含大位阻脲键的功能化聚氨酯丙烯酸酯的制备与性能

以双（2,2,6,6-四甲基-4-哌啶基）癸二酸酯（TMPCA）为软段、1,3-双（1-异氰酸酯-1-甲基乙基）苯（TMXDI）为硬段、甲基丙烯酸异冰片酯（IBOMA）为反应性稀释单体,经甲基丙烯酸羟乙酯（HEMA）封端后得到含有大位阻脲键的聚氨酯丙烯酸酯预聚体;预聚体经紫外光固化,制备得到光敏树脂材料。通过微量热和变温红外对体系中大位阻脲键的热解离机理进行探索,并对光敏树脂的修复性、形状记忆性和二次塑形能力进行了研究。结果表明：大位阻脲键在46～56℃存在吸热效应,预聚体和固化后树脂中均可以观察到异氰酸酯基因（NCO）含量随温度改变发生动态变化,即体系具有动态共价高分子的特点。固化后的光敏树脂修复性能良好,修复后试样的拉伸强度由13.8 MPa恢复至18.4 MPa。此外,含有大位阻脲键的光敏树脂展现出良好的形状记忆和二次塑形能力,并且二次塑形后材料仍能保持80%的弯曲强度。     

新型水溶性共轭嵌段含糖聚合物的合成与表征

以两端溴化的聚9,9-二己基芴作为大分子引发剂, 6-O-甲基丙烯酰基-1,2∶3,4-二-O-异亚丙基-D-吡喃型半乳糖(6-O-Methacryloyl-1,2∶3,4-di-O-isopropylidene-D-galactopyranose, MaIpGa)为单体, 氯化亚铜/1,1,4,7,10,10-六甲基三乙基四胺为催化剂, 通过原子转移自由基聚合(ATRP), 合成了一种新型的具有良好光学性能的三嵌段共聚物聚甲基丙烯酸羟基保护半乳糖酯-聚芴-聚甲基丙烯酸羟基保护半乳糖酯(PMaIpGa-PF-PMaIpGa). 在酸性条件下进一步水解, 得到水溶性的聚甲基丙烯酸半乳糖酯-聚芴-聚甲基丙烯酸半乳糖酯(PMaGa-PF-PMaGa)三嵌段聚合物, 其结构和分子量(分布)通过核磁共振、红外光谱和凝胶渗透色谱(GPC)确证, 并研究了其紫外-可见和荧光光谱特性.     

聚乙二醇共聚对苯二甲酸丁二醇酯的合成及在生物材料中的应用

综述了聚醚酯热塑性弹性体聚忆二醇／聚对苯二甲酸丁二醇酯（PEG／PBT）的合成、组成与性能关系及其在组织工程和药物缓释体系等方面的应用研究进展。PEG／PBT是一类力学性能优良、可降解和生物相容性良好、极具应用潜力的生物材料。     

聚癸二酸丙三醇酯对聚乳酸的改性

以丙三醇和癸二酸为单体通过熔融缩聚制得了聚癸二酸丙三醇酯(PGS),并用其预聚物(p-PGS)对聚L-丙交酯(PLLA)进行共混改性.利用傅立叶变换红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)及凝胶渗透色谱(GPC)法对P-PGS的结构进行表征,并研究了改性后材料的力学性能、两相相容性、亲水性能和细胞相容性.结果表明:P-PGS具有支化分子结构,分散系数约为2.7;共混改性后的材料弹性模量和拉伸强度均有所下降,而断裂伸长率从7 %显著提高到150%左右;PLLA/PGS属于海岛式共混结构,PGS以小于10μm的尺寸均匀分布在PLLA基体中;共混后材料的亲水性也有一定的提高,且几乎保持了PLLA原有的细胞相容性.     

聚三亚甲基碳酸酯的改性研究

聚三亚甲基碳酸酯具有良好的生物降解性能及生物相容性,是一种重要的生物降解医用高分子材料,在生物医用领域具有巨大的潜在应用。本文结合近几年的研究进展,综述了聚三亚甲基碳酸酯改性的三大类方法,详细介绍了聚三亚甲基碳酸酯的功能化方法与途径、讨论了聚三亚甲基碳酸酯与不同类别单体共聚改性的研究现状及性能变化,并总结了共混改性对聚三亚甲基碳酸酯性能的影响,最后介绍了改性后的聚三亚甲基碳酸酯在生物医用领域的应用。     

甲基丙烯酸磺酸基己酯钠盐的共聚合、聚合及其均聚物的抗凝血性能

研究了甲基丙烯酸6-磺酸基己酯钠盐与甲基丙烯酸甲酯、甲基丙烯酸β-羟乙酯及甲基丙烯酸正己酯的共聚合,并测定了它在水及二甲亚砜中的聚合速度关系式。聚甲基丙烯酸6-磺酸基己酯钠盐的抗凝血性能在一定分子量范围内相差不多。     

聚ε-己内酯的微米硅球固定化猪胰脂肪酶促合成

本文采用微米硅球固定化猪胰脂肪酶为催化剂合成聚ε-己内酯, 以期获得具有较高分子量、 良好生物相容性和使用安全性的生物可降解医用高分子材料.     

可注射骨组织工程支架材料

利用微创手术结合组织工程学的原理修复骨缺损具有操作简单、损伤小、费用低等优点,性能优良的可注射骨修复材料是这一治疗方法能否临床应用的关键。能够原位交联固化的可降解高分子是目前最有发展潜力的可注射骨修复材料。目前研究的可交联高分子包括:聚乳酸、聚酸酐、聚富马酸(1,2-丙二醇)酯以及聚磷酸酯等。本文介绍了这几类高分子的合成、交联固化方法以及固化后材料的力学性能、降解性能和生物相容性,并对这几类材料用于微创手术修复骨缺损存在的问题进行了分析,初步提出了相应的对策。     

贻贝启发的抗菌骨粘合剂的制备与性能北大核心CSCD

骨粘合剂因其快速且稳定的骨粘结性能而受到广泛关注。然而,商用粘合剂的较差生物相容性所导致的不良反应限制了其广泛使用。基于贻贝粘附剂的启发,利用氧化透明质酸(OHA)、单宁酸(TA)与聚赖氨酸(PL)三者共混制备了一种生物相容性良好的双交联网络抗菌骨粘合剂。该粘合剂的粘合粘结强度~450 kPa,搭接粘结强度为~250 kPa,其优异的粘附性能,自愈合性与可注射性可以满足多种临床应用场景,其良好的体外生物相容性为骨细胞增殖和组织愈合提供了稳定的生长环境。此外,单宁酸的抗菌性能使该粘合剂可杀死95%以上的金黄葡萄球菌与大肠杆菌,降低了骨折处发生细菌感染的风险。     

聚三亚甲基碳酸酯的研究进展

聚三亚甲基碳酸酯具有良好的生物降解性能及生物相容性,是一种重要的生物降解医用高分子材料,在生物医用领域具有较大的应用前景。本文结合近年来的研究进展,综述了阳离子开环聚合、阴离子开环聚合、配位聚合、酶促开环聚合以及微波开环聚合等方法在聚三亚甲基碳酸酯制备过程中的应用,总结了聚三亚甲基碳酸酯的分子量与物理性能的关系,并重点讨论了聚三亚甲基碳酸酯的体内外降解性能,详细描述了分子量及脂肪酶对聚三亚甲基碳酸酯降解行为的影响,最后总结了聚三亚甲基碳酸酯在生物医用领域的应用。     

Dual‐curable fluorinated poly(methacrylate) copolymers for optical adhesives

In pursuit of photo‐curable adhesive for optical communication, dual‐curable acrylic oligomers (AOs) having alkoxy silane group, fluorine atoms and vinyl group as a pendent group were synthesized by two‐stage reactions. The isocyanate group containing oligomers were firstly synthesized via radical polymerization of acrylic monomers, and followed by urethane reaction with 2‐hydroxy ethyl methacrylate. The dual curing behaviors, e.g. thermal and photo‐cure, were studied by using photo‐differential scanning calorimetry (DSC) and real‐time IR. An optimum adhesive formulation, based on AO (15 g), epoxy acrylate (80 g), isobonyl methacrylate (17 g) and photo‐initiator (3 g), was obtained. As the content of AO was increased in the optical adhesive formulation, refractive index decreased but transmittance increased due to the increase in fluorine content. The optical transmittance at the range of 1.3 to 1.55 μm was higher than 90%. The addition of colloidal silica with the earlier mentioned formulation was helpful in decreasing crosslinking volume shrinkage and the increasing of glass fiber adhesion. The required properties for the optical adhesive, including chemical resistance and thermal resistance, dimension stability, etc. were also investigated. Copyright © 2005 John Wiley & Sons, Ltd.     

Rapid,On‐Command Debonding of Stimuli‐Responsive Cross‐Linked Adhesives by Continuous,Sequential Quinone Methide Elimination Reactions

Adhesives that selectively debond from a surface by stimuli‐induced head‐to‐tail continuous depolymerization of poly(benzyl ether) macro‐cross‐linkers within a poly(norbornene) matrix are described. Continuous head‐to‐tail depolymerization provides faster rates of response than can be achieved using a small‐molecule cross‐linker, as well as responses to lower stimulus concentrations. Shear‐stress values for glass held together by the adhesive reach 0.51±0.10 MPa, whereas signal‐induced depolymerization via quinone methide intermediates reduces the shear stress values to 0.05±0.02 MPa. Changing the length of the macro‐cross‐linkers alters the time required for debonding, and thus enables the programmed sequential release of specific layers in a glass composite material.     

Rapid,On‐Command Debonding of Stimuli‐Responsive Cross‐Linked Adhesives by Continuous,Sequential Quinone Methide Elimination Reactions

Adhesives that selectively debond from a surface by stimuli‐induced head‐to‐tail continuous depolymerization of poly(benzyl ether) macro‐cross‐linkers within a poly(norbornene) matrix are described. Continuous head‐to‐tail depolymerization provides faster rates of response than can be achieved using a small‐molecule cross‐linker, as well as responses to lower stimulus concentrations. Shear‐stress values for glass held together by the adhesive reach 0.51±0.10 MPa, whereas signal‐induced depolymerization via quinone methide intermediates reduces the shear stress values to 0.05±0.02 MPa. Changing the length of the macro‐cross‐linkers alters the time required for debonding, and thus enables the programmed sequential release of specific layers in a glass composite material.     

Fabrication of AgNPs/Silane coated mechanical and washing durable hydrophobic cotton textile for self-cleaning and oil-water separation application

This study deals to develop a simple and facile two-step dip-coating method using silver nanoparticles (AgNPs) and fluorine-free silane monomer, 3-(Trimethoxysilyl) propyl methacrylate (TMSPM) for the fabrication of hydrophobic coating on cotton fabric. The anti-wetting properties, surface morphology, chemical composition, and functionality of the cotton fabric before and after modification were well characterized by contact angle measurement, scanning electron microscope (SEM), and energy-dispersive X-ray spectrum (EDX) and FT-IR respectively. The fabricated cotton fabric displays strong durability against different pH solutions, different soft/hard mechanical treatments including adhesive peeling test, abrasion with tissue paper and finger wiping, home laundering, without losing the hydrophobic property. The contact angle values (water contact angle of 148.3 ?± ?2° and oil contact angle of 0°) imply that the modified cotton has considerable hydrophobic/oleophilic properties. Additionally, the modified hydrophobic/oleophilic cotton fabric exhibits self-cleaning and oil-water separation behavior for both industrial and household importance.     

In situ photocrosslinkable hyaluronic acid‐based surgical glue with tunable mechanical properties and high adhesive strength

Hyaluronic acid (HA), a naturally occurring linear polysaccharide, has been widely used as a key biomaterial in a range of cosmetic and therapeutic applications. Its excellent biocompatibility and bio‐functions related to tissue regeneration encourage the development of HA‐based hydrogels to expand its applications. This study details an in situ forming surgical glue based on photocrosslinkable HA, providing tunable mechanical properties and firm tissue adhesion under wet and dynamic conditions. Depending on the degree of photocrosslinkable methacrylate groups in HA polymer chains, the mechanical properties of hyaluronate methacrylate (HAMA) hydrogels prepared by UV photocrosslinking was improved. Ex vivo adhesion tests revealed that HAMA hydrogels exhibited 3‐fold higher shear adhesive strength compared to gelatin methacryloyl hydrogels and achieved firm adherence to the porcine skin tissue for several weeks. The high adhesive strength of HAMA hydrogels, under dry and wet conditions, suggests that it may have great promise as a tissue adhesive. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 522–530     

Dynamic mechanical properties and swelling of UV‐photopolymerized anionic hydrogels

The tensile dynamic mechanical properties and weight degree of swelling for anionic 2‐hydroxyethyl methacrylate‐co‐acrylic acid hydrogels were observed. Fabrication parameters examined were UV‐photopolymerization exposure time, UV‐photopolymerization intensity, and weight percentage crosslinker. The environmental conditions tested were electrolyte compositions of 0.5 and 0.05 M potassium hydroxide under applied frequencies of 0.1, 1, or 10 Hz. The overall maximum and minimum storage modulus was 1.83 ± 0.18 MPa and 68.5 ± 7.2 kPa, respectively, loss modulus was 432 ± 63 and 7.67 ± 3.22 kPa, respectively, and weight degree of swelling was 14.27 ± 1.27 and 1.95 ± 0.33, respectively. The morphology of fabricated hydrogels was examined using scanning electron microscopy showing a range of porous structures over the fabrication and environmental conditions examined, accounting for the variation in mechanical properties. The properties examined are of interest to researchers fabricating, designing, or modeling active hydrogel‐based microfluidic components. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

NOVEL TRIMETHACRYLATES: SYNTHESIS,CHARACTERIZATION, AND EVALUATION OF NEW MONOMERS FOR IMPROVED DENTAL RESTORATIVES

ABSTRACT

Two novel trimethacrylates, i.e., 1,1,1-tri-[4-(methacryloxyethoxy)-phenyl] ethane (TMPE) and 1,1,1-tri-[4-(2-methyl-2-methacryloxyethoxy)-phenyl]ethane (TMMPE), have been synthesized by reacting methacryloyl chloride with the corresponding hydroxyl intermediates. Both trimethacrylate monomers, having a low viscosity of 11.5 and 13.1 Pa.S, respectively, were blended with TEGDMA at three different weight ratios, i.e., 90/10, 70/30, and 50/50. The mixtures were made visible light-curable (VLC) by the addition of camphorquinone (0.5 wt%) and N,N-dimethyl-aminoethyl methacrylate (1.0 wt%). In addition to evaluation as cured neat resins, VLC formulations with 70% by wt. of silanated microfiller were also prepared and evaluated. The control in both cases was a VLC formulation of BisGMA/TEGDMA (70/30 and 50/50 wt/wt). These new, formulated resins have both improved physical properties and higher double bond conversion than the BisGMA control, as well as decreased linear polymerization shrinkage (LPS). The neat resin having 70/30 (wt/wt) ratio of TMPE/TEGDMA (T7T3, Table 2) exhibited a compressive strength (CS) of 496 (±51) MPa compared to the 70/30 (wt/wt) ratio of BisGMA/-TEGDMA control having 425(±27) MPa. A filled resin having a 90/10 (wt/wt) ratio of TMPE/TEGDMA exhibited a flexural strength (FS) of 122.6(±23) MPa, compared with a similar filled BisGMA/TEGDMA (70/30, wt/wt) resin exhibiting 112.7(±19) MPa. These and other results suggest that these new trimethacrylates have potential application in formulating dental composites with improved performance.     

Influence of gel composition on the solubility parameter of poly(2‐hydroxyethyl methacrylate‐itaconic acid) hydrogels

The solubility parameters of pure poly(2‐hydroxyethyl methacrylate) (PHEMA) and poly(2‐hydroxyethyl methacrylate/itaconic acid) [P(HEMA/IA)] hydrogels were determined by 20 solvents with various solubility parameters in swelling experiments. The solubility parameter of pure PHEMA was 26.93 ± 0.46 (MPa)^1/2. The effect of mole percentages of itaconic acid (IA) in P(HEMA/IA) hydrogels on the solubility parameter was investigated. The measured values were compared to literature and solubility values theoretically determined by group contribution values of van Krevelen and Hoy. The incorporation of IA into the hydrogel system slightly increased the solubility parameter. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1995–2003, 2002     

Reaction Kinetics and Reduced Shrinkage Stress of Thiol-Yne-Methacrylate and Thiol-Yne-Acrylate Ternary Systems

Thiol-yne-methacrylate and thiol-yne-acrylate ternary systems were investigated for polymerization kinetics and material properties and compared to the analogous pure thiol-yne and (meth)acrylate systems. Both thiol-yne-methacrylate and thiol-yne-acrylate systems were demonstrated to reduce polymerization induced shrinkage stress while simultaneously achieving high glass transition temperatures (T(g)) and modulius. Formulations with 70 wt% methacrylate increased the T(g) from 51 ± 2 to 75 ± 1 °C and the modulus from 1800 ± 100 to 3200 ± 400 MPa (44% increase) over the pure thiol-yne system. Additionally, the shrinkage stress was 1.2 ± 0.2 MPa, which is lower than that of the pure methacrylate, binary thiol-yne and thiol-ene-methacrylate control systems which are all > 2 MPa. Interestingly, with increasing methacrylate or acrylate concentration, a decrease and subsequent increase in the shrinkage stress values were observed. A minimum shrinkage stress value (1.0 ± 0.2 MPa) was observed in the 50 wt% methacrylate and 70 wt% acrylate systems. This tunable behavior results from the competitive reaction kinetics of the methacrylate or acrylate homopolymerization versus chain transfer to thiol and the accompanying thiol-yne step-growth polymerization. The crosslinking density of the networks and the amount of volumetric shrinkage that occurs prior to gelation relative to the total volumetric shrinkage were determined as two key factors that control the final shrinkage stress of the ternary systems.     

Mussel-inspired cellulose-based adhesive with underwater adhesion ability

Inspired by mussels, a new cellulose-based (CTP) adhesive was fabricated by simply blending via cellulose nanofibrils (CNFs), tannic acid (TA), and polyethyleneimine (PEI), where the preparation method was green, facile, and simple. The structure and properties were examined by FT-IR, TGA, XRD, SEM, lap shear tensile, and water absorption tests. The results showed that chemical bonds, hydrogen bonds, and chain entanglement were formed among CNFs, TA, and PEI. Compared with the CNF adhesive, the dry shear strength of the CTP adhesive increased 103% to 392.2?±?32.2 kPa. And the wet shear strength of CTP adhesive increased from 0 kPa to 144.7?±?20.1 kPa, indicating that the CTP adhesive can be used in humid or even water environments. Meanwhile, the water absorption of CTP adhesive decreased from 37.9?±?14.1% to 12.8?±?5.9%. It was the introduction of catechol groups and physical–chemical interactions of three components that endow the CTP adhesive with improved dry and wet adhesion strength and water resistance. Moreover, the proposed CTP adhesive could be used on the surface of various materials, including rubber, plastic, paper, wood, metal, and glass. Overall, this work shows that the CTP adhesive has a wide range of application prospects.

Graphical abstract