黄原酸酯调控的氯乙烯的可逆-加成断裂链转移聚合

以三种不同结构的黄原酸酯为调控剂,进行氯乙烯(VC)溶液和细乳液可逆加成-断裂链转移(RAFT)聚合,发现O-乙基黄原酸丙酸乙酯对VC聚合的调控效果良好,氯乙烯RAFT细乳液聚合速率明显大于溶液聚合,VC聚合12h转化率大于90%,但聚氯乙烯(PVC)的分子量分布宽于溶液聚合产物。核磁共振和紫外可见吸收光谱分析证明合成的PVC具有黄原酸酯基端基结构,结构缺陷少。含黄原酸酯基PVC可进一步调控VC及醋酸乙烯酯聚合,进行扩链或得到嵌段共聚物。结合聚合动力学,说明黄原酸酯调控的氯乙烯聚合具有活性特征。     

可逆加成-断裂链转移聚合制备聚氯乙烯-b-聚乙二醇-b-聚氯乙烯共聚物

合成了含黄原酸酯端基的聚乙二醇（X-PEG-X）大分子链转移剂,并以其为可逆加成-断裂链转移试剂调控氯乙烯（VC）溶液和悬浮聚合,合成聚氯乙烯-b-聚乙二醇-b-聚氯乙烯（PVC-b-PEG-b-PVC）三嵌段共聚物。X-PEG-X调控VC溶液聚合得到的共聚物的分子量随聚合时间增加而增大,分子量分布指数小于1.65。X-PEG-X具有水/油两相分配和可显著降低水/油界面张力的特性,以X-PEG-X为链转移剂和分散剂,通过自稳定悬浮聚合也可合成PVC-b-PEG-b-PVC共聚物,共聚物颗粒无皮膜结构,分子量随聚合时间增加而增大;由于VC悬浮聚合具有聚合物富相和单体富相两相聚合特性,共聚物分子量分布指数略大于溶液聚合共聚物。通过乙酸乙烯酯（VAc）扩链反应进一步证实了PVC-b-PEG-b-PVC的“活性”,并合成PVAc-b-PVC-b-PEG-b-PVC-b-PVAc共聚物。水接触角测试表明PVC-b-PEG-b-PVC的亲水性优于PVC。     

可逆加成-断裂链转移聚合制备聚氯乙烯-b-聚乙二醇-b-聚氯乙烯共聚物

合成了含黄原酸酯端基的聚乙二醇(X-PEG-X)大分子链转移剂,并以其为可逆加成-断裂链转移试剂调控氯乙烯(VC)溶液和悬浮聚合,合成聚氯乙烯-b-聚乙二醇-b-聚氯乙烯(PVC-b-PEG-b-PVC)三嵌段共聚物。X-PEG-X调控VC溶液聚合得到的共聚物的分子量随聚合时间增加而增大,分子量分布指数小于1.65。X-PEG-X具有水/油两相分配和可显著降低水/油界面张力的特性,以X-PEG-X为链转移剂和分散剂,通过自稳定悬浮聚合也可合成PVC-b-PEG-b-PVC共聚物,共聚物颗粒无皮膜结构,分子量随聚合时间增加而增大;由于VC悬浮聚合具有聚合物富相和单体富相两相聚合特性,共聚物分子量分布指数略大于溶液聚合共聚物。通过乙酸乙烯酯(VAc)扩链反应进一步证实了PVC-b-PEG-b-PVC的"活性",并合成PVAc-b-PVC-b-PEG-b-PVC-b-PVAc共聚物。水接触角测试表明PVC-b-PEG-b-PVC的亲水性优于PVC。     

用MADIX/RAFT聚合合成聚(N-乙烯基己内酰胺)

MADIX/RAFT聚合是黄原酸酯调控的可逆加成-断裂链转移自由基聚合,它可用于调控非共轭单体的活性/可控自由基聚合。以乙二醇为原料,将乙二醇的两个羟基转化为O-乙基黄原酸酯,得到黄原酸酯双官能团链转移剂(CTA)。用这个CTA调控N-乙烯基己内酰胺(NVCL)的MADIX/RAFT聚合,合成了聚(N-乙烯基己内酰胺)。用1H NMR谱证明了所得聚合物和中间产物的结构。     

CPDB为链转移试剂的脱氢枞酸基单体的RAFT聚合研究

以脱氢枞酸（β-甲基丙烯酰氧基丙基）酯（DAHPMA）为单体,偶氮二异丁腈（AIBN）为引发剂,2-氰基-2-丙基苯并二硫（CPDB）为链转移试剂,在四氢呋喃溶液中进行可逆加成-断裂转移自由基聚合反应（RAFT）制备得到脱氢枞酸基酯均聚物。动力学研究表明了脱氢枞酸基单体可以在RAFT聚合下具有活性可控的特征,同时探讨了CPDB的浓度对松香基单体的RAFT聚合的影响,发现CPDB的浓度对聚合过程的速率和可控性以及相对分子量和相对分子质量分布都有一定的影响。通过核磁证实了该松香基均聚物的成功合成,接触角测试表明该聚合物具有高疏水性。     

星形嵌段共聚物PCL-b-PNVCL的合成

用季戊四醇引发ε-己内酯(ε-CL)开环聚合得到四臂星形PCL,将其末端羟基转变为O-乙基黄原酸酯,以此为大分子链转移剂调控N-乙烯基己内酰胺(NVCL)的RAFT聚合,合成了以季戊四醇为核、以PCL为内臂、PNVCL为外臂的两亲性星形嵌段共聚物,用1H NMR谱证明了所得聚合物的结构。     

黄原酸酯调控N-乙烯基吡咯烷酮的RAFT聚合

聚(N-乙烯基吡咯烷酮)(PNVP)是一种水溶性高分子材料,广泛应用于生物医药和化妆品行业。黄原酸酯类链转移剂尤其适合于调控非共轭乙烯基单体的可逆加成-断裂链转移(RAFT)聚合。本文合成了[1-(O-乙基黄原酸)乙基]苯作为链转移剂,调控N-乙烯基吡咯烷酮(NVP)的RAFT聚合,再用正丁胺氨解得到巯基封端的PNVP,并用~1H NMR和凝胶渗透色谱(GPC)证明得到了分子量分布较窄、具有末端活性基团的PNVP。     

硬质PVC型材专用料生产技术开发(CPE改性PVC专用料的合成)

本文采用悬浮溶胀法进行抗冲改性剂氯化聚乙烯（CPE）与氯乙烯（VC）接枝共聚，合成硬质PVC型材专用树脂，研究了接枝共聚工艺、配方以及对聚合过程和产物结构的影响规律，为工业化提供了基础。     

氯乙烯悬浮聚合减轻粘釜技术概况

工业上生产聚氯乙烯(＊＊C),是由氯乙烯(VC)单体以悬浮聚合、乳液聚合、本体聚合和溶液聚合四种方法进行游离基型聚合而得。其中悬浮聚合工艺成,后处理简单,所得树脂质量较好,适合于多种用途:故得到最广泛的应用。所以,悬浮聚合生产的树脂在PVC生产中占主要地位,其产量约为PVC总产量的 85 ％。‘。     

端羧基黄原酸酯的合成及其在聚偏氟乙烯合成中的应用

以乙基黄原酸钾与2-溴丙酸为原料合成了一种端羧基黄原酸酯,并利用傅里叶红外光谱(FTIR)、氢核磁共振波谱(~1HNMR)对合成的端羧基黄原酸酯进行了表征。利用合成的端羧基黄原酸酯进行偏氟乙烯(VDF)的可逆加成-断裂链转移(RAFT)聚合制备了聚偏氟乙烯(PVDF)。氢谱核磁积分法证明:通过调节VDF单体与端羧基黄原酸酯链转移剂的量比可以合成一系列不同聚合度的聚偏氟乙烯。     

Synthesis of random and block copolymers of vinyl chloride and vinyl acetate by RAFT miniemulsion polymerizations mediated by a fluorinated xanthate

Reversible addition–fragmentation chain transfer miniemulsion (co)polymerizations of vinyl acetate (VAc) and vinyl chloride (VC) are conducted in the presence of a fluorinated xthanate (X1). VAc miniemulsion polymerization can be well controlled by X1, and PVAc with small polydispersity index (PDI, <1.20) are obtained. X1 also shows well mediative effect to VC‐VAc miniemulsion copolymerization, while the PDI of VC‐VAc copolymer is greater than that of PVAc since a chain transfer rate to VC is greater than that to VAc. PVAc‐b‐PVC copolymers are synthesized by VC miniemulsion polymerizations mediated by X1‐terminated PVAc. PDIs of PVAc‐b‐PVC copolymers are greater than that of PVAc and VC‐VAc random copolymers with close monomer compositions, and increase with the increase of VC conversion. This is caused by the increased chain transfer to monomer and the formation of monomer‐rich and polymer‐rich phases during the VC polymerization stage. As‐prepared PVAc‐b‐PVC copolymers exhibit a micro‐phase separated morphology. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45074.     

Controlled synthesis of sulfonated block copolymers having thermoresponsive property by RAFT polymerization of vinyl sulfonate esters

Four vinyl sulfonate ester derivatives, methyl ethenesulfonate (MES), ethyl ethenesulfonate (EES), 2,2,2-trifluoroethyl ethenesulfonate (TFES), and 2,2,2-trichloroethyl ethenesulfonate (TCLES), which are protected forms of vinyl sulfonic acids, were polymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Polymers having relatively narrow molecular weight distributions and pre-determined molecular weights were obtained by the polymerization of all monomers using a suitable xanthate-type chain transfer agent (CTA). The RAFT polymerizations of EES and TCLES were found to proceed in controlled fashions under suitable conditions, as confirmed by the formation of narrow polydispersity products, molecular weights controlled by the monomer/chain transfer agent ratio, and linear increases in molecular weight with conversion. Deprotection of the ethyl group of poly(EES) by LiBr in refluxing 2-butanone proceeded smoothly to give water-soluble poly(lithium vinyl sulfonate). Poly(potassium vinyl sulfonate) was also obtained by the deprotection of poly(TCLES) using potassium tert-butoxide. The syntheses of thermoresponsive block copolymers involving poly(lithium vinyl sulfonate) segments were conducted by RAFT polymerization of N-isopropylacrylamide using poly(EES) macro-CTA, followed by deprotection. The thermally-induced phase separation behavior and assembled structures of the block copolymers were also studied in aqueous solution.     

ACR—g—VC共聚物的合成与性能研究

由两步乳液聚合合成了核－壳结构型ACR胶乳,并进一步通过ACR胶乳存在下的VC悬浮聚合合成ACR－g-VC共聚物,对接枝共聚物的结构和性能进行表征。结果表明：ACR胶乳的存在影响VC悬乳聚合的稳定性,增加分散剂用量能得到颗粒特性较好的共聚树脂;ACR－g-VC共聚物的溶胶聚合度略低于相同聚合温度的均聚PVC,凝胶含量随共聚组成中ACR含量的增加而增加;ACR－g-VC共聚物的塑化时间小于聚合度接近的均聚PVC,而加工转矩大于均聚ACR－g-VC共聚物的冲击强度随ACR含量的增加而增大,且大于ACR含量相当的PVC／ACR共混物。     

Comparison of RAFT polymerization of methyl methacrylate in conventional emulsion and miniemulsion systems

In this study, we have conducted the reversible addition-fragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) in two heterogeneous systems, i.e. conventional emulsion and miniemulsion, with identical reaction conditions. The main objective is to compare the living character in both systems according to the nucleation mechanism, the latex stability, the particle sizes and particle size distributions of latexes, the molecular weights and molecular weight distributions (or polydispersity index, PDI) of PMMA, and the kinetics of the RAFT polymerization. The RAFT agent used in both systems was 2-cyanoprop-2-yl dithiobenzoate (CPDB). The effects of an oil-soluble initiator 2,2′-azobisisobutyronitrile (AIBN) and a water-soluble initiator kalium persulfate (KPS) on the RAFT/emulsion and RAFT/miniemulsion polymerizations were investigated. Methyl-β-cyclodextrin (Me-β-CD) was used as a solubilizer. The average molecular weights and molecular weight distributions (PDIs) of dried PMMA samples were characterized by gel permeation chromatography (GPC). The experimental results showed that the RAFT/miniemulsion polymerization of MMA exhibited better living character than that of RAFT/emulsion polymerization under the conditions of our experiment. The PDI of PMMA in RAFT/miniemulsion polymerization was decreased with the addition of Me-β-CD. However, Me-β-CD did not have influence on the PDI of PMMA prepared in RAFT/emulsion polymerization.     

Controlled free‐radical polymerization of vinyl chloride

Owing to the importance of poly(vinyl chloride) (PVC) as the second‐largest plastic in volume after the polyolefins and above styrene polymers, the control of the free‐radical polymerization of vinyl chloride (VC) is of high industrial and academic interest. But still the term “controlled” polymerization is not yet clearly defined. Often it is used for quasi‐living polymerizations with equilibrium reactions in the initiation and/or termination step or for the control of the molecular weight distribution (MWD), but it can also be applied to several structural aspects such as stereochemistry, branching, or special technical properties. In the present article, the control of chain growth and chain transfer is discussed. It has been well known for many years that the propagation step in the VC polymerization is terminated to a large degree by the rather frequent and temperature‐dependent chain transfer of the growing macromolecules to the monomer. Therefore, the degree of polymerization is strongly governed by the polymerization temperature. However, this transfer step does not result in a controlled or a narrow MWD. By means of free‐radical nitroxide‐mediated polymerization of VC in suspension, PVC with a narrower MWD can be obtained also at higher polymerization temperatures. The resulting PVC with nitroxide end groups can act as a macro‐initiator for various monomers, resulting in two‐block copolymers, which are, e.g., interesting compatibilizers in blends with PVC. J. VINYL ADDIT. TECHNOL., 11:86–90, 2005. © 2005 Society of Plastics Engineers     

Controlled grafting of poly(vinyl acetate) onto starch via RAFT polymerization

A structure‐exact starch‐based xanthate agent was prepared and used as chain transfer agent to mediate RAFT polymerization of vinyl acetate, which offered a convenient way to well control the structure and composition of starch‐g‐poly(vinyl acetate). The structures of the intermediate and the polymer were verified with FTIR and ¹H‐NMR. Gel permeation chromatography measurement results indicated that the polymerization was performed as expected. It was found that the relationship between number average molecular weight and monomer conversion was linear. The polydispersity index of grafted side‐chain ranged from 1.19 to 1.53 and most of them were around 1.2. There was one more degradation stage appeared on the thermogravimetric analysis profile of starch‐g‐poly(vinyl acetate) than that of starch. TEM observation exhibited that the product was able to self‐assemble into micelles in aqueous solution, which suggested the copolymer was amphiphilic. Both the thermal and amphiphilic properties demonstrated the starch‐g‐poly(vinyl acetate) was successfully synthesized as well. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influences of individual and composed poly(vinyl alcohol) suspending agents on particle morphology of suspension poly(vinyl chloride) resin

Effects of individual and composed poly(vinyl alcohol) (PVA) suspending agents on the particle morphology of poly(vinyl chloride) (PVC) resins were investigated and discussed in the view of PVA absorption at the oil/water interface and interfacial behavior. It was shown that the percentage and surface coverage of PVA at the oil/water interface decreased with the increase of the degree of hydrolysis (DH) of PVA in the DH range of 70–98 mol %, while the interfacial tension of VC/PVA aqueous solution increased linearly with the increase of DH of PVA. PVC resin with more regular particle shape, increased agglomeration and fusion of primary particles, lower porosity and higher bulk density, was prepared by using PVA with a higher DH as a suspending agent. This was caused by the occurrence of drop coalescence at the very early stage of VC polymerization, the increase of particle shrinkage, and the lower colloidal protection to primary particles. It was also shown that the interfacial tension of VC/water in the presence of composed PVA suspending agents varied linearly with the weight composition of the composed PVA suspending agents. The particle properties of PVC resin prepared by using the composed PVC suspending agents were usually situated in between the properties of PVC resins prepared by using the corresponding individual PVA suspending agent. The particle morphology and properties of PVC resin could be controlled by the suitable choice of the composed PVA suspending agents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3848–3855, 2003     

Comparison of styrene reversible addition–fragmentation chain‐transfer polymerization in a miniemulsion system stabilized by ammonlysis poly(styrene‐alt‐maleic anhydride) and sodium dodecyl sulfate

In this study, we conducted the reversible addition–fragmentation chain‐transfer (RAFT) polymerization of styrene (St) in a miniemulsion system stabilized by two different stabilizers, ammonlysis poly(styrene‐alt‐maleic anhydride) (SMA) and sodium dodecyl sulfate (SDS), with identical reaction conditions. The main objective was to compare the polymerization kinetics, living character, latex stability, and particle morphology. The macro‐RAFT agent used in both systems was SMA, which was obtained by RAFT solution polymerization mediated by 1‐phenylethyl phenyldithioacetate. The experimental results show that the St RAFT miniemulsion polymerization stabilized by SDS exhibited a better living character than that stabilized by ammonlysis SMA. The final latices were very stable in two systems, but different stabilizers had an obvious effect on the polymerization kinetics, living character, and particle morphology. All of the particles obtained by RAFT miniemulsion polymerization stabilized by SDS were solid, but an obvious core–shell structure was observed in the miniemulsion system stabilized by ammonlysis SMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Controlled synthesis of thermoresponsive polymer via RAFT polymerization of an acrylamide containing l-proline moiety

Reversible addition–fragmentation chain transfer (RAFT) polymerization of N-acryloyl-l-proline methyl ester (A-Pro-OMe) was investigated in order to find suitable conditions to achieve controlled synthesis of amino acid-based polymers with pre-determined molecular weight, narrow polydispersity, well-defined chain end structure, and characteristic thermoresponsive property. The effect of various parameters, such as chain transfer agent (CTA)/initiator ratio, solvent, and temperature, on RAFT polymerization of A-Pro-OMe was examined using benzyl dithiobenzoate as a CTA. Chain-end structure of the resulting poly(A-Pro-OMe) was confirmed by ¹H NMR analysis, MALDI-TOF mass spectroscopy, and chain extension experiment. Thermally induced phase separation behaviors of poly(A-Pro-OMe)s prepared by RAFT and conventional free radical polymerizations were also studied in aqueous solution.