Preparation of silicone‐graft copolymers by homogeneous radical copolymerization in supercritical carbon dioxide

Copolymerizations of 1,1‐dihydroperfluorooctyl methacrylate (FOMA; M₁) and methacryloxypropyl‐terminated polydimethylsiloxane [M‐PDMS (M_n = 5.9 K); M₂] and homopolymerization of M‐PDMS in supercritical CO₂ are described. The homopolymerization of M‐PDMS proceeded homogeneously without difficulty to produce oligomers (M_n = 30 K). The copolymerizations of FOMA and M‐PDMS also proceeded homogeneously over a wide monomer feed ratio. The ratio of M‐PDMS incorporated into the copolymer obtained was almost equal to the monomer feed ratio even up to the high conversion. The reactivity ratio r₁ was determined to be 1.66. DSC examination of the copolymers indicated a microphase‐separated morphology consisting of poly‐FOMA (PFOMA) and PDMS domains for all copolymer compositions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1139–1145, 2000     

An All‐ROMP Route to Graft Copolymers

A new versatile synthesis strategy for macromonomers has been developed that uses the living ring‐opening metathesis polymerization (ROMP) with commercial Grubbs first generation ruthenium initiators. Homopolymers as well as diblock copolymers were end‐functionalized with norbornene derivatives to serve as macromonomers. The graft copolymerization of the macromonomers was also carried out employing ROMP. Well‐defined and highly functional graft copolymers are accessible by this new synthetic route.

     

Macromolecular Architecture Based on Anionically Prepared Poly(ethylene oxide) Macromonomers

Synthesis of poly(ethylene oxide) (PEO) macromonomers carrying a methacyloyl group in one end, and N, N-dimethyl amino, thiophene, styryl and vinyl ether functional groups in the other end was desribed. The general synthetic strategy is based on the living anionic polymerization of ethylene oxide initiated with functional potassium alcoholates, followed by reaction with methacyloyl chloride. These macromonomers were further utilized in various macromolecular architectures through via concurrent or selective thermal free radical, oxidative and photoinitiated free radical and cationic polymerization methods. The use of this synthetic route to prepare graft copolymers possessing completly and perfectly alternating PEO side chains using charge-transfer-complex polymerization was also demonstrated.     

PLA大分子单体与NVP接枝共聚物的初步研究

以辛酸亚锡为催化剂,甲基丙烯酸羟乙酯(HEMA)为共引发剂引发消旋-丙交酯(D,L-LA)开环聚合,制备了末端双键功能化的聚乳酸大分子单体(PLA-HEMA);在此基础上,考察了大分子单体与N-乙烯基吡咯烷酮(NVP)的溶液自由基共聚合反应,并初步研究了共聚单体摩尔比和PLA支链长度对合成的两亲性接枝共聚物性能的影响.结果表明,随大分子单体投料量和PLA支链长度增大,共聚物膜的拉伸强度和模量增大,而亲水性有所下降.     

pH响应性水溶性微凝胶的研制

在反应溶剂介质(乙醇)中，通过加入交联剂以分散共聚方式合成了甲基丙烯酸单封端聚乙二醇(PEG)接枝聚丙烯酸Poly微凝胶．在干燥条件下用电子显微镜对凝胶颗粒的形态进行了观察，发现其粒径分布相对较窄，基本保持球形．考察了起始PEG大分子单体、丙烯酸单体和交联剂等的浓度对凝胶颗粒粒径大小的影响，根据激光光散射的测定结果，发现其粒径在300～1200nm的范围内，可以通过改变聚合反应条件加以控制．同时在不同的pH条件下，得到的凝胶颗粒具有完全不同的溶胀性能，表明该微凝胶具有明显的pH响应性；并且其在水和丙酮等溶剂中都具有良好的溶胀性能．     

Living cationic polymerization of a vinyl ether with an unprotected pendant alkynyl group and their use for the protecting group‐free synthesis of macromonomer‐type glycopolymers via CuAAC with maltosyl azides

An asymmetric bifunctional monomer having both an unprotected alkynyl group and a vinyl ether (VE) group (3‐[2‐(2‐vinyloxyethoxy)‐ethoxy]‐propyne [VEEP]) was newly designed and found that the polymerization of VEEP smoothly proceeded in a controlled manner under a living cationic polymerization condition to give alkyne‐substituted polyVE (polyVEEP) without any protection of the pendant alkynyl function. Next, the use of an initiator with a methacryloyl moiety for the living cationic polymerization of VEEP afforded macromonomer‐type polyVE (MA‐PVEEP) carrying pendant alkynyl groups. The potential ability of the resultant macromonomer as an alkyne‐substituted polymer for the copper(I)‐catalyzed alkyne‐azide cycloaddition (CuAAC) was also confirmed. A novel macromonomer‐type glycopolymer [MA‐P(VE‐Mal)] having pendant maltose residues and a terminal methacryloyl group was successfully synthesized by CuAAC of MA‐PVEEP with maltosyl azide. Thus, a new pathway to the controlled synthesis of macromonomer‐type glycopolymers of free from any protecting/deprotecting processes was demonstrated. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 681–688     

Synthesis of a novel one-handed helical poly(phenylacetylene) bearing poly(l-lactide) side chains

The living ring-opening polymerization of l-lactide was carried out by using organocatalyst to synthesize the molecular weight controlled poly(l-lactide) with an phenylacetylenyl end group (HCCPLLA), then the homopolymerization of HCCPLLA was performed by using two different rhodium catalysts. Low molecular weight poly-PLLA₆-1 (M_w,SEC-MALLS = 46,700) was synthesized by using Rh(nbd)BPh₄ as the catalyst, and higher molecular weight poly-PLLA₆-2 (M_w,SEC-MALLS = 471,000) was synthesized by using the [Rh(nbd)Cl]₂/Et₃N catalyst system. Then high molecular weight poly-PLLA₂₀, poly-PLLA₂₉, and poly-PLLA₆₈ were successfully synthesized by using the [Rh(nbd)Cl]₂/Et₃N catalyst system. The α values of the poly-PLLAs using [Rh(nbd)Cl]₂/Et₃N catalyst system were all in the range of 0.6–0.8, this means that these polymers possess linear flexible chain. It is concluded that [Rh(nbd)Cl]₂/Et₃N was more suitable for the synthesis of the cylindrical polymer brush, poly-PLLA with high molecular weight. The analyses of the CD spectra indicated that poly-PLLA possesses a predominantly one-handed helical conformation, temperature and solvents had significant influences on the helical structure of poly-PLLA.     

In situ Synthesis of Oil Based Polymer Composites Containing Silver Nanoparticles

Using electron transfer reaction and free radical polymerization processes a series of triglyceride oil based polymer‐silver nanocomposites were successfully prepared. The whole process was divided into two simultaneous stages; (i) copolymerization of macromonomers obtained from partial glycerides with styrene and (ii) the reduction of silver nitrate to metallic silver nano particles with radicals stemming from the thermolysis of 2,2′‐azoisobutyronitrile (AIBN). Nanocomposites were characterized by TEM and TGA. The obtained polymer nanocomposite was also examined in view of antibacterial effect against Gram‐positive, Gram‐negative, and Spore forming bacteria. It was demonstrated that nanocomposite samples exhibited an antibacterial effect against these bacteria. Film properties of the samples as potential coating material were also studied. Nanocomposite samples showed better film properties than that of the polymer without silver nanoparticles.     

Star polymers by cross‐linking of linear poly(benzyl‐L‐glutamate) macromonomers via free‐radical and RAFT polymerization. A simple route toward peptide‐stabilized nanoparticles

Poly(benzyl‐L ‐glutamate) (PBLG) macromonomers were synthesized by N‐carboxyanhydride (NCA) polymerization initiated with 4‐vinyl benzylamine. MALDI‐ToF analysis confirmed the presence of styrenic end‐groups in the PBLG. Free‐radical and RAFT polymerization of the macromonomer in the presence of divinyl benzene produced star polymers of various molecular weights, polydispersity, and yield depending on the reaction conditions applied. The highest molecular weight (M_w) of 10,170,000 g/mol was obtained in a free‐radical multibatch approach. It was shown that the PBLG star polymers can be deprotected to obtain poly(glutamic acid) star polymers, which form water soluble pH responsive nanoparticles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis of hydrophilic polymers in supercritical carbon dioxide in the presence of a siloxane‐based macromonomer surfactant: Heterogeneous polymerization of 1‐vinyl‐2 pyrrolidone

Batch free radical polymerization of 1‐vinyl‐2‐pyrrolidone (VP) in supercritical carbon dioxide (scCO₂) was studied in the presence of a reactive polysiloxane surfactant (PDMS‐mMA). Phase behavior investigation showed that when the initial concentration of the surface active macromonomer was higher than 2.5% w/w with respect to the monomer, the reaction mixture, in the absence of efficient stirring, was initially opaque to the visible light, and it slowly turned to an orange tint. Polymerization experiments carried out with surfactant concentration higher than the aforementioned value proceeded with a fast kinetics, and led to the formation of spherical nanoparticles with almost quantitative yields (higher than 98% with a reaction time lower than 70 min). The effect of the concentration of the surface active macromonomer, the initiator and the monomer, and of the density of the fluid phase on the kinetics of the process and on the morphology of the particles was investigated. A marked decrease of the number‐average diameter of the polymer particles with the surfactant concentration was obtained without any particle agglomeration. A dependence on [Initiator]^?0.16 of the particle diameter was observed. Such scaling law exhibits an exponent higher than any previously reported for dispersion processes and rather close to those foreseeable on the basis of Smith–Harkins kinetics for emulsion polymerization. Collected experimental results strongly suggest that the polymerization of VP in the presence of PDMS‐mMA could proceed with a nucleation mechanism different from that postulated in pure dispersion polymerization stabilized by graft‐forming surfactants. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 173–185, 2004