苯乙烯-双烯A交联共聚凝胶、溶胶的生成与转化

本文结合提取、凝胶色谱等方法测定了苯乙烯-双烯A交联共聚过程的转化率曲线。通过研究发现,凝胶在交联共聚一开始就产生,且整个反应过程都在不断地生成;转化率40％以前几乎无溶胶生成,此后生成的溶胶仍不断地向凝胶转化;刚生成溶胶时其分子量高、分布窄,其后分子量变低、分布变宽;T_g以上温度的热处理发生进一步聚合反应,当双烯A摩尔浓度<3.3×10~(-4)时,溶胶分数增加,A-MA摩尔浓度>5.0×10~(-4)时,凝胶分数增加,这是双烯A悬吊双键及单体苯乙烯进一步反应的结果。     

Effect of preparation conditions on the thermal stability of an epoxy-functional inorganic-organic hybrid material system doped with Zr

An inorganic-organic hybrid material system consisting of (3-glycidyloxypropyl)trimethoxysilane, dimethyldimethoxysilane and zirconium(IV) n-propoxide was prepared by the sol-gel method. The influence of processing parameters including Zr content, UV irradiation and sol ageing on the thermal stability of the resultant thin films was characterised by thermogravimetry. It was demonstrated that the crosslinking of epoxy groups in the structure was the primary reason for variation in the thermal stability of the system. As Zr and/or UV irradiation may be employed to crosslink the epoxy groups in the structure, the thermal stability of the system can be tuned by the optimal combination of these two crosslinking methods.     

Effect of gamma irradiation on ethylene–octene copolymers

Two ethylene–octene copolymers (POE) were irradiated with ⁶⁰Co gamma radiation and influence of irradiation atmosphere, absorbed dose and heat treatment of samples on the crosslinking were studied. Thermal properties and crystalline morphology of non-irradiated and irradiated POE were determined by using differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXS), respectively. The Charlesby–Pinner equation was used to describe the relationship between absorbed dose and sol fraction. The gel fraction of irradiated POE was lower and decreased with the increase of octene content when irradiated in oxygen, compared to irradiation in nitrogen atmosphere. The gel fraction increased significantly with the increasing of absorbed dose for the two copolymers. Heat treatment of samples prohibited the crosslinking of irradiated POE. The DSC results indicated that a subtle change of thermal properties of POE was observed before and after gamma irradiation at low dose. No change was found from the WAXS spectra of non-irradiated and irradiated POE. For heat-treating samples, the Charlesby–Pinner equation can not fit perfectly with the relationship between the sol fraction and absorbed dose, but it fits well with the crosslinking reaction of POE pellets.     

Review on the production process and uses of controlled rheology polypropylene—Gamma radiation versus electron beam processing

Controlled rheology polypropylene grades are established commodities in the polymer processing market. However, new types, mainly the so-called high melt strength polypropylene (HMSPP) grades, are being introduced in the last two decades and radiation processing has played an important role. The melt strength properties of a polymer increases with molecular weight and with long-chain branching due to the increase in the entanglement level. As polypropylene (PP) is a linear polymer, the way to improve its elongational viscosity is by the production of a bi-modal polymer. Basell's patents claim the production of long-chain branching on PP by irradiating with electrons under oxygen free atmosphere, followed by two heating steps to allow radical recombination and annihilation reaction. Some other companies have issued patents using electron beam processing, but so far there is no actual production other than the Basell one. As a result of a research joint effort, IPEN, BRASKEM (the biggest Brazilian polymer producer) and EMBRARAD (the major Brazilian radiation processing center) developed a new process to produce HMSPP based on gamma processing. This paper will address some characteristics of each technology and the main industrial opportunities.     

Preparation of the crosslinked polyethersulfone films by high-temperature electron-beam irradiation

The radiation-crosslinked polyethersulfone (RX-PES) films were prepared by means of electron-beam irradiation under nitrogen atmosphere at 230 °C, where the temperature is around the glass transition temperature of PES (222 °C). The gel formation of RX-PES films was observed when the absorbed doses exceeded 300 kGy, which indicated the crosslinking structure formation. The G(S) of 0.10 and G(X) of 0.23 were calculated according to the Y-crosslinking mechanism. The irradiation was also performed at ambient temperature for comparison. There was no gel formation of the irradiated films even for the absorbed doses as high as 2250 kGy. The thermal properties of the original and irradiated PES films were measured by means of DSC and TGA analyses. The chemical structure of the original and the irradiated films was analyzed by means of FT-IR ATR and UV-vis spectroscopies.     

Electron-beam irradiation on poly(propylene carbonate) in the presence of polyfunctional monomers

Poly(propylene carbonate) (PPC) showed predominantly degradation under electron-beam irradiation, accompanied by deterioration of its mechanical performance due to sharp decrease of the molecular weight. Crosslinked PPC was prepared by addition of polyfunctional monomer (PFM) to enhance the mechanical performance of PPC. When 8 wt% of PFM like triallyl isocyanurate (TAIC) was added, crosslinked PPC with a gel fraction of 60.7% was prepared at 50 kGy irradiation dose, which showed a tensile strength at 20 °C of 45.5 MPa, whereas it was only 38.5 MPa for pure PPC. The onset degradation temperature (T_i) and glass transition temperature (T_g) of this crosslinked PPC was 246 °C and 45 °C, respectively, a significant increase related to pure PPC of 211 °C and 36 °C. Therefore, thermal and mechanical performances of PPC could be improved via electron-beam irradiation in the presence of suitable PFM.     

Production and crosslinking of multi-layer tubes (PE & metal) by E-beam

Irradiation crosslinking of PE-tubes has been used for heating floors for about 25 years. Such tubes are also used today for drinking water supply. A further development has been the coating of such tubes with Ethylene-Vinyl-Alcohol-Copolymers (EVAL), in order to prevent oxygen diffusion into the water through the PE tube. For about 15 years composite tubes made of PE and aluminum have been available. These tubes are crosslinked with electron beams. The energy of the accelerated electrons must be adjusted for the particular tube configuration, so that the inner PE-layer will be crosslinked. This paper will concern itself with the manufacture and the crosslinking of composite tubes.     

New applications of 10 MeV electrons for reeled goods

Because of their high penetration capability, electron beams produced by 10 MeV machines are increasingly used for the sterilization processing of medical devices. Worldwide there are already more than 20 such machines in action for this purpose. But compared with electron beam sterilization, the physical crosslinking of plastic products with 10 MeV has not been as much investigated as in the range of low and medium energy. So the products with high wall thickness or big dimensions are still chemically crosslinked as the penetration and power of the beam of existing accelerators was not sufficient for those products. But now radiation crosslinking is possible also for higher dimensions of reeled goods due to higher beam power up to 150 kW, and one machine with different handling systems can be used for sterilization and modification of plastic products.

The aim of our work is to examine the homogeneous crosslinking of industrial products by a 10 MeV/150 kW electron beam as for instance for XLPE-c pipes and heat shrinkable tubes. Furthermore the uniformity of crosslinking especially along the roundness is measured, which is one of the essential quality characteristics.     

GHD室温自交联乳液的聚合及贮存稳定性

采用半连续种子乳液聚合技术合成了含甲基丙烯酸缩水甘油酯(GMA)、甲基丙烯酸羟乙酯(HEMA)和甲基丙烯酸二甲氨基乙酯(DMAEMA)的室温自交联乳液(GHD).实验结果表明,在甲基丙烯酸甲酯(MMA)-丙烯酸丁酯(BA)-GMA种子乳液存在下,聚合温度升高,聚合过程稳定性下降,但乳液的贮存稳定性提高;乳化单体滴加速度加快,种子聚合物的玻璃化温度升高,可减少聚合过程的交联凝聚作用,提高聚合过程的稳定性;而HEMA和DMAEMA用量增加对聚合过程的稳定性没有明显影响,但使乳液的贮存稳定性下降.官能团间的交联凝聚作用可能是影响室温自交联乳液聚合及贮存过程稳定性的关键因素.     

A novel method for monitoring chemical degradation of crosslinked rubber by stress relaxation under tension

This paper describes a novel test method for monitoring chemical degradation of a crosslinked rubber by stress relaxation under tension. An accelerated sulphur cured ethylene propylene diene rubber (EPDM) was subjected to stress relaxation under tension while exposing to 50% aqueous solution of nitric acid (HNO₃). An experimental set up was designed and built in-house for this purpose. The tensile test specimen was stretched to a constant elongation. The stress decay was monitored upon exposure to the harsh chemical. Stress decay was found much faster in the exposure media than in air. Decrosslinking was the main reason for quicker stress decay as observed by decrease in crosslink density. To compare, experiments were conducted by exposing similar specimens in the same exposure media under unstressed conditions. It was found that monitoring chemical degradation under given stressed condition yielded relatively quicker yet reliable and reproducible results.