聚丙烯表面附着促进剂的合成与表征

以氯化聚丙烯为大分子引发剂,以FeCl2作为催化剂,利用原子转移自由基聚合制备一种聚丙烯表面附着促进剂,聚丙烯/聚甲基丙烯酸甲酯接枝共聚物,利用红外、热重及差热分析对其进行表征.实验发现,在很低的加量下,聚丙烯表面附着促进剂可以显著提高丙烯酸树脂对聚丙烯的附着.     

Application of graft copolymers using macromonomer method to two-component polyurethane coatings

Graft copolymers as acrylic polyols in two-component polyurethane coatings were prepared by the free-radical copolymerization of methyl methacrylate, n-butyl methacrylate, n-butyl acrylate, acrylic acid, 2-hydroxyethyl methacrylate and poly(methyl methacrylate)-macromonomers. The poly(methyl methacrylate) macromonomer was prepared by the polymerization of methyl methacrylate in the presence of thiopropionic acid as a transfer agent followed by the reaction with glycidyl methacrylate. These polymers, whose numbers of poly(methyl methacrylate) macromonomer branches and the molecular weights of the poly(methyl methacrylate) macromonomer branches were controlled, offer an advantage over conventional resins with respect to the application/appearance of coatings as well as the final film properties. Some of these advantages were higher solids and a better control of the coating rheology, an increase in the cross-linking reactivity of the polyols with polyisocyanate and improvement in film toughness. The change in the morphological structure of the films under tensile stress was of particular interest.     

Preparation of SBS/poly(styrene–methyl methacrylate) thermoplastic interpenetrating polymer network

SBS as polymer I, poly(styrene–methyl methacrylate) polymerized by atom transfer radical polymerization as polymer II, and a thermoplastic interpenetrating polymer network of SBS/poly(styrene–methyl methacrylate) were prepared by the sequential method. The effects of the polymerization temperature, the composition of the catalyst, the ratio of the monomers studied, and the kinetics at 90°C were also investigated. It was shown that when polymerization was initiated by a BPO/CuCl/bpy (BPO:CuCl:bpy = 1:1:3) system at 90°C, the mass averaged molecular weight of the poly(styrene–methyl methacrylate) increased with monomer conversion, and the polydispersities were kept very low. Fourier transform infrared spectroscopy and gel permeation chromatogram showed that poly(styrene–methyl methacrylate) with low polydispersities had been synthesized. Thus, a thermoplastic interpenetrating polymer network comprised of both narrow molecular‐weight‐distribution components was successfully prepared. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2007–2011, 2003     

Preparation and Characterization of Poly(Methyl Methacrylate) Microbeads by Dispersion Polymerization: Effects of the Medium Composition,Monomer Concentration,Thermal, and Optical Properties

This study investigated the relationship between particle size, particle distribution, thermal, and optical properties of poly(methyl methacrylate) microbeads using dispersion polymerization under various methanol/water (MeOH/H₂O) dispersion medium ratios and methyl methacrylate acid concentrations. The particle size of the poly(methyl methacrylate) microbeads increased when the medium solubility and monomer concentration increased simultaneously. In addition, the molecular weight and polydispersity of the poly(methyl methacrylate) microbeads were increased as the methanol ratio increased. The refractive index increased as the content of the poly(methyl methacrylate) microbeads increased with wavelengths of 546 and 589 nm.     

Polyallene-based graft copolymer via 6-methyl-1,2-heptadien-4-ol and methyl methacrylate

A series of well-defined graft copolymers with a polyallene-based backbone and poly(methyl methacrylate) side chains were synthesized by the combination of living coordination polymerization of 6-methyl-1,2-heptadien-4-ol and atom transfer radical polymerization of methyl methacrylate. We first prepared poly(alcohol) with polyallene repeating units via 6-methyl-1,2-heptadien-4-ol by living coordination polymerization initiated by [(η³-allyl)NiOCOCF₃]₂, followed by transforming the pendant hydroxyl groups into halogen-containing ATRP initiation groups. Next, grafting-from route was used for the synthesis of the well-defined graft copolymer with excellent solubility: poly(methyl methacrylate) was grafted to the backbone via ATRP of methyl methacrylate. This kind of graft copolymer is the first example of graft copolymer via allene derivative and methacrylic monomer.     

Lichtinduzierte Polymerisation, 4. Pfropfcopolymerisation von Methylmethacrylat auf Polyethylenoxid in Gegenwart von Chinolinderivaten

When using poly(ethylene oxide) (PEO) as a polymeric hydrogen donator, grafted polymerization products are obtained upon photoinduced polymerization of methyl methacrylate with quinoline derivatives and PEO. The separation of these graft copolymers from the simultaneously formed homopolymeric poly(methyl methacrylate) (PMMA) and the remainder of not converted PEO can be achieved by subsequent extraction with ethyl acetate and methanol. With that determination of graft yield, degree of grafting, grafting success, and grafting height are possible.     

Synthesis of spike‐ball‐like polystyrene/poly(methyl methacrylate) composite particles via seeded polymerization

A synthesis method for the production of novel spike‐ball‐like polymer particles is presented based on seeded dispersion polymerization of methyl methacrylate monomer in the presence of polystyrene seeds with poly(vinyl alcohol) as stabilizer and myristyl peroxydicarbonate as initiator. The particles resulting from the controlled aggregation of swollen particles during polymerization showed a salami‐like morphology with polystyrene cores and poly(methyl methacrylate) shells. The long spikes had the same morphology and were formed by the step‐by‐step addition of smaller particles on the surface of the larger particles during polymerization. The resulting particles have potential applications as templates to make micron‐sized electronics and biomaterials. © 2017 Society of Chemical Industry     

Compatibility of polyacrylates and polymethacrylates with poly(vinyl chloride): 1. Compatibility and temperature variation

Mixtures of a series of polymethacrylates and polyacrylates with PVC were prepared by solvent casting from methyl ethyl ketone. Some mixtures were also prepared by mechanical mixing and in situ polymerization (polymerization of vinyl chloride monomer in the presence of the other polymer). The mixtures were assessed for compatibility by dynamic mechanical measurements and optical clarity. It was found that all polymethacrylates from poly(methyl methacrylate) to poly(n-hexyl methacrylate) were compatible with PVC as were poly(n-propyl acrylate) and poly(n-butyl acrylate). Higher chain polyacrylates are incompatible. Poly(methyl acrylate) and poly(ethyl acrylate) appear incompatible with PVC when mixtures are prepared by solvent casting, but compatible when prepared by in situ polymerization, and mechanical mixtures show some sign of compatibility. It seems possible that in this case the solvent interferes with the compatibility. Mixtures of PVC with poly(n-hexyl methacrylate), poly(n-butyl acrylate) and poly(n-propyl acrylate) phase separate when heated in the region between 100°C and 160°C indicating the existence of a lower critical solution temperature.     

Thermal properties of PMMA/TiO2 nanocomposites prepared by in-situ bulk polymerization

The surface of anatase TiO₂ nanoparticles, obtained by the controlled hydrolysis of titanium tetrachloride, was modified by 6-palmitate ascorbic acid. The surface modified TiO₂ nanoparticles were dispersed in methyl methacrylate and mixed with a appropriate amount of poly(methyl methacrylate) to obtain a syrup. The nanocomposite sheets were made by bulk polymerization of the syrup in a glass sandwich cell using 2,2′-azobisisobutyronitrile as initiator. The molar masses and molar mass distributions of synthesized poly(methyl methacrylate) samples were determined by gel permeation chromatography. The content of unreacted double bonds in synthesized samples was determined by ¹H NMR spectroscopy. The influence of TiO₂ nanoparticles on the thermal stability of the poly(methyl methacrylate) matrix was investigated using thermogravimetric analysis and differential scanning calorimetry. The synthesized samples of poly(methyl methacrylate) have different molar mass and polydispersity depending on the content of the surface modified TiO₂ nanoparticles. The values of glass transition temperature of so prepared nanocomposite samples were lower than for pure poly(methyl methacrylate), while the glass transition temperature of samples preheated in inert atmosphere was very similar to the glass transition temperature of pure poly(methyl methacrylate). The thermal stability of nanocomposite samples in nitrogen and air was different from thermal stability of pure poly(methyl methacrylate). POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Synthesis of cyclic poly(methyl methacrylate) by the intramolecular cyclization of α-amino, ω-carboxyl heterodifunctional poly(methyl methacrylate)

Summary α-Amino, ω-carboxyl heterodifunctional poly(methyl methacrylate) was prepared by a living anionic polymerization of methyl methacrylate using N,N'-diphenylethylenediamine monolithium amide and succinic anhydride as an initiator and terminator, respectively. Its intramolecular cyclization was carried out to obtain a well-defined cyclic poly(methyl methacrylate). Received: 27 June 2001/Accepted: 16 July 2001     

Radiation polymerization of methyl methacrylate in the presence of liquid crystals

Radiation polymerization of methyl methacrylate (MMA) was studied in the presence of two liquid crystals: N-(p-methoxybenzylidene)-p-butylaniline (MBBA, nematic) and cholesteryl 2-(ethoxy—ethoxy) ethyl carbonate (CHEECO, cholesteric). For comparison, polymerization was also carried out in the presence of benzene and cholesterol. Tacticities of the resultant poly(methyl methacrylate) were determined from nuclear magnetic resonance spectroscopy. Enhancement of syndiotacticity of the polymer obtained in the presence of cholesteric liquid crystal was observed. The rates of polymerization of pure MMA and MMA with different additives at various concentrations were studied. The viscosity-average molecular weights at one dose were also determined. Replica polymerization in the presence of preformed isotactic poly(methyl methacrylate) [i-PMMA] or syndiotactic poly(methyl methacrylate) [s-PMMA] with and without CHEECO was studied. Enhancement of syndiotacticity was observed in the presence of i-PMMA with and without CHEECO.     

甲基丙烯酸甲酯/改性纳米碳酸钙原位非均相聚合

将偶氮二氰基戊酸螯合到纳米碳酸钙表面，引发甲基丙烯酸甲酯非均相聚合，对聚合动力学和聚甲基丙烯酸甲酯(PMMA)在纳米碳酸钙表面的包覆进行了研究。差热扫描量热分析表明偶氮引发剂与纳米碳酸钙螯合后分解温度略有降低；随着螯合引发剂浓度和聚合温度增加，聚合速率增加；随着碳酸钙含量增加，聚合速率降低；PMMA接枝率随聚合转化率增加而增加，而接枝效率下降；随聚合进行，纳米粒子团聚体会剥离成较小粒子，复合粒子的粒径减小。     

Internal stress of epoxy resin modified with acrylic core-shell particles prepared by seeded emulsion polymerization

In order to reduce the internal stress in a cured epoxy resin, the submicron polymer particles were dispersed therein prior to curing. For this purpose, four kinds of poly(butyl acrylate), poly(methyl methacrylate) core-shell particles were prepared by seeded emulsion polymerization for methyl methacrylate with poly(butyl acrylate) seed particles having different particle diameter, and subsequently were powdered by drying at room temperature. It was observed by SEM that poly(butyl acrylate) particles as core were dispersed in the cured epoxy matrix. Poly(methyl methacrylate) as shell seems to dissolve in the matrix. The internal stress of cured epoxy resin decreased with the modification of the particles and the tendency was enhanced with a decreasing in the particle diameter.     

Morphology of latex particles formed by poly(methyl methacrylate)-seeded emulsion polymerization of styrene

Poly(methyl methacrylate)–polystyrene composite particle latexes were prepared by poly(methyl methacrylate)-seeded emulsion polymerization of styrene employing batch, swelling-batch, and semibatch methods. The changes in particle morphology taking place during the polymerization reaction were followed by electron microscopy. Anchoring effect exerted by ionic terminal groups introduced by ionic initiator was found to be the main factor in controlling the particle morphology. The polymer particles obtained by oil-soluble hydrophobic initiators such as azobisisobutyronitrile and 4,4′-azobis-(4-cyanovaleric acid) gave the inverted core-shell morphology. Water-soluble hydrophilic initiator, K₂S₂O₈, also gave the inverted core-shell morphology. However, in this case the occurrence of the halfmoonlike, the sandwichlike, and the core-shell morphologies were also observed depending upon the polymerization conditions. The distribution of terminal ? SO groups on the surface area of polystyrene particles could be controlled by initiator concentration and polymerization temperature. Viscosity of polymerization loci dictated the movement of polymer molecules, thus causing the unevenness of particle shape and phase separation at high viscosity state. Viscosity was controlled by the styrene/poly(methyl methacrylate) ratio, the addition of a chain transfer agent or a solvent which is common to polystyrene and poly(methyl methacrylate).     

Silicone-stabilized nonaqueous emulsion polymerization

Stable dispersions are prepared by free-radical polymerization of methyl methacrylate in aliphatic hydrocarbons containing poly(dimethylsiloxane) modified with mercaptoalkyl side groups. The particles are pictured as being stabilized by a protective layer of solvated poly(dimethylsiloxane). Some important features of the polymerization are described.     

Picosecond excimer fluorescence spectroscopy: applications to local motions of polymers and polymerization monitoring

The local motions of α,ω-bis-(1-pyrene)alkanes and pyrene-labelled poly(methyl methacrylate) polymers in solution were characterized by picosecond excimer fluorescence spectroscopy. The experimental results showed that 1,3-bis-(1-pyrene)propane and 1,10-bis-(1-pyrene)decane have similar local motions that bring two pyrene groups together to form excimers. Further, poly(1-pyrenylmethyl methacrylate) and a copolymer of methyl methacrylate and 1-pyrenylmethyl methacrylate in solution were found to have similar local motions that lead to excimer formation. In addition, the viscosity change during the polymerization of methyl methacrylate was monitored by measuring with picosecond fluorimetry the fluorescence lifetime of a trace amount of 1,3-bis-(1-pyrene)propane dissolved in methyl methacrylate.     

Poly(methyl methacrylate)–cellulose nitrate copolymers. I. Preparation

Poly(methyl methacrylate)–cellulose nitrate copolymers were prepared in the form of rods and sheets by bulk polymerization using benzoyl peroxide as initiator. Suspension polymerization did not succeed in preparing poly(methyl methacrylate)–cellulose nitrate copolymers, especially when cellulose nitrate of 11.4% nitrogen content was used. The parameters such as cellulose nitrate concentration, nitrogen content of cellulose nitrate, the amount of initiator and the reaction time, and the temperature are discussed. The prepared copolymers were irradiated for specified periods of up to 11.83 Mrad. It was found that poly(methyl methacrylate)–cellulose nitrate copolymers did not dissolve in any conventional solvent, but they swelled. Swelling decreases with increasing cellulose nitrate concentrations, nitrogen content of cellulose nitrate, and irradiation dose, indicating the crosslinked structure of the prepared copolymers.     

Modeling methyl methacrylate free radical polymerization in nanoporous confinement

Nanoconfinement of methyl methacrylate free radical polymerization is known to impact the molecular weight and molecular weight distribution of the polymer produced, with results in the literature generally indicating an increase in molecular weight and a concomitant decrease in polydispersity index. In the present work, the mathematical model described by Verros et al. (2005) for free radical bulk polymerization of methyl methacrylate is extended to account for polymerization in nanopores. The model of Verros et al. (2005) incorporates diffusion effects and is capable of describing the conversion and the number- and weight-average molecular weights of the resulting poly(methyl methacrylate) as a function of polymerization time and process conditions. The model is extended by incorporating the effect of nanoconfinement on diffusivity using the scaling reported in the literature. The calculations indicate that nanoconfinement will lead to higher molecular weights and lower polydispersity, and the gel effect will occur earlier. The results are compared to experimental work and implications discussed.     

Damping Properties of Polyorganosiloxane/Poly(methyl methacrylate) Interpenetrating Networks

Interpenetrating polymer networks (IPNs) based on polyorganosiloxane/poly(methyl methacrylate) were prepared via sequential polymerization and the damping and mechanical properties of these materials were studied. The effects of crosslinking in both the first‐ and second‐formed networks were investigated. The experimental results show that the extent of damping of the IPNs was decreased and shifted to higher temperature as the content of poly(methyl methacrylate) was increased; the mechanical properties such as tensile strength and hardness (Shore A) were increased with increasing poly(methyl methacrylate) (PMMA) content. The loss factor peak becomes narrower with increasing crosslinker level in the first‐formed network (polysiloxane network), while increasing crosslinker content in the second‐formed network (PMMA network) results in a broadening of the IPN transition peak and moves the IPN transition to higher temperatures as well.     

纳米铁粒子表面接枝聚合甲基丙烯酸甲酯

采用直流电弧等离子体法制备纳米铁粉,利用甲基丙烯酸(MAA)和盐酸处理纳米铁粉,通过乳液聚合方法,在纳米铁粉存在下MMA原位聚合,形成纳米铁/聚甲基丙烯酸甲酯复合粒子。分析结果表明,MMA在纳米铁粒子表面接枝聚合,纳米铁粉表面的双键参与了聚合反应,所形成的复合粒子具有核壳结构,这种复合粒子具有较高的稳定性。