吡啶基三唑配合物催化下甲基丙烯酸甲酯的原子转移自由基聚合研究

以配体3,5-二-(4-吡啶基)-1,2,4-三唑与CuX形成催化剂,分别以α-溴代异丁酸乙酯和氯化苄为引发剂,环己酮为溶剂,进行了甲基丙烯酸甲酯(MMA)的原子转移自由基聚合(ATRP),同时考察了配比、溶剂量以及温度对聚合速率、聚合物分子量及分子量分布的影响.80℃下的聚合反应速度高于70℃;以环己酮为溶剂,单体与溶剂之比为1∶1.5时可得到较低分子量分布的聚合物.实验结果表明以吡啶基三唑为配合物催化甲基丙烯酸甲酯的聚合过程中,转化率和分子量随时间的增加而增大,聚合反应符合一级动力学规律,所得聚合物分子量分布较窄(1.21～1.46),结合端基分析和扩链反应结果,证明该聚合反应符合"活性"/可控自由基聚合.     

原位生成自引发单体合成支化共聚物

以α-溴代异丁酸叔丁酯为引发剂,二乙烯苯为支化单体,苯乙烯为共聚单体,经原子转移自由基聚合原位生成自引发单体合成支化共聚物。用核磁共振法、凝胶渗透色谱法、三角激光散射法分别对聚合过程和聚合物进行了表征。结果表明：由于苯乙烯的引入,反应体系的交联得到了很好的控制,所得聚合物为支化结构。     

ATRP法合成甲基丙烯酸羟丙酯

以2-溴丙酰溴为溴化剂,在离子液体([Amim]Cl)中与纤维素反应制备大分子引发剂,以溴化亚铜/五甲基二乙烯三胺(CuBr/PMDETA)为引发体系,N,N-二甲基甲酰胺(DMF)及丁酮(Butanone)为溶剂,研究了甲基丙烯酸羟丙酯的原子转移自由基聚合(ATRP)。通过FT-IR,1HNMR和GPC对聚合物进行了分析,考察了聚合反应的活性特征,反应时间、催化体系、溶剂对聚合物分子量及分子量分布的影响。结果表明,反应转换率随时间呈线性增加,且合成反应是可控活性聚合。     

枝化-环化结构共聚物用于酸响应载药体系

将溴代聚乙二醇(PEG2000Br)和缩醛化物二(2-丙烯酰氧基乙氧基)-(4-甲氧基苯基)甲烷(ACD)分别作为引发剂和单体,采用逆向增强原子转移自由基聚合(DE-ATRP)法得到嵌段共聚物聚乙二醇-b-聚[二(2-丙烯酰氧基乙氧基)-(4-甲氧基苯基)甲烷](PEG-b-PACDs)。通过核磁共振氢谱和凝胶渗透色谱表征了该聚合物的结构;用动态光散射和透射电镜表征了胶束的尺寸和形貌。结果表明,聚合物呈现枝化-环化结构,空白胶束的尺寸在70 nm左右,载药胶束尺寸在90 nm左右,胶束的药物包封率为48.7%。在pH为7.4时透析48 h后,药物释放率只有32.5%,在pH为5.4时透析48 h后,药物释放率为68.3%,表明共聚物在酸性条件下具有良好的药物缓释性。     

超支化聚苯乙烯-线型聚四氢呋喃-超支化聚甲基丙烯酸(N,N.二甲胺基乙酯)三嵌段共聚物的制备与表征

合成了超支化聚苯乙烯-线型聚四氢呋喃-超支化聚(甲基丙烯酸N,N-二甲胺基乙酯)三嵌段共聚物(HPS-b-LPTHF-b-HPDMAEMA).首先分别以丙烧醇和2.溴乙醇引发四氢呋喃的阳离子开环聚合,然后得到的聚四氢呋喃(PTHF)末端的羟基用带有援基的三硫代碳酸酯酯化,得到大分子RAFT试剂,并把溴端基用叠氮基取代.接着在大分子RAFT试剂存在情况下,通过自缩合原子转移自由基共聚合分别制得端烧基HPS-b-LPTHF和端叠氮基HPDMAEMA-b-LPTHF两嵌段聚合物.最后将两种两嵌段聚合物通过点击反应偶联得到超支化-线型-超支化三嵌段共聚物HPS-b-LPTHF-b-HPDM AEMA.核磁共振氢谱(1H-NMR)、凝胶渗透色谱(GPC)结果表明:所得产物分子量可控,得到了预期结构的聚合物.     

链转移剂单体存在下自由基NaSCN溶液聚合制备支化聚丙烯腈

以偶氮二异丁腈(AIBN)为引发剂,醋酸乙烯酯(VAc)为第二单体,甲基丙烯酸-3-巯基丙酰氧基乙酯(MMPOE)为链转移剂单体,45%硫氰酸钠(NaSCN)水溶液为溶剂,进行常规自由基共聚反应合成支化聚丙烯腈(BPAN);研究了链转移剂单体含量对聚合物的影响。通过气相色谱(GC)、核磁共振氢谱(1H-NMR)、三检测凝胶渗透色谱(TD-GPC)、旋转流变仪分别对聚合反应过程和聚合产物进行了表征分析。结果表明:在NaSCN水溶液体系中,以MMPOE为链转移剂单体制得了较高支化程度的支化PAN,其支化程度随MMPOE含量的增加而提高,分子量随MMPOE含量的增加而降低;25℃下,15.7%固体含量的支化PAN溶液的零剪切黏度(η0=3.52 Pa·s)仅为其同分子量的线型聚合物溶液黏度(η0=27.7 Pa·s)的12.7%。     

原子转移自由基聚合合成支化聚丙烯腈

以二乙烯苯为支化单体,α-溴代异丁酸叔丁酯为引发剂,CuBr和2,2'-联吡啶为催化体系,利用本体和溶液原子转移自由基聚合合成了支化聚丙烯腈.采用核磁共振谱仪、凝胶渗透色谱仪和多角度激光光散射仪等测试了聚合物结构、相对分子质量及其分布.用无水乙酸钠对支化聚丙烯腈进行末端改性,得到了在硫氰酸钠水溶液中性能稳定、可长期保存的支化聚丙烯腈,而改性对聚合物的耐热性能没有影响.     

脱氢枞酸(β-丙烯酰氧基乙基)酯的合成和表征

以脱氢枞酸为原料,以草酰氯为酰基化试剂(摩尔比1∶1),先合成脱氢枞酸酰氯,然后再与丙烯酸-β-羟基乙基酯酯化(摩尔比1∶1),合成脱氢枞酸(β-丙烯酰氧基乙基)酯,得率75%,质量分数98.5%。用FTIR、GC-MS、13CNMR和DSC对其结构和性能进行了表征。结果表明,脱氢枞酸(β-丙烯酰氧基乙基)酯是一种熔点为59~61℃的白色晶体,在引发剂的存在下,可以发生聚合反应,均聚物玻璃化转变温度约为54.2℃。     

β-二酮钛、锆配合物催化丙交酯本体开环聚合

合成了β-二酮钛、锆配合物：乙酰丙酮钛(Catl)、苯甲酰丙酮钛(Cat2)、二苯甲酰甲烷钛(Cat3)、乙酰丙酮锆(Cat4),并分别成功地催化丙交酯本体开环聚合。结果表明,β-二酮钛、锆配合物催化合成聚乳酸均可达到较高的转化率(高于95%),且Cat4的活性大于Car1。着重研究了催化剂用量(即单体与催化剂物质的量比[LA]/[Cat])、聚合时间及聚合温度对Cat1催化丙交酯本体开环聚合反应的转化率及所得聚乳酸相对分子质量的影响。在以Car1为催化剂,单体与催化剂物质的量比为400,聚合温度130℃,聚合时间30h时,可得到黏均相对分子质量M_η=6．79×10~4的聚乳酸。     

多芳基溴代硅酸酯阻燃剂的合成与应用

以三溴苯酚、四氯化硅及2,3-二溴丙醇为主要原料合成新型阻燃剂2,3-二溴丙氧基-三(三溴苯氧基)硅烷。探讨了加料顺序、溶剂、反应温度、反应时间及物质的量比等对产率的影响,并采用FTIR、1H-NMR和极限氧指数对产品的分子结构及性能进行了表征。该产品为硅、溴协同高效阻燃剂,实验表明:其热稳定性好,应用于聚氯乙烯等材料有良好的阻燃、增塑和成炭防熔融滴落效果。     

偏光片用压敏胶粘剂的合成及性能研究

采用聚合物共混改性的方法,以高、低分子量共聚物共混,使其分子量分布变宽,在保持较好的持粘力的情况下,改善初粘力和剥离强度。实验以丙烯酸丁酯、丙烯酸乙酯为软单体,甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸乙酯等为硬单体,以过氧化苯甲酰BPO为引发剂,甲苯和乙酸乙酯为溶剂,合成了一系列高、低分子量丙烯酸酯共聚物,再通过调节功能性单体丙烯酸AA的含量以及高、低分子量共聚物的共混配比,使压敏胶粘剂的性能得到了很好的改善。     

Synthesis of polystyrene- block -polycarbonate- block - polystyrene and polycarbonate- graft -polystyrene using tandem condensation polymerization and atom transfer radical polymerization

Summary Polystyrene-block-polycarbonate-block-polystyrene was synthesized by atom transfer radical polymerization of styrene using polycarbonate having two 2-bromoisobutyryloxy end groups as the macroinitiator, which was prepared by condensation polymerization of bisphenol A with triphosgene in the presence of chain-stopper, 2-(4-hydroxyphenyl)-2-(4-(2-bromoisobutyryloxy)phenyl)propane. While polycarbonate-graft-polystyrene was synthesized by atom transfer radical polymerization of styrene using polycarbonate having 2-bromoisobutyryloxy side groups as the macroinitiator, which was prepared by condensation of bisphenol and l,l-bis(4-hydroxyphenyl)- 1 -(4-(2-bromoisobutyryloxy)phenyl)ethane with triphosgene. The molecular weights of polystyrene block or graft chains increased linearly with monomer conversion, and their polydispersities were low throughout the blocking or grafting polymerization process. Received: 25 June 2002/Revised version: 23 October 2002/ Accepted: 25 November 2002 Correspondence to Zhifeng Fu     

甲基丙烯酸甲酯的反向原子转移自由基沉淀聚合反应的研究

以甲基丙烯酸甲酯（MMA）为单体,偶氮二异丁腈（AIBN）为引发剂,以氯化铜（CuCl2）/2,4,6-三（二甲氨基甲基）苯酚（DMP-30）为催化体系,以乙醇为溶剂,进行了甲基丙烯酸甲酯的反向原子转移自由基沉淀聚合。聚合反应速率对单体呈一级动力学特征,数均分子量与单体转化率呈线性关系。     

Preparation of hyperbranched polymers by atom transfer radical polymerization

A cheap acrylic AB* monomer, 2‐(2‐chloroacetyloxy)‐isopropyl acrylate (CAIPA), was prepared from 2‐hydroxyisopropyl acrylate with chloroacetyl chloride in the presence of triethylamine. The self‐condensing vinyl polymerization by atom transfer radical polymerization (ATRP), a “living”/controlled radical polymerization, has yielded hyperbranched polymers. All the polymerization products were characterized by proton nuclear magnetic resonance spectroscopy (¹H NMR). CAIPA exhibited distinctive polymerization behavior that is similar to a classical step‐growth polymerization in the relationship of molecular weight to polymerization time, especially during the initial stage of the polymerization. However, a significant amount of monomer remained present throughout the polymerization, which is consistent with typical chain polymerization. Also, if a much longer polymerization time was used, the polymer became gel. As a result of the unequal reactivity of group A* and B*, the polymerization is different from an ideal self‐condensing vinyl polymerization: the branch structures of polymers prepared depend dramatically on the ratio of 2,2'‐bipyridyl to CAIPA. Hyperbranched polymers exhibit improved solubility in organic solvent, however, they have lower thermal stability than their linear analogs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2114–2123, 2002     

Preparation of poly(n-butyl acrylate) by ATRP using initiators for continuous activator regeneration (ICAR) in ionic liquid

The atom transfer radical polymerization (ATRP) of n-butyl acrylate (nBA) using initiators for continuous activator regeneration (ICAR) was successfully carried out in ionic liquid in the presence of a catalyst system of FeCl₃·6H₂O/succinic acid using 2-bromoisobutyrate as the initiator and 2,2′-azobisisobutyronitrile as the reducing agent. The ICAR ATRP of nBA was proved a ‘living’/controlled polymerization such as a linear increase of molecular weights of polymers with monomer conversion and relatively narrow polydispersities (<1.25) when the conversion was beyond 30% and its kinetics in this system was investigated. The polymerization rate increased with temperature and the apparent activation energy was calculated to be 32.84 kJ mol⁻¹. The chain extension experiment was carried out to confirm the controlled manner of the polymerization system. The resultant was characterized by nuclear magnetic resonance and gel permeation chromatography.     

高固体分涂料用含羟基星形丙烯酸酯树脂的制备及性能

以占单体物质的量0.01%的低铜盐用量催化剂体系进行电子转移活化再生催化剂原子转移自由基聚合(ARGET ATRP), 制备了丙烯酸丁酯、甲基丙烯酸甲酯和丙烯酸羟丙酯为单体的线形和六臂星形共聚物。采用折光指数-激光-黏度三检测联用GPC, ¹H NMR和DSC对聚合物的分子结构、共聚组成和玻璃化转变行为进行了研究。将聚合物配制成涂料用树脂溶液, 流变行为研究表明星形聚合物溶液黏度最低。在高固含量时, 星形聚合物降低黏度的优势更明显。在适合喷涂施工的黏度下, 六臂星形共聚物比普通自由基聚合得到的商品化丙烯酸酯树脂的固含量可提高10%。采用异氰酸酯固化剂固化得到的漆膜性能测试表明, 星形聚合物对应清漆的表干时间很短, 同时力学性能达到良好水平。     

Synthesis,characterization, and thermal behavior study of methyl methacrylate polymers containing 4‐carbazole substitutes

A new polymerizable monomer, [4‐(9‐ethyl)carbazolyl]methyl methacrylate ( 2 ), was synthesized by reacting of methacrylic acid and 4‐hydroxymethyl‐9‐ethyl carbazole ( 1 ) by esterification procedure in the presence of N,N′‐dicyclohexylcarbodiimide. The resulting monomer was then polymerized free‐radically to form the poly(methyl methacrylate) containing 4‐(9‐ethyl)carbazolyl pend ent groups. Also, copolymerization of monomer 2 with various acrylic monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, and n‐butyl acrylate by azobisisobutyronitrile as a free radical polymerization initiator gave the related copolymers in high yields. The structure of all the resulted compounds was characterized and confirmed by FTIR and ¹H NMR spectroscopic techniques. The average molecular weight of the obtained polymers was determined by gel permeation chromatography using tetrahydrofurane as the solvent. The thermal gravimetric analysis and differential scanning calorimeter instruments were used for studying of thermal properties of polymers. It was found that, with the incorporation of bulky 4‐(9‐ethyl)carbazolyl substitutes in side chains of methyl methacrylate polymers, thermal stability and glass transition temperature of polymers are increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4989–4995, 2006     

Synthesis and characterization of A-B-A triblock copolymers derived from chloro-telechelic poly(l-lactide): combining ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP)

Ring-opening polymerization (ROP) of l-lactide was combined with atom transfer radical polymerization (ATRP) to produce well-defined linear block copolymers. Poly(l-lactide) (PLLA) was synthesized via ROP using ethylene glycol as an initiator and stannous octoate as a catalyst. The isolated hydroxy-telechelic PLLA was reacted with thionyl chloride and pyridine in toluene to afford chloro-telechelic PLLA (Cl-PLLA-Cl). The latter was employed as a macroinitiator in the synthesis of A-B-A triblock copolymers having either tert-butyl acrylate or benzyl acrylate outer blocks. Outer-block molecular weight was targeted by the mole ratio of monomer (acrylate) to the PLLA chloride initiating sites. The actual incorporation of acrylate into the triblock copolymer was lower than the molar feed ratio as the copolymer became increasingly less soluble upon conversion of acrylate in all cases.     

低分子量聚N-乙烯基甲酰胺-co-乙烯胺的合成

以N-乙烯基甲酰胺为单体,N,N-二甲基甲酰胺和乙酸乙酯为混合溶剂,偶氮二异丁腈为引发剂,十二硫醇为链转移剂,通过沉淀聚合法制备了低分子量的聚N-乙烯基甲酰胺。详细研究了单体质量分数、混合溶剂配比、引发剂用量、链转移剂用量、反应温度及反应时间对聚合反应的影响。在最佳聚合条件下,聚合物收率可达93.1%、聚合物的数均分子量(Mn)为2 975.2,PDI=2.64,且聚合残液可循环利用。然后将所得聚合物在酸性条件下水解,制备了不同胺化度的聚N-乙烯基甲酰胺-co-乙烯胺,产品的数均分子量为1 000~1 400,PDI为1.34~1.40。     

Synthesis, characterization, and controllable drug release of dendritic star-block copolymer by ring-opening polymerization and atom transfer radical polymerization

A series of well-defined dendritic star-block copolymers were successfully synthesized by combination of living ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP) with the hydroxyl-terminated dendrimer polyester. Dendritic star-shaped poly(l-lactide)s (PLLAs) were prepared by bulk polymerization of l-lactide (l-LA) with dendrimer polyester initiator and tin 2-ethylhexanoate catalyst. The number-average molecular weight of these polymers linearly increased with the molar ratio of l-LA to dendrimer initiator. Dendritic star-shaped PLLA was converted into a PLLABr macroinitiator with 2-bromopropionyl bromide. Dendritic star-block copolymers could be obtained via ATRP of 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA). The molecular weight distributions of these copolymers were narrow. The molecular weights of dendritic star-shaped polymers and star-block copolymers could be controlled by the molar ratios of monomer to initiator and monomer conversion. The thermal properties of these dendritic star-shaped polymers and star-block copolymers were investigated. The behavior of model drug chlorambucil release from the copolymer indicated that the rate of drug release could be effectively controlled by altering the pH values of the environment.