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RSC Advances · 2016 ·Vol. 6 ·期 15 ·12479-12485 · IF 3.289

Double-crosslinked network design for self-healing, highly stretchable and resilient polymer hydrogels

Yinlei Lin,Deliu He,Zhifeng Chen,Liying Wang,Guangji Li

Hydrophobic stearyl methacrylate (C18) was captured into sodium dodecyl sulfate (SDS) micelles and self-assembled nanoparticles of an amphiphilic polyurethane macromonomer PU–HEMA were prepared, and they were used as a physical crosslinker and a multifunctional covalent crosslinker, respectively. A reaction system containing acrylamide (AM), the C18 in the micelles and the self-assembled PU–HEMA nanoparticles was designed for constructing chemically and physically double-crosslinked network (CPDN) hydrogels. The prepared CPDN hydrogels have a tensile elongation at break of at least 1400% and can rapidly and fully recover their original shapes in compression experiments, exhibiting superior stretchability and resilience. In addition, the CPDN hydrogels possess a remarkable self-healing behavior and strong self-healing ability even at ambient temperature without the need for any stimulus or healing agent. The novel strategy developed in this study to construct highly stretchable, resilient and self-healing polymer hydrogels is simple yet extremely versatile, thereby opening up a new avenue for the construction of desired functional CPDN hydrogels with excellent mechanical properties.

研究领域: 材料科学 · 化学工程
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POLYMER BULLETIN · 2022 ·Vol. 80 ·期 1 ·331-347 · IF 2.843

Preparation of FK-SA conjugate gel beads with double cross-linking for pH-controllable drug releasing

Wang Zejun,Ren Jiarui,Qian Lizhong,He Yufeng,Song Pengfei,Wang Rongmin

Using feather keratin (FK), a kind of biocompatible natural polymer being extracted from widely available and renewable waste feathers, and sodium alginate (SA) as materials, the FK conjugated SA gel beads (FK-SA-Gbs) were prepared with double cross-linked by calcium ion (Ca 2+ ) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC). After being characterized and analyzed by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD), its pH responsiveness, salt ion responsiveness, and degradability were measured, and the loading capacity of model drug Rhodamine B (RhB) under various physical conditions, the cumulative release rate of the loaded gel beads in different pH buffer solutions were also investigated. The results showed that the FK-SA-Gbs had significant pH sensitivity and sustained release, and various physical conditions can meet the requirements of wound dressings. It indicated FK-SA-Gbs can be used as controlled release drug carriers and are expected to be used as drug carrier materials in biomedical applications. Graphical abstract FK conjugated SA gel beads (FK-SA-Gbs) was prepared by secondary cross-linking with CaCl 2 and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC/HCl) using feather keratin (FK) extracted from waste feathers, which have significant pH sensitivity and sustained release capability.

CAS / MDL: 7758-02-3 9005-38-3
研究领域: 生物材料学 · 药剂学
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ACS Omega · 2021 · IF 3.512

Design and Preparation Technology of Single/Dual-Cross-Linking Copolymers Based on Swida wilsoniana Oil

Ruitong Liu,Jing Yi,Shouhai Li,Jianling Xia,Mei Li,Haiyang Ding,Lina Xu,Xiaohua Yang,Na Yao

To fully utilize the forestry bioresources, a novel dual-cross-linkable resin monomer of MAHSWAGMA was prepared from Swida wilsoniana oil (SWO). FT-IR and 1H-NMR analysis demonstrated the successful synthesis of the target product. Five different cross-linking copolymers, including a polymerized vinyl ester/single-cross-linking (PVESC) polymer, a polymerized epoxy/single-cross-linking (PESC) copolymer, a thermal-photo-initiated/dual-cross-linking (TPIDC) copolymer, a photo-thermal-initiated/dual-cross-linking copolymer (PTIDC), and a thermal-initiated/dual-cross-linking copolymer (TIDC), were obtained with different preparation technologies by different initiated cross-linking processes. Thermal and mechanical properties of the five copolymers were all tested, and the effects of different preparation technologies on the properties of prepared copolymers were investigated. The prepared three dual-cross-linking copolymers had higher hardness, relative cross-linking density, glass transition temperature, and more excellent mechanical property than the other two single-cross-linking copolymers. The PTIDC copolymerized system obtained with photo first and thermal latter initiated dual-cross-linking preparation technology had the most excellent comprehensive properties. This study can provide an ideal idea for the design and preparation of dual-cross-linking copolymers based on forestry vegetable oil.

CAS / MDL: 106-91-2
研究领域: 材料科学 · 林产化学加工工程
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Polymer Chemistry · 2022 ·Vol. 13 ·期 28 ·4144-4153 · IF 5.364

Molecularly engineered dual-crosslinked elastomer vitrimers with superior strength, improved creep resistance, and retained malleability

Lin Wang,Yingjun Liu,Yunhe Qiao,Yuli Wang,Ziwen Cui,Shaoyi Zhu,Fuwei Dong,Sikun Fang,Aihua Du

It is very challenging to prepare elastomer vitrimers that are both robust and dimensionally stable in service. To address this issue, we have initiated a multi-phase design of elastomer vitrimers by incorporating quadruple hydrogen bonds (H-bonds) into vitrimer networks. Specifically, commercialized styrene–butadiene rubber (SBR) was functionalized with the synthesized 5-benzyl-3,6-dioxo-2-piperazineacetic acid (DKP) to introduce amide functionalities, which was then crosslinked by dimercapto-borate via thiol–ene “click” chemistry. The H-bonds between amide moieties functioned as sacrificial units, which could undergo reversible breakage and recombination events, and therefore improve the modulus, ultimate strength, and toughness simultaneously. Moreover, with an aromatic ring and a symmetrical amide group in the structure, the grafted DKP could self-assemble via hydrogen bonds, leading to the formation of a microphase-separated structure in the elastomer matrix. Besides, the creep resistance was improved as the H-bonds were physical crosslinks that imposed additional constraints on chain segment diffusion. Nevertheless, the reprocessability of the network was not affected as the H-bonds and boronic ester crosslinks could dissociate and exchange at elevated temperatures, respectively.

CAS / MDL: 1122-58-3 25952-53-8
研究领域: 材料科学 · 高分子化学
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International Journal of Polymeric Materials and Polymeric Biomaterials · 2023 · IF 3.2

Preparation and properties of a double-crosslinked, high-strength polyvinyl alcohol/acylhydrazone self-healing hydrogel

Jie Mao,Yalei Liu,Lijun Chen,Sui Wang

In this paper, PVA/BDA/ADH gels with good mechanical properties and self-healing properties were prepared using polyvinyl alcohol (PVA), 4,4-biphenyldicarboxaldehyde (BDA), and adipic dihydrazide (ADH) as raw materials. The hydrogel network achieves chemical-physical double cross-linking through acylhydrazone bonds and hydrogen bonds. The as-prepared PVA/BDA/ADH gels have good mechanical properties (the tensile stress of PVA/BDA/ADH gels is about 2 times that of pure PVA hydrogel) due to chemical and physical double cross-linking. It also has good self-healing properties under external conditions. Compared with pure PVA hydrogel, PVA/BDA/ADH gels have more stable self-healing properties.

CAS / MDL: 1071-93-8 9002-89-5
研究领域: 材料科学 · 生物材料
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POLYMER BULLETIN · 2023 · IF 3.2

The effect of strain rate on the tensile properties of nitrile butadiene rubber with dual crosslinked networks

Li Qiuying,Li Xifei,Liu Dekun,Xu Ruiyang,Wei Shaohua

Requirements for the material with high tensile strength and elongation at break are proposed with the development of soft and stretchable electronics. The nitrile butadiene rubber (NBR) crosslinked by coordination bonds has excellent tensile properties and is expected to be used in the flexible electronics field, but the effect of strain rate on tensile properties of crosslinked NBR needs to be further analyzed. In this work, the NBR with dual crosslinked networks was prepared by methods of double ligands crosslinking, covalence-coordination crosslinking, and bimetallic coordination crosslinking. Furthermore, the strain rate sensitivity of tensile properties of NBR with dual crosslinked networks was studied by considering the strain rate as a variable. The results indicated that the strength of the coordination bonds formed by the second ligand had significant effects on the tensile properties of NBR: The coordination bonds with low strength could protect the integrity of the crosslinked network, but the tensile properties of NBR with two different kinds of strong coordination bonds would be more dependent on the strain rate. In covalence-coordination crosslinked or bimetallic crosslinked NBR, the synergy between the two crosslinked networks could not only increase the strength and elongation at break of NBR but also reduce the influence of strain rate on the tensile properties of NBR.

CAS / MDL: 1671-87-0
研究领域: 材料科学 · 高分子化学
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Indirect method for preparing dual crosslinked eutectogels with high strength, stretchability, conductivity and rapid self-recovery capability as flexible and freeze-resistant strain sensors

Yongzhi Liang,Diandian Zou,Yinghe Zhang,Zheng Zhong

The growing demand for stretchable conductor materials in flexible electronic technologies has led to increased focus on developing conductive gels. However, existing hydrogels have poor temperature resistance, and ionogels may have potential toxicity, limiting their use in bio-related applications. This work focuses on the development of the emerging eutectogels with both mechanical and electrical properties, which have traditionally been challenging to achieve. We present an indirect method to prepare dual crosslinked eutectogels that possess high strength, stretchability, conductivity and rapid self-recovery capability. The approach involves using water molecules as a co-solvent to form a deep eutectic solvent through a three-step process, followed by ionically cross-linking poly(acrylamide-co-acrylic acid) with Fe 3+ . The resulting eutectogels have a balanced mechanical strength with a tensile strength up to 6.17 MPa, large stretchability up to 1067%, a modulus of 1.25 MPa, and excellent toughness of 20.95 MJ/m 3 . In addition, the eutectogels exhibit high ionic conductivity of 10.29 mS/cm, rapid self-recovery and low temperature tolerance capability (up to −50 °C). To our knowledge, the eutectogels with balanced tensile strength, toughness, conductivity, and low-temperature tolerance can hardly be achieved. Moreover, the conductive eutectogel also exhibit high sensitivity with a gauge factor of 9.47 at strain of 700% with fast response time, making them promising candidates for soft human-motion sensors that can accurately detect human motions with high sensitivity and good durability over a wide temperature range. The findings provide new insights into developing eutectogels with both mechanical and electrical properties, opening opportunities in flexible electronics, soft robotics, and energy storage devices.

研究领域: 材料科学 · 柔性电子 · 生物医学工程
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APPLIED SURFACE SCIENCE · 2020 · IF 6.182

A fast and dual crosslinking hydrogel based on vinyl ether sodium alginate

Sishi Xu,Wencheng Liang,Guanzhe Xu,Chengjie Huang,Junyong Zhang,Meidong Lang

Optimal modification and gelation strategies of polysaccharide hydrogels have been developed for biomedical applications. Herein, a kind of fast crosslinking alginate hydrogel with superior gel properties was prepared for the first time combining dual crosslinking mechanisms. Firstly, sodium alginate (SA) was modified by vinyl ether side chains through one-step amidation reaction with aminopropyl vinyl ether (APVE) catalyzed by EDC/NHS. Just within 10 s, the grafting product of SA-VE was demonstrated to form hydrogen bonded hydrogel SA-VE/H 2 O spontaneously. Based on this mechanism, a dual crosslinking alginate hydrogel SA-VE/DTT was fabricated through introducing thiol-ene click chemistry reaction with dithiothreitol (DTT) under UV exposure. According to rheological results, the photo-crosslinking process was completed within 5–9 min. Combining hydrogen bonding and thiol-ene click chemistry, the dual crosslinking mechanism was proved to bring the hydrogel system not only fast gelation but also superior storage modulus up to 13373 Pa and excellent stability of over 1 month. All the hydrogels exhibited non-cytotoxicity towards NIH-3T3 fibroblasts. Furthermore, the 26 s rapid hemostasis behavior of SA-VE exhibited in rat tail hemostasis experiment reveals its potential application in wound dressing materials.

研究领域: 生物材料学 · 组织工程 · 再生医学
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY · 2022 · IF 6.76

Conjoined-network induced highly tough hydrogels by using copolymer and nano-cellulose for oilfield water plugging

Jintao Li,Peng Wei,Yahong Xie,Ziteng Liu,Hongjie Chen,Long He

Hydrogels have been widely adopted for in-depth water control in mature oilfields, however, the poor mechanical properties limit their application. Herein, a conjoined-network induced hydrogel was prepared through the in-situ free radical copolymerization of acrylamide (AM), Acrylic acid (AA) and N,N′-methylenebis(acrylamide) (MBA) in the presence of nano-cellulose (CNF/ACNF), and the coordination effect between aluminium ion and carboxyl. The results showed that a small amount of nano-cellulose (0.2 %) increased the compressive strength of the hydrogel by 7 times. The presence of nano-cellulose endowed the hydrogel with excellent thermal stability and high shearing elasticity, at the same time, could effectively reduced the swelling rate that hindered its disintegration in practical application. The evaluation of sand-pack plugging suggested that the double cross-linked nano-cellulose hydrogel presented a significant capacity for efficient water plugging, where the breakthrough pressure gradient was as high as 23.73 MPa, the plugging rate reached 99.9%, and the maximum residual resistance factor was 3902.06. This work provided a novel design of hydrogel with high compressive strength and satisfactory stability for water shutoff and conformance control in heterogeneous oil reservoirs.

研究领域: 材料科学 · 石油工程
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Bioactive Materials · 2024 · IF 18

Injectable double-crosslinked bone cement with enhanced bone adhesion and improved osteoporotic pathophysiological microenvironment for osteoregeneration in osteoporosis

Lingfei Zhao,Chenyu Liu,Xing Chen,Zirui He,Shuiquan Zhang,Anan Zhang,Shuaimin Tang,Zihan Wu,Changsheng Liu,Yuan Yuan

The osteoporotic bone defect caused by excessive activity of osteoclasts has posed a challenge for public healthcare. However, most existing bioinert bone cement fails to effectively regulate the pathological bone microenvironment and reconstruct bone homeostasis in the presence of osteoclast overactivity and osteoblast suppression. Herein, inspired by natural bone tissue, an in-situ modulation system for osteoporotic bone regeneration is developed by fabricating an injectable double-crosslinked PEGylated poly(glycerol sebacate) (PEGS)/calcium phosphate cement (CPC) loaded with sodium alendronate (ALN) (PEGS/CPC@ALN) adhesive bone cement. By incorporating ALN, the organic-inorganic interconnection within PEGS/CPC@ALN results in a 100 % increase in compression modulus and energy dissipation efficiency. Additionally, PEGS/CPC@ALN effectively adheres to the bone by bonding with amine and calcium ions present on the bone surface. Moreover, this in-situ regulation system comprehensively mitigates excessive bone resorption through the buffering effect of CPC to improve the acidic microenvironment of osteoporotic bone and the release of ALN to inhibit hyperactive osteoclasts, and facilitates stem cell proliferation and differentiation into osteoblasts through calcium ion release. Overall, the PEGS/CPC@ALN effectively regulates the pathological microenvironment of osteoporosis while promoting bone regeneration through synergistic effects of drugs and materials, thereby improving bone homeostasis and enabling minimally invasive treatment for osteoporotic defects.

研究领域: 生物材料学 · 骨科医学 · 再生医学
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PROGRESS IN ORGANIC COATINGS · 2024 · IF 6.5

Waterborne polyurethane based on dual crosslinked structure with excellent mechanical properties, water and corrosion resistance

Jiaqi Zhang,Ruixue Zhai,Jingshu Zhang,Jiawei Li,Chengyu Hong,Yiping Xu,Chao Zhou

Due to the increased presence of hydrophilic groups in waterborne polyurethane (WPU) coatings, consequently leading to compromised corrosion resistance and reduced service life. To solve the problem, a series of waterborne polyurethanes were synthesized via internal emulsification using dicyclohexylmethane diisocyanate (HMDI) and polytetrahydrofuran ether diol (PTMG) as the primary raw materials. The triethanolamine (TEOA) was used as a crosslinking agent and corrosion inhibitor, while N- (β-aminoethyl) -γ-aminopropyl trimethyl-(ethyl) oxy-silane (KH-792) was introduced as a coupling agent to establish a system with a dual crosslinking structure. The crosslinking degree of the double network structure can be adjusted by changing the amount of KH-792. Then the influence of KH-792 content on the performance of SWPU dispersions and film were studied. The research shows that the waterborne polyurethane with a KH-792 content of 3 wt% exhibits exceptional mechanical strength, reaching 34.64 MPa, with only 3.32 % water absorption and an adhesion strength of 2.64 MPa. Furthermore, it exhibited a high impedance modulus (2976.4 Ω/cm 2 ) at low frequencies. Therefore, this compound holds promising potential for application in anti-corrosion coatings field.

研究领域: 材料科学 · 化学工程
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PROGRESS IN ORGANIC COATINGS · 2025 · IF 7.3

Fabrication of ionic liquid-functionalized dual cross-linked hydrogel coatings for antibacterial and antifouling applications

Yikun Ji,Mingjun Zou,Kaige Yan,Bin Liu,Shujuan Liu,Qian Ye,Feng Zhou

In this study, a novel ionic liquid-functionalized dual cross-linked hydrogel was developed via ring-opening reaction grafting ionic liquid. The hydrogel matrix containing epoxy groups was first synthesized via a one-pot polymerization reaction of acrylic acid, acrylamide, methylene diarylamide and glycidyl methacrylate, followed by the introduction of Fe 3+ ions to improve its mechanical strength, and then the ionic liquid MIm-Br with amino group was grafted onto the hydrogel matrix by amino-epoxy ring-opening reaction. The resulting ionic liquid-functionalized hydrogel exhibited excellent hydrophilicity and anti-adhesion properties, achieving an antibacterial rate exceeding 98 % against two species of bacteria and a removal rate of over 95 % for two types of algae. The synergistic effect of the hydrogel and the ionic liquid was responsible for these efficient antibacterial and antifouling properties. The hydrogel's high hydrophilicity and low adhesion confer them excellent anti-adhesion effects for bacteria and alga. Meanwhile, the positively charged imidazole ring of MIm-Br interacts with the negatively charged bacterial cell membranes through electrostatic adsorption, altering the cell's membrane permeability and causing leakage of intracellular substances. Moreover, the ionic liquid-functionalized hydrogel exhibited significantly improved swelling properties, water retention and water lubrication performance, enhancing its utility.

研究领域: 材料科学 · 生物医学工程
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