Polyethylene–Silica Nanocomposites with the Structure of Semi‐Interpenetrating Networks

Organic–inorganic nanocomposites with the structure of interpenetrating or semi‐interpenetrating networks are considered as advanced materials, since they have improved thermal and mechanical properties. An alternative approach to the preparation of such hybrid systems is proposed. It is based on the synthesis of silica from the precursor of hyperbranched polyethoxysiloxane by the hydrolytic condensation reaction in the volume of pores of a polymer matrix (bulk porosity is 40 vol%) stretched via the environmental crazing mechanism. Polyethylene–silica nanocomposites with the structure of semi‐interpenetrating networks when the content of silica is not less than 20–25 wt% are obtained. These composites can undergo an additional phase separation at a temperature of 160 °C (above the melting point of polyethylene), which is accompanied by an increase in the size of the polymer phase with the formation of macrophases. At the same time, the environment (orthophosphoric acid), in which the composite is heated, fills the pores that have appeared. As a result, the content of the third component with the new functionality increases up to 50 wt%, which allowed us to impart proton‐conducting properties to the composite material and preserve its shape stability.     

互穿网络结构高吸水性树脂SA-IP-SPS的合成研究

采用氯磺酸磺化法制备了聚乙烯醇硫酸钠（SPS），以工业级丙烯酸和SPS为原料，采用静态溶液聚合法合成了具有良好吸水，吸盐水性能及较高凝胶强度的聚丙烯酸（盐）-聚乙烯醇硫酸钠互穿网络型高吸水性树脂（SA-IP-SPS），合成SA-IP-SPS的最佳条件为：水浴温度：70℃；交联剂用量；1‰；引发剂用量；3‰；初始单体浓度；25%，中和度；50%，在优化的聚合条件下，产物的吸水率可达到1000g/g左右。     

Tuning the Mechanical Properties of BIEE‐Crosslinked Semi‐Interpenetrating,Double‐Hydrophilic Hydrogels

Double‐hydrophilic, semi‐interpenetrating (semi‐IPN) hydrogels are synthesized by encapsulating hydrophilic polyvinylpyrrolidone (PVP) linear chains in structure‐defined 1,2‐bis‐(2‐iodoethoxy)ethane (BIEE)‐crosslinked (poly(2‐(dimethylamino)ethyl methacrylate) (pDMAEMA) hydrogels. A series of semi‐IPN double‐hydrophilic hydrogels are prepared in which the pDMAEMA/BIEE content is kept the same and only the PVP content is varied, from 0 up to 33 wt%. The mechanical properties of the water‐swollen hydrogels are experimentally evaluated under unconfined compressive loading conditions, while a nonlinear hyperelastic constitutive equation is used to predict their mechanical response. No significant difference is found in the mechanical response of the semi‐IPN PVP/pDMAEMA/BIEE hydrogel containing 5 wt% PVP compared to the pDMAEMA/BIEE analog, however, for greater loading percentages (15 and 33 wt% of PVP), the semi‐IPN hydrogels exhibit less stiffness/higher ductility. Furthermore, in vitro biocompatibility studies are carried out for the pDMAEMA/BIEE and the semi‐IPN PVP/pDMAEMA/BIEE, indicating that both the formulations exhibit no toxicity in cultured cells.     

Multiple Shape Memory,Self‐Healable,and Supertough PAA‐GO‐Fe3+ Hydrogel

A multiple shape memory and self‐healing poly(acrylic acid)‐graphene oxide‐Fe³⁺ (PAA‐GO‐Fe³⁺) hydrogel with supertough strength is synthesized containing dual physically cross‐linked PAA network by GO and Fe³⁺. The first GO cross‐linked hydrogel can be reversibly reinforced by immersing in FeCl₃/HCl and pure water and softened by immersing in HCl. The tensile strength is 2.5 MPa with the break strain of 700%. Multiple shape memory capability is found depending on this unique feature, the hydrogel can be fixed in four temporary shapes by adjusting the immersing time in FeCl₃/HCl and pure water, and recovered in sequence by immersing in HCl. This hydrogel also exhibits perfect self‐healing behavior, the cut as‐prepared hydrogel is almost completely healed by immersing in FeCl₃/HCl. Besides, the hydrogel shows enhanced electrical conductivity with the presence of GO and Fe³⁺. This supertough hydrogel provides a new way to design soft actuators.

     

具有网络结构高吸水性树脂的低耗合成与表征

以丙烯酸、丙烯酰胺、2-丙烯酰胺基-2-甲基丙磺酸为单体,N,N-亚甲基双丙烯酰胺为交联剂,采用氧化还原引发剂和水溶液聚合法制备高吸水性树脂。实验结果表明：丙烯酸中和度为80％,单体质量配比为5．0：5．0：2．0,单体总浓度为35％,引发剂浓度为0．5％,交联剂浓度为0.55％时,合成树脂的吸水能力较强,并对其结构进行了红外光谱和SEM基本表征。     

Semi‐interpenetrating polymer network hydrogels based on aspen hemicellulose and chitosan: Effect of crosslinking sequence on hydrogel properties

Semi‐interpenetrating network hydrogel films were prepared using hemicellulose and chemically crosslinked chitosan. Hemicellulose was extracted from aspen by using a novel alkaline treatment and characterized by HPSEC, and consisted of a mixture of high and low molecular weight polymeric fractions. HPLC analysis of the acid hydrolysate of the hemicellulose showed that its major constituent sugar was xylose. X‐ray analysis showed that the relative crystallinity of hydrogels increased with increasing hemicellulose content up to 31.3%. Strong intermolecular interactions between chitosan and hemicellulose were evidenced by FT‐IR analysis. Quantitative analysis of free amino groups showed that hemicellulose could interrupt the chemical crosslinking of chitosan macromolecules. Mechanical testing and swelling experiments were used to define the effective network crosslink density and average molecular weight between crosslinks. Swelling ratios increased with increasing hemicellulose content and mainly consisted of H‐bonded bound water. Results revealed that by altering the hydrogel preparation steps and hemicellulose content, crosslink density and swelling behavior of semi‐IPN hydrogels could be controlled without deteriorating their mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A novel pH‐sensitive gelatin–DNA semi‐interpenetrating polymer network hydrogel

Gelatin and DNA were mixed together in various ratios followed by the addition of glutaraldehyde as a cross‐linker. FT‐IR spectroscopy confirmed the formation of a semi‐interpenetrating polymer network (semi‐IPN) between the gelatin and DNA. The gelatin–DNA semi‐IPN hydrogel underwent, reversibly, remarkable changes in swelling degree in response to the variation of pH. In the low‐pH range, the hydrogel showed a lower swelling degree; with an increment in pH, the hydrogel was highly swollen, which is considered to originate from the complexation and de‐complexation between gelatin and DNA, as was verified by turbidity measurements. Higher contents of DNA result in an increase in the swelling degree, which is presumably due to the easy outward expansion of free DNA moieties. The permeability coefficient, P, for a model molecule, cimetidine, through the semi‐IPN hydrogel membranes was determined in pH 1.0 and pH 12.0 buffer solutions. The results show that the permeation of cimetidine is responsive to pH change, and an evident variation in the P values occurs in response to the pH of the media. Copyright © 2004 Society of Chemical Industry     

Preparation and Characterization of Temperature‐Sensitive Poly(Styrene‐Butadiene‐Styrene)/Poly(N‐Isopropylacrylamide) Hydrogel Elastomer with Interpenetrating Polymeric Networks

A poly(styrene‐butadiene‐styrene)/poly(N‐isopropylacrylamide) (SBS/PNIPAM) hydrogel elastomer with interpenetrating polymeric network structure is prepared by using solution free radical polymerization in benzene/tetrahydrofuran solvent mixture. The characterizations of hydrogel elastomers are investigated by Fourier transform infrared spectroscopy, scanning electron microscope, rheology, equilibrium swelling studies, and oscillatory swelling study. Results show that these hydrogel elastomers exhibit a temperature‐sensitivity inherited from PNIPAM component at the temperature around 30 °C. Besides, change with tetrahydrofuran to different proportion in solvent mixtures, constituent, and properties as gel content, swelling capacity, mechanical strength and volume phase transition degree are affected deeply.     

Synthesis and swelling properties of pH‐sensitive hydrogels based on chitosan and poly(methacrylic acid) semi‐interpenetrating polymer network

A novel semi‐interpenetrating polymer network (semi‐IPN) hydrogel composed of chitosan and poly(methacrylic acid) was synthesized using formaldehyde as a crosslinker. The amount of crosslinker was searched and optimized. The structure of the hydogel was investigated by Fourier transform infrared (FTIR) spectroscopy. The spectrum shows that a structure of polyelectrolyte complex exists in the hydrogel. The effects of pH, ionic strength, and inorganic salt on the swelling behaviors of the hydrogel were studied. The results indicate the hydrogel has excellent pH sensitivity in the range of pH 1.40 to 4.50, pH reversible response between pH 1.80 and 6.80, and ionic strength reversible response between ionic strength 0.2 and 2.0M. The results also show that the hydrogel has a bit higher swelling capacity in a mix solution of calcium chloride (CaCl₂) and hydrochloric acid (HCl) solution than in a mix solution of sodium chloride (NaCl) and HCl. These results were further confirmed through morphological change measured by scanning electron microscope (SEM). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1720–1726, 2005     

Fabrication of Shape‐Memory Aerogel Based on Chitosan/Poly(ethylene glycol) Diacrylate Semi‐Interpenetrating Networks via a Facile and Eco‐Friendly Strategy

While the field of shape memory polymers (SMPs) has developed rapidly, it is still highly challenging to obtain SMPs in the form of aerogels (SMPAs) due to the unique technique used for the fabrication of the aerogels and their high porosity. Herein, a thermally induced SMPA based on chitosan/poly(ethylene glycol) diacrylate (CS/PEGDA) semi‐interpenetrating networks is reported that are produced using an eco‐friendly strategy. The main network is responsible for the shape memory effect (SME) and can be easily tuned by varying the feed ratio of the two PEGDA precursors, which have different molecular weights. The crystalline segment in poly(ethylene glycol) diacrylate (PEGDA) with higher molecular weight acts as the molecular switch, and the PEGDA with lower molecular weight endows the network with an efficient degree of crosslinking. Meanwhile, the chitosan (CS) is interpenetrated into the main network to enhance the aerogel. The SME is realized both at the macroscale and the microscale, as is further demonstrated for three different models with various shapes.     

Preparation and Swelling Properties of Temperature‐Sensitive Semi‐Interpenetrating Polymer Networks Composed of Poly[(N‐tert‐butylacrylamide)‐co‐acrylamide] and Hydroxypropyl Cellulose

Summary: Temperature‐responsive hydrogels based on linear HPC and crosslinked P(NTBA‐co‐AAm) were prepared by the semi‐IPN technique. The structure of these semi‐IPN hydrogels was investigated by FT‐IR spectroscopy. An increase in normalized band ratios (A₂₉₈₀/A₁₆₆₅) was observed with increasing HPC content in the initial mixture. The swelling kinetics and water transport mechanism of these semi‐IPN hydrogels were examined and their temperature responsive behaviors were also investigated by measuring equilibrium swelling ratios and pulsatile swelling experiments. The results showed that these semi‐IPN hydrogels underwent a volume phase transition between 18 and 22 °C irrespective of the amounts of MBAAm and HPC. However, below the volume phase transition temperature, their equilibrium swelling ratios were affected by the amount of MBAAm and HPC. The pulsatile swelling experiments indicated that the lower the MBAAm and the higher HPC contents in semi‐IPN hydrogels the faster the response rate temperature change.

Equilibrium swelling ratios of the semi‐IPN P(NTBA‐co‐AAm)/HPC hydrogels in water shown as a function of temperature.     

Semi‐interpenetrating networks based on poly(N‐isopropyl acrylamide) and poly(N‐vinylpyrrolidone)

Three series of novel semi‐interpenetrating polymer networks, based on crosslinked poly(N‐isopropylacrylamide), PNIPA, and different amounts of the linear poly(N‐vinylpyrrolidone), PVP, were synthesized to improve the mechanical properties and thermal response of PNIPA gels. The effect of the incorporation of the linear PVP into the temperature responsive networks on the temperature‐induced transition, swelling/deswelling behavior, and mechanical properties was studied. Polymer networks with four different crosslinking densities were prepared with varying molar ratios (25/1 to 100/1) of the monomer (N‐isopropylacrylamide) to the crosslinker (N,N′‐methylenebisacrylamide). The hydrogels were characterized by determination of the equilibrium degree of swelling, the dynamic shear modulus and the effective crosslinking density, as well as tensile strength and elongation at break. Furthermore, the deswelling kinetics of the hydrogels was studied by measuring their water retention capacity. The inclusion of the linear hydrophilic PVP in the PNIPA networks increased the equilibrium degree of swelling. The tensile strength of the semi‐interpenetrating networks (SIPNs) reinforced with linear PVP was higher than that of the PNIPA networks. The elongation at break of these SIPNs varied between 22% and 55%, which are 22 – 41% larger than those for pure PNIPA networks. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and Swelling Properties of Hydrolyzed Cottonseed Protein Composite Superabsorbent Hydrogel

A novel protein-based superabsorbent hydrogel was synthesized by graft copolymerization of hydrolyzed cottonseed protein (HCP) and acrylic acid (AA) monomer. This hydrogel was synthesized by solution-based copolymerization, using N,N-methylene bisacrylamide as a crosslinking agent, potassium persulphate and sodium sulfite as the initiators. The effects of the certain variables of the graft copolymerization on the swelling capacity of the hydrogel were measured and its swelling properties in different solutions were investigated as well. This new approach is a promising method in utilizing hydrolyzed cottonseed protein in the production of a superabsorbent polymer with excellent water absorbency and potential use in various applications.     

Preparation and swelling properties of semi‐IPN hydrogels based on chitosan‐g‐poly(acrylic acid) and phosphorylated polyvinyl alcohol

The phosphorylated poly(vinyl alcohol) (P‐PVA) samples with various substitution degrees were prepared through the esterification reaction of PVA and phosphoric acid. By using chitosan (CTS), acrylic acid (AA) and P‐PVA as raw materials, ammonium persulphate (APS) as an initiator and N,N‐methylenebisacrylamide as a crosslinker, the CTS‐g‐PAA/P‐PVA semi‐interpenetrated polymer network (IPN) ssuperabsorbent hydrogel was prepared in aqueous solution by the graft copolymerization of CTS and AA and followed by an interpenetrating and crosslinking of P‐PVA chains. The hydrogel was characterized by Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC) techniques, and the influence of reaction variables, such as the substitution degree and content of P‐PVA on water absorbency were also investigated. FTIR and DSC results confirmed that PAA had been grafted onto CTS backbone and revealed the existence of phase separation and the formation of semi‐IPN network structure. SEM observations indicate that the incorporation of P‐PVA induced highly porous structure, and P‐PVA was uniformly dispersed in the polymeric network. Swelling results showed that CTS‐g‐PAA/P‐PVA semi‐IPN superabsorbent hydrogel exhibited improved swelling capability (421 g·g^?1 in distilled water and 55 g·g^?1 in 0.9 wt % NaCl solution) and swelling rate compared with CTS‐g‐PAA/PVA hydrogel (301 g·g^?1 in distilled water and 47 g·g^?1 in 0.9 wt % NaCl solution) due to the phosphorylation of PVA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

互穿网络水凝胶角膜接触镜材料的合成及性能

通过高聚物分子设计的方法,运用互穿网络(IPN)技术,以吸水倍率为1.7的甲基丙烯酸β-羟乙酯(HEMA)水凝胶为基体材料,以吸水倍率为7~8的交联N-乙烯基吡咯烷酮(PVPP)颗粒为分散相,制备出了互穿程度不同的复合水凝胶角膜接触镜材料。利用SEM和TG分析仪对合成物的结构及热稳定性进行了表征。结果表明,m(PVPP颗粒)∶m(单体HEMA)=10∶90,以w(甘油或PEG400)=35%~45%作致孔剂,通过控制液体HEMA在PVPP颗粒中的渗透程度,可制得膨润率2%~5.3%、拉伸强度430~695 kPa、透光率>92%、含水质量分数45%左右的中等含水量的复合水凝胶角膜接触镜材料。DTG分析发现,在20~40℃,复合水凝胶的脱水速率随着互穿网络程度的提高而降低。     

Open Cell Microcellular Foams of Polylactic Acid (PLA)‐based Blends with Semi‐Interpenetrating Polymer Networks

Microcellular biodegradable polymer foam with an open porous structure was prepared from amorphous poly‐L,D ‐lactic acid (P_{L ,D} LA) blended with polystyrene (PS), or polymethyl methacrylate (PMMA). The blends were prepared by polymerizing either styrene or methyl methacrylate (MMA) in a P_{L ,D} LA matrix. The styrene and MMA monomers are good cell‐opening agents and constituents for an IPN. Pressure‐quench batch foaming was conducted using carbon dioxide as a foaming agent at 80 °C under 10 MPa. The effects of monomers and a cross‐linking agent on the foamability and OCC were investigated. Manipulation of the monomer and the cross‐linking agent concentrations was able to change the viscoelasticity and partial miscibility of the blend and control the cell size at the micron scale as well as open pore content in the range of 20–90%.

     

Synthesis and characterization of pH‐ and temperature‐sensitive silk sericin/poly(N‐isopropylacrylamide) interpenetrating polymer networks

Interpenetrating polymer networks (IPNs) composed of silk sericin (SS) and poly(N‐isopropylacrylamide) (PNIPAAm) were prepared simultaneously. The properties of the resultant IPN hydrogels were characterized by differential scanning calorimetry and SEM as well as their swelling behavior at various temperatures and pH values. The single glass transition temperature (T_g) presented in the IPN thermograms indicated that SS and PNIPAAm form a miscible pair. The swollen morphology of the IPNs observed by SEM demonstrated that water channels (pores present in SEM micrographs) were distributed homogeneously through out the network membranes. The swelling ratio of the IPNs depended significantly on the composition, temperature and pH of the buffer solutions. The dynamic transport of water into the IPN membrane was analyzed based on the Fickian equation. Copyright © 2006 Society of Chemical Industry     

Preparation of All Polyester‐Based Semi‐IPN Elastomers Containing Self‐Associative or Non‐Associative Guest Chains via Post‐Blending Cross‐Linking

Mechanical properties of semi‐interpenetrating polymer network (semi‐IPN) elastomers consisting of chemical networks and self‐associative/non‐associative guest chains are demonstrated. Amorphous low T_g polyesters with thiol side groups (PE‐SH) are first synthesized by melt polycondensation. PE‐SH are then converted to polyesters containing COOH side groups (PE‐COOH) and amide side groups (PE‐amide) through Michael addition reaction of thiol groups with acrylic acid and acrylamide, respectively. Homogeneous semi‐IPN elastomers are obtained by thermal cross‐linking for bulk mixtures of PE‐COOH and PE‐amide in the presence of diepoxy cross‐linkers, where COOH and epoxy groups are reacted to form chemical cross‐links while the amide units form self‐complementary hydrogen bonds. Another sample containing non‐associative chains is also prepared by using polyester with N,N‐dimethylamide units, instead of PE‐amide. Dynamic mechanical analysis reveals that guest chain incorporation systematically brings plateau modulus reduction and a unique relaxation with higher tan δ value depending on the fraction and nature of guest chains. Tensile properties are also affected by the fraction and nature of guest chains; the incorporation of hydrogen bonded chains are beneficial to enhance breaking elongation and toughness without the sacrifice of maximum stress. The knowledge found in this work will be thus beneficial for creating tough soft materials with damping applications.     

Preparation and antidehydration of interpenetrating polymer network hydrogels based on 2‐hydroxyethyl methacrylate and N‐vinyl‐2‐pyrrolidone

This work reports the preparation of 2‐hydroxyethyl methacrylate (HEMA)/N‐vinyl‐2‐pyrrolidone (NVP) interpenetrating polymer network (IPN) hydrogels by UV‐initiated polymerization in the presence of free radical photoinitiator Darocur 1173 and cationic photoinitiator 4,4′‐dimethyl diphenyl iodonium hexafluorophosphate. The polymerization mechanism was investigated by the formation of gel network. The structure and morphology of the HEMA/NVP IPN hydrogels were characterized by fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM). The results showed that the IPN gels exhibited homogeneous morphology. The dehydration rates of HEMA/NVP IPN hydrogels were examined by the gravimetric method. The results revealed that the hydrogels had a significant improvement of antidehydration ability in comparison with poly(2‐hydroxyethyl methacrylate)(PHEMA) hydrogel embedded physically with poly(N‐vinyl‐2‐pyrrolidone)(PVP). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010