Effects of end groups on the thermal response of poly(N‐isopropylacrylamide) microgels

Poly(N‐isopropylacrylamide) (PNIPAM) microgels were prepared through soap‐free emulsion polymerization using 2, 2′‐ azobisobutyronitrile and potassium persulfate as initiator respectively. The thermal response of microgels was researched by measuring the transmittance and the hydrodynamic diameter of the microgels at different temperatures. The result shows that the different structure of the end groups of polymer that come from residues of initiator result in the different thermal response of PNIPAM microgels. The LCST (lower critical solution temperature) of AIBN‐initiator microgels is 5°C lower than that of the KPS‐initiator microgels, whereas the AIBN‐initiated PNIPAM microgels have better thermal response sensitivity. The scanning electron microscope characterization shows that the morphology of AIBN‐initiated PNIPAM microgels is more regular than that of KPS‐initiated. Furthermore, the T_g of the microgels was measured by differential scanning calorimeter and the result indicates that the end groups influences the T_g of microgels severely. This work demonstrated that the hydrophobic end group coming from initiators can decreases the LCST of PNIPAM microgels and increases the thermal response sensitivity, which providing a newly simple but effective method to regulate the thermal response of PNIPAM microgels. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1164‐1171, 2013     

Hydrogel characteristics of a novel temperature‐sensitive polymer,poly(N‐2‐methoxyisopropylacrylamide)

In this study, a novel temperature‐sensitive polymer, poly(N‐2‐methoxyisopropylacrylamide), PNMIPA, in the crosslinked hydrogel form was obtained. The monomer, N‐2‐methoxyisopropylacrylamide (NMIPA) was synthesized by the nucleophilic substitution reactions of acryloyl chloride with 2‐methoxyisopropylamine. Hydrogel matrix of PNMIPA was obtained by the bulk polymerization method. The bulk polymerization experiments were performed at +4°C, by using N,N‐methylenebisacrylamide (MBA) as crosslinker, polyethyleneglycol (PEG) 4000 as diluent, and potassium persulfate (KPS) and tetramethylethylenediamine (TEMED) as the initiator and accelerator, respectively. The same polymerization procedures were applied by changing monomer, initiator, crosslinker and diluent concentrations in order to obtain crosslinked gel structures having different temperature–sensitivity properties. The equilibrium swelling ratio of PNIMPA gel matrices at constant temperature increased with increasing initiator concentration and decreasing monomer concentration. The use of PEG 4000 as diluent in the gel synthesis resulted in about two times increase in equilibrium swelling ratios in the low temperature region. A decrease in the equilibrium swelling ratios of gel matrices started at 30°C and the decrease became insignificant at 55°C. Temperature‐sensitivities were determined in two different media. Distilled water medium was used in order to observe the temperature‐sensitivity of the gel clearly and the phosphate buffer medium was used in order to represent the temperature‐sensitive swelling behavior of the gel when it is used in biological media. Step effect was applied on ambient temperature in two opposite directions in order to examine the dynamic swelling and shrinking behaviors of the gels. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

High glass transition temperature polyester coatings for the protection of stones

Copolymers of lactic acid with mandelic or salicylic acid were synthetized through ring‐opening polymerization (ROP) and tested as protective coatings for stones. Most notably, glass transition temperature (T_g), hydrophobicity, and UV barrier properties were increased, making these materials more suitable as protective coating for outdoor stones than poly(lactic acid). A T_g of 76°C was obtained for the alternating copolymer lactic acid/mandelic acid and it was considerably higher than the one of poly(lactic acid) with similar molecular weight (50–55°C). Furthermore, the introduction of a perfluorinated moiety as chain‐end group, using a perfluoro alcohol as initiator of the ROP process, allowed to increase the hydrophobicity and stability of the new coatings. These polymers showed a good protective efficiency when applied on marble stones and preliminary stability tests under solar light showed low degradation, good stability to photo‐oxidative conditions, and negligible color changes after an aging time of 1000 h. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42323.     

Preparation of poly(styrene‐co‐isobornyl methacrylate) beads having controlled glass transition temperature by suspension polymerization

The styrene (St) and isobornyl methacrylate (IBMA) random copolymer beads with controlled glass transition temperature (T_g), in the range of 105–158°C, were successfully prepared by suspension polymerization. The influence of the ratios of IBMA in monomer feeds on the copolymerization yields, the molecular weights and molecular weight distributions of the produced copolymers, the copolymer compositions and the T_gs of these copolymers was investigated systematically. The monomer reactivity ratios were r₁ (St) = 0.57 and r₂ (IBMA) = 0.20 with benzyl peroxide as initiator at 90°C, respectively. As the mass fraction of IBMA in monomer feeds was about 40 wt %, it was observed that the monomer conversion could be up to 90 wt %. The fractions of IBMA unit in copolymers were in the range of 35–40 wt % and T_gs of the corresponding copolymers were in the range of 119.6–128°C while the monomer conversion increased from 0 to greater than 90 wt %. In addition, the effects of other factors, such as the dispersants, polymerization time and the initiator concentration on the copolymerization were also discussed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Ammonium nitrogen adsorption from aqueous solution by poly(sodium acrylate)s: Effect on the amount of crosslinker and initiator

In this work, we discuss the ammonium nitrogen adsorption and reusability from aqueous solution by using poly(sodium acrylate) (PANa) hydrogels (Polymers 1–6 ) under different amount of crosslinker and initiator. The PANa hydrogels were synthesized from the neutralized acrylic acid (AA) monomer via free radical thermal polymerization by using ammonium persulfate (APS) as an initiator and N,N′-methylene-bisacrylamide (MBA) as a crosslinker. These polymers exhibited glass transition temperatures (T_g) of 68–88°C and T_d values (5% weight loss temperature) in the range of 190–221°C under nitrogen atmosphere. The PANa hydrogels had swollen ratios ranging from 387 to 4,063%, related to the crosslinking density. The final equilibrium adsorption capacity of the polymers was in the range of 20–39 ppm with an initial ammonium nitrogen concentration of 100 ppm. Among them, Polymer 3 without MBA crosslinker displayed the highest swollen characteristic along with the most efficient adsorption capacity. In comparison, the as-prepared high crosslinking density hydrogels showed relative lower adsorption capability but higher reusability. The polymer composition in this work determines the ability to absorb and desorb ammonium nitrogen compound.     

Characterization of crosslinked polystyrene beads and their composite in SBR matrix

Monodisperse crosslinked polystyrene (PS) beads were prepared by a reaction of semibatch emulsion polymerization with styrene monomer, divinylbenzene (DVB) crosslinking agent, and potassium persulfate (K₂S₂O₈) initiator in the absence of emulsifier. The glass transition temperature (T_g) and the mean diameter of the beads were increased from 100 to 135°C and from 402 to 532 nm, respectively, for an incorporation of 2–10 mol % DVB. Crosslinking density was also linearly increased with DVB content. Scanning electron microscopy (SEM) photographs of styrene–butadiene rubber (SBR) composite filled with various contents of PS beads revealed that PS beads are relatively well dispersed without changing the spherical shape of the beads in all ranges of compositions. In stress–strain analysis, elongation at break and tensile strength of SBR composite were increased with the bead content. Applicability of the PS beads as a filler in SBR matrix is tested by plotting Mooney–Rivlin or Guth–Smallwood equations. However, mechanical properties of the composite with the beads were not so excellent as those of the composite with carbon black. Crosslinked PS beads are still tentative as a white color reinforcing filler on the SBR matrix. © 1995 John Wiley & Sons, Inc.     

Liquid crystalline acrylic copolymers for high-solids enamel coatings

Carboxyl functional liquid crystalline (LC) acrylic copolymers were synthesized and were compared with carboxyl functional control copolymers of M?_n about 5000–15,000. Both types were crosslinked with a hexakismethoxymethyl melamine (HMMM) resin at 150°C, a temperature below the clearing points of the LC copolymers. Birefringent phases were visible in the crosslinked films made from LC polymers. FT-IR indicated the presence of unreacted COOH in all crosslinked materials. Unreacted COOH groups in crosslinked LC copolymers appeared only slightly higher than those in crosslinked amorphous copolymers. The potential utility of these LC copolymers as binders for thermosetting coatings was assessed. Variables studied were HMMM content, the length of PHBA grafts, T_g and M?_n of the acrylic copolymer backbone, and functionality. Optimum LC copolymers have low backbone T_g (<O°C) and low functionality (< 7.5 mol %). Cured films of such copolymers have both high hardness (> 35 KHN), high impact resistance (> 80 in. ib), excellent adhesion, and good solvent resistance.     

Accelerant‐promoted free radical polymerization of methacrylates by stabilized nitroxide unimolecular initiators: synthesis and characterization

BACKGROUND: This investigation evaluates the effectiveness of initiator adducts for living and controlled polymerization of methacrylates, crosslinking of dimethacrylates and thermal stabilities of the resulting polymers. Adducts of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy with benzoyl peroxide and with azobisisobutyronitrile were prepared and evaluated as stabilized unimolecular initiators for the free radical polymerization of methacrylate monomers using sulfuric acid as catalyst. The monomers used were methyl methacrylate, triethylene glycol dimethacrylate (TEGDMA) and ethoxylated bisphenol A dimethacrylate (EBPADMA). RESULTS: Successful polymerization was achieved at 70 and 130 °C with reaction times ranging from 45 min to 120 h. The dispersity (D) of poly(methyl methacrylate) (PMMA) was 1.09–1.28. The livingness and extent of control over polymerization were confirmed with plots of M_n evolution as a function of monomer conversion and of the first‐order kinetics. The glass transition temperature (T_g) for PMMA was 123–128 °C. The degradation temperature (T_d) for PMMA was 350–410 °C. T_d for poly(TEGMA) was 250–310 °C and for poly(EBPADMA) was 320–390 °C. CONCLUSION: The initiators are suitable for free radical living and controlled polymerization of methacrylates and dimethacrylates under mild thermal and acid‐catalyzed conditions, yielding medium to high molecular weight polymers with low dispersity, high crosslinking and good thermal stability. Copyright © 2008 Society of Chemical Industry     

Synthesis of heat- and solvent-resistant polymers by radical polymerization of trifluoromethyl-substituted N-phenylmaleimides

The radical polymerization of the three kinds of fluorine-containing maleimides, that is, N-[2-(trifluoromethyl)phenyl]maleimide (2TFPhMI), N-[3-(trifluoromethyl)phenyl]maleimide (3TFPhMI), and N-[4-(trifluoromethyl)phenyl]maleimide (4TFPhMI) was carried out in the presence of a radical initiator in benzene at 60°C. The polymerization reactivity of these fluorine-containing maleimides and the properties of the resulting polymers were examined in comparison with the results for the methyl-substituted phenylmaleimides. The trifluoromethyl-substituted maleimides readily polymerized to give polymers in high yields as well as a methyl-substituted one. The resulting polymers showed an excellent resistance against organic solvents; especially, poly(4TFPhMI) was insoluble in the most common solvents. The onset temperature of thermal decomposition of the fluorine-containing polymers (T_init> = 352–368°C) was similar to that of poly(N-phenylmaleimide) (T_init = 364°C) and slightly lower than those for the methyl-substituted one (T_init = 388–402°C). The glass transition temperature of the polymers was dependent on the position of the trifluoromethyl group. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1703–1708, 1998     

Ultrasound‐assisted emulsion polymerization of poly(methyl methacrylate‐co‐butyl acrylate): Effect of initiator content and temperature

In this study, we propose an efficient method for preparation of large scale, monodisperse poly(methyl methacrylate‐co‐butyl acrylate) latexes by application of the low power ultrasound irradiation. The effect of polymerization temperature and initiator concentration on the polymerization nature, particle size, and particle size distribution were investigated. Results indicated that the ultrasound pulses in the first minutes of polymerization increase instant free radical to monomer ratio as well mixing efficiency which led to higher monomer conversion, improved polymerization rate (especially at first 15 min of the reaction), and remarkable decrease in molecular weight distribution. Transmittance electron microscopy (TEM) and dynamic light scattering (DLS) revealed that the particle size and particle size distribution were significantly affected, particle size decreased, and more uniform particles were obtained. Dynamic mechanical thermal analysis also showed that the initiator concentration affected glass transition temperature (T_g) of the final copolymers and in the case of ultrasound‐assisted emulsion polymerization T_g was in a very good agreement with theoretical predictions for copolymerization. POLYM. ENG. SCI., 56:214–221, 2016. © 2015 Society of Plastics Engineers     

Synthesis and swelling properties of the copolymer of acrylamide with anionic monomers

A series of novel superabsorbent copolymers of acrylamide (AM), sodium allylsulfonate (SAS), sodium acrylate (AA), and N,N′-methylenebisacrylamide (BisA) were synthesized using potassium persulfate (KPS)/N,N,N′,N′-tertramethylethylenediamine (TMEDA) as the initiator. The influences of synthetic variables (monomer concentration, temperature, initiator concentration, and pH) on the polymerization conversion (y°) and swelling properties were studied in detail. These gels should have potential application as water super-absorbents. © 1996 John Wiley & Sons, Inc.     

Reactions of diaminoalkanes with bismaleimides: Synthesis of some unusual polyimides

Michael additions of the secondary diamines N,N′-dimethyl-1,6-hexanediamine ( 14 ) or piperazine to the electrophilic carbon–carbon double bonds of N,N′-bismaleimido-4,4′-diphenylmethane ( 2 ) or N,N′-bismaleimido-1,8-octane ( 4 ) afford four unusual, high-molecular-weight (η_inh = 0.49–2.16 dL/g) polyimides ( 10 – 13 ). The most interesting of these, polymer 12 (the product of 4 and 14 ), is a tough elastomeric resin with a glass transition temperature (T_g) near 0°C; in contrast, 10, 11, and 13 exhibit T_g >86°C. Freshly prepared 12 is soluble and thermoplastic ( 12 is readily compression molded at 110°C), but the bulk polymer crosslinks slowly under ambient laboratory conditions and eventually (48 days) becomes insoluble, while 10, 11, and 13 remain soluble indefinitely. Along with further comparisons of the properties of 10 – 13 , details of the synthesis and characterization of these new polyimides are described. Also discussed are reactions of bismaleimide 2 with 1,6-diaminohexane, which unlike the formation of linear 10 – 13 , generate crosslinked, insoluble products.     

Crosslinking of poly(vinyl acetate) nanolatices by gamma and UV radiation

Poly(vinyl acetate) PVAc, in nanolatices with 10% polymer content, prepared by microemulsion polymerization was crosslinked by gamma and UV radiation. PVAc colloidal nanoparticles (average diameter, Dp = 58 nm) had M_w = 562,000 g/mol and about 95% conversions. PVAc nanolatices irradiated by gamma rays (1–13 kGy) at room temperature without crosslinking agent and by UV light (30–300 s exposure times) in the presence of divinylbenzene and allyl methacrylate showed crosslinking of up to 96% (high gel content), Dp < 100 nm and did not degrade as shown by FTIR spectroscopy. DSC and TGA characterization of irradiated PVAc samples indicated that T_g temperatures increased from 28°C for PVAc to 42°C and 39°C for UV and gamma rays crosslinked PVAc, respectively, whereas 10% weight losses occurred at 261°C for uncrosslinked PVAc and at 320 and 313°C for UV and gamma rays crosslinked PVAc. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers through atom transfer radical polymerization

Poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers have been synthesized successfully through atom transfer radical polymerization of methyl methacrylate using telechelic bromo‐terminated polyurethane/CuBr/N,N,N,N″,N″‐pentamethyldiethylenetriamine initiating system. As the time increases, the number‐average molecular weight increases linearly from 6400 to 37,000. This shows that the poly methyl methacrylate blocks were attached to polyurethane block. As the polymerization time increases, both conversion and molecular weight increased and the molecular weight increases linearly with increasing conversion. These results indicate that the formation of the tri‐block copolymers was through atom transfer radical polymerization mechanism. Proton nuclear magnetic resonance spectral results of the triblock copolymers show that the molar ratio between polyurethane and poly (methyl methacrylate) blocks is in the range of 1 : 16.3 to 1 : 449.4. Differential scanning calorimetry results show T_g of the soft segment at ?35°C and T_g of the hard segment at 75°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) by ATRP using a fluorescein-based initiator

Summary A new fluorescent initiator fluorescein 2-bromoisobutyrate (Flu-Br) was synthesized. The use of Flu-Br as initiator, Me₆TREN as ligand and CuCl as catalyst by atom transfer radical polymerization allowed for chain-end fluoresceined poly(N-isopropylacrylamide) (Flu-PNIPAM) in one step. The polymerization reached high conversion (65%) and low polydispersity (PDI) (1.15∼1.28). The linearity plot of the M_n,GPC and M_n,NMR against conversion and the low PDI revealed the well-controlled polymerization by ATRP. In addition, N-isopropylacrylamide (NIPAM) was copolymerized with hydrophilic N,N-dimethylacrylamide (DMAM) using Flu-Br initiator by ATRP. By changing the feed ratio of NIPAM to DMAM, it was very easy to obtain thermo-sensitive fluorescent copolymers with proper lower critical solution temperature (36.0±0.2 °C, 38.0±0.2 °C). The pH dependence on fluorescence intensity of Flu-PNIPAM displayed a similar behavior to the parent fluorescein.     

Thermal characterizations of semi‐interpenetrating polymer networks composed of poly(ethylene oxide) and poly(N‐isopropylacrylamide)

Poly(N‐isopropylacrylamide) (PNIPAAm)/poly(ethylene oxide) (PEO) semi‐interpenetrating polymer networks (semi‐IPNs) synthesized by radical polymerization of N‐isopropylacrylamide (NIPAAm) in the presence of PEO. The thermal characterizations of the semi‐IPNs were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). The melting temperature (T_m) of semi‐IPNs appeared at around 60°C using DSC. DEA was employed to ascertain the glass transition temperature (T_g) and determine the activation energy (E_a) of semi‐IPNs. From the results of DEA, semi‐IPNs exhibited one T_g indicating the presence of phase separation in the semi‐IPN, and T_gs of semi‐IPNs were observed with increasing PNIPAAm content. The thermal decomposition of semi‐IPNa was investigated using TGA and appeared at around 370°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3922–3927, 2003     

Influence of extenders on thermal and elastic properties of segmented copolyetheresteraramides

Copolyetheresteramides with bisesterdiamide units of a uniform length were synthesized in the current study, and the dynamic mechanical and elastic properties of the copolymers produced were studied. Diols are used to extend the length of uniform bisesterdiamide hard segments. Extenders have a twofold effect: increasing the lamellar thickness of the bisesterdiamide crystals and having the ability to independently adjust the ratio between the hard and soft segment. It was found that polymers containing 1,12‐dodecanediol as an extender possess a multiphase structure. Two glass‐transition temperatures (T_g) were observed along with a very broad melting transition. The T_g at about ?70°C was found to originate from the amorphous polyether phase, the T_g at about 140–175°C was attributed to a glassy aramid‐1,12‐dodecanediol phase. The broad melting transition was caused by the presence of the wide variety of lamellar sizes. This multiphase morphology is probably results from the liquid–liquid demixing of an aramid–polyether and from the aramid‐extender phase. Polymers containing 1,12‐dodecanediol and 13 wt % aramid had an improved elasticity compared to similar polymers without an extender. It is thought this is the result of large isolated, spherically shaped domains become less plastically deformed than the crystalline network of thin lamellae. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1605–1613, 2001     

Synthesis of 4-arms hydroxy-functionalized PMMA-b-PE through combining free radical polymerization with coordination polymerization

The copolymerization of MMA with ethylene was promoted by metallocene complex in the presence of initiator tetra(2,3-epoxy propoxy)silane (I_s), reducing agent Zn and cocatalyst MAO, combining free radical polymerization with coordination polymerization via sequential monomer addition strategy in one-pot to produce 4-arms hydroxy-functionalized PMMA-b-PE. The effects of polymerization conditions such as temperature, time, ethylene pressure and Al/Ti molar ratio on the polymerization performance were investigated. 4-Arms hydroxy-functionalized PMMA-b-PE was obtained by solvent extraction and determined by GPC, MALLS, DSC, FT-IR, WAXD and ¹H(¹³C) NMR. The DSC result indicated that the 4-arms hydroxy-functionalized PMMA-b-PE had one T_g at 87.0 °C and one T_m at 117.0 °C which attributed to T_g of PMMA segment and T_m of PE segment, respectively. The microstructure of 4-arms hydroxy-functionalized PMMA-b-PE was further confirmed by WAXD, FT-IR, and ¹³C NMR analysis. These results demonstrated that the obtained 4-arms block copolymer consisted of PMMA segment and crystalline PE segment.     

High-TG base-soluble copolymers as novolac replacements for positive photoresists

Several high-T_g, phenolic copolymers based on N-(p-hy-droxyphenyl)maleimide with various comonomers were prepared, and the properties of a number of these copolymers were studied. The copolymers were 1:1 in composition and were predominantly alternating. The thermal properties of these copolymers were investigated by differential scanning calorimetry and thermal gravimetric analyses. The chain-stiffening effect of the maleimide group was responsible for T_g's of 200°C and above. T_g was a function of composition and molecular weight. Dissolution rates of thin films of these copolymers were investigated by laser interferometry. The dissolution rates were sensitive to copolymer molecular weight and to the functionality, i. e., the type of phenolic ? OH groups and the concentration of ? OH groups present. When these copolymers were used as binders for NDS (diazonaphthoquinone sulfonate) photochemistry, high-resolution positive images were obtained that were resistant to thermal deformation at 200°C and above.     

New soybean oil–styrene–divinylbenzene thermosetting copolymers. I. Synthesis and characterization

The cationic copolymerization of regular soybean oil, low‐saturation soybean oil (LoSatSoy oil), or conjugated LoSatSoy oil with styrene and divinylbenzene initiated by boron trifluoride diethyl etherate (BF₃·OEt₂) or related modified initiators provides viable polymers ranging from soft rubbers to hard, tough, or brittle plastics. The gelation time of the reaction varies from 1 × 10² to 2 × 10⁵ s at room temperature. The yields of bulk polymers are essentially quantitative. The amount of crosslinked polymer remaining after Soxhlet extraction ranges from 80 to 92%, depending on the stoichiometry and the type of oil used. Proton nuclear magnetic resonance spectroscopy and Soxhlet extraction data indicate that the structure of the resulting bulk polymer is a crosslinked polymer network interpenetrated with some linear or less‐crosslinked triglyceride oil–styrene–divinylbenzene copolymers, a small amount of low molecular weight free oil, and minor amounts of initiator fragments. The bulk polymers possess glass‐transition temperatures ranging from approximately 0 to 105°C, which are comparable to those of commercially available rubbery materials and conventional plastics. Thermogravimetric analysis (TGA) indicates that these copolymers are thermally stable under 200°C, with temperatures at 10% weight loss in air (T₁₀) ranging from 312 to 434°C, and temperatures at 50% weight loss in air (T₅₀) ranging from 445 to 480°C. Of the various polymeric materials, the conjugated LoSatSoy oil polymers have the highest glass‐transition temperatures (T_g) and thermal stabilities (T₁₀). The preceding properties that suggest that these soybean oil polymers may prove useful where petroleum‐based polymeric materials have found widespread utility. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 658–670, 2001