技术领域technical field
本发明涉及高分子化合物技术领域，更具体地，涉及一种聚联苯醚高分子化合物及其制备方法和应用。The present invention relates to the technical field of polymer compounds, more specifically, to a polybiphenyl ether polymer compound and its preparation method and application.
背景技术Background technique
随着科技发展，有机发光材料在二极管、生物和传感等领域得到广泛关注及应用，目前对有机发光材料的研究基于两种材料，即荧光材料和聚集诱导发光材料。荧光材料是传统的发光材料，其缺点是易出现聚集发光猝灭，从而导致其聚集态发光减弱甚至猝灭，而聚集诱导发光材料在稀溶液中一般不发光或弱发光。此外，无论是荧光材料，还是聚集诱导发光材料，其激发及发光均易受环境干扰，且激发发光本身就伴随着环境而改变，例如发光性能易受温度的影响，这就极大地限制了现有发光材料在高温光致发光中的应用。With the development of science and technology, organic light-emitting materials have been widely concerned and applied in the fields of diodes, biology and sensing. The current research on organic light-emitting materials is based on two materials, namely fluorescent materials and aggregation-induced light-emitting materials. Fluorescent materials are traditional luminescent materials. The disadvantage is that they are prone to aggregation luminescence quenching, which leads to weakened or even quenched luminescence in the aggregated state, while aggregation-induced luminescent materials generally do not emit light or emit weakly in dilute solutions. In addition, no matter it is a fluorescent material or an aggregation-induced luminescence material, its excitation and luminescence are easily disturbed by the environment, and the excitation and luminescence itself changes with the environment, for example, the luminescence performance is easily affected by temperature, which greatly limits the current research. There are applications of luminescent materials in high temperature photoluminescence.
虽然现有技术中公开了一种聚苯砜醚三唑及其制备方法和应用，通过在聚三唑树脂结构中引入刚性的基团，以增加聚合物分子链的刚性以及分子链之间的堆积密度，从而限制高分子链段的运动，降低自由体积，进而提高聚合物的玻璃化转变温度和热稳定性，但该聚合物不具备光致发光性能。Although a kind of polyphenylsulfone ether triazole and its preparation method and application are disclosed in the prior art, rigid groups are introduced into the polytriazole resin structure to increase the rigidity of the polymer molecular chain and the connection between the molecular chains. Bulk density, thereby restricting the movement of polymer chain segments, reducing the free volume, thereby improving the glass transition temperature and thermal stability of the polymer, but the polymer does not have photoluminescent properties.
发明内容Contents of the invention
本发明的目的在于克服现有有机发光材料的耐高温性能差，导致其无法在高温环境中具备稳定光致发光性能的缺陷或不足，提供一种聚联苯醚高分子化合物，该高分子化合物不仅在高温环境中具备良好的光致发光性能，还可溶解于各类有机溶剂。The object of the present invention is to overcome the defects or deficiencies of the existing organic luminescent materials, which have poor high temperature resistance performance and cannot have stable photoluminescent performance in a high temperature environment, and provide a polybiphenyl ether polymer compound, the polymer compound Not only has good photoluminescence performance in high temperature environment, but also can be dissolved in various organic solvents.
本发明的另一目的在于提供上述聚联苯醚高分子化合物的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned polybiphenyl ether polymer compound.
本发明的另一目的在于提供上述聚联苯醚高分子化合物在制备有机发光材料中的应用。Another object of the present invention is to provide the application of the above-mentioned polybiphenyl ether polymer compound in the preparation of organic light-emitting materials.
为实现上述发明目的，本发明采用如下技术方案：In order to realize the above-mentioned purpose of the invention, the present invention adopts following technical scheme:
一种聚联苯醚高分子化合物，其结构如式(I)所示：A kind of polybiphenyl ether polymer compound, its structure is as shown in formula (I):
其中，R为中的任一种；n为32～48的整数。Among them, R is Any one of them; n is an integer of 32-48.
本发明的聚联苯醚高分子化合物中含有炔基、叠氮基团和联苯结构，在此特定分子结构中的联苯的双苯共轭结构不仅可以有效地增加聚合物分子链的刚性以及分子链之间的堆积密度，从而限制高分子链段的运动，降低自由体积，进而提高聚合物的玻璃化转变温度和热稳定性；还可以赋予聚联苯醚高分子化合物光致发光特性，使得聚联苯醚高分子化合物在高温环境中具备优异的光致发光性能。The polybiphenyl ether polymer compound of the present invention contains an alkynyl group, an azide group and a biphenyl structure, and the biphenyl conjugated structure of biphenyl in this specific molecular structure can not only effectively increase the rigidity of the polymer molecular chain And the packing density between molecular chains, so as to limit the movement of polymer chain segments, reduce the free volume, and then improve the glass transition temperature and thermal stability of polymers; it can also endow polybiphenyl ether polymer compounds with photoluminescent properties , so that the polybiphenyl ether polymer compound has excellent photoluminescent properties in a high-temperature environment.
具体地，本发明聚联苯醚高分子的玻璃化转变温度(Tg)为132.8～152.4℃，Tdmax(氮气中最大热裂解温度)达到360.5～368.9℃，不仅具有良好的热性能，还可溶于各类有机溶剂中，具有优异的可加工性能。Specifically, the polybiphenyl ether polymer of the present invention has a glass transition temperature (Tg) of 132.8 to 152.4°C, and a Tdmax (maximum thermal cracking temperature in nitrogen) of 360.5 to 368.9°C, which not only has good thermal properties, but is also soluble In various organic solvents, it has excellent processability.
优选地，本发明聚联苯醚高分子化合物中R为Preferably, R in the polybiphenyl ether polymer compound of the present invention is
优选地，所述n为35～45的整数。Preferably, the n is an integer of 35-45.
优选地，本发明所述聚联苯醚高分子化合物的平均分子量为15000～22000。Preferably, the polybiphenyl ether polymer compound of the present invention has an average molecular weight of 15,000-22,000.
本发明还保护一种聚联苯醚高分子化合物的制备方法，包括如下步骤：The present invention also protects a preparation method of a polybiphenyl ether polymer compound, comprising the following steps:
将如式(II)所示的二端基芳卞叠氮单体与如式(Ⅲ)所示的二端基联苯醚炔单体在点击聚合催化剂的作用下进行点击聚合反应，即得所述聚联苯醚高分子；Carry out click polymerization reaction with the two-terminal group aryl azide monomer shown in formula (II) and the two-terminal biphenyl ether alkyne monomer shown in formula (III) under the effect of click polymerization catalyst, to obtain The polybiphenyl ether polymer;
其中，式(Ⅱ)中的R为中的任一种。Among them, R in the formula (II) is any of the.
本发明提供的制备方法以二端基芳卞叠氮单体和二端基联苯醚炔单体通过点击反应高效制备得到，过程简单，无中间产物生成，反应条件温和，反应效率高。The preparation method provided by the present invention is efficiently prepared by a two-terminal aryl azide monomer and a two-terminal biphenyl ether alkyne monomer through a click reaction, the process is simple, no intermediate product is generated, the reaction conditions are mild, and the reaction efficiency is high.
优选地，所述二端基芳卞叠氮单体通过如下过程得到：以4,4'-二甲基联苯、对二甲苯或间二甲苯为原料，与NBS(N-溴代丁二酰亚胺)在引发剂(例如过氧化二苯甲酰)下反应生成苄基溴，苄基溴和叠氮化钠的亲核取代反应即得二端基芳卞叠氮单体。Preferably, the two-terminal aryl azide monomer is obtained through the following process: using 4,4'-dimethylbiphenyl, p-xylene or m-xylene as raw materials, and NBS (N-bromobutane imide) reacts under the initiator (such as dibenzoyl peroxide) to generate benzyl bromide, and the nucleophilic substitution reaction of benzyl bromide and sodium azide obtains the two terminal aryl azide monomers.
4,4'-二甲基联苯、对二甲苯、间二甲苯廉价、易得，成本较低。4,4'-Dimethylbiphenyl, p-xylene, and m-xylene are cheap, easy to obtain, and low in cost.
更为优选地，所述过氧化二苯甲酰、原料和NBS的摩尔比为1:(30-60):(80～120)。More preferably, the molar ratio of the dibenzoyl peroxide, raw material and NBS is 1:(30-60):(80-120).
更为优选地，所述原料与NBS反应的温度为70～80℃，时间为1～5h。More preferably, the reaction temperature of the raw material and NBS is 70-80° C., and the time is 1-5 hours.
更为优选地，原料与NBS的反应体系中还存在溶剂，例如CCl4，所述反应体系中原料的浓度为0.4～0.5g/L。More preferably, there is a solvent, such as CCl4 , in the reaction system of the raw material and NBS, and the concentration of the raw material in the reaction system is 0.4-0.5 g/L.
更为优选地，所述苄基溴和叠氮化钠的摩尔比为1:(2～3)。More preferably, the molar ratio of benzyl bromide to sodium azide is 1:(2-3).
更为优选地，所述原料和NBS反应后还包括减压蒸发，硅胶柱层析的步骤。More preferably, after the reaction of the raw material and NBS, the steps of evaporation under reduced pressure and silica gel column chromatography are also included.
具体地，所述原料和NBS的反应过程为：原料、N-溴代丁二酰亚胺和过氧化二苯甲酰混合，在氮气条件下加入CCl4溶剂，70～80℃下搅拌冷凝回流，过夜反应(反应12h)；过滤后减压蒸发去除溶剂，残余物用石油醚/二氯甲烷(10:1/mL:mL)作洗脱液经硅胶柱层析纯化，即得所述苄基溴。Specifically, the reaction process of the raw material and NBS is as follows: the raw material, N-bromosuccinimide and dibenzoyl peroxide are mixed, CCl4 solvent is added under nitrogen condition, stirring and condensing at 70-80°C under reflux , reacted overnight (reaction 12h); filtered and evaporated under reduced pressure to remove the solvent, and the residue was purified by silica gel column chromatography using petroleum ether/dichloromethane (10:1/mL:mL) as eluent to obtain the benzyl base bromide.
更为优选地，所述亲核取代反应的温度为55～65℃，时间为1～5h。More preferably, the temperature of the nucleophilic substitution reaction is 55-65° C., and the time is 1-5 hours.
更为优选地，所述亲核取代反应的反应体系中还存在溶剂，例如DMF，所述反应体系中苄基溴的浓度为0.4～0.5g/L。More preferably, there is a solvent, such as DMF, in the reaction system of the nucleophilic substitution reaction, and the concentration of benzyl bromide in the reaction system is 0.4-0.5 g/L.
更为优选地，所述亲核取代反应后还包括萃取，洗涤，干燥，减压蒸发，硅胶柱层析的步骤。More preferably, after the nucleophilic substitution reaction, the steps of extraction, washing, drying, evaporation under reduced pressure and silica gel column chromatography are also included.
具体地，所述亲核取代反应的过程为：苄基溴和叠氮化钠加入反应器中，在氮气的氛围下加入DMF溶剂，在55～65℃下搅拌反应过夜，待反应液冷却至室温后倒入去离子水，再用乙醚萃取，收集有机层，用再用饱和食盐水洗涤，经无水硫酸镁干燥，过滤后减压蒸发去除乙醚溶剂，产物用石油醚/二氯甲烷(10:1/mL:mL)作洗脱液经硅胶柱层析即得所述二端基芳卞叠氮单体。Specifically, the process of the nucleophilic substitution reaction is: add benzyl bromide and sodium azide to the reactor, add DMF solvent under nitrogen atmosphere, stir and react overnight at 55-65°C, and wait for the reaction liquid to cool to Pour deionized water after room temperature, then extract with ether, collect the organic layer, wash with saturated brine, dry over anhydrous magnesium sulfate, filter and evaporate under reduced pressure to remove the ether solvent, and the product is washed with petroleum ether/dichloromethane ( 10:1/mL:mL) as the eluent through silica gel column chromatography to obtain the two-terminal aryl azide monomer.
优选地，二端基联苯醚炔单体通过如下过程得到：4,4'二羟基联苯在碳酸钾和溶剂存在的条件下与溴丙炔反应，即得二端基联苯醚炔单体。Preferably, the diphenyl ether alkyne monomer is obtained through the following process: 4,4'dihydroxybiphenyl reacts with propyne bromide in the presence of potassium carbonate and a solvent to obtain the diphenyl ether alkyne monomer body.
更为优选地，所述为4,4'二羟基联苯、3-溴丙炔和碳酸钾的摩尔比为＝10:(10-40):(30～50)。More preferably, the molar ratio of 4,4' dihydroxybiphenyl, 3-bromopropyne and potassium carbonate is =10:(10-40):(30-50).
更为优选地，所述反应的温度为30～80℃，时间为1～5h。More preferably, the temperature of the reaction is 30-80° C., and the time is 1-5 hours.
更为优选地，所述溶剂为DMF(N,N-二甲基甲酰胺)，反应体系中4,4'二羟基联苯的浓度为45～55g/L。More preferably, the solvent is DMF (N,N-dimethylformamide), and the concentration of 4,4'dihydroxybiphenyl in the reaction system is 45-55 g/L.
更为优选地，所述反应后还包括过滤，萃取，洗涤，干燥，减压蒸发的步骤。More preferably, the reaction further includes the steps of filtering, extracting, washing, drying and evaporating under reduced pressure.
具体地，二端基联苯醚炔单体通过如下过程得到：4,4'二羟基联苯、3-溴丙炔、无水碳酸钾和DMF溶剂混合，通入氮气，在30～80℃下搅拌过夜反应，用薄板层析TLC跟踪反应，待反应完全后停止反应，过滤去除碳酸钾，将反应液倒入去离子水，用甲醇萃取3次，收集有机层，再用饱和食盐水洗涤两次，加入无水硫酸镁干燥，减压去除溶剂，得白色固体产物二端基联苯醚炔单体。Specifically, the two-terminal biphenyl ether alkyne monomer is obtained through the following process: 4,4'dihydroxybiphenyl, 3-bromopropyne, anhydrous potassium carbonate and DMF solvent are mixed, nitrogen gas is introduced, and at 30-80°C Stir overnight to react, follow the reaction with thin-plate chromatography TLC, stop the reaction after the reaction is complete, filter to remove potassium carbonate, pour the reaction solution into deionized water, extract with methanol for 3 times, collect the organic layer, and wash with saturated saline Twice, add anhydrous magnesium sulfate to dry, and remove the solvent under reduced pressure to obtain a white solid product diphenyl ether alkyne monomer.
优选地，所述点击聚合催化剂为一价铜盐催化剂。Preferably, the click polymerization catalyst is a monovalent copper salt catalyst.
优选地，所述点击聚合催化剂和二端基芳卞叠氮单体的摩尔比为(1～3):50。Preferably, the molar ratio of the click polymerization catalyst to the diterminated aryl azide monomer is (1-3):50.
优选地，所述点击聚合反应的温度为30～80℃。Preferably, the temperature of the click polymerization reaction is 30-80°C.
优选地，所述二端基芳卞叠氮单体和二端基联苯醚炔单体的摩尔比为1:1。Preferably, the molar ratio of the diterminated aryl azide monomer to the diphenyl ether alkyne monomer is 1:1.
具体地，所述点击聚合反应的过程为：在反应器中依次加入二端基联苯醚炔单体和二端基芳卞叠氮单体，加入DMSO溶剂将其溶解，在氮气氛围的30～80℃下搅拌一段时间。将五水合硫酸铜和抗坏血酸钠溶解在去离子水中，用恒压滴液漏洞逐滴加入反应液中，过夜反应(反应12h)。反应结束后，将反应液倒入饱和的EDTA二钠的饱和水溶液，有沉淀产生，过滤后用去离子水洗涤三次，过滤，将滤饼溶解在DMSO溶剂，倒入甲醇/水的混合溶液，析出沉淀物，用甲醇洗涤2～3次，烘干称重，即得所述聚联苯醚高分子。Specifically, the process of the click polymerization reaction is: sequentially add a diphenyl ether alkyne monomer and a diphenyl azide monomer into the reactor, add DMSO solvent to dissolve it, and dissolve it in a nitrogen atmosphere of 30 Stir at ~80°C for a while. Dissolve copper sulfate pentahydrate and sodium ascorbate in deionized water, add dropwise to the reaction solution with a constant pressure drop hole, and react overnight (reaction 12h). After the reaction is over, pour the reaction solution into a saturated aqueous solution of disodium EDTA, a precipitate occurs, filter and wash with deionized water three times, filter, dissolve the filter cake in DMSO solvent, pour into a mixed solution of methanol/water, Precipitate is precipitated, washed with methanol for 2 to 3 times, dried and weighed to obtain the polybiphenyl ether polymer.
上述聚联苯醚高分子化合物在制备耐高温光致发光器件中的应用，也在本发明的保护范围内。The application of the above-mentioned polybiphenyl ether polymer compound in the preparation of high-temperature resistant photoluminescent devices is also within the protection scope of the present invention.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明提供的聚联苯醚高分子化合物不仅在高温环境中具备优异的光致发光性能，而且可溶于各类有机溶剂，具有较好的加工性能。The polybiphenyl ether macromolecular compound provided by the invention not only has excellent photoluminescent performance in a high-temperature environment, but also is soluble in various organic solvents and has good processing performance.
本发明提供的制备方法以二端基芳卞叠氮单体和二端基联苯醚炔单体通过点击反应高效制备得到，过程简单，无中间产物生成，反应条件温和，反应效率高。The preparation method provided by the present invention is efficiently prepared by a two-terminal aryl azide monomer and a two-terminal biphenyl ether alkyne monomer through a click reaction, the process is simple, no intermediate product is generated, the reaction conditions are mild, and the reaction efficiency is high.
附图说明Description of drawings
图1是二端基联苯醚炔单体Ⅲ及其原料、中间体在DMSO中的1H NMR对比图。Fig. 1 is a comparison chart of1 H NMR of diphenyl ether alkyne monomer III and its raw materials and intermediates in DMSO.
图2是PT1、PT2、PT3的DSC曲线。Fig. 2 is the DSC curve of PT1, PT2, PT3.
图3是PT1、PT2、PT3的TG图。FIG. 3 is a TG diagram of PT1, PT2, and PT3.
图4是PT1、PT2、PT3的DTG图。FIG. 4 is a DTG diagram of PT1, PT2, and PT3.
图5是PT2的激发发射光谱图。Fig. 5 is an excitation emission spectrum diagram of PT2.
具体实施方式Detailed ways
下面结合具体实施方式对本发明作进一步的说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。The present invention will be further described below in conjunction with specific embodiments, but the examples do not limit the present invention in any form. Unless otherwise specified, the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
(1)二端基芳卞叠氮单体Ⅱ-1由以下制备方法制得：(1) Two-terminal aryl azide monomer II-1 is prepared by the following preparation method:
将9.1130g(50mmol)4,4'-二甲基联苯，17.7984g(100mmol)N-溴代丁二酰亚胺，0.2422g(1mmol)过氧化二苯甲酰放入装有回流冷凝管的三口烧瓶中，在氮气条件下加入200mL CCl4溶剂，78℃条件下搅拌冷凝回流，过夜反应。过滤后减压蒸发去除溶剂，残余物用石油醚/二氯甲烷(10:1/mL:mL)作洗脱液经硅胶柱层析纯化的白色固体粉末12.6100g的4,4'-二溴甲基联苯，产率为74.2％；Put 9.1130g (50mmol) 4,4'-dimethylbiphenyl, 17.7984g (100mmol) N-bromosuccinimide, 0.2422g (1mmol) dibenzoyl peroxide into a reflux condenser In a three-necked flask, 200 mL of CCl4 solvent was added under nitrogen, stirred and condensed to reflux at 78° C., and reacted overnight. After filtration, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography using petroleum ether/dichloromethane (10:1/mL:mL) as the eluent. 12.6100 g of 4,4'-dibromo Methylbiphenyl, yield rate is 74.2%;
将1.70g(5mmol)4,4'-二溴甲基联苯，0.780g(12mmol)叠氮化钠，加入到带有转子的三口烧瓶中，在氮气的氛围下加入20mL DMF溶剂，60℃下搅拌反应过夜，待反应液冷却至室温后倒入去离子水(30mL)，再用乙醚萃取(3×20mL)，收集有机层，用再用饱和食盐水(3×20mL)洗涤，经无水硫酸镁干燥，过滤后减压蒸发去除乙醚溶剂，产物用石油醚/二氯甲烷(20:1/mL:mL)作洗脱液经硅胶柱层析得到1.230g白色固体4,4'-联苯二苄基叠氮，即为二端基芳卞叠氮单体Ⅱ-1，产率为93.1％。Add 1.70g (5mmol) of 4,4'-dibromomethylbiphenyl and 0.780g (12mmol) of sodium azide into a three-necked flask with a rotor, add 20mL of DMF solvent under a nitrogen atmosphere, 60°C The reaction was stirred overnight, and after the reaction solution was cooled to room temperature, it was poured into deionized water (30 mL), extracted with diethyl ether (3×20 mL), and the organic layer was collected, washed with saturated brine (3×20 mL), and washed with Dry over magnesium sulfate, filter and evaporate under reduced pressure to remove the ether solvent, and use petroleum ether/dichloromethane (20:1/mL:mL) as the eluent to obtain 1.230 g of white solid 4,4'- Biphenyl dibenzyl azide, which is the two-terminal aryl azide monomer II-1, has a yield of 93.1%.
(2)二端基芳卞叠氮单体Ⅱ-2由以下制备方法制得：(2) The two-terminal aromatic Bian azide monomer II-2 is prepared by the following preparation method:
在装有转子的250mL三口烧瓶中加入17.80g N-溴代丁二酰亚胺(NBS，100mmol)，5.3082g对二甲苯(50mmol)，0.2422g过氧化二苯甲酰(BPO，1mmol)和60mL四氯化碳，在氮气的氛围下78℃冷凝回流12小时后过滤悬浮液，浓缩滤液，用甲醇重结晶得白色晶体(1,4-二-(溴甲基苯)8.2312g，产率为62.4％；Add 17.80g N-bromosuccinimide (NBS, 100mmol), 5.3082g p-xylene (50mmol), 0.2422g dibenzoyl peroxide (BPO, 1mmol) and 60mL of carbon tetrachloride was condensed and refluxed at 78°C for 12 hours under a nitrogen atmosphere, and the suspension was filtered, the filtrate was concentrated, and recrystallized with methanol to obtain 8.2312g of white crystals (1,4-bis-(bromomethylbenzene), the yield 62.4%;
将2.6395g(10mmol)1,4-二-(溴甲基苯)和1.430g(22mmol)叠氮化钠加入装有转子的100mL三口烧瓶中，在氮气氛围下加入20mL DMF，60℃下反应10h，将反应液倒入100mL去离子水中，用30mL无水乙醚萃取三次，收集有机相，再用100mL饱和食盐水洗涤，无水硫酸镁干燥，过滤后蒸发溶剂得1.7216g油状液体对二叠氮苄，即为二端基芳卞叠氮单体Ⅱ-2，产率为91.5％。Add 2.6395g (10mmol) of 1,4-bis-(bromomethylbenzene) and 1.430g (22mmol) of sodium azide into a 100mL three-necked flask equipped with a rotor, add 20mL of DMF under a nitrogen atmosphere, and react at 60°C 10h, the reaction solution was poured into 100mL deionized water, extracted three times with 30mL anhydrous ether, the organic phase was collected, washed with 100mL saturated brine, dried over anhydrous magnesium sulfate, filtered and evaporated to obtain 1.7216g oily liquid parapermia Azobenzyl, which is the two terminal aryl azide monomer II-2, has a yield of 91.5%.
(3)二端基芳卞叠氮单体Ⅱ-3由以下制备方法制得：(3) The two-terminal aryl azide monomer II-3 is prepared by the following preparation method:
在装有转子的250mL三口烧瓶中加入17.80g N-溴代丁二酰亚胺(NBS,100mmol)，5.3083g间二甲苯(50mmol)，0.2422g过氧化二苯甲酰(BPO,1mmol)和60mL四氯化碳，在氮气的氛围下78℃冷凝回流12小时。过滤悬浮液，浓缩滤液，用甲醇重结晶得白色晶体(1,3-二-(溴甲基苯)6.8342g，产率51.8％；Add 17.80g N-bromosuccinimide (NBS, 100mmol), 5.3083g m-xylene (50mmol), 0.2422g dibenzoyl peroxide (BPO, 1mmol) and 60mL of carbon tetrachloride was condensed and refluxed at 78°C for 12 hours under nitrogen atmosphere. The suspension was filtered, the filtrate was concentrated, and recrystallized from methanol to obtain 6.8342 g of white crystals (1,3-bis-(bromomethylbenzene), yield 51.8%;
将2.6395g(10mmol)1,3-二-(溴甲基苯)和1.430g(22mmol)叠氮化钠加入装有转子的100mL三口烧瓶中，在氮气氛围下加入20mL DMF，60℃下反应10h，将反应液倒入100mL去离子水中，用30mL无水乙醚萃取三次，收集有机相，再用100mL饱和食盐水洗涤，无水硫酸镁干燥，过滤后蒸发溶剂得1.7126g油状液体间二叠氮苄，即为二端基芳卞叠氮单体Ⅱ-3，产率为91.0％。Add 2.6395g (10mmol) 1,3-bis-(bromomethylbenzene) and 1.430g (22mmol) sodium azide into a 100mL three-necked flask equipped with a rotor, add 20mL DMF under nitrogen atmosphere, and react at 60°C 10h, the reaction solution was poured into 100mL deionized water, extracted three times with 30mL anhydrous ether, the organic phase was collected, washed with 100mL saturated brine, dried over anhydrous magnesium sulfate, filtered and evaporated to obtain 1.7126g oily liquid Azobenzyl, which is the two terminal aryl azide monomer II-3, has a yield of 91.0%.
(4)二端基联苯醚炔单体Ⅲ由以下制备方法制得：(4) Diphenyl ether alkyne monomer III with two terminal groups is prepared by the following preparation method:
向100mL三口烧瓶中加入2.5027g(10mmol)4,4'二羟基联苯，3.5688g(30mmol)3-溴丙炔，5.5284g(40mmol)无水碳酸钾以及50mL无水DMF溶剂，通入氮气，在60℃温度下搅拌过夜反应，用薄板层析TLC跟踪反应，待反应完全后停止反应，过滤去除碳酸钾，将反应液倒入100mL去离子水，用50mL乙酸乙酯萃取3次，收集有机层，再用饱和食盐水洗涤两次，加入无水硫酸镁干燥，减压去除溶剂，得2.7838g白色固体产物，即为二端基联苯醚炔单体Ⅲ，产率为85.3％。Add 2.5027g (10mmol) 4,4'dihydroxybiphenyl, 3.5688g (30mmol) 3-bromopropyne, 5.5284g (40mmol) anhydrous potassium carbonate and 50mL anhydrous DMF solvent into a 100mL three-necked flask, and blow nitrogen , stirred at 60°C for overnight reaction, tracked the reaction with thin-plate chromatography TLC, stopped the reaction after the reaction was complete, filtered to remove potassium carbonate, poured the reaction solution into 100mL deionized water, extracted 3 times with 50mL ethyl acetate, collected The organic layer was washed twice with saturated brine, dried by adding anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to obtain 2.7838 g of a white solid product, namely diphenyl ether alkyne monomer III, with a yield of 85.3%.
图1是二端基联苯醚炔单体Ⅲ及其原料，中间体的在CDCl3的1H NMR对比图。从图可知，原料-OH的氢在10.54ppm处消失，产物在4.90ppm和3.64ppm分别出现-CH2和C≡CH中氢的特征吸收峰，对产物中1,2,3,4四处峰面积积分比为2:2:2:1，与理论值一致，说明二端基联苯醚炔单体Ⅲ成功制备得到。Fig. 1 is a comparison chart of1 H NMR in CDCl3 of diphenyl ether alkyne monomer III and its raw materials and intermediates. It can be seen from the figure that the hydrogen of the raw material -OH disappears at 10.54ppm, and the product appears at4.90ppm and 3.64ppm respectively. The area integral ratio was 2:2:2:1, which was consistent with the theoretical value, indicating that the diphenyl ether alkyne monomer III was successfully prepared.
实施例1Example 1
一种聚联苯醚高分子化合物(记为PT1)，通过如下过程制备得到：A polybiphenyl ether macromolecular compound (referred to as PT1), prepared by the following process:
将0.2623g(1mmol)二端基联苯醚炔单体Ⅲ和0.2643g(1mmol)4,4'-联苯二苄基叠氮(二端基芳卞叠氮单体Ⅱ-1)装入带有转子的三口烧瓶中，加入20mL DMSO溶剂将其溶解，在氮气氛围下45℃搅拌30min。将0.0125g(5％mmol)五水合硫酸铜和0.0198g(10％mmol)抗坏血酸钠溶解在10mL去离子水中，用恒压滴液漏洞逐滴加入反应液中，过夜反应。反应结束后，将反应液倒入饱和的EDTA二钠的饱和水溶液，有沉淀产生，过滤后用20mL去离子水洗涤三次，过滤，将滤饼溶解在DMSO溶剂，倒入50mL甲醇/水(3:2/v:v)的混合溶液，析出沉淀物，用甲醇洗涤2-3次，烘干称重，得到淡黄色固体粉末0.3995g即为PT1，产率75.9％Put 0.2623g (1mmol) diphenyl ether alkyne monomer III and 0.2643g (1mmol) 4,4'-biphenyl dibenzyl azide (two terminal aryl azide monomer II-1) into In a three-necked flask with a rotor, 20 mL of DMSO solvent was added to dissolve it, and stirred at 45° C. for 30 min under a nitrogen atmosphere. Dissolve 0.0125g (5%mmol) copper sulfate pentahydrate and 0.0198g (10%mmol) sodium ascorbate in 10mL deionized water, add dropwise to the reaction solution with a constant pressure drop hole, and react overnight. After the reaction was over, the reaction solution was poured into a saturated aqueous solution of saturated disodium EDTA, and a precipitate was produced. After filtering, it was washed three times with 20 mL of deionized water, filtered, and the filter cake was dissolved in DMSO solvent, and poured into 50 mL of methanol/water (3 :2/v:v) mixed solution, the precipitate was precipitated, washed 2-3 times with methanol, dried and weighed to obtain 0.3995g of light yellow solid powder, which was PT1, with a yield of 75.9%
实施例2Example 2
一种聚联苯醚高分子化合物(记为PT2)，通过如下过程制备得到：A polybiphenyl ether polymer compound (referred to as PT2), prepared by the following process:
将0.2623g(1mmol)二端基联苯醚炔单体Ⅲ和0.1882g(1mmol)对二叠氮苄(二端基芳卞叠氮单体Ⅱ-2)装入带有转子的三口烧瓶中，加入20mL DMSO溶剂将其溶解,在氮气氛围下45℃搅拌30min。将0.0125g(5％mmol)五水合硫酸铜和0.0198g(10％mmol)抗坏血酸钠溶解在10mL去离子水中，用恒压滴液漏洞逐滴加入反应液中，过夜反应。反应结束后，将反应液倒入饱和的EDTA二钠的饱和水溶液，有沉淀产生，过滤后用20mL去离子水洗涤三次，过滤，将滤饼溶解在DMSO溶剂，倒入50mL甲醇/水(3:2/mL:mL)的混合溶液，析出沉淀物，用甲醇洗涤2-3次，烘干称重，得到淡黄色固体粉末0.3312g即为PT2，产率73.5％。Put 0.2623g (1mmol) diphenyl ether alkyne monomer III and 0.1882g (1mmol) p-diazide benzyl (two-terminal aryl azide monomer II-2) into a three-necked flask with a rotor , adding 20 mL of DMSO solvent to dissolve it, and stirring at 45° C. for 30 min under a nitrogen atmosphere. Dissolve 0.0125g (5%mmol) copper sulfate pentahydrate and 0.0198g (10%mmol) sodium ascorbate in 10mL deionized water, add dropwise to the reaction solution with a constant pressure drop hole, and react overnight. After the reaction was over, the reaction solution was poured into a saturated aqueous solution of saturated disodium EDTA, and a precipitate was produced. After filtering, it was washed three times with 20 mL of deionized water, filtered, and the filter cake was dissolved in DMSO solvent, and poured into 50 mL of methanol/water (3 :2/mL:mL), the precipitate was precipitated, washed 2-3 times with methanol, dried and weighed to obtain 0.3312g of light yellow solid powder which was PT2, and the yield was 73.5%.
实施例3Example 3
一种聚联苯醚高分子化合物(记为PT3)，通过如下过程制备得到：A polybiphenyl ether polymer compound (referred to as PT3), prepared by the following process:
将0.2623g(1mmol)二端基联苯醚炔单体Ⅲ和0.1882g(1mmol)间二叠氮苄(二端基芳卞叠氮单体Ⅱ-3)装入带有转子的三口烧瓶中，加入20mL DMSO溶剂将其溶解，在氮气氛围下45℃搅拌30min。将0.0125g(5％mmol)五水合硫酸铜和0.0198g(10％mmol)抗坏血酸钠溶解在10mL去离子水中，用恒压滴液漏洞逐滴加入反应液中，过夜反应。反应结束后，将反应液倒入饱和的EDTA二钠的饱和水溶液，有沉淀产生，过滤后用20mL去离子水洗涤三次，过滤，将滤饼溶解在DMSO溶剂，倒入50mL甲醇/水(3:2/mL:mL)的混合溶液，析出沉淀物，用甲醇洗涤2-3次，烘干称重，得到淡黄色固体粉末0.3563g即为PT3，产率79.1％。Put 0.2623g (1mmol) diphenyl ether alkyne monomer III and 0.1882g (1mmol) benzyldiazide (two-terminal aryl azide monomer II-3) into a three-necked flask with a rotor , adding 20 mL of DMSO solvent to dissolve it, and stirring at 45° C. for 30 min under a nitrogen atmosphere. Dissolve 0.0125g (5%mmol) copper sulfate pentahydrate and 0.0198g (10%mmol) sodium ascorbate in 10mL deionized water, add dropwise to the reaction solution with a constant pressure drop hole, and react overnight. After the reaction was over, the reaction solution was poured into a saturated aqueous solution of saturated disodium EDTA, and a precipitate was produced. After filtering, it was washed three times with 20 mL of deionized water, filtered, and the filter cake was dissolved in DMSO solvent, and poured into 50 mL of methanol/water (3 :2/mL:mL), the precipitate was precipitated, washed 2-3 times with methanol, dried and weighed to obtain 0.3563 g of light yellow solid powder which was PT3, and the yield was 79.1%.
性能测试Performance Testing
(1)分子量和分布系数的确定(1) Determination of molecular weight and distribution coefficient
对实施例1～3提供的PT1、PT2、PT3的分子量和分布系数进行测定，结果如表1所示。The molecular weights and distribution coefficients of PT1, PT2, and PT3 provided in Examples 1-3 were measured, and the results are shown in Table 1.
表1实施例1～3提供的PT1、PT2、PT3的分子量和分布系数Molecular weight and distribution coefficient of PT1, PT2, PT3 that table 1 embodiment 1～3 provides
(2)热性能测试(2) thermal performance test
对实施例1～3提供的PT1、PT2、PT3的热性能进行测试。The thermal properties of PT1, PT2 and PT3 provided in Examples 1-3 were tested.
Tg测试过程及条件为，以10℃/min的升温速率从40℃升温到300℃，再以30℃/min的降温速率到40℃，最后再以10℃/min的升温速率升温到250℃。The Tg test process and conditions are as follows: heat up from 40°C to 300°C at a heating rate of 10°C/min, then cool down to 40°C at a cooling rate of 30°C/min, and finally rise to 250°C at a heating rate of 10°C/min .
热失重测试为氮气氛围下，保护气流量为30mL/min，吹扫气流量为30mL/min，以10℃/min的升温速率从40℃升温到600℃，得到样品热失重图谱。The thermogravimetric test was carried out under nitrogen atmosphere, the protective gas flow rate was 30mL/min, the purge gas flow rate was 30mL/min, and the temperature was raised from 40°C to 600°C at a heating rate of 10°C/min to obtain the sample thermogravimetric spectrum.
图2为PT1、PT2、PT3的DSC曲线，图3为PT1、PT2、PT3的TG图，图4为PT1、PT2、PT3的DTG图，表2为PT1、PT2、PT3的热性能测试结果，从图2、图3、图4及表2可知，PT1、PT2、PT3具有较佳的耐高温性能。Figure 2 is the DSC curve of PT1, PT2, PT3, Figure 3 is the TG diagram of PT1, PT2, PT3, Figure 4 is the DTG diagram of PT1, PT2, PT3, Table 2 is the thermal performance test results of PT1, PT2, PT3, It can be seen from Figure 2, Figure 3, Figure 4 and Table 2 that PT1, PT2, and PT3 have better high temperature resistance.
表2 PT1、PT2、PT3的热性能测试结果Table 2 Thermal performance test results of PT1, PT2, PT3
(3)发光性能测试(3) Luminous performance test
图5是实施例2中产物PT2的激发发射光谱，由图5可知，在348nm处波长的激发下，PT2在430nm处出现了等强度的发射峰，斯托克斯位移为82nm，发出蓝色荧光。实施例1中的产物PT2和实施例3中的产物PT3在348nm处波长的激发下的发射光谱与实施例2中的PT2基本相同，而且本发明聚联苯醚高分子化合物具备良好的热稳定性，其在高温条件下分子结构不易被破坏，即在高温环境中具备稳定光致发光性能。Figure 5 is the excitation emission spectrum of the product PT2 in Example 2. As can be seen from Figure 5, under the excitation of a wavelength of 348nm, PT2 has an emission peak of equal intensity at 430nm, and the Stokes shift is 82nm, emitting blue fluorescence. The emission spectrum of the product PT2 in Example 1 and the product PT3 in Example 3 under excitation at a wavelength of 348nm is basically the same as that of PT2 in Example 2, and the polybiphenyl ether polymer compound of the present invention has good thermal stability Its molecular structure is not easy to be destroyed under high temperature conditions, that is, it has stable photoluminescence performance in high temperature environment.
(4)溶解性能测试(4) Solubility test
对二端基联苯醚炔单体Ⅲ及实施例1～3所制备得到的PT1、PT2、PT3的溶解性能进行测试，测试过程为用电子天平准确称取0.05g的待测物加入5mL的溶剂中，在常温下不断搅拌，一定时间后，静置，等固相完全沉淀后，间隔一定时间取上层溶液分析，两者浓度基本一致后，结束测试，对比溶解度，若没有待测物残留，则定义其为完全溶解；若待测物残存量为1％～90％，则定义其为部分溶解；若待测物部分残留量大于90％，则定义其为不溶解。Test the solubility of the diphenyl ether alkyne monomer III and the PT1, PT2, and PT3 prepared in Examples 1 to 3. The test process is to accurately weigh 0.05 g of the test substance with an electronic balance and add 5 mL of In the solvent, stir continuously at room temperature. After a certain period of time, let it stand still. After the solid phase is completely precipitated, take the upper layer solution for analysis at a certain interval. After the concentration of the two is basically the same, end the test and compare the solubility. , it is defined as completely dissolved; if the residual amount of the analyte is 1% to 90%, it is defined as partially dissolved; if the residual amount of the analyte is greater than 90%, it is defined as insoluble.
测试结果如表3，其中，“+”表示溶解，“～”表示部分溶解，“-”表示不溶解。从表3可知，可以看出二端基联苯醚炔单体Ⅲ可以很好溶于极性稍强的非质子溶剂中，而PT1～PT3的溶解性相对较好，在强极性非质子溶剂中有较好的溶解性，其主要原因可能就是因为单体Ⅲ有柔性的亚甲基和烷氧基团，引入主链后使分子链的柔性有所提高。The test results are shown in Table 3, wherein "+" means dissolved, "~" means partially dissolved, and "-" means not dissolved. As can be seen from Table 3, it can be seen that the diphenyl ether alkyne monomer III can be well dissolved in a slightly more polar aprotic solvent, while the solubility of PT1-PT3 is relatively good, and in the highly polar aprotic solvent It has better solubility in solvents, and the main reason may be that monomer III has flexible methylene and alkoxy groups, and the flexibility of the molecular chain is improved after being introduced into the main chain.
表3PT1、PT2、PT3的溶解性能测试结果The solubility test result of table 3PT1, PT2, PT3
本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。The above-mentioned embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limiting the implementation of the present invention. For those of ordinary skill in the art, on the basis of the above description, other changes or changes in different forms can also be made. It is not necessary and impossible to exhaustively list all the implementation manners here. All modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the claims of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310342689.5ACN116515105B (en) | 2023-03-31 | 2023-03-31 | A polybiphenyl ether polymer compound and its preparation method and application |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310342689.5ACN116515105B (en) | 2023-03-31 | 2023-03-31 | A polybiphenyl ether polymer compound and its preparation method and application |
| Publication Number | Publication Date |
|---|---|
| CN116515105Atrue CN116515105A (en) | 2023-08-01 |
| CN116515105B CN116515105B (en) | 2024-05-14 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310342689.5AActiveCN116515105B (en) | 2023-03-31 | 2023-03-31 | A polybiphenyl ether polymer compound and its preparation method and application |
| Country | Link |
|---|---|
| CN (1) | CN116515105B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5420275A (en)* | 1990-11-27 | 1995-05-30 | Takeda Chemical Industries, Ltd. | Pyridopyridazine compounds and their use |
| US6162931A (en)* | 1996-04-12 | 2000-12-19 | Molecular Probes, Inc. | Fluorinated xanthene derivatives |
| EP2436673A1 (en)* | 2010-09-30 | 2012-04-04 | Anna Niaraki | Curcumin derivatives with improved physicochemical properties and nanoliposomes surface-decorated with the derivatives with very high affinity for amyloid-beta1-42 peptide |
| CN102585220A (en)* | 2012-01-16 | 2012-07-18 | 浙江大学 | Hyperbranched polytriazole formate as well as preparation method and application thereof |
| CN105906807A (en)* | 2016-06-16 | 2016-08-31 | 华南理工大学 | Polytriazole with intrinsic flame retardance and preparing method and application thereof |
| CN106243352A (en)* | 2016-07-29 | 2016-12-21 | 苏州大学 | A kind of polyphenylene triazole formic acid esters and preparation method and application |
| CN107325284A (en)* | 2017-07-02 | 2017-11-07 | 苏州大学 | A kind of hyperbranched poly phenyl triazole formic acid esters and preparation method and application |
| CN109438700A (en)* | 2018-11-19 | 2019-03-08 | 苏州大学 | A kind of poly- methyl-triazole formic acid esters and the preparation method and application thereof |
| CN109880088A (en)* | 2019-04-04 | 2019-06-14 | 苏州大学 | Polytrimethylsilyl triazole and preparation method and application thereof |
| CN114058007A (en)* | 2021-11-22 | 2022-02-18 | 华南理工大学 | A kind of method that organic base catalyzes alkyne carboxylic acid polymerization to prepare polycarbonyl enol ester compound |
| CN115353622A (en)* | 2022-09-15 | 2022-11-18 | 苏州大学 | Poly 1, 5-substituted triazole and preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5420275A (en)* | 1990-11-27 | 1995-05-30 | Takeda Chemical Industries, Ltd. | Pyridopyridazine compounds and their use |
| US6162931A (en)* | 1996-04-12 | 2000-12-19 | Molecular Probes, Inc. | Fluorinated xanthene derivatives |
| EP2436673A1 (en)* | 2010-09-30 | 2012-04-04 | Anna Niaraki | Curcumin derivatives with improved physicochemical properties and nanoliposomes surface-decorated with the derivatives with very high affinity for amyloid-beta1-42 peptide |
| CN102585220A (en)* | 2012-01-16 | 2012-07-18 | 浙江大学 | Hyperbranched polytriazole formate as well as preparation method and application thereof |
| CN105906807A (en)* | 2016-06-16 | 2016-08-31 | 华南理工大学 | Polytriazole with intrinsic flame retardance and preparing method and application thereof |
| CN106243352A (en)* | 2016-07-29 | 2016-12-21 | 苏州大学 | A kind of polyphenylene triazole formic acid esters and preparation method and application |
| CN107325284A (en)* | 2017-07-02 | 2017-11-07 | 苏州大学 | A kind of hyperbranched poly phenyl triazole formic acid esters and preparation method and application |
| CN109438700A (en)* | 2018-11-19 | 2019-03-08 | 苏州大学 | A kind of poly- methyl-triazole formic acid esters and the preparation method and application thereof |
| CN109880088A (en)* | 2019-04-04 | 2019-06-14 | 苏州大学 | Polytrimethylsilyl triazole and preparation method and application thereof |
| CN114058007A (en)* | 2021-11-22 | 2022-02-18 | 华南理工大学 | A kind of method that organic base catalyzes alkyne carboxylic acid polymerization to prepare polycarbonyl enol ester compound |
| CN115353622A (en)* | 2022-09-15 | 2022-11-18 | 苏州大学 | Poly 1, 5-substituted triazole and preparation method and application thereof |
| Publication number | Publication date |
|---|---|
| CN116515105B (en) | 2024-05-14 |
| Publication | Publication Date | Title |
|---|---|---|
| CN102585220B (en) | Hyperbranched polytriazole formate as well as preparation method and application thereof | |
| CN106243352B (en) | A kind of polyphenylene triazole formic acid esters and preparation method and application | |
| CN107011469A (en) | A kind of side chain type liquid crystal macromolecule with aggregation-induced emission performance and preparation method thereof | |
| CN109535397B (en) | Stable organic light-emitting free radical polymer and OLED (organic light-emitting diode) device based on same | |
| CN105646260B (en) | Diacid monomer, preparation method and its application in polyamide is prepared of the fluorenes containing diphenylamines | |
| CN107132207A (en) | It is a kind of for fluorescent optical sensor of quick detection explosive and preparation method thereof, the method for quick detection explosive | |
| CN104860808B (en) | Two fluorine monomers containing tetraphenyl ethylene group and be used for preparing poly aryl ether ketone polymer | |
| CN107286327A (en) | It is a kind of for fluorescent test paper of quick detection explosive and preparation method thereof, the method for quick detection explosive | |
| CN114605452A (en) | A fluorescent dye fluoroboron compound with aggregation-induced luminescence and large Stokes shift and preparation method thereof | |
| CN109180685B (en) | A kind of liquid crystal material and its preparation method and application | |
| CN116515105B (en) | A polybiphenyl ether polymer compound and its preparation method and application | |
| CN113121302B (en) | Monodisperse polymer with main chain containing fluorene-diacetylene structure and preparation method and application thereof | |
| CN109880088B (en) | Polytrimethylsilyl triazole and preparation method and application thereof | |
| CN101220112A (en) | Aryl group-containing diacetylenic conjugated polymer and its synthesis method | |
| CN102295743A (en) | Fluorescent conjugated polymer containing polyhedral oligomeric silsesquioxane (POSS), its preparation method and application | |
| CN109134929B (en) | Spiro intumescent flame retardant and preparation method thereof | |
| CN108383980B (en) | A thermally induced delayed fluorescence polymer containing diphenylsilicon and carbazole units in its main chain and its preparation method | |
| CN110408007A (en) | A kind of preparation method of POSS hybrid conjugated polymer | |
| CN114573809B (en) | Polyacrylamide compound and preparation method thereof | |
| CN102887915B (en) | Heteronuclear bimetallic complex light-emitting material and preparation method and application thereof | |
| WO2024055383A1 (en) | Polymerized 1,5-substituted triazole, preparation method therefor, and use thereof | |
| CN113583245B (en) | Hyperbranched poly (benzoic acid ester) and preparation method and application thereof | |
| CN113698306B (en) | A kind of diamine compound containing symmetrical double fluorophore structure and its preparation and application, polyamide and polyimide and its preparation and application | |
| CN107033175A (en) | Connected fluorine boron fluorescent dye oligomer of diacetylene and its preparation method and application | |
| CN107151324A (en) | Poly- fragrant imines ether sulfone of thermal response fluorescent type and preparation method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |