DPE法合成双亲性丙烯酸酯嵌段共聚物及用于颜料分散剂的研究

以1,1-二苯基乙烯(DPE)为分子量调节剂,偶氮二异丁腈(AIBN)为引发剂进行甲基丙烯酸丁酯(BMA)的可控自由基聚合(DPE法)。研究了溶剂、DPE用量及反应温度对于聚合的影响,得到分子量分布较窄(PDI=1.43)的含有DPE半醌式休眠种结构的聚甲基丙烯酸丁酯(PBMA)。以PBMA为引发剂引发甲基丙烯酸二甲氨基乙酯(DMAEMA)聚合,得到分子量分布较窄的(PDI=2.0)双亲性嵌段共聚物(PBMA-b-PDMAEMA)。核磁共振氢谱(1H NMR)测得共聚物组成与GPC测试结果相近。差示扫描量热分析(DSC)测试表明嵌段共聚物在11℃和35℃处有两个玻璃化转变温度。色浆的流变和粒径测试及漆膜性能测试表明,将所得双亲性嵌段共聚物作为酞菁蓝颜料分散剂,可以明显提高酞菁蓝颜料在丙烯酸酯树脂中的分散效率。     

ARGET-ATRP合成双亲性嵌段共聚物及对二氧化钛分散效率的影响

以CuBr2（相对于单体物质的量的0.02%或0.01%）和还原剂、配体混合物为催化体系进行甲基丙烯酸 2(N,N-二甲氨基)乙酯（DMAEMA）的电子转移再生催化剂原子转移自由基聚合（ARGET-ATRP）,研究了溶剂、配体和还原剂种类对聚合的影响,得到分子量分布较窄的（PDI=1.56）聚甲基丙烯酸 2(N,N-二甲氨基)乙酯（PDMAEMA-Br）。以PDMAEMA-Br为引发剂引发丙烯酸丁酯进行“一步法”ARGET-ATRP聚合,得到分子量分布很窄的（PDI=1.4）双亲性嵌段共聚物（PDMAEMA-bPBA)。核磁共振氢谱（1H NMR）测得共聚物组成与GPC测试结果相近。差示扫描量热分析（DSC）测试表明嵌段共聚物在-40.1℃和123.5℃处有两个玻璃化转变温度。该方法大大降低了铜盐催化剂的用量,降低了制备成本,使聚合产物的后处理更容易进行。所得双亲性嵌段共聚物可以作为分散剂,明显提高了二氧化钛在环氧树脂中的分散效率。     

ATRP/RAFT技术合成刷型多元共聚物

以十二烷基三硫代碳酸酯(DDMAT)为链转移剂,通过可逆加成-断裂转移自由基聚合(RAFT)技术制备了分子量分布较窄(多分散性指数PDI为1.54)的二嵌段共聚物聚对氯甲基苯乙烯(PVBC-b-PS),再以PVBC结构中的苄基氯为引发点,借助原子转移自由基聚合(ATRP)方法在大分子主链上接枝甲基丙烯酸甲酯(MMA),得到刷型三元共聚物PVBC-b-PS-g-PMMA(PDI=3.38,分子量43 000,VBC重复单元接枝率为12.2%)。     

PGMA-b-PS二嵌段共聚物的RAFT/细乳液合成及表征

以2-(十二烷基三硫代碳酸酯)-2-甲基丙烯酸为链转移剂,利用RAFT/细乳液联合技术合成了相对分子质量分布较窄(PDI=1.53)的大分子链转移剂聚甲基丙烯酸缩水甘油酯。再以该大分子为可逆加成-断裂链转移(RAFT)试剂,通过连续加料的方式加入苯乙烯后进一步引发聚合,得到PGMA-b-PS二嵌段共聚物。采用GPC、FT-IR、1H-NMR、DSC等方法对聚合产物进行了表征。结果表明:合成的聚合物为线型二嵌段共聚物,相对分子质量分布为1.87,该聚合过程具有活性/可控特征。DSC测得二嵌段共聚物具有2个玻璃化转变温度(Tg),分别为77.33℃和98.30℃。此外,还考察了单体加料顺序对聚合过程的影响。     

三嵌段共聚物PS-b-PI-b-PVBC的RAFT合成与表征

采用可逆加成-断裂链转移自由基聚合法,以S-正十二烷基-S'-(α,α'-二甲基-α″-乙酸基)三硫代碳酸酯为链转移剂,偶氮二异丁腈为引发剂,合成窄分子量分布的聚苯乙烯大分子链转移剂(PS-CTA),在PS-CTA存在下,由引发剂依次引发异戊二烯(Ip)和对氯甲基苯乙烯(VBC)聚合,得到三嵌段聚合物PS-b-PI-b-PVBC。运用凝胶色谱、IR、原子力显微镜、1H NMR等技术对产物的结构进行表征。结果表明,所得嵌段共聚物分子量分布较窄(PDI=1.93),聚合过程具有活性/可控特征,聚合物薄膜在热退火后形成微观相分离,平均相区尺寸约为100 nm。     

三嵌段共聚物PS-b-PI-b-PVBC的RAFT合成与表征

采用可逆加成-断裂链转移自由基聚合法,以S-正十二烷基-S'-(α,α'-二甲基-α″-乙酸基)三硫代碳酸酯为链转移剂,偶氮二异丁腈为引发剂,合成窄分子量分布的聚苯乙烯大分子链转移剂(PS-CTA),在PS-CTA存在下,由引发剂依次引发异戊二烯(Ip)和对氯甲基苯乙烯(VBC)聚合,得到三嵌段聚合物PS-b-PI-b-PVBC。运用凝胶色谱、IR、原子力显微镜、1H NMR等技术对产物的结构进行表征。结果表明,所得嵌段共聚物分子量分布较窄(PDI=1.93),聚合过程具有活性/可控特征,聚合物薄膜在热退火后形成微观相分离,平均相区尺寸约为100 nm。     

P2VP-b-PS-b-PI三嵌段共聚物的RAFT合成及表征

以S-十二烷基-S’-(α,α’-二甲基-α’’-乙酸)-三硫代碳酸酯(DDMAT)为链转移剂,通过可逆加成-断裂链转移自由基聚合(RAFT)方法制备了窄分布的聚2-乙烯基吡啶。再以该聚合物为大分子链转移剂,引发苯乙烯的RAFT聚合,得到聚2-乙烯基吡啶-b-聚苯乙烯(P2VP-b-PS)的两嵌段共聚物。以P2VP-b-PS为RAFT试剂,合成聚2-乙烯基吡啶-b-聚苯乙烯-b-聚异戊二烯(P2VP-b-PS-b-PI)的三嵌段共聚物。运用1H NMR、IR和凝胶渗透色谱(GPC)等技术对产物的结构和分子量及分子量分布进行表征,采用原子力显微镜(AFM)观察三嵌段共聚物薄膜的微相分离结构。结果表明,所得三嵌段共聚物P2VP72-b-PS136-b-PI300分子量分布较窄(PDI=1.69),合成过程具有活性/可控聚合特征,聚合物薄膜经溶剂退火处理后出现了明显的微观相分离结构。     

乙烯/1-辛烯嵌段共聚物的合成

以合成的"软段"吡啶胺基铪配合物和"硬段"水杨醛亚胺锆配合物,在二乙基锌链转移剂作用下制备了窄分子量分布的乙烯/1-辛烯嵌段烯烃共聚物。结果表明,链穿梭聚合的活性(以铪催化剂计)能够达到34.8×106g/(mol·h),辛烯插入摩尔分数达到了23.5%,烯烃嵌段共聚物的重均分子量可达到225 kg/mol,分子量分布较窄(分子量分布指数2.0～2.3),嵌段共聚物熔点能够达到115℃以上。通过调节吡啶胺基铪催化剂与水杨醛亚胺锆催化剂的比例可以调控共聚物的嵌段长度及分子量。     

采用ATRP反应合成嵌段共聚物P(n-BMA-b-NIPAM)的研究

采用原子转移自由基聚合(ATRP)反应合成了甲基丙烯酸正丁酯/N-异丙基丙烯酰胺嵌段共聚物(P(n-BMAb-NIPAM))。考察了引发剂、催化剂、反应温度等对聚合反应结果的影响,最终确定较为合适的反应条件,制备出分子量确定、分子量分布较窄的大分子引发剂,并成功引发第二单体继续通过ATRP反应,获得P(nBMA-b-NIPAM)。研究结果表明:所确定的ATRP反应体系能实现n-BMA的可控聚合,获得末端带溴原子的聚甲基丙烯酸正丁酯(P(n-BMA-Br))作为大分子引发剂继续通过ATRP反应引发N-异丙基丙烯酰胺(NIPAM),最后获得分子量确定、分子量分布较窄的嵌段共聚物P(n-BMA-b-NIPAM)。实验证明,利用高价态铜络合体系可以实现单体的可控聚合,而且可以保持聚合物末端较高的卤官能度。     

树枝状聚酯—聚L-赖氨酸（Z）两嵌段共聚物的合成

由2,2-二羟甲基丙酸与2,2-二甲氧基丙烷经过逐级醇酸缩合、催化加氢和端氨基化后得到端基为氨基的树枝状聚酯分子G3-C3H9N2,以此为引发剂引发ω苄氧羰基L-赖氨酸-N-羧酸酐（ω-Z—L—lysine—NCA）开环聚合得到树枝状聚酯-聚L-赖氨酸（Z）两嵌段共聚物。采用^1H—NMR、IR、GPC方法对产物进行表征。结果表明：G3-C3H9N2能有效引发NCA开环聚合,共聚物的分子量可以通过调节单体引发剂比例来控制,所得产物具有较窄的分子量分布系数。     

Preparation of diblock copolymer PBA-<Emphasis Type="Italic">b</Emphasis>-PSt by DPE method in emulsion

Diblock copolymer poly (butyl acrylate)-b-polystyrene (PBA-b-PSt) was prepared by two steps in a complete emulsion system, using DPE (1, 1-diphenylethylene) as free radical control agent. In the first step, butyl acrylate (BA), initiator potassium peroxodisulfate (KPS) and DPE were emulsion polymerized to form P(BA-DPE) precursor. Then the precursor was heated in the presence of a second monomer styrene (St), and block copolymer was synthesized successfully. The structures, molecular weight of precursor and block copolymer were characterized by FTIR, UV–VIS, ¹H-NMR and SEC/MALLS. Influence of DPE on polymerization kinetics was also investigated. Meantime, thermal properties of block copolymer were analyzed by TGA and DSC.     

Self-Compatibilization of poly(butyl methacrylate)/acrylonitrile-co-styrene blends via concentrated emulsion polymerization

Two concentrated emulsions in water were prepared: one from weakly polymerized butyl methacrylate (BMA) and the other one from a weakly polymerized mixture of acrylonitrile (AN) and styrene (St). Each of the concentrated emulsions also contained a small amount of a vinyl-terminated macromonomer (VTM). After the concentrated emulsions were partially polymerized, they were mixed and subjected to complete polymerization. This generated a blend of poly(butyl methacrylate) (PBMA), binary copolymer AN-co-ST (AN—St), and networks containing chains of VTM and those formed from different monomers. The networks constitute compatibilizers between the PBMA and AN—St. Such a preparation method, in which the components and compatibilizer are generated simultaneously, was called self-compatibilization. The blend possesses excellent tensile properties and toughness compared with the ternary copolymer AN—St—BMA and with the solution blends of PBMA/AN—St. The generation of the compatibilizers and the compatibilization mechanism were investigated via kinetic studies. The effects of the VTM, polymerization conditions, and the weight ratio of AN/St were also examined. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of PBMA‐b‐PSt‐b‐PBMA triblock copolymers by atom transfer radical emulsion polymerization

Poly(n‐butyl methacrylate)‐b‐polystyrene‐b‐poly(n‐butyl methacrylate) (PBMA‐b‐PSt‐b‐PBMA) triblock copolymers were successfully synthesized by emulsion atom transfer radical polymerization (ATRP). Difunctional polystyrene (PSt) macroinitiators that contained alkyl chloride end‐groups were prepared by ATRP of styrene (St) with CCl₄ as initiator and were used to initiate the ATRP of butyl methacrylate (BMA). The latter procedure was carried out at 85°C with CuCl/4,4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) as catalyst and polyoxyethylene (23) lauryl ether (Brij35) as surfactant. Using this technique, triblock copolymers consisting of a PSt center block and PBMA terminal blocks were synthesized. The polymerization was nearly controlled, ATRP of St from those macroinitiators showed linear increases in the number average molecular weight (Mn) with conversion. The block copolymers were characterized with infrared (IR) spectroscopy, hydrogen‐1 nuclear magnetic resonance (¹HNMR), and differential scanning calorimetry (DSC). The effects of the molecular weight of macroinitiators, concentration of macroinitiator, catalyst, emulsion, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP were also reported. POLYM. ENG. SCI., 45:1508–1514, 2005. © 2005 Society of Plastics Engineers     

Poly(n-butyl methacrylate) end-capped polyrotaxanes via ATRP initiated with α-cyclodextrin and Pluronic 17R4 based inclusion complexes

A series of polyrotaxane (PR)-based triblock copolymers comprising a PR middle block and poly(n-butyl methacrylate) (PBMA) flanked blocks were prepared via bulk ATRP of n-butyl methacrylate initiated with polypseudorotaxanes self-assembled from α-cyclodextrins (α-CDs) with 2-bromoisobutyryl terminated Pluronic 17R4 at 35 °C. Their structure was verified by ¹H NMR, FTIR, GPC, WXRD and TGA analyses. The dethreading of entrapped α-CDs during the polymerization process was effectively impeded through an elaborated choice of Pluronic 17R4, a PPG–PEG–PPG triblock copolymer, in which α-CDs site-selectively include with the middle PEG block and are inhibited by the flanked PPG blocks. The degree of polymerization of attached PBMA blocks appeared to be tunable to some extent. The polydispersity index of the resulting PR-based triblock copolymers is in a low range of 1.28–1.50. As an attempt toward the materialization of these unique supramolecular polymers, a selected sample was dissolved in methylene dichloride and electrospun into micro-sized particles. Nevertheless, they can be not only casted into tough films but also melt extruded into sticks.     

Synthesis of ABA triblock copolymers of N-substituted maleimides and methacrylates by group transfer polymerization

Summary ABA type block copolymerization of N-phenylmaleimide (NPM), N-hexyl maleimide (NHM), methyl methacrylate (MMA), and butyl methacrylate (BMA) was investigated by group transfer polymerization (GTP) with [1,5-bis (trimethylsilyloxy)-1,5-dimethoxy-1,4-pentadiene] (1) as difunctional initiator. A novel block copolymers (2) of NPM and MMA (or BMA) could be prepared by sequential addition of NPM to the living PMMA (or PBMA) produced with 1. The reaction did not exhibit the characteristics of living polymerization when NPM was added. The resulting copolymers showed good thermal stability. On the other hand, gelation occurred in GTP of NHM.     

Poly(methyl acrylate) and copolymer of acrylic acid and butyl acrylate prepared by γ‐irradiation in the presence of 1,1‐diphenylethene: Synthesis and application in emulsion polymerization

Poly(methyl acrylate) and amphiphilic copolymer of butyl acrylate and acrylic acid were prepared in the presence of 1,1‐diphenylethene (DPE) by γ‐irradiation‐induced polymerization. The influences of polymerization time, amounts of DPE in system on conversion, molecular weight (MW), and its distribution (M_w/M_n) were studied. The results indicate that the polymerization in the presence of DPE and initiated by γ‐irradiation shows the character of controlled radical reaction. The prepared copolymer was used as the polymeric emulsifier in the emulsion polymerizations of butyl acrylate (BA) and styrene (St), respectively, to assess the possibility of making monodisperse latices of relatively high solids content (～ 35–45%) in an one‐step batch process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

苯乙烯-丁二烯-苯乙烯-甲基丙烯酸酯嵌段共聚物的合成与表征

用正丁基锂为引发剂,环已烷和四氢呋喃为混合溶剂,以苯乙烯、丁二烯、甲基丙烯酸酯为单体,按阴离子顺序加料方法合成了聚苯乙烯-丁二烯-苯乙烯-甲基丙烯酸酯嵌段共聚物,共聚物经GPC、IR、DSC、TEM等测试方法表征。结果表明,在30 ℃左右、1,1-二苯基乙烯(DPE)戴帽和LiCl配合的条件下,合成了窄分布(MWD<1.3)聚苯乙烯-丁二烯-苯乙烯-甲基丙烯酸酯嵌段共聚物,成功地在SBS中引入了一小段极性链段。     

Preparation and shear properties of carbon nanotubes/poly(butyl methacrylate) hybrid material

Composites containing carbon nanotubes (CNTs) in a poly(butyl methacrylate) (PBMA) have been prepared by in situ polymerization. Scanning electron microscopy and high‐resolution transmission electron microscope showed that CNTs were well dispersed into PBMA matrix and wrapped with PBMA. The infrared spectrum illustrated that CNTs were covalently linked with PBMA through a C C bond. Owing to this covalent linkage, the composites had a better solubility in organic solvents and had higher thermal stability over pure PBMA. The direct shear testing showed strong mechanical behavior with up to 200% increase in Young's modulus. The possible strengthening mechanism was discussed. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Synthesis and characterization of poly(n‐butyl methacrylate)‐b‐polystyrene diblock copolymers by atom transfer radical emulsion polymerization

Poly(n‐butyl methacrylate) (PBMA)‐b‐polystyrene (PSt) diblock copolymers were synthesized by emulsion atom transfer radical polymerization (ATRP). PBMA macroinitiators that contained alkyl bromide end groups were obtained by the emulsion ATRP of n‐butyl methacrylate with BrCH₃CHCOOC₂H₅ as the initiator; these were used to initiate the ATRP of styrene (St). The latter procedure was carried out at 85°C with CuCl/4,4′‐di(5‐nonyl)‐2,2′‐bipyridine as the catalyst and polyoxyethylene(23) lauryl ether as the surfactant. With this technique, PBMA‐b‐PSt diblock copolymers were synthesized. The polymerization was nearly controlled; the ATRP of St from the macroinitiators showed linear increases in number‐average molecular weight with conversion. The block copolymers were characterized with IR spectroscopy, ¹H‐NMR, and differential scanning calorimetry. The effects of the molecular weight of the macroinitiators, macroinitiator concentration, catalyst concentration, surfactant concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP are also reported. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2123–2129, 2005