Synthesis and characterization of oil sorbers based on docosanyl acrylate and methacrylates copolymers

Docosanyl acrylate (DCA) monomer was copolymerized with different monomer feed ratios of cinnamoyloxy ethyl methacrylate (CEMA) or methyl methacrylate (MMA) monomer to produce different compositions for DCA/CEMA or DCA/MMA copolymer with low conversions.¹H NMR spectroscopy was used to confirm the copolymer structure. DCA was crosslinked with different mol % of CEMA or MMA using dibenzoyl peroxide as initiator and various weight percentages of either 1,1,1‐trimethylolpropane triacrylates or 1,1,1‐trimethylolpropane trimethacrylates crosslinkers. The effects of monomer feed composition, crosslinker concentration, and the hydrophobicity of the copolymer units on swelling properties of the crosslinked polymers were studied through the oil absorbency tests. The network parameters, such as polymer solvent interaction (χ), effective crosslink density (υ_e), equilibrium modulus of elasticity (G_T), and average molecular weight between crosslinks (M_c), were determined and correlated with the structure of the synthesized copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of novel crosslinked poly[glycidyl methacrylate–poly(ethylene glycol) methyl ether methacrylate] as gel polymer electrolytes

In this study, glycidyl methacrylate was copolymerized with poly(ethylene glycol) methyl ether methacrylate to obtain a copolymer {poly[glycidyl methacrylate–poly(ethylene glycol) methyl ether methacrylate] [P(GMA–PEGMA)]}, which was crosslinked with α,ω‐diamino poly(propylene oxide) (Jeffamine) at various weight ratios and molecular weights to form novel gel polymer electrolytes (GPEs). The crosslinked copolymers were characterized by Fourier transform infrared spectroscopy and thermal analysis. The crosslinked polymers were amorphous in the pristine state and became crystallized after they were doped with lithium electrolyte. Furthermore, the crosslinking degree of the crosslinked polymers increased with increasing weight ratio of Jeffamine, and both the swelling properties and mechanical behaviors of the crosslinked polymers were heavily affected by the weight ratio and molecular weight of Jeffamine. The ionic conductivity (σ) of the GPEs from the crosslinked copolymers was determined by alternating‐current impedance spectroscopy. A higher molecular weight and increased weight ratio of Jeffamine resulted in a higher σ. The GPE based on P(GMA–PEGMA) crosslinked with an equal weight of Jeffamine D2000 exhibited the highest σ of 8.29 × 10⁻⁴ S/cm at 25°C and had a moderate mechanical strength. These crosslinked copolymers could be potential candidates for the construction of rechargeable lithium batteries. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

New polymers from plant oil derivatives and styrene‐maleic anhydride copolymers

In this study, styrene maleic anhydride copolymer (SMA2000, Styrene : Maleic Anhydride 2 : 1) is grafted and/or crosslinked with epoxidized methyl oleate, epoxidized soybean oil, methyl ricinoleate (MR), castor oil (CO), and soybean oil diglyceride. Base catalyzed epoxy‐anhydride and alcohol‐anhydride polyesters were synthesized by using the anhydride on SMA, the epoxy or secondary alcohol groups on the triglyceride based monomers. The characterizations of the products were done by DMA, TGA, and IR spectroscopy. SMA‐epoxidized soy oil and SMA‐CO polymers are crosslinked rigid infusible polymers. SMA‐epoxidized soy oil and SMA‐CO showed T_g's at 70 and 66°C, respectively. Dynamic moduli of the two polymers were 11.73 and 3.34 Mpa respectively. SMA‐epoxidized methyl oleate, poly[styrene‐co‐(maleic anhydride)]‐graft‐(methyl ricinoleate), and SMA‐soy oil diglyceride polymers were soluble and thermoplastic polymers and were characterized by TGA, GPC, DSC, NMR, and IR spectroscopy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Swelling and Network Parameters of Oil Sorbers Based on Alkyl Acrylates and Cinnamoyloxy Ethyl Methacrylate Copolymers

Cinnamoyloxy ethyl methacrylate (CEMA) monomer was copolymerized with different monomer feed ratios of alkyl acrylate, such as dodecyl and octadecyl acrylate DDA and ODA, respectively. The monomers were copolymerized with different mole% to produce different compositions for each CEMA/alkylacrylate copolymer with low conversion. ¹HNMR was used to determine the copolymer compositions. The monomer reactivity ratios of each CEMA/alkylacrylate copolymer were determined using Fineman-Ross and Kelen-Tudos methods. CEMA was copolymerized with DDA or ODA and crosslinked using azobis isobutyronitrile (AIBN) as the initiator and 1% weight content of either 1,1,1-trimethylolpropane triacrylate (TPT) or 1,1,1-trimethylolpropane trimethacrylate (TPT_m) crosslinkers. The swelling parameters, such as the maximum oil absorbency (Q _max), characteristic oil sorbency (Q), characteristic swelling time (T), and swelling rate constant (k), were evaluated for the synthesized sorbers. The network parameters, such as the polymer solvent interaction (χ), effective crosslink density (υ _e), equilibrium modulus of elasticity (G _T), average molecular weight between crosslinks (M _c), and the theoretical crosslink density (υ _t), were determined and correlated with the structure of the synthesized sorbers.     

Studies of crosslinked styrene–alkyl acrylate copolymers for oil absorbency application. I. Synthesis and characterization

The prepolymers for a novel oil absorbent were synthesized by copolymerizing styrene with 2‐ethylhexyl acrylate (EHA), lauryl acrylate (LA), lauryl methacrylate (LMA), and stearyl acrylate (SA). Suspension polymerization was carried out using benzoyl peroxide (BPO) as an initiator with a varying monomer feed ratio, and the copolymers were characterized by FTIR, ¹H‐NMR, DSC, and a solubility test. The copolymers were random copolymers with a single phase, and their compositions were similar to those in the monomer feed. The T_g of the copolymer could be controlled by varying the styrene/acrylate ratio. Acrylates introduced the crosslinking to linear polymers as a side reaction. Crosslinked copolymers were synthesized by adding divinylbenzene (DVB) as a crosslinking agent. At a low degree of crosslinking (0.5 wt % DVB), the T_g of the crosslinked copolymers was lower than or similar to that of the uncrosslinked ones. At a high degree of crosslinking, the T_g increased with increasing crosslinking density. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 903–913, 2000     

Preparation and lithographic performance of novel copolymers having acid labile pendant alicyclic ether moieties

A series of methacrylic copolymers derived from methacrylic acid (MAA), methyl methacrylate (MMA), n-butyl methacrylate (BM), and bornyl methacrylate (BMA) with various feed molar ratios was synthesized. In order to introduce acid labile alicyclic ether groups, the pendant carboxyl groups of copolymers were further functionalized with unsaturated alicyclic ethers of 2,3-dihydrofuran (DHF), 3,4-dihydro-2H-pyran (DHP), and 3,4-dihydro-2-methoxy-2H-pyran (DHMP). The existence of alicyclic bornyl groups was found to increase the thermal and plasma etching resistance of polymers but to decrease the sensitivity and contrast. Copolymers having pendant carboxyl groups can be crosslinked in the presence of photoacid after sufficient heat treatment. Acid catalyzed dehydration of pendant carboxylic acids may also cause the crosslinking of polymers. The thermogravimetric properties of copolymers, exposure characteristic curves and lithographic evaluation of the positive tone photoresist were all investigated. A line and space pattern resolution of 0.3 μm was also achieved.     

Flow behavior in a corotating twin‐screw extruder of pure polymers and blends: Characterization by fluorescence monitoring technique

The objective of this work was to investigate the flow behavior of pure polymers and blends, especially miscible polymer/polymer systems, in a corotating twin‐screw extruder (TSE) using an online fluorescence monitoring device. An immiscible blend was also studied for the sake of comparison. The fluorescence signal was obtained by using synthesized fluorescence tracers added to the melt at very low concentrations. These tracers consisted of two styrene‐maleic anhydride copolymers (SMA) labeled with anthracene. The investigated blends were SMA8 (8 wt % of MA in SMA)/polystyrene (PS), SMA14 (14 wt % of MA in SMA)/styrene acrylonitrile copolymer (SAN), and poly(methyl methacrylate) (PMMA)/ethyl acrylate‐methyl methacrylate copolymer (PMMAEA). The residence time distribution (RTD), the mean residence time (t ), the dimensionless variance (σ_θ²), the Peclet number (Pe) and the fluorescence peak intensity distribution of pure polymers and binary polymer systems were investigated and interpreted in terms of polymers rheological properties. It was observed that polymers presenting higher viscosity or higher pressure showed longer residence time. A difference in behavior was also observed for the RTD of miscible and immiscible blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Stereoregular poly(alkyl methacrylate)s: polymer-polymer and copolymer-polymer blends

Amorphous blends of isotactic and syndiotactic poly(methyl methacrylate) were found to be compatible. To evaluate the interaction between these tactic polymers, random copolymers of isotactic poly(methyl/ethyl methacrylate) were blended with syndiotactic poly(methyl methacrylate). Only the copolymers with an ethyl methacrylate content below 45% were compatible with syndiotactic poly(methyl methacrylate). Using a Flory-Huggins type treatment of copolymer mixtures, the segmental interaction parameters for poly(methyl methacrylate) with poly(ethyl methacrylate) and for isotactic with syndiotactic poly(methyl methacrylate) were calculated. The interaction parameter for the tactic poly(methyl methacrylate) pair was found to be small and negative.     

Poly(lactide)-based supramolecular polymers driven by self-complementary quadruple hydrogen bonds: construction,crystallization and mechanical properties

A series of poly(lactide) (PLA)-based supramolecular polymers based on linear PLLA-b-PCL-b-PLLA triblock copolymers (PLLA, poly(l -lactide); PCL, poly(ε-caprolactone)) or/and three-arm star (PCL-b-PDLA)₃ block copolymers (PDLA, poly(d -lactide)) were synthesized. The effects of the structure and composition on crystal structure, crystallization behavior, spherulite morphology and mechanical properties of the synthesized supramolecular polymers were investigated. The results of DSC and polarized optical microscopy indicated that the supramolecular polymer exhibited poor crystallization ability with respect to PCL/PLA block copolymer, and the crystallinity of the supramolecular polymer with alternating PCL/PLA multiblock structure was stronger than that with similar crosslinked network structure. The presence of molten PCL blocks disturbed the orientation of lamellae, forming spherulites with feather-like dendrites, and ring-banded spherulites were observed as the molecular weight of the PLA blocks increased. The results of tensile tests demonstrated that supramolecular polymers with larger molecular weight of PLA blocks showed the pronounced ductile fracture. On this basis, stereocomplexed supramolecular polymers were also synthesized, and it was found that the stereocomplex crystals had a significant impact on the crystallization and mechanical properties of the supramolecular polymers. Therefore, in this work a novel technique for manufacturing toughened PLA-based material and tuning its performances is proposed, which may promote the application of PLA-based materials in more fields. © 2022 Society of Industrial Chemistry.     

Synthesis and photopolymerization of acrylic acrylate copolymers

Acrylate‐functionalized copolymers were synthesized by the modification of poly(butyl acrylate‐co‐glycidyl methacrylate) (BA/GMA) and poly(butyl acrylate‐co‐methyl methacrylate‐co‐glycidyl methacrylate). ¹³C‐NMR analyses showed that no glycidyl methacrylate block longer than three monomer units was formed in the BA/GMA copolymer if the glycidyl methacrylate concentration was kept below 20 mol %. We chemically modified the copolymers by reacting the epoxy group with acrylic acid to yield polymers with various glass‐transition temperatures and functionalities. We studied the crosslinking reactions of these copolymers by differential scanning calorimetry to point out the effect of chain functionality on double‐bond reactivity. Films formed from acrylic acrylate copolymer precursors were finally cured under ultraviolet radiation. Network heterogeneities such as pendant chains and highly crosslinked microgel‐like regions greatly influenced the network structure and, therefore, its viscoelastic properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 753–763, 2002     

Frontal copolymerization of 2‐hydroxyethyl methacrylate and ethylene glycol dimethacrylate without porogen: comparison with suspension polymerization

Networked, crosslinked poly[(2‐hydroxyethyl methacrylate)‐co‐(ethylene glycol dimethacrylate)] (HEMA‐EGDM) was synthesized by frontal polymerization (FP) using azobisisobutyronitrile as initiator. HEMA‐EGDM copolymers of similar composition were also synthesized by suspension polymerization. The two sets of copolymers were characterized for functional groups (IR), pore volume (mercury intrusion porosimetry), surface area (nitrogen adsorption) and morphology (scanning electron microscopy). FP‐generated polymeric network structures had higher internal pore volumes and surface areas but their surface morphologies were inferior to those of copolymers synthesized by suspension polymerization. Copyright © 2004 Society of Chemical Industry     

Preparation and characterization of proton‐conducting crosslinked diblock copolymer membranes

The synthesis and properties of crosslinked diblock copolymers for use as proton‐conducting membranes are presented. A polystyrene‐b‐poly(hydroxyl ethyl methacrylate) diblock copolymer at 56 : 44 wt % was sequentially synthesized via atom transfer radical polymerization. The poly(hydroxyl ethyl methacrylate) (PHEMA) block was thermally crosslinked by sulfosuccinic acid (SA) via the esterification reaction between  OH of PHEMA and  COOH of SA. Proton nuclear magnetic resonance and Fourier transfer infrared spectra revealed the successful synthesis of the diblock copolymer and the crosslinking reaction under the thermal condition of 120°C for 1 h. The ion‐exchange capacity continuously increased from 0.25 to 0.98 mequiv/g with increasing SA concentration because of the increasing number of charged groups in the membrane. However, the water uptake increased up to an SA concentration of 7.6 wt %, above which it decreased monotonically (maximum water uptake ∼ 27.6%). The membrane also exhibited a maximum proton conductivity of 0.045 S/cm at an SA concentration of 15.2 wt %. The maximum behavior of the water uptake and proton conductivity with respect to the SA concentration was considered to be due to a competitive effect between the increase of ionic sites and the crosslinking reaction according to the SA concentration. All the membranes were thermally quite stable at least up to 250°C, presumably because of the block‐copolymer‐based, crosslinked structure of the membranes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

新型遇油膨胀橡胶的制备与性能研究

以甲基丙烯酸十八酯(SMA)、甲基丙烯酸丁酯(BMA)和甲基丙烯酸甲酯(MMA)为单体,采用悬浮聚合法合成了高吸油树脂SMA-g-BMA和SMA-g-BMA-g-MMA。分别以吸油树脂和SMA单体为改性剂,以三元乙丙橡胶(EPDM)为基胶,制备了遇油膨胀橡胶(OSR)。结果表明,用吸油树脂制备的遇油膨胀橡胶力学性能优于用SMA单体制备的遇油膨胀橡胶。当吸油树脂用量为20份且SMA∶BMA=1∶2时,OSR拉伸强度为15.2MPa。对汽油、柴油、机油和甲苯的吸收率分别为330%,326%,250%和502%。     

Initiation system effects in the cationic copolymerization of tetrahydrofuran (THF)

Summary Macromonomeric peroxy initiator, poly tetrahydrofuran (poly-THF=inimer) were synthesized via cationic polymerization of THF by the mono- (t-BuBP) and tetra-bromo methyl benzoyl peroxides (BDBP)/ZnCl₂ initiating system. The macromonomers were characterized by ¹H-NMR, IR, and GPC techniques. Methyl methacrylate (MMA) polymerization initiated by poly-THF inimers at 80°C and different times in bulk gave crosslinked poly-THF-b-polymethyl methacrylate block copolymers. Swelling ratios of the crosslinked block copolymers obtained by taking in same amounts of poly-THF inimer and MMA monomer in CHCl₃ were decreased versus time. It was compared the results obtained from t-BuBP-, BDBP-ZnCl₂ initiating systems with t-BuBP-, BDBP-AgSbF₆ initiating systems for THF monomer. Poly(THF-b-MMA) crosslinked block copolymers containing undecomposed peroxide groups initiated the thermal polymerization of styrene, S, were used to obtain poly(THF-b-MM_A-b-S) crosslinked multicomponent copolymers at 90°C. The crosslinked multi component copolymers were investigated sol-gel analysis and swelling ratios in CHCl₃. "Active" poly(THF-b-MM_A) having peroxygen group were used in the free radical coupling reaction of poly butadien (Poly Bd). Poly(THF-b-MM_A)-polybutadien crosslinked blend soluble graft copolymers were obtained. Received: 31 July 2001/Revised version: 16 June 2002/ Accepted: 5 July 2002     

A facile method of using sulfobetaine‐containing copolymers for biofouling resistance

Antifouling materials are desirable for many biomedical applications. In this work, the poly(sulfobetaine methacrylate‐co‐butyl methacrylate) (PSB) copolymers were investigated for their antifouling properties. The copolymers were synthesized via a simple free‐radical polymerization with feed ratio of the zwitterionic sulfobetaine methacrylate (SBMA) varying from 0 to 20 mol %. The polymer composition was verified by nuclear magnetic resonance. The enzyme‐linked immunosorbent assay and surface plasmon resonance were used to evaluate protein adsorption on a series of PSB copolymers from the single protein solution of fibrinogen, undiluted human blood serum, and undiluted human blood plasma. Results show that the protein adsorption amount decreased with the increasing content of SBMA in the copolymers. The adsorption levels achieved by PSB containing 20 mol % SBMA (PSB20) were only 4, 17, and 15 ng/cm² from fibrinogen, serum, and plasma, respectively, which represented 99%, 90%, and 90% reduction compared with the adsorption amounts on poly(butyl methacrylate) with no SBMA. The PSB20 film also completely inhibited endothelial cell attachment. Fouling resistance of PSB polymers can be well correlated with their receding water contact angles, which represent the polymer surface compositions in aqueous environment. The excellent antifouling abilities of PSB copolymers, combined with the facial synthesis method, commercial availability of all monomers, and low cost, render them highly promising for wide practical applications. The polymers can be applied versatilely as both solvent‐cast films and surface coatings. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40789.     

Mechanical properties of poly(vinyl chloride) blends and corresponding graft copolymers

The mechanical properties of the poly (vinyl chloride) (PVC) and poly (glycidyl methacrylate) [poly (GMA)] blend system and the PVC and poly (hydroxyethyl methacrylate) [poly (HEMA)] blend system and their crosslinked films were investigated. At the same time, the mechanical properties for the corresponding graft copolymers such as PVC-g-GMA, PVC-g-HEMA, and their crosslinked films were also investigated in this study. The results showed that the tensile strengths for PVC–poly (GMA) blend systems were higher than those for PVC-g-GMA graft copolymer, and the tensile strengths for PVC-g-HEMA were higher than those for PVC-poly (HEMA) blend systems. However, the mechanical properties for the PVC–poly (GMA) blend system were not affected by the crosslinking of the blend system, but those for PVC-poly (HEMA) and their graft copolymers decreased with an increase of the equivalent ratio ([NCO]/[OH]) of the crosslinker. Finally, the surface hydrophilicity of the PVC-g-HEMA graft copolymer and PVC-poly (HEMA) blends were also assessed through measuring the contact angle. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 307–319, 1998     

Synthesis and characterization of hydrogels containing biodegradable polymers

BACKGROUND: Amphiphilic block and graft copolymers constitute a very interesting class of polymers with potential for biomedical applications, due to their special characteristics, which derive from the combination of properties of hydrophilic and hydrophobic moieties. In this work, the synthesis and biodegradation of poly(2‐hydroxyethyl methacrylate)‐graft‐poly(L ‐lactide) are studied. RESULTS: The graft copolymers were synthesized using the macromonomer technique. In a first step, methacryloyl‐terminated poly(L ‐lactide) macromonomers were synthesized in a wide molecular weight range using different catalysts. Subsequently, these macromonomers were copolymerized with 2‐hydroxyethyl methacrylate in order to obtain a graft copolymer. These new materials resemble hydrogel scaffolds with a biodegradable component. The biodegradation was studied in hydrolytic and enzymatic environments. The influence of different parameters (molecular weight, crystallinity, ratio between hydrophilic and hydrophobic components) on the degradation rate was investigated. CONCLUSION: Based on this study it will be possible to tailor the release properties of biodegradable materials. In addition, the materials will show good biocompatibility due to the hydrophilic poly(2‐hydroxyethyl methacrylate) hydrogel scaffold. This kind of material has potential for many applications, like controlled drug‐delivery systems or biodegradable implants. Copyright © 2008 Society of Chemical Industry     

Tacticity of methacrylic copolymers and their crosslinked polymers studied by pyrolysis–gas chromatography

Diad tacticity of methyl methacrylate (MMA) sequences in the copolymers of MMA and various acrylates and their crosslinked polymers was characterized by pyrolysis–gas chromatography (Py‐GC) based on the relative peak intensities of the diastereomeric MMA tetramers in the pyrograms. The diad tacticity in the copolymers synthesized at a given temperature proved to be almost consistent with that of corresponding MMA homopolymers (PMMA) prepared under the same conditions. Furthermore, the diad tacticity of PMMAs was also consistent with that of the corresponding crosslinked polymers. These results suggest that the tacticity of MMA sequences in the polymer chains would be dominated by polymerization temperature, independent of the copolymerization and crosslinking. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2140–2144, 2000     

SYNTHESIS,CHARACTERIZATION, AND THERMAL STABILITY OF HOMOPOLYMER AND COPOLYMER OF SOME 3-ARYL-2-HYDROXYPROPYL METHACRYLATES

Three new hydroxypropyl methacrylates having three different aryl rings were synthesized by addition of 2,3-epoxypropyl aromatic hydrocarbon to methacrylic acid. The monomers prepared are 3-phenyl-2-hydroxypropyl methacrylate, 3-tolyl-2-hydroxypropyl methacrylate, (THPMA), and 3-naphtyl-2-hydroxypropyl methacrylate. The homopolymers of these monomers and two different copolymers, [poly(THPMA-co-BMA)], were obtained from polymerization at 60°C in 1,4-dioxane solution using AIBN as initiator. All the monomers and the polymers were characterized by FT-IR and ¹H and ¹³C NMR techniques. Solubility parameters of the polymers and average molecular weight of poly(THPMA) were determined. Thermal stabilities of the polymers were given as comparing with each other by using TGA curves. Thermal degradation of poly(THPMA60%-co-BMA40%) was studied in detail.     

Copolymerization of N‐substituted maleimide with alkyl acrylate and its industrial applications

A series of new copolymers with desired thermal stability and mechanical properties for applications in leather industry were synthesized from various substituted maleimides and alkyl acrylates. Polymerization was carried out by a free‐radical polymerization using benzoyl peroxide (BPO) as initiator. The monomers and polymers synthesized were characterized by elemental analysis, IR, and nuclear magnetic resonance (NMR). Interestingly, these polymers were soluble in common organic solvents. Copolymer composition and reactivity ratios were determined by ¹H‐NMR spectra. The molecular weights of the polymers were determined by gel permeation chromatography. The homo‐ and copolymer of maleimide showed single‐stage decomposition (ranging from 300–580°C). The initial decomposition temperatures of poly[N‐(phenyl)maleimide] [poly(PM)], poly[N‐4‐(methylphenyl)maleimide] [poly(MPM)] and poly[N‐3‐(chlorophenyl)maleimide] [poly(CPM)] were higher compared to those of the copolymers. Heat‐resistant adhesives such as blends of epoxy resin with phenyl‐substituted maleimide‐co‐glycidyl methacrylate copolymers with improved adhesion property were developed. Different adhesive formulations of these copolymaleimides were prepared by curing with diethanolamine at two different temperatures (30°C and 60°C). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1870–1879, 2001