CN114507308A - 一种氧介导自由基聚合的方法 - Google Patents
一种氧介导自由基聚合的方法 Download PDFInfo
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- CN114507308A CN114507308A CN202210277416.2A CN202210277416A CN114507308A CN 114507308 A CN114507308 A CN 114507308A CN 202210277416 A CN202210277416 A CN 202210277416A CN 114507308 A CN114507308 A CN 114507308A
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- polymerization
- chain transfer
- porphyrin
- oxygen
- molecular weight
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 37
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- C08F4/50—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkaline earth metals, zinc, cadmium, mercury, copper or silver
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Abstract
本发明公开了一种氧介导自由基聚合的方法,所述的方法以卟啉基共价有机骨架(COFs)材料作为催化剂,以胺做助催化剂,在氧介导下进行可逆加成‑断裂链转移聚合(RAFT),制备分子量精确、窄分子量分布的聚合物;同时,该方法所用卟啉基共价有机骨架材料,稳定性强,催化效率高,循环性能优,是构建好氧条件下光诱导RAFT聚合高效异相催化剂的理想平台。
Description
技术领域
本发明属于高分子领域,更具体地,涉及一种氧介导可控自由基聚合的方法。
背景技术
可控自由基聚合(CRP)技术在制备结构精确、功能齐全的聚合物和先进材料方面备受关注。在过去的几十年里,CRP技术的发展取得了一些革命性的创新,如原子转移自由基聚合(ATRP)、可逆加成-断裂链转移(RAFT)聚合、氮氧化物介导聚合(NMP)、可逆络合介导聚合(RCMP)等。其中,RAFT聚合单体普适性强,十分有利于含特殊官能团烯类单体的聚合反应,有广阔的工业应用前景。光聚合技术反应条件温和,以光刺激反应进行,绿色清洁,能耗低,一定程度上抑制副反应或解聚反应的发生。光诱导RAFT聚合技术已成为备受研究者关注的可控自由基聚合技术之一。
氧分子是一种强自由基清除剂,虽然上述技术对多种反应条件、溶剂和官能团的耐受性都非常强,但氧分子对碳自由基中心的清除性,极大阻碍了自由基的传播,阻止聚合物链的进一步延伸,使可控聚合技术在工业应用中面临极具挑战性。目前,清除氧气采用的是物理气体置换法,如通过惰性气体吹扫法或冷冻泵解冻循环法,实现高效清除氧分子目的,但其操作繁琐,过程复杂限制了在工业过程的应用。化学方法是通过引入还原剂等外部添加剂来清除氧再生活化剂,通过消耗足够的自由基来溶解氧,并将氧转化为活性氧,进一步将其淬灭,以获得无氧环境。然而,此类化学方法适配的聚合技术大多单体普适性较差。开发对氧的耐受度高、与多种单体相容性好、操作简单的新技术是耐氧可控自由基聚合技术的发展趋势。
卟啉及其衍生物作为光催化剂可以将三线态氧转化为单线态氧,实现耐氧的光诱导RAFT聚合,但其存在小分子催化剂在目标产物中的残留问题。开发高效、稳定的异相光催化剂是解决这一难题的理想途径,但是,寻找可持续的稳定的异相光催化剂来催化氧介导的光诱导CRP仍然是一个挑战。因此,本发明提供一类特定结构的卟啉基共价有机骨架材料(COFs)用于氧介导可逆加成-断裂链转移聚合,该催化原理为卟啉活性单元与基态氧通过能量转移作用形成具有活性的单线态氧,在胺助催化剂作用下单线态氧被还原成为超氧阴离子,并与RAFT引发剂作用形成活性自由基引发可控聚合,其结构稳定,光吸收性能优异,可回收循环使用,光聚合效果理想,是稳定的可持续的光催化剂。
发明内容
本发明的目的在于提供一种氧介导自由基聚合的方法。
为了实现本发明的目的采取的技术方案是:
一种氧介导自由基聚合的方法,室温条件下,以卟啉基COFs做异相催化剂(0.1-20毫克),胺做助催化剂(0.1-1毫升,与链转移剂摩尔比例在1-100之间),单体(1-3 毫升,与链转移剂摩尔比例在100-1000之间)、链转移剂(10-50 毫克)和溶剂(1-2毫升)按一定比例加入,在空气氛围中,用LED灯带绕圈照射,进行可逆加成-断裂链转移聚合,通过控制光照的反应时间,得到分子量可控、窄分子量分布的聚合物。
优选地,进行RAFT聚合反应时,所述催化剂为卟啉基COFs,具有如下分子结构:
其中:R是对苯二酚、对苯二酚二甲醚、三联苯或9,10-双(苯乙炔基)蒽,M是H2、Zn、Cu或Co。
优选地,所述卟啉基COFs的制备方法为:在溶剂和催化剂存在条件下,醛基单体通过与氨基单体缩合反应得到;所述溶剂为1,2-二氯苯、正丁醇、均三甲苯、1,4-二氧六环、甲苯、对二甲苯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的一种或多种;所述催化剂为6 M的醋酸;所述醛基单体为2,5-二羟基对苯二甲醛、2,5-二甲氧基苯-1,4-二甲醛、[1,1':4',1''-三苯基]-4,4''-二甲醛、4,4'-[蒽-9,10-二基双(乙炔-2,1-二基)]二苯甲醛中的一种;所述氨基单体为4,4',4'',4'''-(卟啉-5,10,15,20-四)苯胺、Zn配位4,4',4'',4'''-(卟啉-5,10,15,20-四)苯胺、Cu配位4,4',4'',4'''-(卟啉-5,10,15,20-四)苯胺、Co配位4,4',4'',4'''-(卟啉-5,10,15,20-四)苯胺中的一种;所述缩合反应的温度为100-180℃。
优选地,进行RAFT聚合反应时,所述助催化剂为三乙胺(TEA)、三乙醇胺(TEOA)、三(2-二甲氨基乙基)胺(Me6TREN)中的一种。
优选地,进行RAFT聚合反应时,所述单体为甲基丙烯酸甲酯(MMA)、甲基丙烯酸苄酯(BzMA)、甲基丙烯酸苯酯(PhMA)、甲基丙烯酸丁酯(BMA)、甲基丙烯酸叔丁酯(t-BuMA)、甲基丙烯酸缩水甘油酯(GMA)、甲基丙烯酸羟乙酯(HEMA)、甲基丙烯酸聚乙二醇酯(PEGMA)、甲基丙烯酸二乙氨基乙酯(DEAMA)、甲基丙烯酸甲氧基乙酯(OEMA)中的一种或多种。
优选地,进行RAFT聚合反应时所述链转移剂为4-氰基-4-(硫代苯甲酰硫基)戊酸(CPADB)、2-巯基-S-硫代苯甲酰乙酸、2-氰基-2-丙基苯并二硫、2-(十二烷基三硫代碳酸酯基)-2-甲基丙酸、双(羧甲基)三硫代碳酸盐中的一种或多种。
优选地,进行RAFT聚合反应时,所述溶剂为乙腈(MeCN)、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC)、二甲基亚砜(DMSO)中的一种。
优选地,进行RAFT聚合反应时,所述灯带为13 W m-1, 15 mW cm-2的LED各色灯带。
本发明相对于现有技术,具有如下的优点及有益效果:
(1)本发明提出的一种氧介导自由基聚合的方法,以卟啉基共价有机骨架(COFs)作为催化剂,稳定性强,催化性能佳,可以循环使用。
(2)本发明提出的一种氧介导自由基聚合的方法,在氧气存在条件下,以胺作为助催化剂,实现光诱导RAFT聚合,无需除氧,拓展光诱导RAFT聚合的应用范围。
(3)本发明提出的一种氧介导自由基聚合的方法,利用光能诱导聚合,低能耗、绿色环保。
附图说明
图1是实施例1产物H2-TCPP-DHTA-COFs的X射线衍射(XRD)图;
图2是实施例1产物Zn-TCPP-DHTA-COFs的X射线衍射(XRD)图;
图3是实施例1产物光诱导聚合过程示意图;
图4是氧气中白色LED照射下1 mg实施例1产物(1)、[CPADB]:[TEA]=1:10催化聚合所得分子量(M n)、分散度(PDI)与转化率的关系图和由GPC所测得的聚合物产物的流出曲线图;
图5是氧气中白色LED照射下1 mg实施例1产物(1)、[CPADB]:[TEA]=1:10催化聚合所得聚合动力学曲线;
图6是氧气中白色LED照射下1 mg实施例1产物(2)、[CPADB]:[TEA]=1:10催化聚合所得分子量(M n)、分散度(PDI)与转化率的关系图;
图7是氧气中白色LED照射下1 mg实施例1产物(2)、[CPADB]:[TEA]=1:10催化聚合所得聚合动力学曲线;
图8是氧气中红色LED照射下1 mg实施例1产物(1)、不同TEA浓度催化聚合所得分子量(M n)、分散度(PDI)与转化率的关系图;
图9是氧气中红色LED照射下1 mg实施例1产物(1)、不同TEA浓度催化聚合所得聚合动力学曲线;
图10是氧气中红色LED照射下1 mg实施例1产物(2)、不同TEA浓度催化聚合所得分子量(M n)、分散度(PDI)与转化率的关系图;
图11是氧气中红色LED照射下1 mg实施例1产物(2)、不同TEA浓度催化聚合所得聚合动力学曲线;
图12是H2-TCPP-DHTA-COFs催化的使用PMMA-SCS作为大分子引发剂进行扩链聚合的凝胶渗透色谱(GPC)图;
图13是H2-TCPP-DHTA-COFs催化的时间控制实验的聚合动力学曲线;
图14是Zn-TCPP-DHTA-COFs催化的时间控制实验的聚合动力学曲线;
图15是H2-TCPP-DHTA-COFs催化的氧气控制实验的聚合动力学曲线;
图16是Zn-TCPP-DHTA-COFs催化的氧气控制实验的聚合动力学曲线;
图17是循环实验后H2-TCPP-DHTA-COFs的X射线衍射(XRD)图谱;
图18是循环实验后Zn-TCPP-DHTA-COFs的X射线衍射(XRD)图谱。
具体实施方式
为了使本发明的目的、技术方案及优点更加清晰明了,以下结合说明附图及实施例,对本发明进行详细说明。此处所描述的具体实施例仅用于解释本发明,并不用以限定本发明。
实施例1:
(1)4,4',4'',4'''-(卟啉-5,10,15,20-四)苯胺(H2-TCPP)的合成:将4-硝基苯甲醛(22.0 g,145 mmol)、丙酸(600 mL)和醋酸酐(24 mL)加入到1000 mL的烧瓶中,在N2中回流。随后,通过注射器添加吡咯(10 mL),混合物反应12 h。将混合物冷却至室温后,放入冰箱过夜,过滤得到固体,再用蒸馏水(200 mL)和甲醇(500 mL)洗涤,然后真空干燥。随后,固体在吡啶(160 mL)中N2保护下回流12 h,混合物冷却至室温,过滤得到黑色固体,丙酮洗涤得到紫色固体。将产物和SnCl2·2H2O(18.0 g,7.97 mmol)加入热浓盐酸(500 mL)溶液中,N2气氛下回流过夜。将混合物用冰水冷却至0℃,用浓缩氨水中和至pH = 8,得到绿色粗产物。最终产物H2-TCPP以丙酮为溶剂,经重结晶纯化。1H NMR (600 MHz, CDCl3): δ 8.90(s, 8 H), 7.99 (s, 8H), 7.05 (s, 8H), 4.00 (s, 8H), -2.71 (s, 2H)。TOF-MS:Calcd for (M+H)+ 675.29, Found 675.30。
(2)Zn配位4,4',4'',4'''-(卟啉-5,10,15,20-四)苯胺(Zn-TCPP)的合成:将H2-TCPP(0.5 g,0.74 mmol)和ZnCl2(1 g,7.3 mmol))加入到混合溶剂(CH3OH/DMF/CH3Cl = 3/5/15,v/v/v))中,在N2气氛下回流24 h,反应后真空脱去有机溶剂。用蒸馏水(200 mL)洗涤残渣,得到最终产物Zn-TCPP(0.53 g, 98%)。TOF-MS: Calcd for (M+H)+ 737.21, Found737.21。
(3)2,5-二羟基对苯二甲醛(DHTA)的合成:将2,5-二甲氧基苯-1,4-二甲醛(DMTA,1.0 g,5.2 mmol)和溴化四丁基铵(0.5 g,1.6 mmol)加入HBr溶液(10 mL)中,回流反应,TLC监测反应。反应物反应完成后,加入蒸馏水(20 mL),用CH2Cl2萃取混合物。取有机层,真空去除溶剂,得到最终产物DHTA(0.77 g,~90%)。1H NMR (600 MHz, CDCl3): δ 10.25 (s,2 H), 9.99 (s, 2H), 7.27 (s, 2H)。
(4)H2-TCPP-DHTA-COFs(1)的合成:将H2-TCPP(14.8 mg,0.02 mmol)和DHTA(7.3mg,0.04 mmol)置于Schlenk管(5 mL)中,加入o-DCB(0.5 mL)和n-BuOH(0.5 mL),并加入乙酸(6M aq.,0.1 mL)作为催化剂。用液氮快速冷冻,冷冻-泵抽-解冻3次。在120℃加热3天,产生黑色沉淀。用四氢呋喃洗涤,四氢呋喃索氏提取洗涤12 h。120℃下真空干燥2 h得到成品H2-TCPP-DHTA-COFs(1)(产率~72%)。
(5)Zn-TCPP-DHTA-COFs(2)的合成:将Zn-TCPP(29.5 mg,0.04 mmol)和DHTA(13.2mg,0.08 mmol)置于Schlenk管(5 mL)中,加入o-DCB(0.5 mL)和n-BuOH(0.5 mL),并加入乙酸(6M aq.,0.1 mL)作为催化剂。用液氮快速冷冻,冷冻-泵抽-解冻3次。在120℃加热3天,产生黑色沉淀。用四氢呋喃洗涤,四氢呋喃索氏提取洗涤12 h。120℃下真空干燥2 h得到成品Zn-TCPP-DHTA-COFs(2)(产率~80%)。
图1、2是实施例1产物M-TCPP-DHTA-COFs(M = H2,Zn)的X射线衍射(XRD)图,可以看出实施例1产物具有高的结晶度,是共价有机骨架材料。
实施例2:
取实施例1产物(1) H2-TCPP-DHTA-COFs 1 mg、MMA(2 mL,18.6 mmol)、CPADB(26mg,0.093 mmol)、TEA(134 μL,0.93 mmol)和DMAC(1 mL)加入4 mL的玻璃瓶中,塞上橡胶塞,用白色LED灯带(13W m-1,15mW cm-2)照射。在预先设计的时间取微量混合物,用凝胶渗透色谱仪(GPC)测定转化率、分子量M n和分子量分布M w/M n等参数。
图3为聚合过程示意图;图4为分子量M n、分子量分布M w/M n与转化率的关系图和由GPC所测得的聚合物产物的流出曲线图;图5为ln(M 0/M t)随时间t变化的聚合动力学曲线,其中M 0为初始单体浓度,M t为t时刻单体浓度,图中可以看出ln(M 0/M t)-t呈线性关系,表明聚合速率与单体浓度呈一级反应,结合图4、图5,说明该聚合条件下可得到分子量可控且具有窄分子量分布的聚合物。
目标产物聚合情况通过凝胶色谱仪测出,从图4中的GPC的流出曲线图可知所得聚合物具有窄分子量分布。
实施例3:
取实施例1产物(2) Zn-TCPP-DHTA-COFs 1 mg、MMA(2 mL,18.6 mmol)、CPADB(26mg,0.093 mmol)、TEA(134 μL,0.93 mmol)和DMAC(1 mL)加入4 mL的玻璃瓶中,塞上橡胶塞,用白色LED灯带(13W m-1,15mW cm-2)照射。在预先设计的时间取微量混合物,用凝胶渗透色谱仪(GPC)测定转化率、分子量M n和分子量分布M w/M n等参数。
图6为分子量M n、分子量分布M w/M n与转化率的关系图,图7为聚合动力学曲线,两者结合说明该聚合条件下可得到分子量可控且窄分子量分布的聚合物。
实施例4:
取实施例1产物(1) H2-TCPP-DHTA-COFs 1 mg、MMA(2 mL,18.6 mmol)、CPADB(26mg,0.093 mmol)、TEA(0;67 μL,0.47 mmol;134 μL,0.93 mmol)和DMAC(1 mL)加入4 mL的玻璃瓶中,塞上橡胶塞,用红色LED灯带(13W m-1,15mW cm-2)照射。在预先设计的时间取微量混合物,用凝胶渗透色谱仪(GPC)测定转化率、分子量M n和分子量分布M w/M n等参数。
图8为分子量M n、分子量分布M w/M n与转化率的关系图,图9为聚合动力学曲线,两者结合说明该聚合条件下可得到分子量可控且窄分子量分布的聚合物。
实施例5:
取实施例1产物(2) Zn-TCPP-DHTA-COFs 1 mg、MMA(2 mL,18.6 mmol)、CPADB(26mg,0.093 mmol)、TEA(0;27 μL,0.17 mmol)和DMAC(1 mL)加入4 mL的玻璃瓶中,塞上橡胶塞,用白色LED灯带(13W m-1,15mW cm-2)照射。在预先设计的时间取微量混合物,用凝胶渗透色谱仪(GPC)测定转化率、分子量M n和分子量分布M w/M n等参数。
图10为分子量M n、分子量分布M w/M n与转化率的关系图,图11为聚合动力学曲线,两者结合说明该聚合条件下可得到分子量可控且窄分子量分布的聚合物。
实施例6:
取实施例1产物H2-TCPP-DHTA-COFs 1 mg、MMA(2 mL,18.6 mmol)、CPADB(26 mg,0.093 mmol)、TEA(134 uL,0.93 mmol)和DMAC(1 mL)加入4 mL的玻璃瓶中,塞上橡胶塞,用红色LED灯带(13W m-1,15mW cm-2)照射。在规定的反应时间后,用微量的混合物测定单体转化率。其他的混合物用过量的乙醚重沉淀。产物在少量THF中溶解,用乙醚沉淀,进行3次。将粉色沉淀物过滤得到大分子引发剂PMMA-SCS。用凝胶渗透色谱仪(GPC)测定其分子量M n和分子量分布M w/M n。
取实施例1产物H2-TCPP-DHTA-COFs 1 mg、BzMA(18.6 mmol)、大分子引发剂PMMA-SCS(0.093 mmol)、TEA(134 uL,0.93 mmol)和DMAC(1 mL)加入4 mL的玻璃瓶中,塞上橡胶塞,用红色LED灯带(13W m-1,15mW cm-2)照射。预设反应时间后取微量混合物,用凝胶渗透色谱仪(GPC)测定。
图12为使用PMMA-SCS作为大分子引发剂进行扩链聚合的GPC图,可以看出聚合后GPC曲线的峰有明显左移,分子量变大,且所得嵌段聚合物保持窄分子量分布,说明PMMA-SCS引发了聚合,聚合物链端具有良好的端基保真度。
实施例7:
取实施例1产物M-TCPP-DHTA-COFs(M = H2,Zn) 1 mg、MMA(2 mL,18.6 mmol)、CPADB(26 mg,0.093 mmol)、TEA(134 uL,0.93 mmol)和DMAC(1 mL)加入4 mL的玻璃瓶中,塞上橡胶塞,用红色LED灯带(13W m-1,15mW cm-2)照射。在预定的反应时间内,关闭光源,将小瓶置于黑暗中以进行进一步的反应,重复开灯关灯。在预先设计的时间取微量混合物,用凝胶渗透色谱仪(GPC)测定转化率、分子量M n和分子量分布M w/M n等参数。
图13、14为时间控制实验的聚合动力学曲线,在黑暗中聚合几乎不进行,说明聚合受光的严格控制。
实施例8:
取实施例1产物M-TCPP-DHTA-COFs(M = H2,Zn) 1 mg、MMA(2 mL,18.6 mmol)、CPADB(26 mg,0.093 mmol)、TEA(134 uL,0.93 mmol)和DMAC(1 mL)加入4 mL的玻璃瓶中,塞上橡胶塞,用红色LED灯带(13W m-1,15mW cm-2)照射。在预先设计的时间取微量混合物,用凝胶渗透色谱仪(GPC)测定转化率、分子量和分散度等参数。然后用铝包好玻璃瓶,在0ºC下用氮气吹扫30 min,在红色LED灯下连续辐照样品。
图15、16为氧气控制实验的聚合动力学曲线,在N2中聚合几乎不进行,说明聚合受氧气的严格控制。
实施例9:
将M-TCPP-DHTA-COFs(M = H2,Zn)(1 mg)、MMA(2 mL,18.6 mmol)、CPADB(26 mg,0.093 mmol)、TEA(134 uL,0.93 mmol)和DMAC(1 mL)加入4 mL的玻璃瓶中,塞上橡胶塞,反应体系在室温下用红色LED灯带照射。在预先设计的时间采集微量样品,用凝胶渗透色谱仪(GPC),测定单体转化率、分子量M n和分子量分布M w/M n。反应后,用THF清洗玻璃瓶,离心得到催化剂,用丙酮彻底洗涤后,用THF溶剂进行过夜索氏提取洗涤。
图17、18为循环实验后的实施例1产物M-TCPP-DHTA-COFs(M = H2,Zn)的X射线衍射(XRD)图谱,聚合前后XRD图谱在5o以前都有明显的峰,说明催化剂可重复使用。
实施例10:
取实施例1产物H2-TCPP-DHTA-COFs 0.5 mg或Zn-TCPP-DHTA-COFs 1 mg,CPADB(26 mg,0.093 mmol)、M(t-BA、DEAMA、HPMA或OEMA):CPADB = 200:1、TEA(134 uL,0.93mmol)和DMAC(1 mL)加入4 mL的玻璃瓶中,塞上橡胶塞,用红色LED灯带(13W m-1,15mW cm-2)照射。在预先设计的时间取微量混合物,用凝胶渗透色谱仪(GPC)测定转化率、分子量M n和分子量分布M w/M n等参数,如下表:
表1 M-TCPP-DHTA-COFs(M = H2,Zn)催化不同功能单体的PET-RAFT聚合
上述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的辐射范围之内所作的任何修改、替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种氧介导自由基聚合的方法,其特征在于,室温条件下,以卟啉基共价有机骨架材料做催化剂,胺做助催化剂,单体、链转移剂和溶剂按一定比例加入,在空气氛围中,用LED灯带绕圈照射,进行可逆加成-断裂链转移聚合,通过控制光照的反应时间,得到分子量可控、窄分子量分布的聚合物。
3. 如权利要求2所述的方法,其特征在于,所述卟啉基共价有机骨架材料的制备方法为:在溶剂和催化剂存在条件下,醛基单体通过与氨基单体缩合反应得到;所述溶剂为1,2-二氯苯、正丁醇、均三甲苯、1,4-二氧六环、甲苯、对二甲苯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的一种或多种;所述催化剂为醋酸、对甲基苯磺酸中的一种;所述醛基单体为2,5-二羟基对苯二甲醛、2,5-二甲氧基苯-1,4-二甲醛、[1,1':4',1''-三苯基]-4,4''-二甲醛、4,4'-[蒽-9,10-二基双(乙炔-2,1-二基)]二苯甲醛中的一种;所述氨基单体为4,4',4'',4'''-(卟啉-5,10,15,20-四)苯胺、Zn配位4,4',4'',4'''-(卟啉-5,10,15,20-四)苯胺、Cu配位4,4',4'',4'''-(卟啉-5,10,15,20-四)苯胺、Co配位4,4',4'',4'''-(卟啉-5,10,15,20-四)苯胺中的一种;所述缩合反应的温度为100 - 180℃。
4.如权利要求1所述的方法,其特征在于,进行可逆加成-断裂链转移聚合反应时,所述助催化剂为三乙胺、三乙醇胺、三(2-二甲氨基乙基)胺中的一种。
5.如权利要求1所述的方法,其特征在于,进行可逆加成-断裂链转移聚合反应时,所述单体为甲基丙烯酸甲酯、甲基丙烯酸苄酯、甲基丙烯酸苯酯、甲基丙烯酸丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯、甲基丙烯酸聚乙二醇酯中的一种或多种。
6.如权利要求1所述的方法,其特征在于,进行可逆加成-断裂链转移聚合反应时,所述链转移剂为4-氰基-4-(硫代苯甲酰硫基)戊酸、2-巯基-S-硫代苯甲酰乙酸、2-氰基-2-丙基苯并二硫、2-(十二烷基三硫代碳酸酯基)-2-甲基丙酸、双(羧甲基)三硫代碳酸盐中的一种或多种。
7.如权利要求1所述的方法,其特征在于,进行可逆加成-断裂链转移聚合反应时,所述溶剂为乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜中的一种。
8. 如权利要求1所述的方法,其特征在于,进行可逆加成-断裂链转移聚合反应时,所述灯带为13 W/m, 15 mW/cm2的LED各色灯带。
9.如权利要求1所述的方法,其特征在于,反应时间为1-60小时。
10.如权利要求1所述的方法,其特征在于,助催化剂与链转移剂的摩尔比例在1-100之间;单体与链转移剂的摩尔比例在100-1000之间。
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