化学扩链法/固相缩聚法对聚对苯二甲酸乙二醇酯的结晶与流变性能的影响EI北大核心CSCD

以异氰尿酸三缩水甘油酯(TGIC)为扩链剂,通过化学扩链法对聚对苯二甲酸乙二醇酯(PET)粒料进行预扩链,然后通过固相缩聚(SSP)法对预扩链产物实现进一步扩链改性。研究了扩链剂用量、固相缩聚温度和时间对扩链PET特性黏度、流变性能和结晶性能的影响。结果表明,当TGIC含量为1.0%时,预扩链产物的特性黏度最高,达到了0.84 d L/g。在随后的固相缩聚中,当反应温度为200℃,反应时间为3 h时,扩链PET的特性黏度达到最大值1.91 d L/g。固相缩聚后,扩链PET熔体表现出明显的剪切变稀现象,并且弹性在熔体中更占优势。同时,扩链PET的结晶度从30.7%降低至24.8%,结晶温度从191.6℃提高至212.7℃。     

化学扩链法/固相缩聚法对聚对苯二甲酸乙二醇酯的结晶与流变性能的影响

以异氰尿酸三缩水甘油酯(TGIC)为扩链剂,通过化学扩链法对聚对苯二甲酸乙二醇酯(PET)粒料进行预扩链,然后通过固相缩聚(SSP)法对预扩链产物实现进一步扩链改性。研究了扩链剂用量、固相缩聚温度和时间对扩链PET特性黏度、流变性能和结晶性能的影响。结果表明,当TGIC含量为1.0%时,预扩链产物的特性黏度最高,达到了0.84 d L/g。在随后的固相缩聚中,当反应温度为200℃,反应时间为3 h时,扩链PET的特性黏度达到最大值1.91 d L/g。固相缩聚后,扩链PET熔体表现出明显的剪切变稀现象,并且弹性在熔体中更占优势。同时,扩链PET的结晶度从30.7%降低至24.8%,结晶温度从191.6℃提高至212.7℃。     

反应挤出马来酸酐接枝聚甲基乙撑碳酸酯的结构与热性能

通过反应挤出制备马来酸酐接枝聚甲基乙撑碳酸酯(PPC-g-MA),采用红外光谱分析、滴定法、溶液黏度测试等方法表征了PPC-g-MA的结构,通过热重分析和稳态粘弹流变性能测试,研究了接枝物的热性能,分析了PPC-g-MA结构与热性能的关系。PPC-g-MA的红外谱图显示在1640cm-1处出现碳碳双键伸缩振动吸收峰,说明MA成功接枝到PPC主链上。MA添加量由0.5phr增加至5phr,PPC-g-MA的接枝率、特性黏度和热稳定性先提高后降低。当MA添加量为0.5phr时,PPC-g-MA的接枝率为0.224%,此时产物的初始分解温度(T-5%)比纯PPC升高了8.2℃,特性黏度提高了1.22,复数黏度降低10%所消耗的时间延长了1875s;当MA添加量增加到1phr时,PPC-g-MA的接枝率和T-5%同时达到最大值,分别为0.284%和264.8℃。研究表明当MA添加量低于1phr时,产物的接枝率和特性黏度高,可提高PPC热性能。     

亚磷酸三苯酯对聚乳酸/聚丁二酸丁二醇酯共混体系性能的影响EI北大核心CSCD

通过熔融共混法制备了不同含量亚磷酸三苯酯(TPPi)的亚磷酸三苯酯/聚乳酸(PLA)/聚丁二酸丁二醇酯(PBS)共混物,利用红外光谱、核磁共振、X射线衍射、熔体流动速率、流变性能和力学性能测试对TPPi/PLA/PBS共混体系的结构、结晶性能、流变性能和力学性能进行了研究。结果表明,TPPi主要作为酯化促进剂参与反应,共混体系的结构基本保持不变;TPPi的加入未改变共混物的结晶结构;当TPPi用量≤0.4phr时,TPPi的扩链作用使得PLA与PBS之间的相容性得到一定的改善;随着TPPi用量的增加,共混物的拉伸强度和冲击强度呈先增加后减小的趋势,当TPPi用量为0.4phr时,分别达到最大值63.7 MPa和4.56kJ/m2,较PLA/PBS共混物分别提高了24.4%和44.3%。     

亚磷酸三苯酯对聚乳酸/聚丁二酸丁二醇酯共混体系性能的影响

通过熔融共混法制备了不同含量亚磷酸三苯酯(TPPi)的亚磷酸三苯酯/聚乳酸(PLA)/聚丁二酸丁二醇酯(PBS)共混物,利用红外光谱、核磁共振、X射线衍射、熔体流动速率、流变性能和力学性能测试对TPPi/PLA/PBS共混体系的结构、结晶性能、流变性能和力学性能进行了研究。结果表明,TPPi主要作为酯化促进剂参与反应,共混体系的结构基本保持不变;TPPi的加入未改变共混物的结晶结构;当TPPi用量≤0.4phr时,TPPi的扩链作用使得PLA与PBS之间的相容性得到一定的改善;随着TPPi用量的增加,共混物的拉伸强度和冲击强度呈先增加后减小的趋势,当TPPi用量为0.4phr时,分别达到最大值63.7 MPa和4.56kJ/m2,较PLA/PBS共混物分别提高了24.4%和44.3%。     

扩链剂亚磷酸三苯酯对r-PETG结构与性能的影响

以亚磷酸三苯酯(TPPi)为扩链剂,通过反应加工技术对回收的聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯(rPETG)进行扩链改性。采用旋转流变仪、红外光谱仪和凝胶渗透色谱仪研究了TPPi添加量对r-PETG的结构与性能的影响。结果表明,当TTPi质量分数为2.0%时,r-PETG的数均相对分子量(Mn)由2.52×10~4提高到3.35×10~4;端羧基含量由100mol/kg降低到50mol/kg;零剪切黏度(η_0)由3435.8Pa·s增至27944.5Pa·s;特征松弛时间(τ0)由0.94s延长到30.91s;拉伸强度从41.2MPa增加到了62.3MPa,无缺口冲击强从38.4kJ/m~2大幅度提高至66.8kJ/m~2。改性后r-PETG分子链的结构类型没有变化,仍保持线型链结构。     

苯乙烯-丙烯酸缩水甘油酯共聚物支化改性聚乳酸的结构与性能

以一种苯乙烯-丙烯酸缩水甘油酯共聚物(Joncryl○RADR-4370S)为扩链剂,通过熔融挤出支化改性聚乳酸(PLA),制备了高支化聚乳酸材料,并通过转矩流变仪及毛细管流变仪、GPC、DMA、万能拉伸试验机等研究了不同扩链剂用量对支化改性聚乳酸流变性能、重均相对分子质量及其分布、链结构、动态力学性能和力学性能的影响。结果表明,随着扩链剂含量的增加,支化聚乳酸的平衡扭矩、熔体黏度、重均相对分子质量及其分布(PDI)、拉伸强度、断裂伸长率和缺口冲击强度先增大后减少,储能模量增大,在四氢呋喃溶剂中的链构象由棒状向线团状、球状演变。扩链剂用量为1.5 phr时,支化聚乳酸的平衡扭矩、重均相对分子质量、拉伸强度、断裂伸长率和缺口冲击强度均达到最大值,分别为15.80 N·m,1.96×105,89.6 MPa,7.5%和35.0 k J/m2;扩链剂用量为0.9 phr时,支化聚乳酸的相对分子质量分布最宽,为2.04。     

长支链化聚乳酸/聚丁二酸丁二醇酯的流变特性与发泡性能

为提高熔体强度,以均苯四甲酸酐(PMDA)、异氰尿酸三缩水甘油酯(TGIC)为扩链剂,对聚乳酸(PLA)/聚丁二酸丁二醇酯(PBS)共混体系进行长支链化改性,通过挤出发泡制备PLA/PBS发泡材料。采用转矩流变仪、旋转流变仪、扫描电镜研究了扩链剂用量对PLA/PBS体系流变性能和发泡性能的影响。结果表明,扩链剂PMDA和TGIC联合使用能有效对PLA/PBS体系进行长支链化改性,得到具有一定长支链结构的体系,提高了其熔体强度、弹性和拉伸黏度,改善了PLA/PBS体系的发泡性能。当扩链剂质量分数为0.8%时,发泡材料的泡孔密度达到4.96×107cm-3,平均孔径为60μm,泡孔规整且分布均匀。     

聚对苯二甲酸乙二醇脂回收料扩链增黏改性研究

使用六亚甲基-1,6-二异氰酸酯(HMDI)、邻苯二甲酸酐(PA)、苯乙烯-甲基丙烯酸甲酯与甲基丙烯酸缩水甘油酯共聚物(KL-E4370)、巴斯夫扩链剂Joncryl~?(ADR-4468)、环氧扩链剂、端基环氧基硅油对聚对苯二甲酸乙二醇酯回收料(R-PET)进行扩链改性。研究了单一扩链剂的种类、用量对R-PET的特性黏度、端羧基含量、熔指、结构、结晶性能的影响。结果表明:水分对特性黏度有一定的影响,R-PET经真空干燥后,特性黏度增加了6.54%~12.01%;筛选出ADR-4468为最优扩链剂,当添加质量分数为1.0%时,R-PET的特性黏度由0.48dL/g上升到0.69dL/g,端羧基含量显著降低。     

二异氰酸酯扩链聚2,5-呋喃二甲酸乙二酯

以2,4-甲苯二异氰酸酯(TDI)为扩链剂,对生物基聚2,5-呋喃二甲酸乙二酯(PEF)进行扩链,探讨了扩链剂用量(NCO/OH摩尔比)、反应时间、反应温度等因素的影响。采用红外光谱、核磁共振氢谱、元素分析、差示扫描量热法、X射线衍射分析了扩链PEF的分子结构、热性能和结晶性能。结果表明,当扩链剂用量n(NCO)/n(OH)=1~3,反应时间为30min,反应温度为230℃时扩链效果较好;扩链后PEF的特性黏度最高达1.24dL/g,重均相对分子质量(Mw)最高达28.8×104;扩链后PEF的结晶能力降低,热稳定性能相对提高。     

光交联透明质酸水凝胶的制备及性能

采用甲基丙烯酸缩水甘油酯(GMA)对透明质酸(HA)进行化学改性,然后在紫外辐射下交联成水凝胶。随着GMA与HA物质的量比的增加(分别为10、20和50),HA分子链上的GMA取代度分别为2.8%、16.9%和45.2%,由此制得的水凝胶其交联点间平均分子质量分别为9.33×105g/mol、7.95×105g/mol、6.54×105g/mol;水凝胶的内部孔径逐渐变小;水凝胶的存储模量(G′)分别为70 Pa、101 Pa和160Pa,损耗模量(G″)分别为6.6 Pa、7.8 Pa和12.6 Pa;水凝胶的降解失重速率逐渐减慢,在120h时的失重百分率分别为63%、39.4%和30.8%。结果表明,GMA与HA物质的量比的增加有利于水凝胶交联密度的提高,力学性能的增强和降解速率的降低。     

Evaluation of thermal,mechanical, and electrical properties of PVDF/GNP binary and PVDF/PMMA/GNP ternary nanocomposites

Graphene nanoplatelet (GNP) was incorporated into poly(vinylidene fluoride) (PVDF) and PVDF/poly(methyl methacrylate) (PMMA) blend to achieve binary and ternary nanocomposites. GNP was more randomly dispersed in binary composites compared with ternary composites. GNP exhibited higher nucleation efficiency for PVDF crystallization in ternary composites than in binary composites. GNP addition induced PVDF crystals with higher stability; however, PMMA imparted opposite effect. The binary composite exhibited lower thermal expansion value than PVDF; the value further declined (up to 28.5% drop) in the ternary composites. The storage modulus of binary and ternary composites increased to 23.1% and 53.9% (at 25 °C), respectively, compared with PVDF. Electrical percolation threshold between 1 phr and 2 phr GNP loading was identified for the two composite systems; the ternary composites exhibited lower electrical resistivity at identical GNP loadings. Rheological data confirmed that the formation of GNP (pseudo)network structure was assisted in the ternary system.     

Cure and mechanical properties of recycled NdFeB-natural rubber composites

Magnetic polymer composites containing recycled neodymium-iron-boron (NdFeB) powder and natural rubber (NR) were prepared by the two-roll mill technique. Their mechanical and cure properties were studied as a function of NdFeB loading from 0–120 phr. With increasing magnetic loading, the cure time of the NdFeB-NR composites were exponentially decreased because of the reduction of the polymer chain crosslink. The tensile strength of the NR compound, related to the cure characteristics, was reduced by 40% by the addition of 10 phr NdFeB fillers because of the inhibition of the stress-induced crystallization. However, the variation in loading from 30–90 phr has modest effects on the tensile strength as well as elongation at break and the hardness. Furthermore, recycled NdFeB-NR composites had higher modulus and lower percentage of swelling in this magnetic loading regime. Simple tests confirmed the distribution of magnetic stray field around pieces of NdFeB-NR composites.     

Temperature gradient interaction chromatography and MALDI-TOF mass spectrometry analysis of stereoregular poly(ethyl methacrylate)s

Temperature gradient interaction chromatography (TGIC) was applied for the separation of stereoregular poly(ethyl methacrylate) (PEMA) according to the tacticity. The three PEMA samples with differing tacticity (rr triad content 0, 53, and 91%) prepared by anionic polymerization were used. C18 bonded silica and a mixture of CH2Cl2 and CH3CN (30/70, v/v) were used as stationary and mobile phase, respectively. TGIC was able to separate the PEMA samples, showing the increasing retention in the order of decreasing rr triad contents; however TGIC elution peaks of the three PEMAs were not fully resolved but, rather, were partially overlapped. To isolate the tacticity effect from the molecular weight effect on the TGIC retention, the PEMA samples were fractionated by TGIC, and the accurate molecular weight of the fractions was determined by MALDI-TOF mass spectrometry. The fractions showed a much narrower molecular weight distribution than the mother PEMAs. The TGIC fractions of similar molecular weight but with different tacticity were fully resolved by TGIC, but mother PEMAs were not. These results indicate that the retention in TGIC is affected by both tacticity and molecular weight.     

On promoting dispersion and intercalation of bentonite in high density polyethylene by grafting vinyl triethoxysilane

Vinyl triethoxysilane grafted high density polyethylene (HDPE-g-YDH151)/Bentonite (BT) composites were prepared via melt compounding and compared with HDPE/BT composites. FTIR proved that HDPE-g-YDH151 is chemically bonded to BT sheets. XRD, SEM and TEM results indicated that the introduction of YDH151 promoted the dispersion and intercalation of BT into HDPE. Consequently, HDPE-g-YDH151/BT composites show satisfied mechanical properties, e.g., the composite with 2phr BT has an elongation at break 29% higher and Young’s modulus 32% higher than that of HDPE-g-YDH151.Comparatively, BT aggregated in HDPE/BT composites and all the mechanical properties decreased. Because of high interfacial adhesion between HDPE-g-YDH151 matrix and exfoliated BT, which reduces the mobility of crystallizable PE chain segments, and subsequently reduces the crystallization ability. In comparison, the addition of BT to HDPE did not affect the crystallization behavior of the later.     

Novel toughened polylactic acid nanocomposite: Mechanical,thermal and morphological properties

The objective of the study is to develop a novel toughened polylactic acid (PLA) nanocomposite. The effects of linear low density polyethylene (LLDPE) and organophilic modified montmorillonite (MMT) on mechanical, thermal and morphological properties of PLA were investigated. LLDPE toughened PLA nanocomposites consisting of PLA/LLDPE blends, of composition 100/0 and 90/10 with MMT content of 2 phr and 4 phr were prepared. The Young’s and flexural modulus improved with increasing content of MMT indicating that MMT is effective in increasing stiffness of LLDPE toughened PLA nanocomposite even at low content. LLDPE improved the impact strength of PLA nanocomposites with a sacrifice of tensile and flexural strength. The tensile and flexural strength also decreased with increasing content of MMT in PLA/LLDPE nanocomposites. The impact strength and elongation at break of LLDPE toughened PLA nanocomposites also declined steadily with increasing loadings of MMT. The crystallization temperature and glass transition temperature dropped gradually while the thermal stability of PLA improved with addition of MMT in PLA/LLDPE nanocomposites. The storage modulus of PLA/LLDPE nanocomposites below glass transition temperature increased with increasing content of MMT. X-ray diffraction and transmission electron microscope studies revealed that an intercalated LLDPE toughened PLA nanocomposite was successfully prepared at 2 phr MMT content.     

新型抗菌聚乙烯塑料制备及性能研究

采用熔融共混法制备得到具有负离子释放功能的低密度聚乙烯(LDPE)/稀土复合矿粉(Eli)、LDPE/Eli/吡啶硫铜锌(ZPT)(LDPE/Eli/ZPT)两种LDPE抗茵塑料.通过对其结晶行为、抗菌性能及抗菌持久性系统研究表明:Eli的加入对LDPE有异相成核作用;Eli用量为1份时,LDPE/Eli复合材料负离子释放量为790 ions/co,与公园中负离子释放量相当,抗菌率达到45%以上;ZPT用量为0.15份时,LDPE/Eli/ZPT复合体系对大肠杆菌(E. coli)抗菌率达到98.21%,对金黄色葡萄球菌(S. aureus)抗菌率达到96.15%,经过30天的水洗后,其抗菌率仍能保持82.14%(E coli)和81.25%(S.aureus).     

Dynamic viscoelastic properties of collagen gels in the presence and absence of collagen fibrils

We measured the dynamic viscoelasticities of collagen gels prepared and modified by four different methods: i) collagen gels cross-linked by 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) after their preparation, ii) collagen gels cross-linked simultaneously with their preparation, iii) collagen gels irradiated with gamma rays after their preparation, and iv) collagen gels directly formed from an acidic collagen solution by gamma-cross-linking. Dynamic viscoelasticities of all samples were measured using a rheometer before and after heating for 30 min at 80 °C. The collagen gels sequentially cross-linked by 125 mM EDC after preparation and then heated exhibited mechanically strong properties (storage modulus G′, 7010 Pa; loss modulus G″, 288 Pa; Young's modulus E, 0.012 in the rapidly-increasing phase and 0.095 in the moderately-increasing phase; tensile strain, 5.29; tensile stress σ, 0.053). We generally conclude that the G′ value decreases when gels without fibrils are heated. On the other hand, well cross-linked collagen gels with thick fibrils, such as gels sequentially cross-linked with 125 mM EDC after preparation or gamma-cross-linked conventional gels irradiated at 40 kGy, exhibit a distinct increase in G′ value after heating. Those gels also have thick, twisted, or fused fibrils of collagen.     

Quantitative mapping of surface elastic moduli in silica-reinforced rubbers and rubber blends across the length scales by AFM

The surface elastic moduli of silica-reinforced rubbers and rubber blends were investigated by atomic force microscopy (AFM)-based HarmoniX material mapping. Styrene–butadiene rubbers (SBR) and ethylene–propylene–diene rubbers (EPDM) and SBR/EPDM rubber blends with varying concentrations of silica nanoparticles (0, 5, 10, 20, 50 parts per hundred rubber, phr) were prepared to investigate the effect of different composition on the resulting morphology, filler distribution and elastic moduli of a specific rubber or rubber blend sample. For SBR, the elastic modulus values varied from 0.5 MPa for unfilled SBR to 5 MPa for 50 phr reinforced SBR with the increase in the concentration of filler. For EPDM, the corresponding values increased from 1.4 MPa for unfilled EPDM to 4.5 MPa for 50 phr reinforced EPDM. Local stiff and soft domains in silica-reinforced SBR and EPDM rubbers and rubber blends were identified by HarmoniX AFM imaging. While the stiff silica particles show modulus values as high as 2 GPa, the rubber matrix reveals modulus values in the range of ca. 30 MPa for the rubber blends to ca. 300 MPa for the unfilled rubbers. The lower value of elastic modulus of the EPDM phase in the blend, compared to the blank EPDM compound can be attributed to the presence of Sunpar oil in the compound which has a very good affinity with EPDM and decreases the rubber modulus. The elastic moduli maps revealed an increase of the areal fraction of silica particles showing an intrinsic surface modulus value with rising silica content in the compound preparation mixture. HarmoniX AFM measurements revealed the formation of larger silica aggregates in EPDM in contrast to SBR where isolated silica particles were observed. For silica-reinforced rubber blends a phase separation into a soft (ca. 40 MPa) and a significantly harder phase could be observed (ca. 500 MPa–1.5 GPa) indicating the incorporation of silica particles in the SBR phase. Using HarmoniX AFM imaging significantly higher surface elastic moduli were observed compared to those obtained by bulk tensile testing. Possible reasons for the observed differences between bulk modulus values and those measured by AFM are discussed in detail, including the aspect of different averaging procedures like inherent to surface probing by AFM versus bulk tensile testing, different filler distributions in SBR and EPDM and the AFM modulus calibration procedures.