An analysis of the role of nonreactive plasticizers in the crosslinking reactions of a rigid resin

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multiple components. Using a combination of infrared spectroscopy, thermal analysis, and low field NMR, we have elucidated the role of a new class of nonreactive plasticizers on the crosslinking reaction between hexamethylenetetramine (HMTA) and phenol formaldehyde resin. These two seemingly dissimilar reactants are responsible for the exceptionally high mechanical strength in a number of organic–inorganic composites. The efficiency of the curing reaction is characterized by the changing functionality of HMTA. Infrared active vibrations are used to characterize the changing molecular structures as a function of temperature. The T₁ spin‐lattice relaxation time is used for the characterization of segmental dynamics of the chains in the formation of the crosslinked product. The segmental mobility depends on the amount of crosslinking and the stiffness of the chain. This study shows that this new class of nonreactive plasticizer can induce highly crosslinked structures without any of the environmental impact of the current technology. An efficient crosslinking reaction in phenolic resin can be achieved by using methyl benzoate as a nonreacting plasticizer. Low field NMR, in conjunction with infrared spectroscopy (mid and near) and DSC, clarified the crosslinking reaction mechanism and the ensuing structure. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 206–213     

Synthesis of polymers bearing 1,3‐benzoxazine moiety in the side chains from poly(allylamine) and their crosslinking behaviors

A polymer bearing 1,3‐benzoxazine moiety in the side chain was synthesized successfully from poly(allylamine) based on a stepwise strategy consisted of three steps: (1) treatment of poly(allylamine) with salicylaldehyde to convert the amino group in the side chain into the corresponding o‐(iminomethyl)phenol moiety, (2) reduction of the o‐(iminomethyl)phenol to obtain the corresponding o‐(aminomethyl)phenol moiety, and (3) formation of 1,3‐benzoxazine moiety by the reaction of the o‐(aminomethyl)phenol with formaldehyde. The content ratio of benzoxazine moieties and o‐(aminomethyl)phenol moieties in the polymer were tunable by varying amount of formaldehyde. The presence of o‐(aminomethyl)phenol moieties exhibited a significant promoting effect on the crosslinking reaction. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Facile synthesis,characterization, and potential applications of two kinds of polymeric pH indicators: Phenolphthalein formaldehyde and o‐cresolphthalein formaldehyde

Two kinds of applicable polymeric pH indicators were synthesized by the reaction of phenolphthalein and o‐cresolphthalein with formaldehyde under alkaline conditions by a one‐pot method. The synthesized products were fully characterized with Fourier transform infrared, ¹H NMR, ultraviolet–visible spectroscopy, and gel permeation chromatography. The results indicated that the reaction was a typical phenol formaldehyde reaction. The dosage of formaldehyde and the reaction time were well controlled to obtain soluble polymers, instead of crosslinked products. The polymeric‐pH‐indicator‐immobilized poly(vinyl alcohol) (PVA) membranes were easily fabricated and had good long‐term stability under highly basic conditions and a fast equilibrium response. Moreover, the phenolphthalein formaldehyde immobilized PVA membrane had a linear response from pH 10.0 to 14.0, and so it has promise as a optical transducer for high pH value determinations. The o‐cresolphthalein formaldehyde immobilized PVA membrane had a nonlinear response from pH 9.0 to 13.0. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1019–1027, 2005     

高邻位高分子量热塑性酚醛树脂研制

改变传统合成工艺,在高温高压无催化剂条件下,合成了无金属杂质的高邻位高分子量热塑性酚醛树脂。考察了苯酚与甲醛加成缩合反应过程中原料种类、原料配比、反应温度及反应压力等因素对酚醛树脂结构性能的影响。通过软化点测试仪、核磁共振谱仪等研究了酚醛树脂合成过程中各个参数对酚醛树脂结构性能的影响。在酚／醛比为1：0．7,210℃、...     

Functionalization of polymeric surfaces by simple photoactivation of C?H bonds

A universal photoassisted pathway to functionalize polymeric surfaces is presented by transferring the inert surface sp³ C? H bonds into reactive groups, such as ? SO₃H, ? NH₂, ? SH, and ? COOH. The proposed method uses acetone as photoinitiator and different phenols with a para substituent XR as the reactants. Acetone excited by UV irradiation acts as a pair of scissors cutting both the surface C? H bonds of the polymer substrate and the O? H bonds of phenol, leading to the formation of carbon‐centered surface chain free radicals and oxygen‐centered phenoxy free radicals. By coupling of these two radicals, a variety of functional X groups with an R spacer from XR species of different phenol reactants were readily bonded to the polymeric surfaces, where phenol reactants included 4‐hydroxylbenzene sulfonic acid for ? SO₃H, p‐aminophenol and tyramine for ? NH₂, 4‐hydroxythiophenol for ? SH, and tyrosine for ? COOH. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and crosslinking behavior of a novel linear polymer bearing 1,2,3‐triazol and benzoxazine groups in the main chain by a step‐growth click‐coupling reaction

The click‐coupling reaction was applied to polycondensation, to synthesize a high‐molecular weight prepolymer having benzoxazine moieties in the main chain. For the polycondensation, a bifunctional N‐propargyl benzoxazine was synthesized from bisphenol A, propargylamine, and formaldehyde. The propargyl group was efficiently used for the copper(I)‐catalyzed alkyne‐azide “click” reaction with p‐xylene‐α,α′‐diazide, to give the corresponding linear polycondensate having 1,2,3‐triazole junctions. The polycondensation proceeded in N,N‐dimethylformamide (DMF) at room temperature. By this highly efficient “click‐” polycondensation reaction, the benzoxazine ring in the monomer was successfully introduced into the polymer main chain without any side reaction. The obtained polymer (=prepolymer) underwent thermal crosslinking to afford the corresponding product, which was insoluble in a wide range of organic solvents and exhibited higher thermal stability than the polymer before crosslinking. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2316–2325, 2008     

木质素对酚醛/木质素嵌段共聚树脂制备的影响及反应机理

以工业木糖生产残渣为原料, 用不同条件下碱提取得到的碱木质素液与苯酚和甲醛原位反应制备酚醛/木质素嵌段共聚树脂. 以所制备树脂中甲醛释放量最小为原则, 得到木质素的最佳提取条件: 碱浓度5%(质量分数), 固液体积比1:12, 反应时间3 h. 在此条件下树脂中甲醛释放量为0.115%, 相应的胶合强度为1.197 MPa, 均远优于GB/T14074-2006中对于一类胶合板用酚醛胶的要求(甲醛释放量≤0.3%, 胶合强度≥0.7 MPa). 实验结果表明, 碱木质素液能参与到反应中, 提高酚醛/木质素嵌段共聚树脂的热稳定性及胶合强度, 降低甲醛释放量, 有利于树脂的储存及应用. 同时讨论了碱木质素与苯酚和甲醛的可能反应机理.     

2-Oxo-2-polyfluoroalkylethane-1-sulfones and -sulfamides in the Biginelli and ‘retro-Biginelli’ reactions

2-Oxo-2-polyfluoroalkylethane-1-sulfones and -sulfamides react with aryl aldehydes and urea under Biginelli reaction conditions to yield 4-hydroxy-4-polyfluoroalkyl-5-sulfonyl-6-aryl-tetrahydropyrimidinones. The latter compounds on reaction with hexamethylenetetramine (HMTA) under thermal conditions undergo ‘retro-Biginelli’ reaction involving replacement of the 6-aryl substituent of the pyrimidinone cycle with a hydrogen atom donated by HMTA. Hexamethylenetetramine was employed for the first time in place of formaldehyde in the reported one-step Biginelli protocol for the synthesis of fluorinated sulfonyl-containing 6-unsubstituted tetrahydropyrimidinones.     

Synthesis and properties of a deuterated phenolic resin

A highly deuterated novolac‐type phenolic resin was prepared by polycondensation of deuterated phenol and formaldehyde using oxalic acid as an acid catalyst. The polycondensation of deuterated monomers and the formation of the highly deuterated phenolic resin were confirmed by the gel permeation chromatography, IR, and ¹H NMR analyses. With the exception of hydroxyl groups, the degree of deuteration was estimated to be more than 98%. The polymer conformation in THF solution was evaluated by the scaling exponent of the Mark–Houwink–Sakurada equation. The exponent of the deuterated phenolic resin is 0.26 in THF at 40 °C and is close to that of a nondeuterated phenolic resin, which suggests that phenolic resins behave like a compact sphere irrespective of deuteration. The curing behavior of the deuterated phenolic resin with hexamethylenetetramine was confirmed by differential scanning calorimetry analysis. The cured highly deuterated phenolic resin exhibits a lower incoherent neutron scattering background than that of the nondeuterated phenolic resin, which suggests that the former is suitable for matrix resins with low incoherent backgrounds for small‐angle neutron scattering studies of thermosetting resins. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Isobutylene‐rich macromonomers: Dynamics and yields of peroxide‐initiated crosslinking

New isobutylene‐rich elastomers bearing multiple pendant styrenic, acrylic, maleimidic, vinylic, and allylic functional groups have been prepared and examined in the context of peroxide‐initiated crosslinking. Halide displacement from brominated poly(isobutylene‐co‐isoprene) (BIIR) by the requisite carboxylate nucleophiles in homogeneous toluene solutions provide the desired esters in quantitative yield without complications from dehydrohalogenation or premature crosslinking. Heating the resulting macromonomers with dicumyl peroxide to 160 °C under solvent‐free conditions gives thermoset derivatives, with reaction rates and yields depending markedly on functional group structure. In general, high cure extents can only be achieved using highly reactive pendant functional groups, owing to the competitive balance between crosslinking through C?C oligomerization, and degradation through β‐scission of backbone macroradical intermediates. Independent control of crosslinking rates and cure extents is gained through the use of nitroxyl radical traps bearing acrylate functionality. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 123–132     

Structure–property relationship in high urethane density polyurethanes

The structure–property relationship of polyurethane (PU) homopolymers synthesized by the stoichiometric combination of 1,6‐hexamethylene diisocyanate (HDI) and low‐molecular‐weight glycols with different structure is investigated by the analysis of PU elastic modulus obtained by means of high‐resolution peak force atomic force microscopy. Different experimental techniques are employed to understand the role of block structure influence on hydrogen bonding distribution, crystallinity, thermal transitions, and crystal packaging within the PU. The results show that glycols with bulky side groups have more impediments to self‐assemble into hydrogen‐bonded and packed macromolecular structures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 739–746     

One‐pot synthesis of terpolymers with long l‐lactide rich sequence derived from propylene oxide,CO2, and l‐lactide catalyzed by zinc adipate

We report here an efficient one‐port synthesis of terpolymers from PO, CO₂, and l ‐lactide (LLA) with long LLA rich sequence using the cheapest zinc adipate as catalyst. The copolymerizations were carried out under various experimental conditions to find out the optimal conditions. The terpolymer yields increase significantly from 151 to 417 (g polymer per g zinc) by the introduction of LLA as a third monomer. The polycarbonate moiety selectivity increases by nearly 60% at relatively high polymerization temperature (80 °C). Moreover, the differences in reaction kinetic of polycarbonate and polyester moieties were observed by in situ infrared monitoring. As confirmed by XRD and DSC, the synthesized terpolymers are a kind of semicrystalline polymer in which the crystalline PLA segment function as strong noncovalent crosslinking domains. Consequently, it exhibits much better thermal properties as well as remarkable higher mechanical strength compared with amorphous polycarbonate PPC. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1734–1741     

Flame‐retardant epoxy resins from o‐cresol novolac epoxy cured with a phosphorus‐containing aralkyl novolac

A novel phosphorus‐containing aralkyl novolac (Ar‐DOPO‐N) was prepared from the reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) first with terephthaldicarboxaldehyde and subsequently with phenol. The chemical structures of the synthesized compounds were characterized with Fourier transform infrared, ¹H and ³¹P NMR, and elemental analysis. Ar‐DOPO‐N blended with phenol formaldehyde novolac was used as a curing agent for o‐cresol formaldehyde novolac epoxy, resulting in cured epoxy resins with various phosphorus contents. The epoxy resins exhibited high glass‐transition temperatures (159–177 °C), good thermal stability (>320 °C), and retardation on thermal degradation rates. High char yields and high limited oxygen indices (26–32.5) were observed, indicating the resins' good flame retardance. Using a melamine‐modified phenol formaldehyde novolac to replace phenol formaldehyde novolac in the curing composition further enhanced the cured epoxy resins' glass‐transition temperatures (160–186 °C) and limited oxygen index values (28–33.5). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2329–2339, 2002     

硼酸与甲阶酚醛树脂的配位反应及配合物的结构

本文通过对溶液pH值的测定和外光谱分析，研究了硼酸与甲阶酚醛树脂的配位反应。结果表明：在室温下硼酸能与甲阶酚醛树脂中的羟基发生配位反应，并产生H^ 使溶液的pH值降低；溶液的酸性强弱与甲阶酚醛树脂中的羟甲基含量和硼酸的用量有关；硼酸以硼酸根离子的形式与树脂中的酚羟基和邻位羟甲基发生配位反应，形成了一个含有两个氧原子和一个硼原子的六元环，使甲阶酚醛树脂发生交联。     

Liquid crystalline supramolecular crosslinked polymer complexes of ditopic rylenebisimides and P4VP

Perylenebisimide and naphthalenebisimide (PBI‐PDP and NBI‐PDP) end functionalized with pentadecyl phenol is designed as ditopic hydrogen bonding acceptors to form supramolecular crosslinked network with poly(4‐vinyl pyridine) (P4VP). The pristine PBI‐PDP has been grown as single crystals from DCM‐MeOH (dichloromethane‐methanol) mixture at room temperature, which revealed a P21 space group. Noticeably, the pentadecyl alkyl chain shields the aromatic perylene core on both sides resulting in the absence of π–π interaction in single‐crystal assembly. The naphthalenebisimide derivative exhibits thermotropic liquid crystalline behavior, while both the molecules exhibits lyotropic liquid crystalline phases in tetrahydrofuran (THF), which were characterized using a combination of differential scanning calorimeter, X‐ray diffraction, and polarized light microscopy. The hydrogen‐bonded complex of both the rylenebisimides with P4VP preserves the mesomorphic properties in THF. The electron transport mobility measured by space charge limited current measurements reveals a two orders of magnitude increase in the charge transport in the P4VP complex compared to that of the pristine molecule. The average electron mobility obtained is μ _e,avg: 10^?3 cm²/Vs for P4VP‐PBI compared to μ _e,avg: 10^?5 cm²/Vs for pristine PBI derivative. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 951–959     

Assembled Organoruthenium(II) for Formaldehyde Decomposition and Hydrogen Production

Formaldehyde decomposition is not only an attractive method for hydrogen production, but also a potential approach for gaseous formaldehyde removal. In this research, we prepare some assembled organoruthenium through coordination reaction between Ru(p-Cymene)Cl₂ and bridge-linking ligands. It is a creative approach for Ru(p-Cymene)Cl₂ conversion into heterogeneous particles. The rigidity of bridge-linking ligand enables assembled organoruthenium to have highly ordered crystalline structure, even show clear crystal lattice with spacing of 0.19 nm. XPS shows the N−Ru bond are formed between bridge-linking ligand and Ru(p-Cymene)Cl₂. The assembled organoruthenium has high abundant active sites for formaldehyde decomposition at low temperature. The reaction rate could increase linearly with temperature and formaldehyde concentration, with a TOF of 2420 h⁻¹ at 90 °C. It is promising for gaseous formaldehyde decomposition in wet air or nitrogen. Formaldehyde conversion is up to 95 % over Ru-DAPM is 4,4′-diaminodiphenylmethane at 90 °C in air. Gaseous formaldehyde decomposition is a two-steps process under oxygen-free condition. Firstly, formaldehyde dissolve in water, and be converted into hydrogen and formic acid through formaldehyde-water shift reaction. Then intermediate formic acid will further decompose into hydrogen and carbon dioxide. We also find formaldehyde decomposition is a synergetic catalysis process of oxygen and water in moist air. Oxygen is conducive to formic acid desorption and decomposition on the active sites, so assembled organoruthenium exhibit slightly higher conversion for formaldehyde decomposition in moist air. This work proposes a distinctive method for gaseous formaldehyde decomposition in the air, which is entirely different from formaldehyde photocatalysis or thermocatalysis oxidation.     

The Reaction Mechanism of the Transetherification and Crosslinking of Melamine Resins

Melamine formaldehyde resins (MFR) are well known resins in the wood board and paper coating market. Etherified MFR's are applied as crosslinkers in the automotive coating industry. In Europe the growth of the market and the research activities are relatively small. On the other side in comparison to other polymers outstanding properties are possible to realize. So the development of new melamine ether resins (MER) was started. MER is a partly methylolated and fully etherified resin with a highly stable “thermoplastic” processing range. The MER's themselves are transparent granulates with enough stability for storage and transport. The crosslinking reaction can be started either by thermal or acidic catalytic activation, without losses of formaldehyde. Transetherifications with oligomeric diols can lead to more elastic and higher molecular melamine polyether resin (MPER) structures. The reaction mechanism and the crosslinking kinetics of the partly methylolated melamine ethers of methanol in comparison to the fully methylolated hexamethylol melamine ether will be discussed in this paper.     

Temperature‐dependent changes in the hydrogen bonded hard segment network and microphase morphology in a model polyurethane: Experimental and simulation studies

Hydrogen bonding between hard segments has a critical effect on the morphology and properties of polyurethanes. Influence of temperature on hydrogen bonded urethane network and melting behavior of a model semicrystalline segmented polyurethane was investigated by experiments and simulations. Polyurethane was synthesized by the stoichiometric reaction between p‐phenylene diisocyanate and poly(tetramethylene oxide) (PTMO) with a molecular weight of 1000 g/mol. Simulations were carried out using dissipative particle dynamics (DPD) and molecular dynamics (MD) approaches. Experimental melting behavior obtained by various techniques was compared with simulations. DPD simulations showed a room temperature microphase morphology consisting of a three‐dimensional hydrogen‐bonded urethane hard segment network in a continuous and amorphous PTMO matrix. The first‐order melting transitions of crystalline urethane hard segments observed during the continuous isobaric heating in DPD and MD simulations (340–360 K) were in reasonably good agreement with those observed experimentally, such as AFM (320–340 K), WAXS (330–360 K), and FTIR (320–350 K) measurements. Quantitative verification of the melting of urethane hard segments was demonstrated by sharp discontinuities in energy versus temperature plots obtained by MD simulations due to substantial decrease in the number of hydrogen bonds above 340 K. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 182–192     

Retracted: Effective and Green One‐Pot Multicomponent Synthesis of Novel Derivatives of 4H‐Pyrans in the Presence of Hexamethylenetetramine as Catalyst in Water Medium

Hexamethylenetetramine (HMTA) catalyzes synthesis of new polyfunctionalized 4H‐pyrans by reaction of aromatic aldehyde, malononitrile, and β‐keto esters via one‐pot three‐component procedure in water medium. Addition of reactants was performed by two methods led to achieve similar results. Using HMTA in catalytic amount not only represents the economic face of the reaction, but also due to the use of water, a green and safe reaction condition is organized. Thus, the current strategy provides the benefits of high productivity, convenient operation, and environmental friendliness. Structure of all products was proved by elemental analysis, IR, ¹H‐NMR, and ¹³C‐NMR spectroscopy.     

Studies of the formation of thermosetting resins. XII. Computer simulation of the reactions of phenols with formaldehyde

The mechanism of the reaction of phenols with formaldehyde was studied by computer simulation. At first starting molecules were stored in a computer and the hypothetical reaction yielded conditions like the reactivity ratio of hydroxymethyl group to formaldehyde and that of orthohydrogen to parahydrogen. The molecular weight distribution of the hypothetical product in the computer was compared with that of the prepared resin determined from GPC measurement. Reaction mechanisms were discussed. We also confirmed, by computer simulation, that the rate of methylenation is larger than that of hydroxymethylation in an acid-catalyzed system and that the reactivity ratio of hydroxymethyl group to formaldehyde is 5–12 for the reaction of phenols such as o-cresol, p-cresol, and phenol with formaldehyde. The opposite results were obtained in a base-catalyzed system. It also became apparent that information regarding molecular structures, such as the number of branches, the number of phenolic nuclei in the longest chain, and the number of o,o′-,o,p′- and p,p′-methylene linkages, can be obtained by computer simulation. The most probable values of these factors for 10 mer of a phenol–formaldehyde condensation molecule are 2, 7, 2, 5, and 2.