CN109384868A - 丙烯酸酯类单体光诱导电子转移可逆加成-断裂链转移聚合的引发体系 - Google Patents
丙烯酸酯类单体光诱导电子转移可逆加成-断裂链转移聚合的引发体系 Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明公开了丙烯酸酯类单体光诱导电子转移可逆加成‑断裂链转移(PET‑RAFT)聚合技术的光敏剂、聚合方法及其引发体系,该引发体系所含组分及各组分摩尔分数为:单体20‑400份,CDB链转移试剂1‑20份,光敏剂0.001‑0.1份,溶剂体积分数20%‑80%,所述组合物在绿光直接照射下能够发生光聚合化学反应,本发明所用的光敏剂首次将多面体笼状硅氧烷(POSS)与金属卟啉通过点击化学来结合,使用的光敏剂毒性小,聚合反应条件温和。与四苯基锌卟啉催化的聚合反应相比,空间位阻较大的POSS的引入,阻止了金属卟啉的聚集,大大增加了聚合反应的速率。光聚合制得的均聚物分子量随转化率的增长而线性增加,并且聚合物的分子量分布较窄,此项发明解决了卟啉类光敏剂的聚积问题,拓宽了光聚合技术的应用领域。
Description
技术领域
在本发明涉及一种用于可见光活性自由基聚合的引发体系,具体是涉及在室温条件 下,由含叠氮基多面体笼状硅氧烷(POSS)通过点击化学连接上金属卟啉得到的新型光敏剂,以及链转移试剂,丙烯酸酯类单体和溶剂组成的聚合体系。使用该引发体系,可以实现丙烯酸酯类单体的可见光诱导电子转移可逆加成-断裂链转移(PET-RAFT)聚合。
背景技术
近年来,光控可逆-失活自由基聚合(RDRP)因为其光源廉价丰富、常温条件聚合、操作简便、环境友好、以及控制聚合开启和关闭便捷等优点引起了人们的广泛关注。Boyer及其同事利用三(2-苯基吡啶)合铱(fac-[Ir(ppy)3])作为光氧化还原催化剂,成功地开发了可见光控制的可逆加成-裂解链转移(RAFT)聚合(文献)。利用光氧化还原催化剂在光照下通过光诱导电子转移(PET)活化链转移剂(CTA),产生引发RAFT聚合的自由基发生聚合,即PET-RAFT聚合。此后的科研工作者们将光致发光催化剂延伸到金属卟啉族,并成功实现在较宽的可见光波长范围内实现了PET-RAFT聚合。尽管金属卟啉具有优异的光化学性质,但由于π-π堆叠相互作用,卟啉在溶液中发生聚集会导致卟啉激发态的严重自猝灭,这将减少其作为PET-RAFT聚合的光氧化还原催化剂的效率。因此,防止金属卟啉的聚集和提高PET-RAFT聚合效率是金属卟啉催化PET-RAFT需要解决的重要问题之一。
发明内容
本发明的目的是提供一种用于丙烯酸酯类单体光诱导电子转移可逆加成-断裂链转移(PET-RAFT)聚合的光敏剂以及高效率,低成本和易操作的PET-RAFT光聚合方法。
用于丙烯酸酯类单体光诱导电子转移可逆加成-断裂链转移(PET-RAFT)聚合的光敏剂为锌卟啉-POSS,主要通过三个步骤合成得到,分别是合成含叠氮基多面体笼状硅氧烷、合成含炔基四苯基锌卟啉及合成锌卟啉-POSS。
第一步合成含叠氮基多面体笼状硅氧烷
在250mL圆底烧瓶中,加入7.5 g溶于150 mL干燥四氢呋喃的三硅羟基七异丁基多面体笼状硅氧烷(POSS-(OH)3)(9.45 mmol)溶液,随后加入2.64 mL重蒸的三乙胺,冰浴下通氮气30 min后,快速加入2.96 mL 3-氯丙基三氯硅烷(18.9mmol),继续通氮气10 min后,密闭条件下0 ℃下反应一小时,再移至室温环境搅拌反应五小时。反应结束后,抽滤除去体系中的不溶物,将混合溶液减压旋蒸至大约30mL,在300mL乙腈中沉淀三次,旋蒸,得到白色粉末7.2g。
在100 mL圆底烧瓶中,加入6 g (3-氯丙基)七异丁基多面体笼状硅氧烷(POSS-Cl)(6.8mmol)和4.4 g叠氮化钠(68mmol),随后加入40 mL 四氢呋喃与20mL的N,N-二甲基甲酰胺,80℃下回流反应48 h。反应结束后,旋除溶剂,并溶解于200 mL二氯甲烷中,用饱和食盐水水洗三次,有机层用无水硫酸镁干燥,抽滤,旋蒸,得到5.6g白色粉末状固体含叠氮基多面体笼状硅氧烷(POSS-N3)。
第二步合成含炔基四苯基锌卟啉
在1000 mL三口烧瓶加入10.8mL苯甲醛(108 mmol)、4.44 g对羟基苯甲醛(36 mmol),以丙酸为溶剂,加480 mL,控制油浴锅温度为40 ℃,在此温度下对溶液进行抽真空、通氮气反复三次,无水无氧的环境下加热135 ℃,缓慢滴加10 mL干燥过的吡咯(144 mmol),反应4h,反应结束后,冷却至室温,旋除约240 mL左右丙酸后倒入冰甲醇,放置在冰箱中过夜沉淀,抽滤得到大量紫色晶体,其组份为一系列卟啉类化合物,所得产物用层析柱分离,淋洗剂为三氯甲烷/甲醇(v/v = 95/5)。最终得到0.98g纯净的单羟基四苯基卟啉(H2TPP-OH)(1.5mmol)。
在250 mL圆底烧瓶加入0.57 g H2TPP-OH(0.9 mmol)、1.08 g溴丙炔(9 mmol)、和1.25 g无水碳酸钾(9 mmol),往烧杯中倒入100 mL丙酮,通氮气 30 min,在58 ℃下回流反应24 h。反应完毕后减压除去丙酮,粗产品通过硅胶层析柱分离,淋洗剂为二氯甲烷/石油醚(v/v = 1/1),最终得到0.55 g紫色固体含炔基四苯基锌卟啉alklyne-H2TPP(0.82mmol)。
在250 mL圆底烧瓶加入0.45 g alklyne-H2TPP(0.67 mmol)、1.48 g二水合乙酸锌(6.8 mmol)、240 mL二氯甲烷/甲醇混合溶剂(v/v = 3/1),室温搅拌2 h。反应停止后除去混合溶剂,用二氯甲烷溶解,并用饱和食盐水萃取三次,有机层用无水硫酸镁干燥。抽滤、旋除溶剂,得到0.48 g鲜红色固体炔基四苯基锌卟啉。
第三步合成锌卟啉-POSS
取40 mg炔基四苯基锌卟啉、72 mg POSS-N3溶解在15 mL四氢呋喃中,倒入50 mL圆底烧瓶,并加入7.75 mg抗坏血酸钠,通氮气30 min,称量15 mg五水合硫酸铜溶于0.2 mL水中,用注射器注入烧瓶,继续通氮气10 min,40 ℃下密闭反应24小时。反应结束后除去溶剂,溶解在50 mL乙酸乙酯中,用饱和食盐水水洗,有机层用无水硫酸镁干燥,抽滤,旋蒸,粗产品用硅胶层析柱分离,淋洗剂为乙酸乙酯/石油醚(v/v = 1/2),得到纯净的锌卟啉-POSS(ZnTPP-POSS)。
本发明所采用的具体技术方案为:首先室温条件下,以10 W绿色LED灯带为光源,向玻璃瓶里加入丙烯酸酯类单体,二硫代苯甲酸异丙苯酯CDB链转移剂,锌卟啉-POSS光敏剂,二甲基亚砜反应溶剂和转子,用橡皮塞密封。接下来开始除氧操作,可以用针头采用鼓泡法除氧,通入30分钟的氮气,将氧气赶出来;也可以在聚合管中反应,采用液氮冷冻然后抽真空再将体系熔融通氮气,如此往复三次除去氧气。随后将装有反应体系物质的玻璃瓶放入光引发聚合反应装置中,反应温度为室温,光源为10 W的LED绿色灯带。
本发明能够分别实现了甲基丙烯酸甲酯(MMA),丙烯酸丁酯(BA),以及甲基丙烯酸缩水甘油酯(GMA)等丙烯酸酯类单体的光诱导电子转移可逆加成-断裂链转移(PET-RAFT)聚合。
在优选的配比条件下,聚合反应动力学曲线呈很好的线性关系,且聚合物的相对分子质量分布较窄(PDl < 1.3)。
本发明所用的锌卟啉-POSS催化剂可通过光诱导电子转移机制来活化可逆加成断裂链转移聚合。在可见光的激发下,光氧化还原催化剂从基态激发到能量最低的三线态。硫代碳酸酯的氧化还原电势比处在激发态的光氧化还原催化剂电势高。所以氧化还原催化剂可通过光诱导电子转移的过程来还原硫代碳酸酯化合物,产生的自由基可引发单体的RAFT聚合。在二硫酯类化合物链转移剂存在时,体系同时存在聚合物增长链与二硫酯化合物的可逆加成、加成物的可逆断裂以及链转移反应,使得聚合体系具有可控性,并最终得到均聚物以及嵌段共聚物。空间位阻较大的POSS阻止了金属卟啉的聚集并且提高了PET-RAFT聚合效率。
本发明提供的制备方法简便易行,清洁环保,具有较强的实用性。
附图说明
图1是ZnTPP-POSS在CDCI3中的核磁氢谱
图2是10W绿色灯带照射条件下光引发聚合反应装置图。
图3为实施例中不同浓度的ZnTPP-POSS光敏剂下的动力学图。
图4为实施例中数均分子量、PDI与转化率的关系(ZnTPP-POSS光敏剂浓度为50ppm)
图5为实施例中ZnTPP与ZnTPP-POSS在三种不同浓度下的聚合单体转化率对比图(光照时间48 h)
图6为实施例中ZnTPP-POSS为光敏剂时的开关实验(光敏剂浓度为50 ppm)
具体实施方式
以下通过一些实例具体地描述本发明,但本发明不受这些实例的限定。
实施例一,锌卟啉-POSS/CDB引发体系下MMA单体的光聚合(催化剂浓度100 ppm)
2mL单体MMA在二甲基亚砜(DMSO)溶剂(2 mL)中的体积分数为50 %。按照摩尔比[MMA]:[CDB]:[锌卟啉-POSS]=200:1 :0.02,分别将上述原料加入到 12 mL单支口玻璃瓶中。用橡胶塞密封。用鼓泡法除氧,用细针通入氮气,另外一个针出气,如此持续半个小时,使聚合反应在氮气气氛中于10 W绿色灯带照射条件下进行。具体反应装置如图 1所示。分别在不同的时间间隔下,用注射器从反应体系中少量取样,样品用于进行核磁测试算转化率。样品用甲醇沉淀三次,真空干燥至恒重,得到浅红色粉末,用THF相的GPC测量分子量及其分布。
在该配比条件下,聚合物分子量随转化率的增长而线性增加。反应48 h,单体转化率达39.06 %,聚合产物Mn=11700,PDI = 1.11。
比较例一,锌卟啉/CDB引发体系下MMA单体的光聚合(催化剂浓度100 ppm)
2 mL单体MMA在二甲基亚砜(DMSO)溶剂(2 mL)中的体积分数为50 %。按照摩尔比[MMA]:[CDB]:[锌卟啉-POSS]=200:1:0.02,分别将上述原料加入到 12 mL单支口玻璃瓶中。用橡胶塞密封。用鼓泡法除氧,其他操作参照实施例一。
在该配比条件下,聚合物分子量随转化率的增长而线性增加。反应48 h,单体转化率达39.06%,聚合产物Mn= 6600,PDI = 1.13。
当体系中的光敏剂不含POSS时,反应48小时,单体转化率达27.25 %,说明空间位阻较大的POSS阻止了金属卟啉的聚集从而提高了PET-RAFT聚合的效率。POSS的存在对卟啉光诱导电子转移可逆加成-断裂链转移(PET-RAFT)聚合有影响。
实施例二,锌卟啉-POSS/CDB引发体系下MMA单体的光聚合(催化剂浓度50 ppm)
参照实施例一进行锌卟啉-POSS/CDB引发体系下的MMA单体的光聚合。MMA单体为2 mL,其中 [MMA]:[CDB]:[锌卟啉-POSS]的摩尔比为200:1 :0.01。不同时间段所取样品用甲醇沉淀三次,真空干燥至恒重,得到浅红色物质。48 h时,单体转化率为 51.02%,GPC测得聚合产物Mn = 9800,PDI = 1.12。此外,在聚合过程中,聚合物分子量随转化率的增长而线性增加,并且聚合物的分子量分布较窄(小于1.3),符合活性聚合的规律。在光照时间48 h后,将聚合装置的电源关闭,避光12 h后取样测得单体转化率为 51.13 %。
比较例二,锌卟啉/CDB引发体系下MMA单体的光聚合(催化剂浓度50 ppm)
取2 mL单体MMA,其中单体在二甲基亚砜(DMSO)溶剂(2 mL)中的体积分数为50 %。按照摩尔比[MMA]:[CDB]:[锌卟啉-POSS] = 200:1 :0.01,分别将上述原料加入到 12 mL单支口玻璃瓶中。用橡胶塞密封。用鼓泡法除氧,其他操作参照实施例一。在该配比条件下,聚合物分子量随转化率的增长而线性增加。反应48 h,单体转化率达25 %。
实施例三,锌卟啉-POSS/CDB引发体系下MMA单体的光聚合(催化剂浓度25 ppm)
参照实施例一进行锌卟啉-POSS/CDB引发体系下的MMA单体的光聚合。取2 mL单体MMA,单体在二甲基亚砜(DMSO)溶剂(2mL)中的体积分数为50 %。其中[MMA]:[CDB]:[锌卟啉-POSS] 的摩尔比为200:1:0.005。不同时间段所取样品用甲醇沉淀三次,真空干燥至恒重,得到浅红色物质。48 h时,单体转化率为 34.25 %,GPC测得聚合产物Mn = 7700,PDI =1.15。此外,在聚合过程中,聚合物分子量随转化率的增长而线性增加,并且聚合物的分子量分布较窄(小于1.3),符合活性聚合的规律。
比较例三,锌卟啉/CDB引发体系下MMA单体的光聚合(催化剂浓度25 ppm)
单体MMA在二甲基亚砜(DMSO)溶剂(2 mL)中的体积分数为50 %。按照摩尔比[MMA]:[CDB]:[锌卟啉]=200:1 :0.005,分别将上述原料加入到 12 mL单支口玻璃瓶中,并加入转子。用橡胶塞密封。用鼓泡法除氧,绿光光照48 h,其他操作参照实施例一。
在该配比条件下,聚合物分子量随转化率的增长而线性增加。反应48 h,单体转化率达20.28 %。
Claims (4)
1.一种用于丙烯酸酯类单体可见光引发的PET-RAFT聚合的体系,其特征在于:该 聚合体系包括单体、光敏剂、链转移试剂和溶剂;单体与链转移剂的摩尔比20–400:1 - 20,链转移剂与光敏剂的摩尔比1–20:0.005-0.03,反应温度为室温,反应时间为2 -60h;所述光敏剂为金属卟啉的衍生物,链转移试剂为二硫代苯甲酸异丙苯酯CDB,溶剂为二甲基亚砜。
2.根据权利要求1所述的引发体系,其特征在于:聚合引发体系所用光敏剂为对金属卟啉通过叠氮与炔基的点击化学反应连接上空间位阻较大的POSS来防止金属卟啉的聚集。
3.根据权利要求1所述的引发体系,其特征在于:链转移试剂为三硫代碳酸酯链转移试剂或二硫代碳酸酯链转移试剂。
4.权利要求1至3任一项所述的引发体系实现丙烯酸单体光聚合的方法,其特征在于:采用绿色LED照射。
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CN113234184A (zh) * | 2021-05-18 | 2021-08-10 | 深圳大学 | 亚甲基蓝光敏剂及在光芬顿引发raft反应中的应用 |
CN116162191A (zh) * | 2023-04-26 | 2023-05-26 | 清华大学 | 一种可见光诱导的光催化自由基聚合的方法 |
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CN113234184A (zh) * | 2021-05-18 | 2021-08-10 | 深圳大学 | 亚甲基蓝光敏剂及在光芬顿引发raft反应中的应用 |
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