聚甲基丙烯酸甲酯-丙烯酸酰胺嵌段共聚物的合成与表征

引发剂;苯胺;聚甲基丙烯酸甲酯-丙烯酸酰胺嵌段共聚物的合成与表征     

Low cost bifunctional initiators for bidirectional living cationic polymerization of olefins. I. isobutylene

We describe the discovery of novel low cost bifunctional initiators 2,4,7,9‐tetramethyl‐tricyclo[6.2.0.0³⁶]deca‐1(8),2,6‐triene‐4,9‐diol (bBCB‐diOH) and 4,9‐dichloro,2,4,7,9‐tetramethyl‐tricyclo[6.2.0.0³⁶]deca‐1(8),2,6‐triene (bBCB‐diCl), for living cationic bidirectional polymerization of olefins, for example, isobutylene. bBCB‐diOH was quantitatively synthesized in one step by UV radiation of commercially available diacetyl durene (DAD) and bBCB‐diCl by hydrochlorination of bBCB‐diOH. These molecules, in conjunction with TiCl₄ coinitiator, initiate the living polymerization of isobutylene. Livingness was demonstrated by linear conversion versus molecular weight (MW) plots and narrow MW distributions. Polymerizations are slower than those initiated by the universally used “hindered” bifunctional initiator 5‐tert‐butyl‐1,3‐bis(1‐chloro‐1‐methyl)benzene and are suitable for rate studies. Herein, we report the synthesis, by the use of bBCB‐diCl, of relatively low MW (M _n < 3000 g mol^?1) allyl‐telechelic polyisobutylene (PIB) used for the synthesis of PIB‐based polyurethanes and that of relatively high MW (M _n > 30,000) living PIB telechelics for the synthesis of thermoplastic elastomers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3716–3724     

Synthesis of poly(2‐vinyl pyridine)‐b‐poly(n‐hexyl isocyanate) amphiphilic coil‐rod block copolymer by anionic polymerization

A well‐defined amphiphilic coil‐rod block copolymer, poly(2‐vinyl pyridine)‐b‐poly(n‐hexyl isocyanate) (P2VP‐b‐PHIC), was synthesized with quantitative yields by anionic polymerization. A low reactive one‐directional initiator, potassium diphenyl methane (DPM‐K), was very effective in polymerizing 2‐vinyl pyridine (2VP) without side reactions, leading to perfect control over molecular weight and molecular weight distribution over a broad range of initiator and monomer concentration. Copolymerization of 2VP with n‐hexyl isocyanate (HIC) was carried out in the presence of sodium tetraphenyl borate (NaBPh₄) to prevent backbiting reactions during isocyanate polymerization. Terminating the living end with a suitable end‐capping agent resulted in a P2VP‐b‐PHIC coil‐rod block copolymer with controlled molecular weight and narrow molecular weight distribution. Cast film from a chloroform solution of P2VP‐b‐PHIC displayed microphase separation, characteristic of coil‐rod block copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 607–615, 2005     

提高烃类燃料热沉的研究进展

吸热型烃类燃料是一种热安定性好、可以利用其化学热沉的燃料,其热沉能够满足高超音速飞行的需要。本文论述了燃料热安定性、催化脱氢、催化裂解、引发裂解、超临界裂解等对吸热型烃类燃料热沉的影响,重点论述了引发裂解在吸热型烃类燃料中的裂解优势,提出引发裂解在高超音速飞行器上具有诱人的应用前景。     

γ-poly(glutamic acid) as an initiator of cationic polymerization of N-vinylcarbazole and N-vinyl-2-pyrrolidone

The cationic polymerization of vinyl monomers initiated by biosynthesized γ-poly(glutamic acid) (γ-PGA) powder surface was carried out in a heterogeneous system. It was found that the polymerization of N-vinylcarbazole (NVC) and N-vinyl-2-pyrrolidone (NVPD) is initiated by γ-PGA powder. The grafting of polymers onto γ-PGA surface was scarcely observed. The apparent activation energy of the polymerization of NVC and NVPD was estimated to be 20.2 and 24.8 kJ/mol, respectively. The polymerization was totally inhibited by the addition of triethylamine and pyridine, but not hydroquinone. The polymerization rate in nitrobenzene was larger than that in toluene. These results indicated the cationic nature of the polymerization. γ-PGA treated with KOH did not show the initiating activity of the polymerization. Therefore, carboxyl groups on γ-PGA powder surface play an important role in the initiation of the polymerization. It may be suggested that the polymerization is initiated by proton addition to monomer from carboxyl groups on γ-PGA powder surface and the propagation proceeds with carboxylate anion on the surface as counter ion. © 1993 John Wiley & Sons, Inc.     

Living radical polymerization of vinyl chloride initiated with iodoform and catalyzed by nascent Cu0/tris(2‐aminoethyl)amine or polyethyleneimine in water at 25 °C proceeds by a new competing pathways mechanism

The first example of living radical polymerization of vinyl chloride carried out in water at 25 °C is reported. This polymerization was initiated by iodoform and catalyzed by nascent Cu⁰ produced by the disproportionation of Cu^I in the presence of strongly Cu^II binding ligands such as tris(2‐aminoethyl)amine or polyethyleneimine. The resulting poly(vinyl chloride) was free of structural defects, had controlled molecular weight and narrow molecular weight distribution, contained two ～CHClI active chain ends, and had a higher syndiotacticity (62%) than the one obtained by conventional free‐radical polymerization at the same temperature (56%). This novel polymerization proceeds, most probably, by a combination of competitive pathways that involves activation by single electron transfer mediated by nascent Cu⁰ and degenerative chain transfer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3283–3299, 2003     

An efficient synthetic-route to prepare [2,3,6-tri-O-(2-bromo-2-methylpropionyl]-β-cyclodextrin)

The efficient approach for the synthesis of [2,3,6-tri-O-(2-bromo-2-methylpropionyl]-β-cyclodextrin) (21Br-β-CD) is described. The reaction between 2-bromoisobutyric bromide and β-cyclodextrin was performed directly in 1-methyl-2-pyrrolidione solvent, leading to much less complicated procedures and higher yield (up to 89.5%) compared with those reported previously (17% yield). The product is an extremely useful initiator in synthesizing star polymers with well-defined structures using atom transfer radical polymerization for biomedical applications.     

Modification of Polymer Substrates with Low Surface Free Energy Material by Low‐Temperature Cured Polybenzoxazine

The B‐ala/AIBN PBZ system has a high extent of ring‐opening of oxazine because phenol‐containing oligomers are formed at the early stage of the curing process. As a result, the B‐ala/AIBN PBZ system possesses a relatively stronger intramolecular hydrogen bonding and lower surface energy than the pure B‐ala system at low temperature curing. In this context, poly(4‐vinyl pyridine), poly(4‐vinyl phenol) thin films and polycarbonate substrates, which lack liquid resistance, possess low surface free energy after modification with B‐ala/AIBN = 5/1 PBZ.

     

Intramolecular chain reaction of artemisinin oxidation

The intramolecular chain oxidation of artemisinin was analyzed using the parabolic model. The competition of the mono- and bimolecular peroxy radicals formed from artemisinin was considered. Artemisinin is predominantly oxidized via the intramolecular chain mechanism to form polyatomic hydroperoxides. This results in the situation when, under aerobic conditions, artemisinin is transformed from the monofunctional into polyfunctional initiator with several hydroperoxide groups. The enthalpy was calculated, and the activation energies and rate constants of the intramolecular reactions of the artemisinin peroxy radicals, as well as those of their bimolecular reactions with C-H, S-H, and O-H bonds of biological substrates and their analogs, were calculated in the framework of the parabolic model. A new kinetic scheme for artemisinin oxidation was proposed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 267–275, February, 2008.     

Thermal stability and toughening of epoxy resin with polysulfone resin

The cure behavior, thermal stability, and mechanical properties of diglycidylether of bisphenol A (DGEBA)/polysulfone (PSF) blends initiated by 1 wt % N‐benzylpyrazinium hexafluoroantimonate as a cationic latent catalyst were investigated. The DGEBA/PSF content was varied within 100/0–100/40 wt %. Latent properties were studied through the measurement of the conversion as a function of the curing temperature, and the cure activation energy (E_a) was studied by the Kissinger method with a dynamic differential scanning calorimetry analysis. The thermal stabilities, largely based on the integral procedural decomposition temperature (IPDT) and decomposed activation energy (E_t), were investigated by the measurement of thermogravimetric analysis. For the mechanical properties of the casting specimens, the critical stress intensity factor (K_IC) test was performed, and their fractured surfaces were examined with scanning electron microscopy. E_a, IPDT, E_t, and K_IC increased with PSF increasing in the neat epoxy resin up to 30 wt %. However, there was a marginal decrease in the blend system in both the thermal and mechanical properties due to the phase separation between DGEBA and PSF. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 121–128, 2001