Polymer Journal最新文献

{"title":"Surface orientation of amphiphilic block copolymers via thermal annealing","authors":"Hayate Narumi, Yukari Oda","doi":"10.1038/s41428-024-00999-2","DOIUrl":"10.1038/s41428-024-00999-2","url":null,"abstract":"The surface aggregation states of the amphiphilic diblock copolymer films, which are consistent with polyacrylates and polystyrene, were examined. The hydrophilic polyacrylates presented a lower surface free energy (γ) at room temperature, resulting in surface segregation. A perpendicular microdomain orientation was achieved after thermal annealing above the glass transition temperature of both components. As the annealing temperature increased, the surface became hydrophobic while maintaining this orientation due to polystyrene segregation. The key to this process is appropriate thermal annealing, considering the entropic contribution to γ from differences in molecular motion between the two components.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 3","pages":"335-339"},"PeriodicalIF":2.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555225","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rapid and highly efficient recombination of crosslinking points in hydrogels generated via the template polymerization of dynamic covalent three-dimensional nanoparticle crosslinkers","authors":"Mahmoud H. Othman, Yoshihiro Ito, Jun Akimoto","doi":"10.1038/s41428-024-00996-5","DOIUrl":"10.1038/s41428-024-00996-5","url":null,"abstract":"Dynamic covalent bonds (DCBs) can be used as crosslinking points to induce self-healing and thermoplastic properties in hydrogels because the bonding and dissociation between molecules can be controlled by external stimuli. However, once DCBs dissociate, molecules diffuse inside the gel, delaying DCB reformation. In this study, a hydrogel was prepared via template polymerization using phenylboronic acid-coated nanoparticles to control the mobility of the molecules and the density of the DCB crosslinking points. Interestingly, the loss modulus, but not the storage modulus, of the hydrogel changed with temperature according to the formation/dissociation of boronic ester bonds. Furthermore, compared with conventional hydrogels, the hydrogels prepared here exhibited very rapid changes in physicochemical properties in response to changes in temperature because the high density of three-dimensional DCB crosslinking points limits the diffusion of molecules inside the gel. As a result, the prepared hydrogel showed rapid self-healing and thermoplastic properties as the temperature changed. A novel hydrogel (TempGel(NP)) was synthesized through template polymerization of phenylboronic-acid-coated nanoparticles with tris(hydroxymethyl)methyl acrylamide (THMAAm). This process forms dynamic boronic ester crosslinks, creating a highly dense and uniform three-dimensional network. The innovative structure exhibits reversible thermal responsiveness, enabling rapid bond dissociation and reformation upon temperature changes. The dense packing around nanoparticles minimizes molecular diffusion, ensuring superior self-healing, high thermal hysteresis, and tunable viscoelastic properties. This innovative design provides a robust platform for advanced applications in smart materials, biomedical devices and responsive hydrogels.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 3","pages":"315-325"},"PeriodicalIF":2.3,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00996-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555247","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Improvement in the toughness and compatibility of poly(lactic acid)/starch acetoacetate through reactive melt-kneading with amine-modified silicone","authors":"Kazuki Shibasaki, Yu-I Hsu, Hiroshi Uyama","doi":"10.1038/s41428-024-00971-0","DOIUrl":"10.1038/s41428-024-00971-0","url":null,"abstract":"Nonbiodegradable plastic pollution has taken centerstage because of its negative impacts on ecosystems, and poly(lactic acid) (PLA)/starch blends, which are biodegradable plastics, have attracted increased attention as sustainable materials. However, the poor compatibility between hydrophobic PLA and hydrophilic starch causes their composites to become brittle. In this study, to improve the compatibility between PLA and starch, the hydroxyl groups of starch were modified with acetoacetate, and amine-modified silicone was used as the compatibilizer. The acetoacetyl group readily reacts with primary amines under mild conditions to form enamines and is expected to react rapidly during the melt-kneading process. The amino groups also react with the decomposed PLA end groups via condensation. Therefore, amine-modified silicone is considered a suitable compatibilizer for PLA and starch acetoacetate (SAA). PLA/SAA/amine-modified silicone blends were prepared via melt-kneading. The toughness of PLA/SAA was improved by approximately 15 times when 3 wt% amine-modified silicone was added. Furthermore, in the SEM observation of the tensile fracture surface, it was found that the dispersibility of SAA in PLA was improved such that SAA and PLA were indistinguishable. This approach can contribute to the widespread use of biodegradable plastics in packaging materials and single-use plastics. In this study, to improve the compatibility of PLA and starch, the hydroxyl groups of the starch were modified with acetoacetic acid, and amine-modified silicone was used as a compatibilizer. PLA/SAA/amine-modified silicone blends were prepared by melt-kneading. The toughness of PLA/SAA was improved by about 15 times by adding 3 wt% amine-modified silicone. This approach can contribute to the widespread use of biodegradable plastics in packaging materials and single-use plastics.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 3","pages":"303-314"},"PeriodicalIF":2.3,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00971-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555233","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and two-dimensional ordering of asymmetrically polymer–brush–decorated cellulose nanocrystals","authors":"Yuji Kinose, Seitaro Fujimoto, Keita Sakakibara, Yoshinobu Tsujii","doi":"10.1038/s41428-024-00994-7","DOIUrl":"10.1038/s41428-024-00994-7","url":null,"abstract":"Rod-shaped cellulose nanocrystals (CNCs) are typically obtained by hydrolyzing cellulose nanofibers bearing an formyl group at their reducing end. In this study, we prepare CNCs bearing densely grafted polymer brushes of different molecular weights (asymmetrically polymer-brush–decorated CNCs; aPB-CNCs). aPB-CNCs exhibit good dispersion in organic solvents and form a monolayer at the air/water interface. The compression of this monolayer induces a phase transition of a long polymer brush at the reducing end and a change in the orientation of the CNC core due to repulsive interactions. A CNC is identified as a key intermediate, possessing dormant moieties for reversible addition–fragmentation polymerization and atom transfer radical polymerization at the reducing end and other surfaces, respectively (bifunctional dormant CNC). This functional CNC facilitates the polymerization of a wide range of monomers and enables the synthesis of aPB-CNCs with diverse chemical properties. The developed synthetic route not only provides a basis for exploring the ordered structure of nanoparticles but is also useful for modifying the reducing ends of CNCs. Cellulose nanocrystals (CNCs) bearing densely grafted polymer brushes of different molecular weights (asymmetrically polymer-brush–decorated CNCs; aPB-CNCs) were synthesized via a CNC intermediate possessing two types of dormant moieties for controlled radical polymerization at the reducing end and other surfaces, respectively. The aPB-CNCs exhibited good dispersion in organic solvents and form a monolayer at the air/water interface. The compression of this monolayer induced a phase transition of a long polymer brush at the reducing end and a change in the orientation of the CNC core due to repulsive interactions.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 3","pages":"269-277"},"PeriodicalIF":2.3,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00994-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555254","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Review of bioderived and biodegradable polymers/block-copolymers and their biomedical and electronic applications","authors":"Ping-Jui Yu, Yan-Cheng Lin, Wen-Chang Chen","doi":"10.1038/s41428-024-00980-z","DOIUrl":"10.1038/s41428-024-00980-z","url":null,"abstract":"The growing awareness of eco-friendly and high-value materials has attracted many researchers to green chemistry. With versatile advantages, biodegradability is the paramount property for waste disposal or recycling, and it can determine whether a product is environmentally sustainable. Moreover, bioderived materials are crucial because the reprocessed products are difficult to handle after recycling. Therefore, biodegradable and bioderived materials can address increasing environmental issues via recycling approaches and reprocessing products. Combining these sustainable concepts, block copolymers (BCPs) with self-assembling characteristics have been extensively investigated for use in biobased materials, green processing, and recyclable electronic applications. This mini-review introduces the design and syntheses of the starting biobased monomers, prepolymers, and block copolymers. Then, their degradability and recyclability are evaluated. Due to their significant potential, biobased and biodegradable BCPs hold great promise in biomedical and optoelectronic applications. Bioderived materials are value-added by recycling excessive residues to gain a new life for themselves. Biodegradable materials can address increasing environmental issues via recycling approaches and reprocessing products. Concerning these attractive advantages, in the first part of this review, commodity polymers from biosources and their recycling and biodegradable pathways are described. The second part summarizes the recent advances of bioderived and biodegradable block copolymers in biomedical and electronic applications, including drug carriers, field-effect transistors, and nonvolatile memory. This review sheds light on the bright perspective of bioderived and biodegradable polymers.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 3","pages":"233-247"},"PeriodicalIF":2.3,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555238","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Salt concentration dependency of the hydrated swollen structure of cholinephosphate-type polyzwitterion brushes","authors":"Takumi Komiya, Norifumi L. Yamada, Motoyasu Kobayashi","doi":"10.1038/s41428-024-00991-w","DOIUrl":"10.1038/s41428-024-00991-w","url":null,"abstract":"The swollen thicknesses of zwitterionic polymer brushes with phosphorylcholine (PC), cholinephosphate (CP), sulfobetaine, and carboxybetaine groups were measured in aqueous sodium chloride (NaCl) or calcium chloride (CaCl2) solutions via force curve measurements by scanning probe microscopy (SPM) and neutron reflectivity measurements. PC and CP have different charge positions in betaine units consisting of ammonium and phosphate. The PC-type polymer brush did not distinctly reduce the swollen thickness in either the NaCl or CaCl2 solution, even at 1000 mM. However, the swollen thickness of the CP-type polymer brushes was clearly reduced in the aqueous CaCl2 solution. Unlike the phosphate of PC, which is located inside the betaine unit, the phosphate of CP tends to form insoluble calcium phosphate, resulting in the collapse of the brush structure. The effect of calcium ion on the swelling structure of polymer brushes bearing phosphorylcholine (PC) and cholinephosphate (CP) groups in aqueous solution were investigated by scanning probe microscopy and neutron reflectivity measurements. The CP-type polymer brushes formed collapsed structure in the aqueous CaCl2 solution because the phosphate of CP, which is located outside the betaine unit, strongly interacts with calcium ions to form insoluble calcium phosphate. In contrast, no significant change was observed in the swollen thickness of the PC-type polymer brush in the aqueous CaCl2 solution.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 3","pages":"291-301"},"PeriodicalIF":2.3,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555237","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Control of surface structure and properties by side chain effects of polymers","authors":"Takuya Matsumoto","doi":"10.1038/s41428-024-00976-9","DOIUrl":"10.1038/s41428-024-00976-9","url":null,"abstract":"Polymer surfaces and interfaces have received much attention in industrial fields because of their functional properties, including appearance, surface protection, reflectivity, anti-fouling, water-repellency, anti-fogging, anti-icing, adhesion, and gas permeability/barrier characteristics. In addition, because polymer surfaces have notably different properties and dynamic behaviors from bulk materials, many academic researchers have been interested in and contributed to the research on polymer surfaces and interfaces in recent decades. The properties and structure at the polymer surface and interface strongly depend on the chemical structure, conformation, and dynamics of the polymer chains. In this review, the impacts of the structure and dynamics of designed polymer side chains on the surface and interface properties and their mechanism are described. In particular, the control of the molecular conformation and dynamics leads to their characteristic surface and interface properties. Polymer surfaces have notably different properties and dynamic behaviors from bulk materials. The properties and structure at the polymer surface and interface strongly depend on the chemical structure, conformation and dynamics of the polymer chains. In this review, the impacts of the structure and dynamics of designed polymer side chains on the surface and interface properties and their mechanism are described. In particular, the control of the molecular conformation and dynamics leads to their characteristic surface and interface properties.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 3","pages":"249-258"},"PeriodicalIF":2.3,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00976-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555231","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rates of increase and decrease for each block of poly(3-hydroxybutyrate)(P3HB)-b-poly(3-hydroxybutyrate-co-3-hydroxyvalerate)(P3HBV) and P3HBV-b-P3HB during biosynthesis by Ralstonia Eutropha","authors":"Takahiko Nakaoki, Haruto Nakamura, Ren Yashita","doi":"10.1038/s41428-024-00989-4","DOIUrl":"10.1038/s41428-024-00989-4","url":null,"abstract":"The number-average molecular weights (Mns) of the first and second blocks of the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P3HBV)-b-poly(3-hydroxybutyrate) (P3HB) and P3HB-b-P3HBV block copolymers biosynthesized from Ralstonia eutropha were investigated. Pentanoic acid and glucose were used as carbon sources for the biosynthesis of the blocks of P3HBV and P3HB, respectively. The cultivation time for the first carbon source was fixed at 72 h, and that for the second carbon source was varied. The first and second blocks for P3HBV-b-P3HB and P3HB-b-P3HBV showed a decrease and increase in the Mn, respectively; this indicates that degradation and polymerization proceeded at the initial end of the first block and at the other end of the second block, respectively. In the biosynthesis of P3HBV-b-P3HB, the rates of decrease and increase in the Mn for the P3HBV and P3HB blocks were 9.0 × 103 and 2.9 × 104 g/(mol∙h), respectively. For P3HB-b-P3HBV, the rates of decrease and increase in the Mn were 2.6 × 103 and 2.0 × 103 g/(mol∙h) for P3HB and P3HBV, respectively. The number-average molecular weights (Mns) of the first and second blocks of the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P3HBV)-b-poly(3-hydroxybutyrate) (P3HB) and P3HB-b-P3HBV block copolymers biosynthesized from Ralstonia eutropha were investigated. The first and second blocks for both P3HBV-b-P3HB and P3HB-b-P3HBV showed a decrease and increase in the Mn, respectively; this indicates that degradation and polymerization proceeded at the initial end of the first block and at the other end of the second block, respectively.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 3","pages":"327-334"},"PeriodicalIF":2.3,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555224","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reversible modulation of polymer chain mobility by selective cage opening and closing of pendant boratrane units","authors":"Akira Takahashi, Masahiro Yamanishi, Atsushi Kameyama, Hideyuki Otsuka","doi":"10.1038/s41428-024-00986-7","DOIUrl":"10.1038/s41428-024-00986-7","url":null,"abstract":"As a simple and versatile methodology for large modulation of polymer chain mobility, we report the selective opening and closing reactions of cage-shaped triethanolamine borate (TEAB) at polymer side chains and their effect on the thermal properties of the parent polymers. A series of TEAB-pendant polymethacrylates was synthesized by common free-radical polymerization using TEAB-containing methacrylate. Boron vertex removal from the pendant TEAB groups proceeded quantitatively via hydrolysis at room temperature to afford triethanolamine (TEA), an open cage structure. Differential scanning calorimetry revealed that the pendant TEAB/TEA interconversion induces a large variation in the glass transition temperature (Tg) of the parent polymers up to 166 °C, as a result of the contrasting conformational flexibility of the rigid TEAB and flexible TEA. Regeneration of the pendant TEAB group (cage closing) also proceeded in a highly selective manner by adding a commercially available borate ester to the TEA-pendant polymer. The mechanism underlying the high reaction selectivity was investigated using density functional theory calculations. The borated product showed a comparable Tg to that of the pristine TEAB-pendant polymer, demonstrating the efficiency of TEAB/TEA interconversion for reversible and large modulation of polymer chain flexibility. Selective opening and closing reactions of cage-shaped triethanolamine borate (TEAB) at polymer side chains and their effect on the thermal properties of the parent polymers are reported. The conversion of TEAB-pendant polymethacrylates into the triethanolamine (TEA) counterparts was quantitatively achieved by hydrolysis of the pendant TEAB groups. The side chain conversion resulted in a large variation in glass transition temperature (Tg). Regeneration of pendant TEAB group also proceeded in a highly selective manner and almost recover the original Tg, demonstrating the reversible and large modulation of polymer chain flexibility.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 3","pages":"259-268"},"PeriodicalIF":2.3,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00986-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Degradation of stable thermosetting epoxy resins mediated by bases in amide solvents","authors":"Yasunori Minami, Tomoo Tsuyuki, Hayato Ishikawa, Yoshihiro Shimoyama, Kazuhiko Sato, Masaru Yoshida","doi":"10.1038/s41428-024-00979-6","DOIUrl":"10.1038/s41428-024-00979-6","url":null,"abstract":"Thermosetting epoxy resins are widely used in our society for adhesives, electronic devices, and building materials owing to their hardness and chemical stability; however, their robustness hinders their ability to chemically degrade to monomers and related low-molecular-weight molecules. Herein, we report the degradation of various thermosetting epoxy resins prepared from bisphenol A diglycidyl ether as a typical epoxy agent and various curing agents, such as diamino arenes, dithiols, and acid anhydrides. The degradation proceeded smoothly when sodium tert-butoxide was used as an activator in a 1,3-dimethyl-2-imidazolidinone solvent at 150 °C to form bisphenol A as a monomer precursor in high yields without any pretreatment. The proposed degradation method was successfully applied to cross-linked thermosetting epoxy resins derived from 4,4’-diaminodiphenylsulfone, a heat-resistant curing agent, commercially available adhesives, and carbon fiber-reinforced composite materials. When composite materials are used, the carbon fibers can be recovered intact. The degradation of various thermosetting epoxy resins prepared from bisphenol A diglycidyl ether as a typical epoxy agent and various curing agents, such as diamino arenes, dithiols, and acid anhydrides proceeded smoothly with sodium tert-butoxide in 1,3-dimethyl-2-imidazolidinone (DMI) solvent at 150 °C to form bisphenol A in high yields. Amide solvents effectively promoted depolymerization and allowed insoluble cross-linked thermosetting epoxy resins to undergo the reaction.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 2","pages":"149-162"},"PeriodicalIF":2.3,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00979-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143121602","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}