CN105037415B - 一种双核钒络合物及制备方法和用途 - Google Patents
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Abstract
本发明提供了如式I所示的双核钒络合物，还提供了该络合物的制备方法和用途。本发明的双核钒络合物制备方法简便，毒性低，催化活性高，分子量分布窄，还可以根据需求有效控制聚合物的分子量，具有广泛的市场应用前景。
Description
技术领域
本发明涉及一种双核钒络合物及其用途。
背景技术
近年来，由于其生物安全性，聚乳酸、聚乙醇酸、乳酸氨基酸共聚物等生物降解聚合物的市场需求急剧增长。尤其是聚乳酸，它受到了人们很大的关注(Chemical Routesfor the Transformation of Biomass into Chemicals,Chem.Rev.2007,107,2411；Polymers from renewable resources:A perspective for a special issue ofpolymer reviews,Polym.Rev.,2008,48,1；Synthetic polymer scaffolds for tissueengineering,Chem.Soc.Rev.,2009,38,1139)。
在工业上，这些生物降解聚合物均可通过相应单体的开环聚合反应制备得到，该反应需要使用催化剂。目前，异辛酸亚锡(Sn(Oct)2)是目前工业上通常采用的一种催化剂。但是，近年来的研究发现，异辛酸亚锡具有细胞毒性。由于聚合反应后无法将催化剂从聚合物中彻底去除，从而对上述生物降解聚合物在人类药用、医用材料时的使用留下了安全隐患，尤其当这些植入如脑组织或神经组织等对毒性敏感的组织或对儿童使用时(Kineticsof the ring-opening polymerization of D,L-lactide using zinc(II)octoate ascatalyst，Polym.Int.,2012,61,265；Application of the lithium and magnesiuminitiators for the synthesis of glycolide,lactide,and epsilon-caprolactonecopolymers biocompatible with brain tissue，2006，Biomed Mater Res Part A 79A:865–873)。
因此，有必要探寻一种优于传统催化剂异辛酸亚锡的无锡低毒催化剂。
钒是一种毒性很低的金属，发明人在之前的工作中(Vanadium procatalystsbearing chelatingaryloxides:structure–activity trends inethylenepolymerisation，Dalton Trans.2010,39,5595)，以联酚作为配体与钒络合，得到了具有催化烯烃聚合反应活性的钒络合物。但是，这些钒络合物，尤其当配体中包括三个或四个酚结构时，它们在开环聚合反应中的应用却有着很大的限制(Thermodynamics,Kinetics,andMechanisms of Cyclic Esters Polymerization，ACS Symposium Series,Vol.764，Chapter 13,pp 160–198；A journey into the electrochemistry of vanadiumcompounds，Coord.Chem.Rev.，in press，doi:10.1016/j.ccr.2015.02.022)。
因此，目前亟需一种具有良好开环聚合催化活性的钒络合物。
发明内容
为解决上述问题，本发明提供了式(I)所示的双核钒络合物或其溶剂化物：
其中，X选自烷基或芳香基；
R1和R11分别独立地选自烷基或芳香基；
R2-R10、R12-R20分别独立地选自氢、烷基、芳香基或卤素。
进一步优选地，它具有式(Ⅱ)所示的结构：
R1和R11分别独立地选自烷基或芳香基；
R2、R4、R7、R9、R12、R14、R17和R19分别独立地选自氢、烷基、芳香基或卤素。更进一步优选地，R2、R4、R7、R9、R12、R14、R17和R19分别独立地选自正丙基、异丙基、正丁基、异丁基、叔丁基或仲丁基。
进一步优选地，在上述化合物中。R1、R11选自异丙基或叔丁基。
进一步优选地，所述双核钒络合物具有式(Ⅲ)所示的结构：
本发明还提供了一种制备式(Ⅲ)所示双核钒络合物的方法，它是以化合物(Ⅳ)和三-异丙基基正钒酸(Ⅴ)为原料，在无水无氧环境下，于甲苯中回流制备得到的，所述化合物(Ⅳ)和三-异丙基基正钒酸(Ⅴ)的摩尔比为1∶2，制备路线如下：
进一步优选地，所述溶剂化物为二氯甲烷溶剂化物。
进一步优选地，所述溶剂化合物为化合物(Ⅲ)·2CH2Cl2(C70H100O8V2·2CH2Cl2)。
本发明还提供了所述溶剂化物C70H100O8V2·2CH2Cl2的晶型：
该晶型属于单斜晶系，空间群为P21/c，晶胞参数为 β＝92.329(6)°，ρcalc＝1.227Mg/m3。
本发明还提供了双核钒络合物或其溶剂化合物或其晶型作为开环聚合反应催化剂或烯烃聚合反应催化剂的用途。进一步优选地，所述开环聚合反应的单体为丙交酯(Lactide)，所述丙交酯包括L-丙交酯和D-丙交酯。
本发明还提供了所述双核钒络合物或其溶剂化合物或其晶型在制备聚乳酸中的用途。
经实验证明，本发明的双核钒络合物或其晶型可以作为开环聚合反应的催化剂，具有下述优点：
(1)制备方法简便，时间短，收率高。以化合物(Ⅳ)和三-异丙基基正钒酸(Ⅴ)为原料，在甲苯中回流12小时即反应完全，收率达83％。
(2)毒性低，催化活性高。
(3)可以根据需求有效控制聚合物的分子量，分子量分布窄，PDI(Polydispersityindex，多分散指数)介于1.05～1.11之间。
(4)相比于Sn(Oct)2，可以在更低的温度(45℃)下催化反应，适用范围更广。
显然，根据本发明的上述内容，按照本领域的普通技术知识和惯用手段，在不脱离本发明上述基本技术思想前提下，还可以做出其它多种形式的修改、替换或变更。
以下通过实施例形式的具体实施方式，对本发明的上述内容再作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下的实例。凡基于本发明上述内容所实现的技术均属于本发明的范围。
附图说明
图1为本发明钒络合物(Ⅲ)的X-射线衍射晶体结构图。
图2中曲线为本发明聚乳酸的GPC图，Molar mass表示重均分子量。
图3为本发明聚乳酸的1HNMR图。
具体实施方式
化合物(Ⅲ)、化合物(Ⅳ)通过现有技术的方法制备(参照4-Formyl amino-n-methyl piperidine derivatives,the use thereof as stabilizers and organicmaterial stabilized therewith，Patent:US2003/83406A1,2003；Synthesis,structure,and reactions of vanadium acid esters VO(OR)3:Trans esterification andreaction with oxalic acid，Zeitschrift fur Anorganische und Allgemeine Chemie,2000，vol.626,#10p.2125-2132)，所用主原料购自阿法埃莎、阿拉丁试剂等试剂公司，为分析级。所用甲苯等溶剂均经除水除氧预处理。络合物的制备及其催化反应均在氮气保护手套箱(LS800D，购自成都德力斯实业有限公司)中进行。
实施例1 本发明双核钒络合物的制备及表征
1、本发明双核钒络合物的制备
将化合物(Ⅳ)4.1g(4.44mmol)和化合物(Ⅴ)VO(iPrO)32.10mL(8.90mmol)于甲苯30mL中回流12h。冷却，真空干燥除去挥发成分,之后用二氯甲烷30mL萃取残留物。于0℃下静置得到棕色固体化合物，棕色固体化合物C70H100O8V2·2CH2Cl24.32g，收率83％。
2、本发明双核钒络合物的表征
2.1 元素分析
真空干燥12h后进行元素分析。分子式C70H98V2O8·2CH2Cl2，实测值(理论值)如下：
C：67.01％(67.55％)；H：7.86％(8.49％)。
2.2 红外光谱
IR:1572w,1408w,1260s,1225w,1189w,1149w,1093bs,1019bs,873w,862w,799s,722w,663w,601w.1H NMR(CDCl3):δ＝7.38–7.14(overlapping m,8H,arylH),6.77(s,4H,arylH),6.33(s,2H,CH),5.64(sept,3JHH 4.0Hz,2H,CHMe2),5.29(s,4H,CH2Cl2),1.61(d,3JHH 4.0Hz,12H,CHMe2),1.44(s,36H,C(CH3)3),1.23(s,36H,C(CH3)3).51V NMR(CDCl3)δ＝-449.7(w1/2＝688Hz)。
2.3 核磁
1H NMR(CDCl3):δ＝7.38–7.14(overlapping m,8H,arylH),6.77(s,4H,arylH),6.33(s,2H,CH),5.64(sept,3JHH 4.0Hz,2H,CHMe2),5.29(s,4H,CH2Cl2),1.61(d,3JHH4.0Hz,12H,CHMe2),1.44(s,36H,C(CH3)3),1.23(s,36H,C(CH3)3)。
51V NMR(CDCl3)δ＝-449.7(w1/2＝688Hz)。
2.4 晶体结构
晶体结构如图1所示。
晶体数据如下所示
C70H100O8V2分子量(Formulaweight)1171.37；
单斜晶系(Monoclinic),P21/c,
β＝92.329(6)；
Z＝2，密度(Density)(calculated)＝1.227Mg/m3；
晶体尺寸(crystal size)0.09x 0.03x 0.01mm3；
单胞中电子的数目F(000)1260；
吸光系数(Absorption coefficient)0.349mm-1；
温度(Temperature)100(2)K；
波长(wavelength)0.71075nm；
theta角范围(theta range for data collection)2.450～25.095°；
衍射指标范围(Index ranges)-13≤h≤13,-12≤k≤8,-33≤l≤28；
衍射点收集(reflections collected)17727；
独立衍射点(independent reflections)5568[R(int)＝0.1786]；
theta完整性(completeness to theta)25.095°98.8％；
全矩阵最小二乘法对F2进行修正(refinement method Full matrix leastsquares on F2)：
数据限制性参数(Data/restraints/parameters)5568/0/372；
基于F2的GOOF值(Goodness of fit on F2)1.058；
对于可观测衍射点的残差因子R值(Final R indices[I>2sigma(I)])R1＝0.0987,wR2＝0.1841；
对于全部衍射点的残差因子R值(R indices(all data))R1＝0.2293,wR2＝0.2427；
精修后残余电子密度的峰、谷值(Largest diff.peak and hole)0.585和
键长和键角[°]如下所示：
V(1)–O(1) 1.575(4),
V(1)–O(2) 1.777(4),
V(1)–O(3) 1.750(5),
V(1)–O(4) 1.759(5)；
O(2)–V(1)–O(3)109.4(2),
V(1)–O(2)–C(1)139.7(5),
V(1)–O(3)–C(17)151.7(4),
V(1)–O(4)–C(40)130.1(5)。
实施例2 本发明双核钒络合物催化合成聚乳酸
凝胶渗透色谱(GPC)分析采用下述仪器：
Shimadzu GPC仪器，装有LC-20A泵，DGU-20A3脱气装置，CTO-20A柱温箱，RID-10A示差检测器，2个Shodex硅胶柱(KF-803和KF-804)和1个保护柱(KF-G)。40℃下，四氢呋喃(HPLC级)作为流动相，流速为1mL/min。用窄分子量分布的聚苯乙烯校准。
1、不同条件下的催化
开环聚合反应采用Schlenk技术进行，具体如下：
将装有搅拌磁子的两颈烧瓶与配有氩气和泵的Schlenk线相连，经火焰烘烤干燥三分钟，经充氩气-放真空操作至少3次后，加入2g L-丙交酯、适量的苯甲醇(作为引发剂)和催化剂。充氩气-放真空操作三次后，用注射器经橡胶塞向上述混合物中加入新蒸的7mL甲苯(以形成2M的溶液)。保持聚合反应在45℃、60℃或80℃下进行。加入1mL 0.1M的盐酸溶液终止聚合反应。用注射器取出经不同聚合时间的产物，在磁子搅拌下于冷甲醇中沉淀，以除去残余的催化剂。将所得沉淀物过滤，甲醇洗涤，干燥以备测定，结果如表1所示。
表1 本发明络合物(Ⅲ)对L-丙交酯开环聚合的影响
| 催化剂 | LA:Cat:OH | 温度℃ | 时间/h | Mn,GPC | Mn,NMR | PDI | 产率/％ |
| 本发明 | 200:1:1 | 80 | 36 | 11000(6380)* | 9410 | 1.11 | 58 |
| 60 | 31 | 5450(3160) | 3480 | 1.06 | 28 | ||
| 200:0.7:1 | 45 | 31 | 3930(2280) | nd | 1.04 | 3 | |
| 200:0.5:1 | 80 | 36 | 5040(2925) | 3270 | 1.05 | 15 | |
| Sn(Oct)2 | 200:1:1 | 80 | 34 | 16800(9740) | 4480 | 1.23 | 80 |
| 60 | 31 | 10850(6290) | nd | nd | 60 | ||
| 45 | 不反应 |
注：LA:Cat:OH表示丙交酯：催化剂：苯甲醇(摩尔比)。
*表示分子量(molar mass)分布范围，分别为统计最高分子量和最低分子量平均值。
从表1的结果可以看出，本发明的络合物在45-80℃之间，均能可以有效催化L-丙交酯的开环聚合反应，而Sn(Oct)2在45℃下无法催化反应。
同时，本发明络合物可以根据需求有效控制聚合物的分子量，分子量分布窄，PDI介于1.06～1.11之间，也优于Sn(Oct)2。其中，80℃时，产率较高；LA:Cat:OH为200:1:1时，产率较高，Mn较大。
2、聚乳酸的GPC表征
聚乳酸为在LA:Cat:OH比例为200:1:1,反应温度为80℃,反应时间为36h条件下得到的产物。
GPC痕迹图如图2所示，Mw＝7028g/mol，PDI＝1.11。
3、聚乳酸的核磁表征
聚乳酸的1HNMR谱图如图3所示。从结果可以看出，本发明络合物起到了催化反应的作用。
综上所述，本发明的双核钒络合物，制备方法简便，毒性低，催化活性高，分子量分布窄，还可以根据需求有效控制聚合物的分子量，具有广泛的市场应用前景。
Claims (6)
1.式(Ⅲ)所示的双核钒络合物或其溶剂化物：
所述溶剂化物为化合物(Ⅲ)·2CH2Cl2(C70H100O8V2·2CH2Cl2)。
2.一种制备权利要求1中式(Ⅲ)所示双核钒络合物的方法，其特征在于：它是以化合物(Ⅳ)和三-异丙基正钒酸(Ⅴ)为原料，在无水无氧环境下，于甲苯中回流制备得到的，所述化合物(Ⅳ)和三-异丙基正钒酸(Ⅴ)的摩尔比为1∶2，制备路线如下：
3.权利要求1所述溶剂化物C70H100O8V2·2CH2Cl2的晶型，其特征在于：
该晶型属于单斜晶系，空间群为P21/c，晶胞参数为 β＝92.329(6)°，ρcalc＝1.227Mg/m3。
4.权利要求1或3所述双核钒络合物或其溶剂化合物或其晶型作为开环聚合反应催化剂或烯烃聚合反应催化剂的用途。
5.根据权利要求4所述的用途，其特征在于：所述开环聚合反应的单体为丙交酯。
6.权利要求1或3所述双核钒络合物或其溶剂化合物或其晶型在制备聚乳酸中的用途。
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