氟塑料-30的辐射交联

F-30—乙烯和三氟氯乙烯的一种交替共聚物,它在一定的条件下容易辐射交联。交联后的F-30其力学性能有显著提高。 关于F-30的分子量测定,还没有报道。我们利用Flory的弹性理论,在熔点以上测定了F-30的应力-应变曲线,计算得交联G值为1.4,根据Charlesby-Pinner关系式我们得到F-30的凝胶化剂量为1.6兆拉特,并由所得数据估算出F-30的重均分子量为2.1×10~5。     

聚偏氟乙烯的辐射交联及其交联度的XPS表征

本文首次用XPS研究了聚偏氟乙烯的辐射交联机理,交联度的XPS表征。计算出聚偏氟乙烯的β值为0.7,发现聚偏氟乙烯的辐射交联的溶胶分数与辐照剂量的关系符合我们提出的通式^[1]。用XPS方法求得聚偏氟乙烯的凝胶化剂量为1.59mrad。     

Spectroscopic evidence for radiation-induced crosslinking of poly(tetrafluoroethylene)

Direct spectroscopic evidence for radiation-induced crosslinking of poly(tetrafluoroethylene) (PTFE) is presented for all x-ray and electron dose levels above which it is possible to distinguish between deliberately introduced radiation damage and the x-ray damage inherent in obtaining an x-ray photoelectron spectrum (XPS). The C (1s) spectrum obtained after irradiation with 2 keV electrons for all doses greater than 1 μA-min/cm² consists of a four-peak spectrum identical to that previously obtained for plasma-polymerized tetrafluoroethylene and assigned to carbon atoms with variable numbers of bound F atoms (CF₃, CF₂, CF₁, and CF₀). X-ray irradiated PTFE can be fitted with the same four-peak spectrum. At or below an electron dose level of 1 μA-min/cm², the radiation damage is comparable to that produced by the x-ray dose necessary to obtain an XPS spectrum. The CF₁ and CF₀ components increase with increasing electron dose, and at high electron doses dominate the spectrum. With increasing dose the CF₃ component approaches a constant value while both the CF₂ component and the total F : C ratio decreases. These four components are those expected to result from radiation-induced crosslinking reactions of the polymer and are consistent with previous suggestions that crosslinking is the basis of radiation patterned adhesion to PTFE. © 1993 John Wiley & Sons, Inc.     

辐照聚甲苯硫醚的研究

用电子束在室温室气中对聚甲苯硫醚（ＰＭＰＳ）进行了辐照．用ＸＰＳ、ＩＲ、ＤＳＣ和ＴＧ对辐射交联及伴随的化学变化进行了表征．结果表明，ＰＭＰＳ的辐射交联发生在苯环上，ＸＰＳ能用于高聚物交联的表征．     

辐射交联顺-1,4-聚丁二烯的网络结构特性和力学性能

本文根据Flory的溶胀理论和橡胶弹性理论,考察了顺-1 4-聚丁二烯辐射交联产物的化学网络和物理缠结网络结构特性及其对固体力学性能的影响。结果表明,交联产物的物理缠结网络密度远远大于化学交联网络密度。随着辐照剂量的增大,化学交联密度增高,物理缠结数下降。探讨了交联、缠结密度与Mooney-Rivlin方程的常数项C_1和C_2的关系。C_1来自化学交联网络的贡献;C_2来自物理缠结的贡献。物理缠结网络主要贡献于交联物体在小形变下的起始弹性模量G_0;化学交联网络则主要贡献于交联物体在大形变下的非线性弹性,即断裂强度(?)_B。     

Crsslinking effect of ultrahigh molecular weight polyethylene-low molecular weight polyethylene blend films produced by gelation/crystallization from solutions

Polyethylene-polyethylene blend films were prepared by gelation/crystallization from semidilute solution by using ultrahigh molecular-weight (mw) polyethylene (UHMWPE) (mw=6×10⁶) and low molecular weight polyethylene (LMWPE) (mw=4×10⁴). The UHMWPE/LMWPE compositions chosen were 50/50, 67/33, and 91/9. Elongation was carried out in a hot oven at 115–130°C. The drawn films were exposed to an electron beam under nitrogen flow. Radiation doses chosen were 10, 20, 40, and 100 Mrad. crosslinking caused a significant effect in improving high temperature resistance for the blend film with draw ratio of 20 in the case of irradiation doses less than 20 Mrad. The elongation beyond 20 times and high doses beyond 20 Mrad hampered the crosslinking effect and the specimens were easily torn manually. This is thought to be due to the fact that the excess irradiation dose causes main chain scission apart from crosslinking.     

RADIATION CROSSLINKING OF BRANCHED POLY (VINYL ACETATE)

In the present work, radiation crosslinking of different branched poly (vinyl acetate) have beemstudied and the validity of the relationship between sol fraction and radiation dose: R(S+S~(1/2)=1/U_(1qo)+p′_o/q_oR~βto branched poly(vinyl acetate) have been assured.     

Radiation-induced degradation of polyethylene: Role of amorphous region in the formation of oxygenated products and the mechanical properties

Quenched samples of linear low density, medium density and two kinds of high density polyethylene films were irradiated with γ-rays from a ⁶⁰Co source in vacuum and in air at room temperature with irradiation doses ranging from 0 to 100 Mrad. On irradiation in vacuum the extent of crosslinking was about one-and-a-half times greater in the linear low density polyethylene (LLDPE) than in the high density polyethylene (HDPE). On the other hand, irradiation in air produced more crosslinking in high density polyethylene (HDPE). Growth of trans-vinylene unsaturation was found around 10 Mrad in all the samples. Initial increase in elongation and breaking strength (below 5 Mrad) occurred, which was followed by a decrease with increasing dose. LLDPE showed some elongation even at 50 Mrad, while the other samples became brittle and broke at doses far below this value. The mechanism of oxidative degradation is discussed.     

新型絮凝剂F－717对抗生素M－90发酵液预处理研究

本文设计了九种有机、无机絮凝剂对新抗Ｍ—９０发酵液预处理的方法研究，探索了以新型絮凝剂Ｆ－７１７与ＺｎＳＯ４、ＡｌＣｌ３等各种絮凝剂的加入量对发酵液滤速，光密度与效价的关系。     

COORDINATION CROSSLINKING OF NITRILE RUBBER FILLED WITH COPPER SULFATE PARTICLES

By incorporating copper sulfate(CuSO_4)particles into acrylonitrile butadiene rubber(NBR)followed by heat pressing,a novel vulcanization method is developed in rubber through the formation of coordination crosslinking.This method totally differs from traditional covalent or non-covalent vulcanization approaches of rubber.No other vulcanizing agent or additional additive is involved in this process.By analyzing the results of DMA,XPS and FT-IR,it is found that the crosslinking of CuSO_4 particles filled NBR was induced by in situ coordination between nitrogen atoms of nitrile groups (-CN)and copper ions(Cu~(2 ))from CuSO_4.SEM and EDX results revealed the generation of a core(CuSO_4 solid particle)- shell(adherent NBR)structure,which leads to a result that the crosslinked rubber has excellent mechanical properties. Moreover,poly(vinyl chloride)(PVC)and liquid acrylonitrile-butadiene rubber(LNBR)were used as mobilizer to improve the coordination crosslinking of CuSO_4/NBR.The addition of PVC or LNBR could lead to higher crosslink density and better mechanical properties of coordination vulcanization.In addition,crystal water in CuSO_4 played a positive role to coordination crosslinking of rubber because it decreased the metal point of CuSO_4 and promoted the metal ionization.     

Swelling behaviors of polyelectrolyte hydrogels containing sulfonate groups

Series of maleate monoester and diester monomers based on poly(ethylene glycol) monomethyl ether (MPEG) were copolymerized using the ionizable 2‐acrylamido‐2–methyl propane sulfonic acid (AMPS) via different dose rate of electron‐beam irradiation (40–150 kGy). The crosslinking of the copolymers were carried out in aqueous acidic solutions at pH 1 or in the presence of 1% N,N‐methylene bisacrylamide (MBA) as crosslinking agent. The final equilibrium water content and swelling capacities for the prepared hydrogels were determined in aqueous solutions at pH 1, 6.8, and 12 and in aqueous salt solutions at 298 K. Swelling equilibria for prepared hydrogels were determined in different molar salt solutions of NaCl, KCl, CaCl₂, Na₂SO₄, K₂SO₄, and CaSO₄. The swelling ratios of gels in pure water and in the salt solutions were found to depend on the counterion species in the increasing sequence of Ca²⁺, Na⁺ and K⁺. Copyright © 2002 John Wiley & Sons, Ltd.     

EFFECT OF IRRADIATION TEMPERATURE ON GENERAL EQUATION OF SOL FRACTION-DOSE RELATIONSHIP FOR FLUOROPOLYMERS

In this paper, the effect of irradiation temperature on sol fraction-dose relationship of tluoropolymers was studied. It was found that the increasing of irradiation temperature can result in the decreasing of βvalue of fluoropolymer, which increases the crosslinking probability of fluoropolymer. The relationship between crosslinking parameter βand irradiation temperature (T_i)of fluoropolymer is established as follows:β=2.2×10~(-3) T_g+4×10~(-4)(T_g-T_i)+0.206.values of some tluoropolymers calculated from the above expression are in agreement with the experimental values.     

Pluronic F-127: An Efficient Delivery Vehicle for 3-(1'-hexyloxy)ethyl-3-devinylpyropheophorbide-a (HPPH or Photochlor)

To determine the impact of delivery vehicles in photosensitizing efficacy of HPPH, a hydrophobic photosensitizer was dissolved in various formulations: 1% Tween 80/5% dextrose, Pluronic P-123 and Pluronic F-127 in 0.5%, 1% and 2% phosphate buffer solutions (PBS). HPPH was also conjugated to Pluronic F-127, and the resulting conjugate (PL-20) was formulated in PBS. Among the different delivery vehicles, only Pluronic P-123 displayed significant vehicle cytotoxicity, whereas Pluronic F127 was nontoxic. Compared to PL-20, HPPH formulated in Tween80 and Pluronic F-127 showed higher cell-uptake, but lower long-term retention in Colon26 cell compared to PL-20. The higher retention of PL-20 was similarly observed during in vivo uptake with BALB/c mice baring Ct26 tumors. In contrast to the in vitro uptake experiments, PL-20 showed slightly higher uptake compared to HPPH formulated in Tween or Pluronic-F127. A significant difference in pharmacokinetic profile was also observed between the HPPH-Pluronic formulation and PL-20. Under similar in vivo treatment parameters (drug dose 0.47 µmol kg⁻¹, light dose: 135 J cm⁻² at 24 h post-injection of PS), HPPH formulated either in Tween or Pluronic F-127 formulation showed similar in vivo PDT efficacy (20–30% tumor cure on day 60), whereas PL-20 showed 40% tumor cure (day 60).     

过硫酸铵水溶液对聚乙烯表面作用的研究

本文利用X光电子能谱(XPS)及其它技术对过硫酸铵水溶液处理聚乙烯表面改进粘合性的作用机理进行了研究。结果表明,过硫酸铵的氧化作用使聚乙烯表面引入酮、醛、羧基等含氧基团,使其粘合强度显著提高。高密度聚乙烯表面的氧化深度小于40,低密度聚乙烯的均匀氧化深度在40—90之间。处理后的聚乙烯表面未发现明显的交联产物。     

Solid-State Photochemical [2+2] Cycloaddition Reaction of MnII Complexes

Three Mn^II complexes have been synthesized under similar experimental conditions. Of these [Mn₂(benzoate)₄(L)₂] (where L=4-styrylpyridine or 4spy, 1 and 2-fluoro-4′-styrylpyridine or 2F-4spy, 3 ) are paddlewheel complexes, but crystallized in different space groups. Whereas [Mn₂(benzoate)₄(3F-4spy)₄] (3F-4spy=3-fluoro-4′-styrylpyridine), 4 is a dinuclear complex having different stoichiometry from 1 and 3 with two pairs of 3F-4spy ligands aligned in face-to-face manner. An irreversible phase transition occurs from the space group P2₁/c to C2/c when 1 was heated up to 125 °C to 2 in a single-crystal-to-single-crystal fashion or when ground 1 to powder. 2 is isomorphous and isostructural to 3 . Complimentary π–π interactions in head-to-tail alignment of the styrylpyridine ligands furnishes 1D aggregates in 1 – 3 which are congenial to undergo [2+2] cycloaddition reaction under UV light. Whereas, face-to-face alignment of the 4spy pairs in 4 is expected to provide a head-to-head photoproduct. All the Mn^II complexes are indeed found to be photoreactive. To our surprise, contrary to their Zn^II analogues, 2 and 3 were not found to be photosalient. The percentage volume expansion during the photoreaction as determined from the density measurements, was found to be too low (3.2 and 4.6 % respectively for 2 and 3 ) to have this behavior.     

Dendritic polymers based on poly(ethylene glycol) -co- poly(glycolic acid) -co- methacrylate and 2.0 G -polyamidoamine- metharylamide: Design, characterization, and in vitro degradation, and drug release properties

In this paper, the properties of the complete degradation process of newly synthesized multi-block 2.0 G-polyamidoamine-double bond (PAMAM-DB) and resoluble poly (ethylene glycol) -co- poly (glycolic acid) -co- methacryloyl chloride (PEG-co-PGA-co-DB, 4KG5-DB) macromonomers were reported. Rectangular shaped samples were prepared by crosslinking the components using both chemical and photo initiators and exposure to UV light. The aims of the study were to examine the effects of the vitro degradation and drug delivery of the crosslinking group on the properties of photocrosslinked hydrogels. The experimental variable was PAMAM-DB: 4KG5-DB ratio. The effects of this variable on local PH, water uptake, mass loss, and drug release were explored. Polymers were characterized by ¹H NMR, ¹³C NMR, FT-IR, and SEM. Our study revealed that polymers with 40%, 50%, 60% 4KG5-DB (mass fraction) showed more excellent mechanical properties, 40% also showed outstanding vitro degradation properties. In vitro drug release, however, 60% drug released mechanism seemed to approach the Fickian diffusion and possessed more excellent drug release properties compared with formulation 40% and 50%. In general, an increase ratio of 4KG5-DB led to a higher density of tree-like polymer which resulted in slower of degradation and drug release. Incorporation of 4KG5-DB into the polymer was critical for maintaining integrity and increasing hydrophilicity during degradation. These results obtained suggest that this system could be potential as a material for bone replacement and controlled delivery of drugs.     

EFFECT OF GAMMA RAYS IN THE PREPARATION OF POLYMER AND HYDROGEL FROM ACRYLAMIDE MONOMER

The formation of polymer and hydrogel from aqueous solutions having 20, 30 and 40% concentrations ofacrylamide monomer by γ-ray irradiation processing in the dose range 0.06-30 kGy using a Co-60 source and theircharacterization have been observed. Polymer conversion and gel fraction are found to depend on radiation doses. Polymerconversion increases with the increase of dose, depending on the solution concentration, where maximum conversion isachieved at 0.18, 0.16 and 0.10 kGy for 20%, 30% and 40% concentrations, respectively. On the other hand, gel fractionincreases with dose from the gel point (0.12 kGy) for all concentrations, where 100% conversion of gel occurs at doses≥5 kGy. Tensile strength, viscosity and molecular weight (M_w) of polymer samples increase with both the dose and theconcentration, showing a high value of M_w up to≈10~8. Swelling of hydrogels under water with respect to time varies due tothe variation of cross-linking density formed in the gels and the maximum swelling mainly occurs within 24 h. A remarkable change of surface morphology reveals characteristic features of monomer, polymer and hydrogel films.     

PMMA-PEO共混体系的辐射交联

<正> 聚甲基丙烯酸甲酯(PMMA)是典型的辐射裂解型聚合物。经辐照后,PMMA主链发生无规断裂。在聚合物共混体系中,PMMA是否能发生交联,这是辐射化学中一个非常重要的研究课题之一,也是一项探索性工作。 PMMA-PEO共混体系是可以分子水平共溶的体系。本文试图将共混体系的相容性与共混体系中的裂解型聚合物的辐射效应联系起来,讨论PMMA-PEO共混体系的辐射交联。     

Optimal method for preparing sulfonated polyaryletherketones with high ion exchange capacity by acid-catalyzed crosslinking for proton exchange membrane fuel cells

Sulfonated polyaryletherketones (SPAEK) bearing four sulfonic acid groups on the phenyl side groups were synthesized. The benzophenone moiety of polymer backbone was further reduced to benzydrol group with sodium borohydride. The membranes were crosslinked by acid-catalyzed Friedel-Crafts reaction without sacrifice of sulfonic acid groups and ion exchange capacity (IEC) values. Crosslinked membranes with the same IEC value but different water uptake could be prepared. The optimal crosslinking condition was investigated to achieve lower water uptake, better chemical stability (Fenton's test), and higher proton conductivity. In addition, the hydrophilic ionic channels from originally course and disordered could be modified to be narrow and continuous by this crosslinking method. The crosslinked membranes, CS4PH-40-PEKOH (IEC = 2.4 meq./g), reduced water uptake from 200 to 88% and the weight loss was reduced from 11 to 5% during the Fenton test compared to uncrosslinked one (S4PH-40-PEK). The membrane showed comparable proton conductivity (0.01–0.19 S/cm) to Nafion 212 at 80°C from low to high relative humidity (RH). Single H₂/O₂ fuel cell based on the crosslinked SPAEK with catalyst loading of 0.25 mg/cm² (Pd/C) exhibited a peak power density of 220.3 mW/cm², which was close to that of Nafion 212 (214.0 mW/cm²) at 80°C under 53% RH. These membranes provide a good option as proton exchange membrane with high ion exchange capacity for fuel cells.     

Synthesis of [18F]F-γ-T-3, a Redox-Silent γ-Tocotrienol (γ-T-3) Vitamin E Analogue for Image-Based In Vivo Studies of Vitamin E Biodistribution and Dynamics

Vitamin E, a natural antioxidant, is of interest to scientists, health care pundits and faddists; its nutritional and biomedical attributes may be validated, anecdotal or fantasy. Vitamin E is a mixture of tocopherols (TPs) and tocotrienols (T-3s), each class having four substitutional isomers (α-, β-, γ-, δ-). Vitamin E analogues attain only low concentrations in most tissues, necessitating exacting invasive techniques for analytical research. Quantitative positron emission tomography (PET) with an F-18-labeled molecular probe would expedite access to Vitamin E’s biodistributions and pharmacokinetics via non-invasive temporal imaging. (R)-6-(3-[¹⁸F]Fluoropropoxy)-2,7,8-trimethyl-2-(4,8,12-trimethyltrideca-3,7,11-trien-1-yl)-chromane ([¹⁸F]F-γ-T-3) was prepared for this purpose. [¹⁸F]F-γ-T-3 was synthesized from γ-T-3 in two steps: (i) 1,3-di-O-tosylpropane was introduced at C6-O to form TsO-γ-T-3, and (ii) reaction of this tosylate with [¹⁸F]fluoride in DMF/K₂₂₂. Non-radioactive F-γ-T-3 was synthesized by reaction of γ-T-3 with 3-fluoropropyl methanesulfonate. [¹⁸F]F-γ-T-3 biodistribution in a murine tumor model was imaged using a small-animal PET scanner. F-γ-T-3 was prepared in 61% chemical yield. [¹⁸F]F-γ-T-3 was synthesized in acceptable radiochemical yield (RCY 12%) with high radiochemical purity (>99% RCP) in 45 min. Preliminary F-18 PET images in mice showed upper abdominal accumulation with evidence of renal clearance, only low concentrations in the thorax (lung/heart) and head, and rapid clearance from blood. [¹⁸F]F-γ-T-3 shows promise as an F-18 PET tracer for detailed in vivo studies of Vitamin E. The labeling procedure provides acceptable RCY, high RCP and pertinence to all eight Vitamin E analogues.