起始劑之用途，可避免分散不均及增加分子內質子或電子轉移效率，本發明任一單分子型二苯甲酮衍生物使用於光吸收劑及光起始劑之用途。其有別於過去習知技藝具差異化，其新穎、進步及實用效益無誤。故可有效改進習知缺失，使用上有相當大之實用性。綜觀上述，本創作實施例所揭露之具體構造，確實 能提供光起始劑之應用，以其整體化學結構而言，既未曾見諸於同類產品中，申請前亦未見公開，誠已符合專利法之法定要件，爰依法提出發明專利申請。 The present invention is a single-molecule benzophenone derivative related to a photoinitiator for absorption in the visible light band. The absorption band causes different photoreaction speeds, which is characterized by the use of monomolecular benzophenone derivatives as photoinitiators, which can avoid uneven dispersion and increase the efficiency of intramolecular proton or electron transfer. Molecular benzophenone derivatives are used as light absorbers and photoinitiators. It is different from the past knowledge and skills, and its novelty, advancement and practical benefits are unmistakable. Therefore, it can effectively improve the lack of knowledge, and has considerable practicality in use. Looking at the above, the specific structure disclosed in this creative embodiment is indeed It can provide the application of photoinitiator. In terms of its overall chemical structure, it has not been seen in similar products, nor has it been disclosed before application. Since it has met the statutory requirements of the Patent Law, it has filed an application for a patent for invention in accordance with the law.
惟以上所述者，僅為本創作之一較佳實施例而已，當不能以此限定本創作實施之範圍，即大凡依本創作申請專利範圍及創作說明書內容所作之等效變化與修飾，皆應仍屬本創作專利涵蓋之範圍內。 However, the above is only one of the preferred embodiments of this creation, and should not be used to limit the scope of implementation of this creation, that is, all equivalent changes and modifications made in accordance with the scope of the patent application for this creation and the content of the creation specification are all Should still be within the scope of this creation patent.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5229238A (en) * | 1990-04-27 | 1993-07-20 | Takasago International Corporation | Electrophotographic photoreceptor comprising a benzodithiafulvene derivative charge transport material |
| US5378519A (en) * | 1992-04-28 | 1995-01-03 | Canon Kabushiki Kaisha | Electroluminescent device |
| CN101029095A (en) * | 2007-02-13 | 2007-09-05 | 武汉大学 | Mono-stripped hydrogen light initiating agent, its production and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5229238A (en) * | 1990-04-27 | 1993-07-20 | Takasago International Corporation | Electrophotographic photoreceptor comprising a benzodithiafulvene derivative charge transport material |
| US5378519A (en) * | 1992-04-28 | 1995-01-03 | Canon Kabushiki Kaisha | Electroluminescent device |
| CN101029095A (en) * | 2007-02-13 | 2007-09-05 | 武汉大学 | Mono-stripped hydrogen light initiating agent, its production and use |
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