立构三嵌段聚丁二烯的合成及其加氢产物的性能

用α -甲基萘锂作为双官能团引发剂 ,通过丁二烯在环己烷中进行负离子聚合 ,达到一定转化率后 ,加入极性改性剂 ,继续聚合至结束 ,合成了不同嵌段比的 1,2 - 1,4 - 1,2立构三嵌段聚丁二烯 ,并用三异丁基铝及 2 -乙基己酸钴作为加氢催化剂 ,制备了氢化立构嵌段聚丁二烯。考察了不同极性改性剂及其用量和聚合温度对聚丁二烯微结构的影响 ,分析表征了立构嵌段聚丁二烯及氢化物。结果表明 ,当引发剂用量一定时 ,极性改性剂 /引发剂的摩尔比越大 ,1,2 -链节摩尔分数越高 ;当加入极性改性剂时 ,1,2 -链节摩尔分数随聚合温度的降低而增加 ,1,2 -嵌段的生成宜控制在 0℃ ;立构三嵌段聚丁二烯的相对分子质量分布很窄 ,且存在 2个玻璃化转变温度。氢化物的结晶度为 30 % ,为 (1-丁烯 -乙烯 - 1-丁烯 )三嵌段共聚物 ,呈现热塑性弹性体的行为 ;当其特性黏数大于 2 0dL·g-1,且聚1-丁烯的质量分数为 2 0 %～ 6 0 %时 ,其力学性能较好。     

High density polyethylene/ultra high molecular weight polyethylene blend. II. Effect of hydroxyapatite on processing,thermal, and mechanical properties

Hydroxyapatite (HA) is part of bone mineral composition. Several attempts have been made to incorporate HA into high density polyethylene (HDPE) to produce bone replacement biomaterials since neat HDPE is not suitable as bone replacement. The blending of HDPE with ultra high molecular weight polyethylene (UHMWPE) up to 50% by weight was performed with the aim of improving the toughness of composites. Reinforcement of blend with HA of up to 50% by weight was carried out. Methods of characterizing the composites included density, differential scanning calorimetry, thermal gravimetric analysis, ash content, and morphological examination using scanning electron microscope. For the mechanical properties of the composites, tensile, flexural, and impact tests were carried out. Incorporation of HA into HDPE has resulted in the brittleness of the composites. Blending of HDPE with UHMWPE in the presence of HA was found to improve the mechanical properties and promote a ductile failure of the resulting composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3931–3942, 2006     

An FTIR spectroscopic study of the photodegradation and thermal degradation of wool

The effect of sunlight on untreated, sulphamic acid-treated and FBA-treated wool has been investigated using infra-red spectroscopy coupled with second-derivative spectral analysis. The effect of heat on untreated and treated wool fabrics has also been studied. Changes in the oxidised cystine species were observed as a result of both thermal oxidation and photo-oxidation.     

DSC study on the thermal properties of sunflower proteins according to their water content

The use of sunflower protein isolate for the manufacturing of biodegradable materials by thermomechanical means requires a characterization of its thermal properties. After modelling of its hydration properties, DSC analysis shows a relaxation phenomenon at 60°C and makes it possible, despite the changes in state of the absorbed water, to determine its glass transition temperature. The evolution of this temperature according to the water content of the samples is then modelled and compared to that of more common proteins.     

Thermoplastic elastomeric hydrogenated styrene-butadiene elastomer: Optimization of reaction conditions,thermodynamics, and kinetics

Thermoplastic elastomeric hydrogenated styrene—butadiene (HSBR) elastomer was prepared by diimide reduction of styrene-butadiene rubber in the latex stage. The products were characterized by infrared, ¹H-NMR, ¹³C-NMR spectroscopy, and differential scanning calorimetry (DSC). The standard free energy change, ΔG⁰ at 298°K is −44.7 × 10⁴ kJ/mol, indicating that the formation of HSBR is thermodynamically feasible. The value of heat change of the reaction at constant volume, ΔU_T is −41.6 × 10⁴ kJ/mol. The effect of different reaction parameters on the level of hydrogenation, calculated from nuclear magnetic resonance spectroscopy, was also investigated. The degree of hydrogenation increases with the increase in reaction time, temperature, the concentration of reactants and catalyst. A maximum of 94% hydrogenation was obtained under the following conditions: time, 4 h; temperature, 45 ± 2°C; pH, 9.36; cupric sulphate (CuSO₄ · 5H₂O) catalyst concentration, 0.0064 mmol; hydrazine concentration, 0.20 mol; and hydrogen peroxide concentration, 0.26 mol. The diimide reduction of SBR is first-order with respect to olefinic substrate, and the apparent activation energy is 9.5 kJ/mol. The glass transition temperature increases with the increase in saturation level due to development of crystalline segments. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1151–1162, 1997     

LDPE/PEG插层剥离改性氮化硼导热复合材料的制备及其性能

以聚乙二醇(PEG)为插层剂,通过机械球磨法制备了PEG插层剥离改性氮化硼.以低密度聚乙烯(LDPE)为基体,PEG插层剥离改性氮化硼为导热填料,采用双辊开炼、压片成型制备LDPE/PEG插层剥离改性氮化硼导热复合材料,研究了改性氮化硼用量及粒径对复合材料导热性能、力学性能和电绝缘性能的影响.结果表明:随着PEG插层剥...     

DSC法对阳离子染料可染共聚酯热性能的研究

利用差示扫描量热法(DSC)对阳离子染料可染共聚酯即高温高压型(CDP)及常压沸染型(ECDP)的熔融和结晶过程进行了研究。结果表明:无定形CDP的玻璃化转变温度(T_g)、冷结晶温度(T_(ch))高于PET,但其熔点(T_m)低于PET,无定形ECDP的T_g与T_m低于PET和CDP,且随第四单体聚乙二醇(PEG)的含量及相对分子质量((?)_n)的增加而降低,其结晶速率随PEG的(?)_n及含量的增加而增加。对于等温结晶的共聚酯,1,3-间苯二甲酸双羟乙酯-5-磺酸钠(SIPE)的引入及PEG含量的增加,共聚酯的熔融焓(△H_m)及T_m下降;当PEG含量相同时,随PEG (?)_n增加,ECDP的△H_m及T_m均增加。     

Synthesis and characterization of phosphonate and aromatic-based polynorbornene polymers derived from the ring opening metathesis polymerization method and investigation of their thermal properties

In the present study, phosphonate ester, phosphonic acid, and aromatic (phenyl, naphthalene, anthracene) groups containing polymers were synthesized by the ROMP method to analyze thermal properties of these polymers. Thermal stability of the synthesized polymers is tested by thermal gravimetric analysis under nitrogen, air, and microscale combustion calorimetry analysis. Analysis shows that thermal behavior is directly related to the phosphorus level in the copolymer series. All the polymers are thermally stable under nitrogen and air up to 900 °C. Synergistic charring effect under air was observed between aromatic groups and phosphonic acid functionality in the copolymer series. Anthracene units have a greater potential to form carbonaceous char than the naphthalene and phenyl units. Phosphonate ester and naphthalene units bearing copolymers (P3A) gave 8.13% char yield at 900 °C under air. Phosphonic acid derivatives of this polymer, P3D, gave a highest char residue of 17.15% under the same condition. The introduction of phosphonate and phosphonic acid in each copolymer series is also beneficial in reducing the peak heat release rate (PHRR). Cleavage of the phosphonate ester bearing homopolymer (P4) to phosphonic acid (P4A) causes a sharp decrease in the PHRR ratio from 274 to 28.2 W/g. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47085.     

LLDPE/LDPE blends. I. Rheological,thermal, and mechanical properties

Structure and mechanical properties were studied for the binary blends of a linear low density polyethylene (LLDPE) (ethylene‐1‐hexene copolymer; density = 900 kg m⁻³) with narrow short chain branching distribution and a low density polyethylene (LDPE) which is characterized by the long chain branches. It was found by the rheological measurements that the LLDPE and the LDPE are miscible in the molten state. The steady‐state rheological properties of the blends can be predicted using oscillatory shear moduli. Furthermore, the crystallization temperature of LDPE is higher than that of the LLDPE and is found to act as a nucleating agent for the crystallization of the LLDPE. Consequently, the melting temperature, degree of crystallinity, and hardness of the blend increase rapidly with increases in the LDPE content in the blend, even though the amount of the LDPE in the blend is small. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3153–3159, 1999     

Preparation and properties of ester or cyano group substituted ring-opening polymers and their hydrogenated derivatives

Ester or cyano substituted tetracyclo [4.4.0.1^2,5.1^7,10]dodec-3-enes (1) were synthesized and their metathesis ring-opening polymerization was examined. The tungsten-based ternary catalyst system polymerized them very well. The polymers showed high glass transition temperatures (T_g) and no evidence of crystallization (e.g., the T_g of the polymer derived from 8-methyl-8-methoxycarbonyl substituted monomer (1a) was 207°C, and colorless transparent films could be casted from the solution of the polymer). The stability of these high T_g polymers were too unstable, so practical thermal molding methods could not be applied to them. The hydrogenation of these polymers with a palladium catalyst decreased T_g and greatly increased thermal stability. The physical and thermal properties of the hydrogenated polymers were thoroughly investigated. Monomer 1 was successfully copolymerized with other cyclic olefins. The resultant copolymers were hydrogenated, giving thermally stable polymers. In all cases examined in this study, a decrease of T_g by hydrogenation was about 35°C, regardless of the monomer structure. These results indicate that the main-chain mobility is the major contribution to the decrease of T_g. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 367–375, 1997     

自增强HDPE棒材的结构及力学性能

通过扫描电子显微镜、差示扫描量热法、广角X射线衍射分析与力学性能测试,研究了自增强高密度聚乙烯(HDPE)棒材微观结构特点和力学性能。结果表明,自增强HDPE棒材呈现明显的皮芯结构,表皮的结晶度高达75．88％,芯部的组织和结构与普通注塑试样最相近;与普通HDPE试样相比,自增强HDPE棒材的微晶尺寸和结晶度大幅提高,晶面间距几乎未变化,内部存在大量的微纤结构。制备的自增强HDPE棒材的拉伸强度和弯曲强度分别为220．6 MPa和152．9 MPa,均为未增强试样的近10倍。     

Synthesis and properties of hydrogenated natural rubber

A series of hydrogenated natural rubbers, HNRs, were prepared by homogenous hydrogenation using H₂ gas with a rhodium catalyst (chlorotris(triphenylphosphine)rhodium) in toluene. The HNRs were linear polymers with molecular weights greater than 800,000. These rubbers were vulcanized using sulfur and peroxide compounds. Vulcanized 100% HNR has a low glass transition temperature (T_g = ?43°C) and excellent abrasion resistance, and is resistant to oxidation and ozonolysis ageing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3957–3963, 2007     

Crystallization and melting behavior of HDPE in HDPE/teak wood flour composites and their correlation with mechanical properties

The nonisothermal crystallization behavior and melting characteristics of high‐density polyethylene (HDPE) in HDPE/teak wood flour (TWF) composites have been studied by differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD) methods. Composite formulations of HDPE/TWF were prepared by varying the volume fraction (?_f) of TWF (filler) from 0 to 0.32. Various crystallization parameters evaluated from the DSC exotherms were used to study the nonisothermal crystallization behavior. The melting temperature (T_m) and crystallization temperature (T_p) of the composites were slightly higher than those of the neat HDPE. The enthalpy of melting and crystallization (%) decrease with increase in the filler content. Because the nonpolar polymer HDPE and polar TWF are incompatible, to enhance the phase interaction maleic anhydride grafted HDPE (HDPE‐g‐MAH) was used as a coupling agent. A shift in the crystallization and melting peak temperatures toward the higher temperature side and broadening of the crystallization peak (increased crystallite size distribution) were observed whereas crystallinity of HDPE declines with increase in ?_f in both DSC and WAXD. Linear correlations were obtained between crystallization parameters and tensile and impact strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Differences in the molecular weight and the temperature dependences of self-diffusion and zero shear viscosity in linear polyethylene and hydrogenated polybutadiene

Within the context of a generalized coupling model we can support the hypothesis that, while the mode of relaxation for self diffusion (D) and shear flow (η) are the same, the entanglement interactions are different. We assume that there are two distinct coupling parameters n_D and n_η for self diffusion and shear flow respectively. The model predicts the molecular weight and temperature dependences to be scaled by the relevant coupling parameters as:

for melts with Arrhenius temperature dependences. We have found that n_n=0.43 and 0.42 for polyethylene (PE) and hydrogenated polybutadiene (HPB) which scale η as M^3.5 and M^3.4. Also the apparent flow activation energies $\text{E1}{}_{\mathrm{a}}$ of 6.35 kcal mole^?1 for PE and 7.2 kcal mol^?1 for HPB scale to primitive activation energies E_a of 3.6 and 4.2 kcal mole^?1 for PE and HPB respectively. On the other hand the M^?2 dependence of D results in n_D=1/3. Then the reported activation energies for self-diffusion in PE and HPB of 5.49 and 6.2 kcal mole^?1 scale to primitive activation energies of 3.7 and 4.1 kcal mole^?1, respectively.     

HDPE/LLDPE/POE薄膜性能的研究

采用线型低密度聚乙烯（LLDPE）和热塑性弹性体乙烯-辛烯共聚物（POE）对高密度聚乙烯（HDPE）薄膜进行改性,研究了LLDPE和POE对共混体系薄膜力学性能、加工性能的影响,探讨了LLDPE增强HDPE的机理。结果表明,加入一定量LLDPE,使HDPE／LLDPE薄膜的拉伸强度较纯HDPE薄膜有所增加,而单位冲击破损质量则有所下降。当w（LLDPE）为15％时,HDPE／LLDPE薄膜的拉伸强度提高21．6％,薄膜的单位冲击破损质量降低23．0％。在HDPE／LLDPE/POE三元体系中,当w（POE）,w（LLDPE）分别为10％,15％时,薄膜的拉伸强度、单位冲击破损质量、断裂伸长率比纯HDPE薄膜分别提高2．3％,113％。36．0％,综合性能良好。     

HDPE/PA 6/有机蒙脱土复合体系的结构及性能

采用熔融共混法制备高密度聚乙烯(HDPE)/聚酰胺(PA)6/有机蒙脱土(OMMT)多元复合材料,借助X射线衍射仪、扫描电子显微镜、透射电子显微镜等分析了OMMT对HDPE/PA 6体系结构、性能的影响及作用机理。加入的少量OMMT以剥离形态分散在基体中,能起到较好的增容作用,并且改善了材料的冲击性能。但OMMT的加入使材料的熔体流动速率降低,剪切黏度增大。     

合成橡胶常压氢化及产物性能

简介了合成橡胶的３种常压氢化方法：（１）用水溶性Ｗｉｌｋｉｎｓｏｎ催化剂在常压氢下使合成胶所合成胸乳在常压与氢化。指出第３种方法最有发展前景,用此方法除了可制备氢化度高的丁腈胶乳外,不可制备具有热塑性弹性体性质的氢化丁苯胶乳及氢化聚丁二烯胶乳;最后二者不经硫化即可用于制备老化的浸渍制品、涂料、粘接剂、复合垫片等。     

Solvothermal preparation and characterization of maleic anhydride grafting high density polyethylene copolymer

In this article, the grafting copolymerization of maleic anhydride (MAH) onto high density polyethylene (HDPE) was carried out through solvothermal process. Infrared spectra (IR) revealed that MAH had been successfully grafted onto the HDPE backbone. The influences of the reaction parameters on the grafting copolymerization, e.g., the concentration of the initiator, MAH and HDPE content, reaction time, reaction temperature, comonomer, and different solvents were also studied. Further studies found that MAH could be grafted onto HDPE in both good solvents and poor solvents, which was much different from the traditional solution grafting method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Evaluation of heat treatment regimes and their influences on the properties of powder‐printed high‐density polyethylene bone implant

A two‐step heat treatment was utilized as a means to improve the mechanical properties of a high‐density polyethylene structure which was fabricated using the three‐dimensional printing technique. It was found that the relationship between structure and properties was strongly influenced by heat treatment conditions including treatment times (15–60 min) and treatment temperatures (140–180 °C) of both primary and secondary steps. The use of primary heating at 180 °C for 15 min and secondary heating at 160 °C for 60 min resulted in the highest tensile modulus and strength, 0.7 GPa and 14.8 MPa, respectively. The changes in both shrinkage and tensile properties were governed by the level of residual porosity and quality of polyethylene interface in samples which were both influenced by the degree of thermally induced densification and binder degradation. Empirical correlations between porosity and shrinkage or tensile properties were found to be power functions. Copyright © 2010 Society of Chemical Industry     

Structure and properties of PP/POE/HDPE blends

This work was aimed to counteract the effect of ethylene‐α‐olefin copolymers (POE) by reinforcing the polypropylene (PP)/POE blends with high density polyethylene (HDPE) particles and, thus, achieved a balance between toughness and strength for the PP/POE/HDPE blends. The results showed that addition of HDPE resulted in an increasing wide stress plateau and more ductile fracture behavior. With the increase of HDPE content, the elongation at break of the blends increased rapidly without obvious decrease of yield strength and Young's modulus, and the notched izod impact strength of the blends can reach as high as 63 kJ/m² at 20 wt % HDPE loading. The storage modulus of PP blends increased and the glass transition temperature of each component of the blends shifted close to each other when HDPE was added. The crystallization of HDPE phase led to an increase of the total crystallinity of the blend. With increasing HDPE content, the dispersed POE particle size was obviously decreased, and the interparticle distance was effectively reduced and the blend rearranged into much more and obvious core‐shell structure. The fracture surface also changed from irregular striation to the regularly distant striations, displaying much obvious character of tough fracture. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011