Synthesis and characterization of the biodegradable polycaprolactone-graft-chitosan amphiphilic copolymers

A novel synthetic approach to biodegradable amphiphilic copolymers based on poly (epsilon-caprolactone) (PCL) and chitosan was presented, and the prepared copolymers were used to prepare nanoparticles successfully. The PCL-graft-chitosan copolymers were synthesized by coupling the hydroxyl end-groups on preformed PCL chains and the amino groups present on 6-O-triphenylmethyl chitosan and by removing the protective 6-O-triphenylmethyl groups in acidic aqueous solution. The PCL content in the copolymers can be controlled in the range of 10-90 wt %. The graft copolymers were thoroughly characterized by H-1 NAM, C-13 NMR, FT-IR and DSC. The nanoparticles made from the graft copolymers were investigated by H-1 NMR, DLS, AFM and SEM measurements. It was found that the copolymers could form spherical or elliptic nanoparticles it? water. The amount of available primary amines on the surface of the prepared nanoparticles was evaluated by ninhydrin assail, and it can be controlled by the grafting degree of PCL.

聚（ε-己内酯）泡沫塑料制备与性能研究

随着人们环保意识的普遍提高，可生物降解材料已经成为了世界范围的研究热点。开展可生物降解高分子泡沫塑料的结构与性能的研究，对以可生物降解的高分子泡沫塑料替代不能生物降解的泡沫塑料，遏制白色污染，保护生态环境，具有重要的科学价值和社会意义。本工作选用聚（ε-己内醋）（PCL）为原料，通过辐射方法引发PCL交联，提高其熔体粘度和强度；以AC为发泡剂，制备PCL泡沫材料：添加无机纳米粒子-碳酸钙，进一步提高PCL的发泡倍率。研究辐射剂量、凝胶含量、分子量、AC发泡剂含量、碳酸钙含量等因素对制备泡沫塑料的影响，优化组合，获得PCL泡沫材料。主要研究结果如下：1．采用辐照交联的方法实现了PCL的交联，凝胶含量最高可达到41％；2．交联后的PCL热稳定性略有下降，结晶性能基本没有变化。但是，抗张性能变化很大，弹性模量提高（260MPa-430MPa），断裂伸长率下降（1500％-30％）。由此推测，提高了PCL的熔体强度；3．制备出了PCL泡沫塑料，发泡倍率可控制在2-12范围内。其中，发泡倍率与发泡剂含量、PCL分子量关系密切。当辐照计量大于5Mrad后，辐照计量对发泡倍率影响不大，但是，对泡孔的结构影响很大，即辐照剂量大，得到的泡孔直径小；4．体系中添加CoCO_3使得PCL的发泡倍率进一步提高，最高可达到15倍，并且使泡孔数量增加，体积减小。添加30wt％碳酸钙，PCL泡沫塑料的孔径为147μm，单位体积泡孔数为29.6*10~8cell/cm~3，壁厚4.48μm。

Blends of Poly(lactic acid) with Thermoplastic Acetylated Starch

Blends of poly(lactic acid)(PLA) and thermoplastic acetylated starch(ATPS) were prepared by means of the melt mixing method. The results show that PLA and ATPS were partially miscible, which was confirmed with the measurement of T-g by dynamic mechanical analysis(DMA) and differrential scanning calorimetry(DSC). The mechanical and thermal properties of the blends were improved. With increasing the ATPs content, the elongation at break and impact strength were increased. The elongation at break increased from 5% of neat PLA to 25% of the blend PLA/ATPS40. It was found that the cold crystallization behavior of PLA changed evidently by addition of ATPS. The cold crystallization temperature(T-cc) of each of PLA/ATPS blends was found to shift to a lower temperature and the width of exothermic peak became narrow compared with that of neat PLA.

Effect of gamma-radiation on the thermal and mechanical properties of a commercial poly(butylene adipate-co-terephthalate)

BACKGROUND: Poly(butylene adipate-co-terephthalate) (PBAT) has attracted wide interest as a biodegradable polymer. However, its use is restricted in certain applications due to its low melting point.RESULTS: PBAT was treated using gamma-radiation. The radiation features were analyzed using Soxhlet extraction, and the ratio of chain scission and crosslinking and gelation dose were determined using the classical Charlesby-Pinner equation. The results showed that PBAT is a radiation-crosslinkable polymer. The degree of crosslinking increased with increasing radiation dose; the relation between sol fraction and dose followed the Charlesby-Pinner equation. Differential scanning calorimetry analyses showed that the melting temperature (T-m) and the heat of fusion (Delta H-m) of PBAT exhibited almost no change in the first scan. The second scan, however, showed a decrease in T-m and Delta H-m. The glass transition temperature of irradiated PBAT increased with increasing radiation dose.

Effect of peroxide crosslinking on thermal and mechanical properties of poly(epsilon-caprolactone)

Poly(epsilon-caprolactone) (PCL), a saturated polyester, derived from ring-opening polymerization of epsilon-caprolactone, was chemically crosslinked with various amounts of benzoyl peroxide (BPO) by a two-step method by first evenly dispersing the BPO into the PCL matrix and then crosslinking at elevated temperature. The gel fraction increased with an increase in BPO content. The modified Charlesby-Pinner equation was used to calculate the ratio of chain scission and crosslinking. The results showed that both scission and crosslinking occurred, and that crosslinking predominated over scission. The number-average molecular weight between the crosslinks determined by the rubber elasticity theory using the hot set test showed a decrease with increasing BPO content. The melting temperature and crystallinity decreased with an increase in BPO content, and the crystallization temperature increased after crosslinking. Dynamic mechanical analysis results showed a decrease in the glass transition temperature as a result of chemical crosslinking of PCL. This was explained by the observed reduction in crystallinity and the increase in free volume due to restrictions in chain packing.

Thermal and mechanical properties of poly(epsilon-caprolactone) crosslinked with gamma radiation in the presence of triallyl isocyanurate

Poly(epsilon-caprolactone) was crosslinked by gamma radiation in the presence of triallyl isocyanurate. The influence of gamma-radiation crosslinking on the thermal and mechanical properties of poly(epsilon-caprolactone)/triallyl isocyanurate was investigated. Differential scanning calorimetry analyses showed differences between the first and second scans. Dynamic mechanical analysis showed an increase in the glass-transition temperature as a result of the radiation crosslinking of poly(epsilon-caprolactone). Thermogravimetric analysis showed that gamma-radiation crosslinking slightly improved the thermal stability of poly(epsilon-caprolactone). The 7 radiation also strongly influenced the mechanical properties. At room temperature, crosslinking by radiation did not have a significant influence on the Young's modulus and yield stress of poly(E-caprolactone). However, the tensile strength at break and the elongation at break generally decreased with an increase in the crosslinking level. When the temperature was increased above the melting point, the tensile strength at break, elongation at break, and Young's modulus of poly(epsilon-caprolactone) were also reduced with an increase in the crosslinking level. The yield stress disappeared as a result of the disappearance of the crystallites.

Crosslinked poly (epsilon-caprolactone) initiated by benzoyl peroxide

Poly(epsilon-caprolactone) (PCL) was chemically crosslinked with various amounts of benzoyl peroxide (BPO) The effect of BPO contents, crosslinking temperature and time on the crosslinking reaction was studied. The thermal, mechanical, and biodegradable properties of crosslinked PCL were also examined by DSC and DMA etc. The results showed that the melting temperature, crystallinity and glass transition temperature decreased with increase in BPO contents, while the crystallization temperature increased with increase in BPO content. The Young's modulus and elongation at break generally decreased with increase in BPO content. Moreover, the crosslinked PCL still had biodegradable ability.

Synthesis and crystallization behaviors of poly(styrene-b-isoprene-b-epsilon-caprolactone) triblock copolymers

The triblock copolymers, poly(styrene-b-isoprene-b-epsilon-caprolactone)s (PS-b-PI-b-PCL) have been synthesized successfully by combination of anionic polymerization and ring-opening polymerization. Diblock copolymer capped with hydroxyl group, PS-b-PI-OH was synthesized by sequential- anionic polymerization of styrene and isoprene and following end-capping reaction of EO, and then it was used as macro initiator in the ring-opening polymerization of CL. The results of DSC and WAXD show big effect of amorphous PS-b-PI on the thermal behaviors of PCL block in the triblock copolymers and the lower degree of crystalline in the triblock copolymer with higher molecular weight of PS-b-PI was observed. The real-time observation on the polarized optical microscopy shows the spherulite growth rates of PCL27, PCL328 and PS-b-PI-b-PCL344 are 0.71, 0.46 and 0.07 mu m s(-1), respectively. The atomic force microscopy (AFM) images of the PS90-b-PI66-b-PCL-(28) show the columns morphology formed by it's self-assembling.

Poly(L-lactide)/starch blends compatibilized with poly(L-lactide)-g-starch copolymer

The poly(L-lactide) (PLLA)/starch blends were prepared by the PLLA grafting starch (PLLA-g-St) copolymers as a compatibilizer, and their thermal, mechanical and morphological characterizations were performed to show the better performance of these blends compared to the virgin PLLA/starch blend without the compatibilizer, including PLLA crystallinity, interfacial adhesion between the PLLA matrix and starch dispersive phases, mechanical test, medium resistance, and contact angle. The 50/50 composite of PLLA/starch compatibilized by 10% PLLA-g-St gave a tensile strength of 24.7 MPa and an elongation at break of 8.7%, respectively, vs. 11.3 MPa and 1.5%, respectively, for the simple 50/50 blend of PLLA/starch.