The effect of hydroxyspiro‐orthocarbonates on the cationic photopolymerization of an epoxy resin and on the mechanical properties of the final polymer

It is well known that bicyclic compounds like spiro‐orthocarbonates (SOCs) have the ability to reduce or eliminate the shrinkage produced during polymerization. In the work reported, four different SOCs were prepared, two of them with one and two hydroxyl groups, respectively, another with two alkoxy groups and one reference compound without substituents. It was found that the SOCs with hydroxyl groups increased the photopolymerization rate and conversion of an epoxycycloaliphatic monomer, while the compound with butoxy groups had an antagonistic effect, reducing both photopolymerization rate and conversion, due to the basic character of the ether groups. The reference compound did not display accelerating effects but it did increase slightly the conversion. Dynamic mechanical analysis revealed that the SOC with two hydroxyl groups increased the values of storage modulus of the obtained polymer in comparison with the polymer from pristine monomer. This may be due to the multifunctionality of this compound that induced a higher level of crosslinking, while the SOC with one hydroxyl group had the opposite effect, decreasing the viscoelastic property values of the polymer due to chain‐transfer reactions originated by the hydroxyl groups. The SOC with two hydroxyl groups was the more efficient of the studied compounds in reducing the shrinkage of the cured polyether. Copyright © 2011 Society of Chemical Industry     

Molecular design of novel network polymers

Cationic, anionic, and radical ring-opening polymerization of spiro and bicyclic monomers, and their application to network polymers have been developed. Bicyclo orthoesters (BOEs), spiro orthoesters (SOEs), and spiro orthocarbonates (SOCs) were polymerized by cationic double ring-opening. Bicyclobis(γ-butyrolactone)s and spirobis(γ-butyrolactone)s were copolymerized with epoxides by anionic alternating ring-opening. Polymers from SOCs bearing exomethylene groups consisted of ring-opened and vinyl polymerized units. The degree of ring-opening of SOCs depended upon the number of rings and steric hindrance. The radical polymerization of vinylcyclopropanone cyclic acetals depended on the ring-size. With the monomers bearing 5- and 6-membered acetal rings, single ring-opened polymers were obtained. With the monomer bearing 7-membered acetal ring, the polymer mainly consisted of double ring-opened unit. These monomers could be crosslinked by bifunctionalization. Poly(cyclic orthoester)s linked by covalent bonds with dithiols to bifunctional SOEs were crosslinked by acid catalysts, and the reversible crosslinking-depolymerization system could be controlled by temperature.     

Dental restorative composites containing methacrylic spiroorthocarbonate monomers as antishrinking matrixes

In this work, the synthesis of two new antishrinking methacrylic monomers of spiroorthocarbonate type, SOC-IP-UDMA and SOC-UDMA, is discussed, along with studies of their performance as polymeric matrix in dental composites. The monomers were photoactive with components of a conventional resin composite. In order to study the photocuring kinetics of these SOC monomers, a real-time test was performed using FTIR spectroscopy. It was found that SOCs promoted higher double bond conversions (DC) than conventional methacrylic monomer bis-GMA (48%), reaching a DC value of 68% for SOC-UDMA and 75% for SOC-IP-UDMA. The shrinkage stress that accompanies curing of dental composites was measured by a universal testing machine. These new monomer SOCs are capable of reducing the shrinkage up to 51.1% and 27.7% for both methacrylic monomers when they were compared with bis-GMA as control. Also, a dynamical mechanical analysis was conducted on the dental composites, obtaining a higher modulus and a range of T _g values from 80 to 100 °C. Others parameters like flexural properties, solubility, and sorption water were determined, obtaining values better than or equal to the parameters established by the standard ISO 4049. These monomers can be considered as alternative matrixes to replace bis - GMA in dental composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47114.     

螺环原碳酸酯类膨胀单体的合成

膨胀单体和膨胀聚合反应的特点是在聚合过程中能产生体积膨胀 ,可以用于环氧树脂粘合剂的改性研究。膨胀单体中很重要的一类是螺环原碳酸酯。本文综述此类单体的合成方法。     

Rheological properties of methylcellulose aqueous gels under dynamic compression: Frequency sweep and validity of scaling law

The aqueous methylcellulose (MC) gels are characterized with a dynamic mechanical analyzer (DMA) under dynamic vertical compression. During the frequency sweeps of MC gels at different temperatures, the storage modulus is observed to be higher than loss modulus at lower frequencies. Both of the storage and loss modulus increases with frequency, but the rate of increase is higher for loss modulus. This leads to the first crossover between E′ and E″ during the frequency scan. For the frequency scan at a high temperature (80°C), a higher rate of increase is observed in storage modulus beyond the first crossover frequency. This leads to the second crossover between storage and loss modulus. Optical microscopy results indicate the presence of core–shell microstructure in aqueous MC gels. The first crossover is possibly due to the shell–sol transition, whereas the second crossover is due to the sol–shell–core transition. The validity of scaling laws at and around the first‐crossover point (shell–sol transition) is checked. The scaling law is valid at the first‐crossover point, but it is invalid around it. Alternate scaling equations based on reduced parameters are also used to check the universality. Irrespective of temperature, scaling laws are valid for reduced parameters. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Nanosilica‐reinforced Epoxidized natural rubber nanocomposites: Effect of Epoxidation level on morphological and mechanical properties

Epoxidized natural rubbers (ENRs) with three different epoxide contents (i.e., 20, 35, and 50 mol% indicated as ENR20, ENR35, and ENR50, respectively) were prepared. They were then reinforced with 3‐methyacryloxypropyl trimethoxysilane‐modified nanosilica (MPTS‐SiO₂). Influence of epoxide level in ENR molecules on morphological, mechanical, and dynamic mechanical properties of the ENR nanocomposites was investigated. The scanning electron microscopy results revealed larger agglomerates of SiO₂ were found in the ENR composites with higher epoxide content. Furthermore, the strength and moduli of the ENR nanocomposites increased with increasing epoxide content. However, the optimal tensile strength and elongation at break were observed in the nanocomposites with the intermediate level of epoxide contents. The correlation between the strength properties and the interfacial silica‐matrix adhesion indicated that the maximum interfacial adhesion of the nanocomposites was observed in the nanocomposite with ENR35. Also, DMA results indicated stronger interaction between ENR35 and MPTS‐SiO₂ due to higher storage modulus. POLYM. COMPOS., 38:1151–1157, 2017. © 2015 Society of Plastics Engineers     

Stress reduction in phase‐separated,cross‐linked networks: Influence of phase structure and kinetics of reaction

A mechanism for polymerization shrinkage and stress reduction was developed for heterogeneous networks formed through ambient, photo‐initiated polymerization‐induced phase separation (PIPS). The material system used consists of a bulk homopolymer matrix of triethylene glycol dimethacrylate (TEGDMA) modified with one of three nonreactive, linear prepolymers (poly‐methyl, poly‐ethyl, and poly‐butyl methacrylate). At higher prepolymer loading levels (10–20 wt %), an enhanced reduction in both shrinkage and polymerization stress is observed. The onset of gelation in these materials is delayed to a higher degree of methacrylate conversion (～15–25%), providing more time for phase structure evolution by thermodynamically driven monomer diffusion between immiscible phases prior to network macro‐gelation. The resulting phase structure was probed by introducing a fluorescently tagged prepolymer into the matrix. The phase structure evolves from a dispersion of prepolymer at low loading levels to a fully co‐continuous heterogeneous network at higher loadings. The bulk modulus in phase‐separated networks is equivalent or greater than that of poly(TEGDMA), despite a reduced polymerization rate and cross‐link density in the prepolymer‐rich domains. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40879.     

Catalytic double ring-opening polyaddition of spiro orthoester with acid chloride for shrinkage-controlled molding

In order to develop a casting resin for precision molding, a curing method without shrinkage during the polymerization was achieved by the double ring-opening addition reaction of spiro orthoester (SOE) and acid chloride using cationic catalysts. Tetraphenylphosphonium halides (TPPXs) were found to be effective catalysts for the reaction. The catalytic reaction of SOE with acid chloride proceeded even at 25 °C to give the corresponding adduct. Polyaddition of a bifunctional SOE-XII with trifunctional 1,3,5-pentanetricarbonyl trichloride gave a cured material at 30 °C in the presence of tetraphenylphosphonium bromide (TPPB) of 1 mol%, accompanied by a negligible shrinkage of 0.21%. Gelation time was shortened with increase in the amount of catalyst and reaction temperature in the curing process. The obtained products were crosslinked copolymers that showed variable mechanical properties dependent on the curing temperature and monomer structure. This is the first demonstration of shrinkage-controlled molding in the absence of heating or cooling process.     

PET‐ionomers and PETi/MMT nanocomposites: A comparison of the effect of ionic groups on their crystallinities and physical properties

Poly(ethylene terephthalate) (PET) and PET/modified montmorillonite (A10‐MMT) nanocomposites containing up to 3 mol% of dimethyl 5‐sulfoisophthalte sodium salt (DMSi) were prepared by in situ polymerization (PETi and PETNi, respectively). In results from transmission electron microscopy (TEM, ∼ 10 nm), clusters were observed with sizes of 30 nm at an ionic content of 3 mol%. Clusters were not observed in the PETNi samples due to the favorable interaction between the positively charged edges of the clay platelets and the negatively charged ionic groups. On the other hand, the degree of exfoliation was considerably improved by the small ionic content. Remarkable increases in the storage moduli of PETi and PETNi were also observed with increasing DMSi content in the glassy region. However, the storage modulus of PETi decreased rapidly in the rubbery region above the transition temperature as temperature increased. The dynamic viscosity of PETNi decreased with DMSi content, indicating that ion‐pair sites located at the clay edges acted as selective plasticizers in the PET ionic region. Moreover, the introduction of a small ionic content into the PET matrix led to a decrease in crystallinity and slower crystallization rates than in the pure PET. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Polypropylene nanocomposites with oxo‐degradable pro‐oxidant: Mechanical,thermal, rheological,and photo‐degradation performance

The objective of the study was to generate degradable polypropylene nanocomposites by incorporation of pro‐oxidant and different fillers like silica, silicate, and thermally reduced graphene. Graphene‐based composites exhibited higher crystallinity attributed to better dispersion and high aspect ratio platelets. Graphene composites with 2.5% additive content significantly enhanced the peak degradation temperature to 464°C as compared to 448°C for pure polymer. The processing conditions used for the nanocomposite generation were optimum as a uniform distribution of filler particles (or platelets) was observed in the PP matrix. The tensile modulus of the graphene composite with 2.5% additive content was 80% higher than pure PP, as compared to 60 and 30% for silicate and silica composites, respectively. Similarly, the storage modulus of the graphene nanocomposite with 1% additive content had 30% increment at 40°C as compared to pure PP. PP‐additive blends as well as PP nanocomposites with silica and silicate were observed to attain 100% degree of embrittlement within 6 months of UV exposure at 30°C. Graphene composites, though, had delayed photo‐degradation due to UV absorption by the platelets and high aspect ratio platelets acting as oxygen barrier for PP matrix, but the pro‐oxidant was successful in attaining controlled degradation. POLYM. ENG. SCI., 56:1229–1239, 2016. © 2016 Society of Plastics Engineers     

Dynamic mechanical and melt rheological properties of sulfonated poly(butylene succinate) ionomers

A series of poly(butylene succinate) ionomers (PBSi) containing 5-sodium sulfoisophthalate units were prepared by bulk polymerization of succinic acid and 1,4-butanediol in the presence of dimethyl 5-sulfoisophthalate sodium salt (DMSI) up to 5 mol% of diacid monomer. Conspicuous variation of the storage modulus for PBSi was observed, depending on the content of DMSI. The increasing rate of cluster T_g was lower compared to those of amorphous polymer-based ionomers. These results were probably due to the lower clustering ability of semi-crystalline PBSi as compared with amorphous-based ionomers. Non-contact atomic force microscopy confirmed that the size of PBSi-3 clusters was about 40∼50 nm, demonstrating that the clusters were aggregated. Melt rheological analysis was carried out to investigate the effects of ionic groups on the rheological properties as a function of temperature or shear force in the molten state. The melt viscosities of PBSi showed higher values than the parent PBS up to about 190 °C, while with further increasing temperature a falling inflection region of melt viscosity was observed. It was suggested that the relaxation of PBSi chains was due to the thermal dissociation of ionic aggregates.     

Rheology of concentrated sulfonated poly(ether ether ketone) solutions

Sulfonated polyether ether ketone (SPEEK), an ionic polymer, has been shown to be a potential candidate for fuel cell electrolyte as a proton exchange membrane. Rheological behavior of SPEEK solutions is of great interest to understand the molecular associations as well as due to implications in membrane processing. In this work, SPEEK of various degrees of sulfonation (58–80) was prepared and rheology of concentrated solutions of SPEEK was studied. The rheological properties were evaluated using steady and oscillatory shear. It was found that steady shear viscosity and storage modulus at any given concentration, is the highest for the lowest degree of sulfonation SPEEK solutions in N‐methyl‐2‐pyrrolidone. The low frequency plateau in storage modulus was observed at some combinations of degrees of sulfonation and concentrations, indicating gel‐like behavior in these SPEEK solutions. No significant change in rheological behavior was observed with different polar solvents. Increase of several orders of magnitude in viscosity, storage and loss moduli were observed with increasing concentrations. The role of hydrophobic aggregation and inter‐chain associations in determining rheology of SPEEK solutions is argued based on comparisons with other material systems. The rheological behavior of SPEEK solutions with 70 as the degree of sulfonation, suggests crossover from hydrophobic‐hydrophilic balance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40044.     

Synthesis and characterization of sulfonated liquid crystalline polyesters

Liquid crystalline polyesters based on hexanediol, dimethyl 4,4′‐biphenyldicarboxylate, and various levels of dimethyl 5‐sodiosulfoisophthalate (0–20 mol%) were prepared using a conventional melt polymerization process. The presence and quantification of the ionic functionality was surveyed using ¹H NMR spectroscopy. Solution viscosities and corresponding molecular weights decreased when the ionic monomer concentration exceeded a critical value (higher than 3 mol%). Differential scanning calorimetry indicated a maximum in the isotropic transition temperature versus ionic modification at approximately 10 mol%. Dynamic mechanical analysis indicated that the glass transition temperature was suppressed due to ionic association at high concentrations (greater than 3 mol%) of ionic functionality. Polarized light microscopy and wide‐angle X‐ray diffraction were used to identify the smectic liquid crystalline and crystalline phases. © 2002 Society of Chemical Industry     

3D‐Printing of High‐κ Thiol‐Ene Resins with Spiro‐Orthoesters as Anti‐Shrinkage Additive

Tri(ethylene glycol) divinyl ether and the spiro‐orthoester 2‐((allyloxy)methy)‐1,4,6‐trioxospiro[4.4]nonane can be formulated in different ratios and crosslinked by thiol‐ene reactions. The spiro‐orthoester is used as anti‐shrinkage additive, enabling shrinkage reduction of up to 39%. Addition of a radical photoinitiator for the thiol‐ene reaction and a cationic photoinitiator for the double ring‐opening of the spiro‐orthoester enables dual‐curing for application in 3D‐printing. The formulation free of the spiro‐orthoester shows gelation during the printing process and, correspondingly, low resolution. The formulations containing the spiro‐orthoester exhibit higher resolutions in the range of 50 µm. The resins containing mixtures of tri(ethylene glycol) divinyl ether and the spiro‐orthoester show permittivities as high as 10⁴. The dielectric loss factor of the resins is in the range of 0.5–7.6, and the conductivity in the range of 1.3?10^?11 to 2.0?10^?11 S cm^?1. These high‐κ materials can be 3D‐printed by digital light processing for the next generation of electronic materials.     

Synthesis and characterization of new dextran‐acrylamide gels

Dextran‐acrylamide gels were synthesized in a single step reaction by using 4,4′‐azobis(4‐cynovaleric acid) as bi‐functional initiator at 60°C. Corresponding acrylamide (AaM) gels in the absence of dextran were also prepared for comparison. Several parameters such as reaction period (6, 12, and 24 h), monomer and crosslinker concentrations were varied and their effects on the properties of gels were investigated. Gels were characterized by their mechanical and swelling behaviors and in terms of structural changes using SEM. It was observed that swelling degree decreased by increasing the monomer concentration due to formation of more crosslinking points that cause tighter network structure. Mechanical measurements showed that elastic modulus of AaM gels was higher than that of dextran‐AaM gel which indicating the importance of dextran concentration on the flexibility of the network. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Modification of rubber powder with peroxide and properties of polypropylene/rubber composites

Waste tire powder was functionalized in the presence of various concentrations of allylamine and benzoyl peroxide. Fourier transform infrared spectroscopy studies confirmed the presence of allylamine on the surface of the rubber powder. The surface energy of the functionalized rubber powder revealed that the introduction of allylamine onto the rubber powder surface increased the surface activity. Improvements in the tensile strength, elongation at break, and storage modulus were observed for polypropylene/modified rubber powder/maleic anhydride grafted polypropylene, and this was attributed to an improvement in the compatibility due to the chemical interaction between the rubber powder and compatibilizer. Evidence for the reaction between the rubber surface and compatibilizer was observed in Fourier transform infrared studies. This peroxide‐initiated monomer‐grafting technique is feasible for large‐scale processes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2237–2243, 2007     

Drying mechanisms and stress development in aqueous alumina tape casting

Mass loss, shrinkage, Young’s modulus evolution and stress development of aqueous (alumina + latex) tape cast suspensions were observed during drying. Mass loss showed a constant drying rate period, followed by a falling rate period. Concurrently a linear shrinkage rate has been observed in the thickness direction, up to a drying point after which shrinkage abruptly stops. End of constant drying rate and end of shrinkage were not necessarily concomitant and depend on the latex/alumina ratio in the tape. A Young’s modulus value appears in the tape cast suspensions at the transition from liquid to solid like state. Then an increase of Young’s modulus is observed corresponding to latex film formation. The stresses generated by drying in the tape exhibited a first period of increase due to capillary pressure in the pores, a small relaxation immediately followed by a second stress increase due to latex film formation, and a stress plateau at the end of latex coalescence. Alumina powder granulometry and surface tension of the liquid had a preponderant influence on the first stress maximum whereas the properties of the latex and the drying conditions dominated the second stress maximum. By increasing latex proportion up to 25 wt.% on alumina basis, it was possible to make the first and the second stress rise concomitant.     

Low profile unsaturated polyester resin–clay nanocomposite properties

Unsaturated polyester (UP)/organically modified clay (OMC) nanocomposites were prepared by multistep simultaneous mixing of UP oligomer chain, styrene (St) monomer, and OMC. X‐ray diffraction, transmission electron microscopy, dynamic mechanical thermal analysis, and scanning electron microscopy data were in support of the formation of a partially intercalated nanocomposite. The glass transition temperatures of the nanocomposites revealed that the crosslinking reaction occurred homogeneously inside and outside of the OMC galleries. Adding 3 wt% OMC improved the flextural and storage modulus of UP by 31.5% and 30.2%, respectively. The Izod impact strength of UP was also improved by 51.7% at 1 wt% of OMC loading. Similar results were obtained for low‐profile UP/St/OMC nanocomposites. Resin shrinkage data measured by inhouse constructed apparatus showed that, at an OMC content of 3 wt%, the UP/St/OMC/low profile additive (LPA) system cannot provide superior volume shrinkage control. But, it is found that the use of nanoscale reinforcement in the UP systems is able to restore flextural and storage moduli loss when using LPAs. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Maleimido-functionalized spirobislactone having enhanced volumetric expansion on polymerization

An approach to enhancing the volumetric expansion on polymerization of spirobislactone is proposed. This approach suggests a molecular modification of spirobislactone through attaching a rigid pendant segment bearing maleimido group to its aromatic ring. An additional volumetric expansion is achieved from loose molecular packing in cured resins due to the steric hindrance effect among rigid pendent segments. Thus a new monomer, maleimido-functionalized spirobislactone (MFS), is prepared. In order to evaluate the volumetric expansion of MFS during curing, tetraglycidyl 4,4′-diamino diphenyl methane (TGDDM) is employed to cure with MFS. The volumetric expansion of MFS on curing is measured to be 12.3%, higher than that of net spirobislactone monomer. The existence of loose molecular packing in MFS/epoxy cured resins is demonstrated by morphology observation of the cured resin stained by the phosphotungstic acid (PTA), and the stained regions are observed to be nanoparticles. Such a cured resin, prepared from 20 mol% of MFS and 80 mol% of TGDDM epoxy resin, shows excellent toughness (Charpy impact strength 13,000 J/m²) and good mechanical strength (flexural strength 120 MPa, storage flexural modulus 4.2 GPa). Its glass transition temperature by dynamic mechanical thermal analysis (DMA) attains 227 °C, much higher than that of the cured resin from net spirobislactone and epoxy resin.     

Crystallization and morphology of metallocene polyethylenes with well‐controlled molecular weight and branching content

The crystallization and morphology of some metallocene polyethylenes with well‐controlled molecular weight and branching content were investigated by DSC, WAXD, PLM and SALS. The banded spherulites observed in linear PE are not seen in crystallization of branched PEs. The small spherulites with small lamellae or fringed micelle crystals are formed when branching content is higher, as suggested by PLM and SALS. The expansion of the unit cell was observed by WAXD as the molecular weight and branching content increased. At even higher branching content (more than 7 mol%), a shrinkage of the unit cell was seen, probably due to a change of crystal morphology from lamellar‐like crystals to fringed micelle‐like crystals. Crystallization temperature, melting point and crystallinity are greatly decreased for branched PEs compared with linear PEs. The equilibrium melting temperature cannot be determined via the Hoffman–Weeks approach for branched PEs since T_m is always 5–6 °C higher than T_c and there is no intercept with the T_m = T_c line. Our results show a predominant role of branches in the crystallization of polyethylene. © 2003 Society of Chemical Industry