Thermal polymerization of methyl (meth)acrylate via reversible addition-fragmentation chain transfer (RAFT) process

Thermal polymerization of methyl (meth)acrylate (MMA) was carried out using 2-cyanoprop-2-yl-1-dithionaphthalate (CPDN) and cumyl dithionaphthalenoate (CDN) as chain transfer agents. The kinetic study showed the existence of induction period and rate retardation, especially in the CDN mediated systems. The molecular weights of the polymers increased linearly with the monomer conversion, and the molecular weight distributions (M_w/M_ns) of the polymers were relatively narrow up to high conversions. The maximum number-average molecular weights (M_ns) reached to 351?900 g/mol (M_w/M_n = 1.47) and 442?400 g/mol (M_w/M_n = 1.29) in the systems mediated by CPDN and CDN, respectively. Chain-extension reactions were also successfully carried out to obtain higher molecular weight PMMA and PMMA-block-polystyrene (PMMA-b-PSt) copolymer with controlled structure and narrow M_w/M_n. Thermal polymerization of methyl acrylate (MA) in the presence of CPDN, or benzyl (2-phenyl)-1-imidazolecarbodithioate (BPIC) also demonstrated “living”/controlled features with the experimented maximum molecular weight 312?500 g/mol (M_w/M_n = 1.57). The possible initiation mechanism of the thermal polymerization was discussed.     

Film formation and mechanical properties of the alkoxysilane-functionalized poly (styrene-co-butyl acrylate) latex prepared by miniemulsion copolymerization

Alkoxysilane-functionalized poly (styrene-co-butyl acrylate) latex was prepared via miniemulsion copolymerization of γ-methacryloxypropyltrimethoxysilane (MPS), styrene and butyl acrylate using AIBN at neutral condition. The effects of initiator types, pH values, and MPS contents on the premature cross-linking of the latex particles and the mechanical properties of the films were investigated by the swelling experiments and dynamic mechanical analysis. It was found that the storage modulus of the latex films and the glass transition temperature (T_g) increased with increasing MPS content. The acidification of latex prior to film formation and annealing the latex films could improve the mechanical properties of the films.     

Anionic polymerization of (meth)acrylic monomers: anionic polymerization of tert-butyl methacrylate in toluene

The anionic polymerization of tBMA initiated by an organolithium compound in toluene at low temperature (−78 °C and 0 °C) has been revisited. Under these experimental conditions, no ‘livingness’ is reported, consistently with formation of an important fraction of oligomers (M_n = 650). © 1999 Society of Chemical Industry     

Atom transfer radical polymerization of styrene and methyl (meth)acrylates initiated with poly(dimethylsiloxane) macroinitiator: Synthesis and characterization of triblock copolymers

Poly(dimethylsiloxane)(PDMS)‐based triblock copolymers were successfully synthesized via atom transfer radical polymerization (ATRP) initiated with bis(bromoalkyl)‐terminated PDMS macroinitiator (Br‐PDMS‐Br). First, Br‐PDMS‐Br was prepared by reaction between the bis(hydroxyalkyl)‐terminated PDMS and 2‐bromo‐2‐methylpropionyl bromide. PSt‐b‐PDMS‐b‐PSt, PMMA‐b‐PDMS‐b‐PMMA and PMA‐b‐PDMS‐b‐PMA triblock copolymers were then synthesized via ATRP of styrene (St), methyl methacrylate (MMA) and methyl acrylate (MA), respectively, in the presence of Br‐PDMS‐Br as a macroinitiator and CuCl/PMDETA as a catalyst system at 80 ^oC. Triblock copolymers were characterized by FTIR, ¹H‐NMR and GPC techniques. GPC results showed linear dependence of the number‐average molecular weight on the conversion as well as the narrow polydispersity indicies (PDI < 1.57) for the synthesized triblock copolymers which was lower than that of Br‐PDMS‐Br macroinitiator (PDI = 1.90), indicating the living/controlled characteristic of the reaction. Also, there was a very good agreement between the number‐average molecular weight calculated from ¹HNMR spectra and that calculated theoretically. Results showed that resulting copolymers have two glass transition temperatures, indicating that triblock copolymers have microphase separated morphology. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of amphiphilic graft copolymer poly(ethylene oxide)-graft-poly(methyl acrylate)

A novel well-defined amphiphilic graft copolymer of poly(ethylene oxide) as main chain and poly(methyl acrylate) as graft chains is successfully prepared by combination of anionic copolymerization with atom transfer radical polymerization (ATRP). The glycidol is protected by ethyl vinyl ether first, then obtained 2,3-epoxypropyl-1-ethoxyethyl ether (EPEE) is copolymerized with EO by initiation of mixture of diphenylmethyl potassium and triethylene glycol to give the well-defined poly(EO-co-EPEE), the latter is deprotected in the acidic conditions, then the recovered copolymer [(poly(EO-co-Gly)] with multi-pending hydroxyls is esterified with 2-bromoisobutyryl bromide to produce the ATRP macroinitiator with multi-pending activated bromides [poly(EO-co-Gly)_(ATRP)] to initiate the polymerization of methyl acrylate (MA). The object products and intermediates are characterized by NMR, MALDI-TOF-MS, FT-IR, and SEC in detail. In solution polymerization, the molecular weight distribution of the graft copolymers is rather narrow (M_w/M_n < 1.2), and the linear dependence of Ln [M₀]/[M] on time demonstrates that the MA polymerization is well controlled.     

Acetylation of poly(2-hydroxyethyl acrylate) gel beads obtained from sedimentation polymerization

Sedimentation polymerization of an aqueous 2-hydroxyethyl acrylate solution with some crosslinkers was carried out using a simple sedimentation polymerization apparatus to give millimeter-size and very narrow size distributed poly(2-hydroxyethyl acrylate) (PHEA) gel beads. Also, heterogeneous acetylation of the resulting PHEA gel beads with acylating agents such as acetic anhydride, a mixture of acetic anhydride and pyridine, and chloroacetic anhydride was performed under various conditions. The selective esterification of PHEA gel beads proceeded smoothly in toluene from surface to give a novel core-shell type gel consisting of an unreacted core and acetylated shell, and finally afforded almost quantitatively acetylated PHEA gel. The unreacted core became small while maintaining a spherical shape during reaction. The reaction resembled to that of the corresponding cylindrical PHEA gel, and was strongly affected by the network structure of the obtained PHEA gel beads and the reactivity of acylating agents.     

(甲基)丙烯酸烷基酯的负离子聚合Ⅰ.聚合特点及适用的单官能团引发剂体系

综合分析了近年来有关(甲基)丙烯酸烷基酯负离子聚合所取得的成就,包括该类单体对负离子聚合的重要意义、聚合难点和解决办法.介绍了聚合特点和单官能团引发剂体系.     

常规乳液聚合下提高(甲基)丙烯酸高碳醇酯转化率的途径

以丙烯酸十八酯、甲基丙烯酸甲酯为共聚单体,反应型乳化剂MIXSTAR 6550和非反应型非离子乳化剂NOVELUTION 390复配作为复合乳化剂,过硫酸铵为引发剂,研究了乳化剂用量、3种质子[H ⁺]及[H ⁺]浓度对聚合稳定性、丙烯酸十八酯共聚活性及总单体转化率的影响。结果表明:反应型乳化剂MIXSTAR 6550具有将强憎水的丙烯酸高碳醇酯摆渡到乳胶粒或增溶胶束中的能力,同时强的质子[H ⁺]降低了丙烯酸高碳醇酯的活化能,使丙烯酸高碳醇酯在常规乳液聚合条件下可与其他丙烯酸酯共聚。即使丙烯酸高碳醇酯引入量为45%,总单体转化率也可达97%以上,实现了(甲基)丙烯酸高碳醇酯在常规乳液聚合下可与其他单体进行理想共聚的目的。     

1,2,3-Triazolium-based poly(acrylate ionic liquid)s

Nitroxide-mediated radical polymerization of a tailor-made acrylate carrying a 1,2,3-triazole group with an undecanoyl spacer affords a well-defined (M_n = 7860 g mol⁻¹ and D = 1.39) neutral polyacrylate precursor. A series of 1,2,3-triazolium-based poly(ionic liquid)s (TPILs) is then obtained by straightforward quaternization of the 1,2,3-triazole groups with methyl iodide and subsequent anion metathesis reactions. Among the prepared materials, TPIL with bis(trifluoromethane)sulfonimide anion exhibits low glass transition temperature (T_g = −40 °C), high thermal stability (T_d10 = 325 °C) and anhydrous ionic conductivity of 4 × 10⁻⁶ S cm⁻¹ at 30 °C, as measured by differential scanning calorimetry, thermogravimetric analysis and broadband dielectric spectroscopy, respectively.     

Synthesis and evaluation of poly (N-vinyl caprolactam)-co-tert-butyl acrylate as kinetic hydrate inhibitor

Low dosage kinetic hydrate inhibitors(KHIs) are a kind of alternative chemical additives to high dosage thermodynamic inhibitors for preventing gas hydrate formation in oil & gas production wells and transportation pipelines.In this paper,a new KHI,poly(N-vinyl caprolactam)-co-tert-butyl acrylate(PVCapco-TBA),was successfully synthesized with N-vinyl caprolactam(NVCap) and tert-butyl acrylate.The kinetic inhibition performances of PVCap-co-TBA on the formations of both structure Ⅰ methane hy...     

Polysiloxane-poly(fluorinated acrylate) interpenetrating polymer networks: Synthesis and characterization

Combinations of fluorinated and silicone based elastomers were elaborated through the in situ synthesis of interpenetrating polymer networks (IPNs). The PDMS network was formed by dibutyltindilaurate catalyzed addition between the hydroxy end groups of α,ω-(3-hydroxypropyl)polydimethylsiloxane (PDMS) and a pluriisocyanate cross-linker. The poly(fluorinated acrylate) (polyAcRf6) network was obtained from free-radical copolymerization of a fluorinated acrylate with ethylene glycol dimethacrylate in the presence of dicyclohexyl peroxydicarbonate as the initiator. IPNs with different relative weight proportions of the fluorinated vs silicone partners were characterized by DMTA and DSC. Density refractive index and contact angle measurements reveal a satisfactory interpenetration degree of PDMS and polyAcRf6 networks. In addition, these materials present an unusual variation of density values and of the surface properties as a function of the relative weight composition.     

Synthesis and properties of a poly(sodium acrylate) bioadhesive nanocomposite

Poly(sodium acrylate) (PNaA) based nanocomposites were synthesized using different nanosilver loadings via redox solution polymerization at room temperature and under full exposure to the atmosphere. The nanocomposites exhibited increasing antibacterial activity with increased nanosilver content. Biocompatibility was determined using an MTT assay; no significant cytotoxicity was observed at the examined nanosilver loadings. Adhesion was measured using a tensile test and the stress versus strain curve showed an acceptable stress development in the model tissue using bioadhesive containing 2 wt% nanosilver. Introducing a second, more degradable polymer to the system as an interpenetrating polymer network enabled tuning the bioadhesive degradation rate.     

Surface segregation and miscibility in blends of poly(vinylidene fluoride-co-hexafluoro-acetone) with poly(butyl acrylate)

The surface segregation in poly(butyl acrylate) (PBA)/poly(vinylidene fluoride-co-hexafluoro-acetone) [P(VDF-HFA)] blends was confirmed by X-ray photoelectron spectroscopy (XPS), and is thought to be caused because the surface tension of P(VDF-HFA) is smaller than that of PBA. The PBA/P(VDF-HFA) blends were miscible at room temperature and exhibited a lower critical solution temperature (LCST) phase behavior. Thus, it was considered that the surface segregation of the P(VDF-HFA) component in PBA/P(VDF-HFA) blends was caused by the difference in surface tension between the components. Depth profiles [In(<Ø₁ (d) -Ø^b ₁) vs. depth (d), where Ø₁ (d) and Ø^b ₁ are the volume fractions at depth d from the surface and into the bulk, respectively] for PBA/P(VDF-HFA) blends were constructed by the mean-field treatment. The ln(Ø₁(d) - Ø^b ₁) vs. d plots for the PBA/P(VDF-HFA) blends could be approximated by a straight line.     

Synthesis and physicochemical characterization of a well-defined poly(butadiene 1,3)-block-poly(dimethylsiloxane) copolymer

For the first time, order-order and order-disorder transitions were detected and characterized in a model diblock copolymer of poly(butadiene-1,3) and poly(dimethylsiloxane) (PB-b-PDMS). This model PB-b-PDMS copolymer was synthesized by the sequential anionic polymerization (high vacuum techniques) of butadiene 1,3 (B) and hexamethylciclotrisiloxane (D₃), and subsequently characterized by nuclear magnetic resonance (¹H and ¹³C NMR), size exclusion chromatography (SEC), Fourier Transform infrared spectroscopy (FTIR), Small-Angle X-ray scattering (SAXS) and rheology. SAXS combined with rheological experiments shows that the order-order and order-disorder transitions are thermoreversible. This fact indicates that the copolymer has sufficient mobility at the timescale and at the temperatures of interest to reach their equilibrium morphologies.     

Synthesis and properties of metal poly(butyl acrylate)

Butyl acrylate colloids were obtained by codeposition at 77 K of the monomer with several metals such as Pd, Au, Ag, Cu, Zn, Cd, Ga, In, Ge, Sn, Sb, and Bi. The colloids were polymerized with different amounts of an initiator (AIBN) at 65°C for 0.5 h and a wide range of viscosity‐average molecular weights (M _v, 10⁴–10⁵ g/mol) were obtained depending upon the metal used. The metal colloid concentration and stability are reported. The thermal stability and metal composition are also described. The polymers are stable even at 400°C, with Ga–poly(butyl acrylate) being the most stable at 407°C. The metal content ranged between 0.10 and 1.32% w/w for the highest MW fraction and between 0.11 and 1.09% w/w for the lowest MW fraction. Polymers with several colors were obtained depending on the metal used. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 547–550, 1999     

端羟基聚丙烯酸异辛酯及聚丙烯酸异辛酯-氨酯的制备及表征

采用原子转移自由基聚合(ATRP)合成了分子量与设计分子量(2000)大小相符的聚丙烯酸异辛酯,再以N-甲基单乙醇胺作为亲核试剂,对活性端基溴进行亲核取代,得到了分子量可控、分子量分布较窄的线型端羟基聚丙烯酸异辛酯。以此为原料与甲苯二异氰酸酯(TDI)反应,制备得到了聚丙烯酸异辛酯-氨酯。利用核磁共振谱(1HNMR)、差示扫描量热仪(DSC)、热重示差扫描量热仪(TGA)对合成的端羟基聚丙烯酸异辛酯及聚丙烯酸酯异辛酯-氨酯的结构、热稳定性等进行了表征。结果表明,利用端羟基聚丙烯酸异辛酯成功地制备了聚丙烯酸异辛酯-氨酯,由凝胶渗透色谱仪(GPC)测得其分子量为10200,玻璃化转变温度为-54℃,是一种新型的丙烯酸酯与聚氨酯的共聚物。     

含硅(甲基)丙烯酸酯在涂料工业中的研究和应用进展

综述了含硅(甲基)丙烯酸酯单体的种类、制备方法、聚合物的表面性能及其在表面处理、涂料和紫外光固化、电子束固化领域中的研究和应用进展。     

水溶性含氟丙烯酸酯乳液的合成研究进展

含氟丙烯酸酯类聚合物因具有突出的成膜性能及耐老化性能而成为优良的成膜材料。其中,水溶性含氟丙烯酸酯乳液的合成研究,具有广泛的单体种类,聚合方式简单多样,在涂料领域受到了广泛的应用和关注。选择合适的乳液共聚单体及聚合工艺,不仅能够根据实际需要调节含氟聚合物的分子结构,而且可以获得最佳含氟量,以满足特殊性能需要的含氟丙烯酸酯乳液。综述了水溶性含氟丙烯酸酯乳液的聚合方法、常用含氟单体和非氟单体以及改性研究进展。     

The preparation of poly(glycidyl acrylate)-polypyrrole gel-electrolyte and its application in dye-sensitized solar cells

A microporous hybrid of poly(glycidyl acrylate)-polypyrrole (PGA-PPy) was synthesized by a two-step solution polymerization. Using this hybrid as polymer host, a gel-electrolyte with high conductivity of 12.83 mS cm⁻¹ was prepared. The researches by scanning electron microscopy (SEM), Fourier transform infrared spectra (FTIR), and cyclic voltammetry (CV) show that the microporous structure and functional groups for PGA allows the higher absorbency and good ionic salt tolerance for the electrolyte, the introduction of PPy causes a lower charge-transfer resistance and higher electrocatalytic activity for the I₃⁻/I⁻ redox reaction for the electrolyte. Based on the electrolyte, a dye-sensitized solar cell with a light-to-electrical energy conversion efficiency of 5.03% is achieved, under illumination with a simulated solar light of 100 mW cm⁻² (AM 1.5).     

Acetylation of poly(2-hydroxyethyl acrylate) gel and synthesis of core-shell type gel

Heterogeneous esterification of poly(2-hydroxyethyl acrylate) (PHEA) gel with acylating agents such as acetic anhydride, a mixture of acetic anhydride and pyridine, and chloroacetic anhydride was carried out under various conditions. The selective esterification of PHEA gel proceeded smoothly in toluene from surface to give a novel core-shell type gel (gel capsule) consisting of a hydrophilic unreacted core and hydrophobic acetylated shell, and finally afford almost quantitative acetylated PHEA gel. The reaction was strongly affected by kinds and concentration of acylating agents. The swelling of the obtained gel capsule was studied. Although the gel capsule obtained from the esterification of PHEA gel with acetic anhydride showed much the same swelling behavior as the original PHEA gel, the shell layer resulting from the esterification of PHEA gel with a mixture of acetic anhydride and pyridine showed a high degree of esterification and worked as a permeability barrier of water.