共混聚酯与纳米蒙脱土复合物的流变性能

采用RH2000型毛细管流变仪对熔融共混制备的聚对苯二甲酸乙二酯(PET)/聚对苯二甲酸丙二酯(PTT)与纳米蒙脱土(MMT)复合物的流变性能进行了研究.结果表明:PET/PTT共混熔体及PET/PTT/MMT复合物熔体均为假塑性流体;复合物熔体的零切黏度(η0)小于PET/PTT共混熔体的η0,MMT的加入起到增塑剂作用;复合物熔体的黏流活化能高于PET/PTT熔体的黏流活化能,说明对PET/PTT/MMT复合物熔体而言,更适合使用调节温度的方法来控制其流动性.     

再生聚酯的流变性能研究

以废旧聚酯(PET)纺织品为原料,加入不同量的乙二醇使其醇解,经液相增黏制得再生PET切片。采用毛细管流变仪对再生PET及纯PET的流变行为进行了对比研究。结果表明:再生PET流体为非牛顿假塑性流体,其流变行为与纯PET基本相同;在同一温度和剪切速率下,再生PET的熔体特性黏数小于纯PET熔体特性黏数;再生PET的黏流活化能(Eη)大于纯PET的Eη,最高达到246.1 kJ/mol;不同再生PET对温度有不同的敏感性,在纺丝加工时应采用不同工艺。     

高黏度聚酯流变行为的研究

采用毛细管流变仪研究了高黏度聚酯(PET)的表观黏度及黏流活化能随温度(280～300℃)及剪切速率(20～104s-1)的变化。结果表明:高黏度PET熔体随着剪切速率的增加出现切力变稀现象,随着熔体温度升高,剪切速率对熔体的表观黏度的影响降低;高黏度PET的黏流活化能随着剪切速率的提高而降低;在温度为300℃,剪切速率为3 000 s-1时,高黏度PET熔体具有较好的流动性。     

PET-PEN共聚酯的合成研究

以2,6-萘二甲酸(NDA)、对苯二甲酸或2,6-萘二甲酸二甲酯(NDC)、对苯二甲酸二甲酯与乙二醇为原料,在2 L聚合反应装置上,采用直接酯化法或酯交换法合成聚对苯二甲酸乙二酯(PET)-聚2,6-萘二甲酸乙二酯(PEN)共聚酯(PETN),探讨了PETN的合成反应条件。结果表明:直接酯化法较酯交换法更加可行易控;直接酯化法反应条件:酸/醇摩尔比为1:(1.3～1.5),NDA摩尔分数(相对于酸的总量)为28%,酯化阶段无需催化剂,酯化反应温度220～250℃,缩聚反应温度280～295℃,合成的PETN特性黏数达0.65～0.85 dL/g;钛系催化剂的催化活性优于锑系催化剂,且添加比例小,添加量为8～50μg/g时,即可得到高特性黏数的PETN。     

PET-PTT共聚酯的结晶和纺丝性能

在酯交换和缩聚反应之前同时加入对苯二甲酸(PTA)、乙二醇和第三单体1,3-丙二醇(PDO)制备共聚酯(PET-PTF)。用热台显微镜和X射线衍射等研究了PET-PTT的结晶行为。分析了PDO添加量对PET-PTT纤维的可纺性和力学性能的影响。结果表明：PET-PTT的起始结晶温度比普通PET低20～30℃,结晶度降低。随着PDO添加量的增加,PET-PTT纤维的断裂强度降低;PDO质量分数为12%较好,PET-PTT的POY纺丝速度可达3500m/min,断裂强度2．05cN/dtex,断裂伸长率134%。     

生物降解共聚酯流变性能研究

采用英国Rosand公司RH7型毛细管流变仪对国内自制生物降解共聚酯的流变性能进行了研究,并与国外同类产品进行了比较。结果表明：国内外共聚酯熔体均属非牛顿流体;与国外产品相比,国内共聚酯的熔体黏度较低,对温度的敏感性相对较大;国外产品在低剪切速率下对温度的敏感性相对较小;国内产品在加工性能方面还有待提高。     

含TiO_2的PET的流变性能研究

采用毛细管流变仪研究了含二氧化钛(TiO2)的聚对苯二甲酸乙二醇酯(PET)的流变性能,计算得到非牛顿指数(n)和粘流活化能(Eη)。结果表明:含TiO2的PET所能达到的最高剪切速率高于纯PET,其剪切粘度、纺丝温度及纺丝速度均高于纯PET;在280,285,290℃时,含TiO2的PET的n小于纯PET,295℃时,大于纯PET;含质量分数0.32%TiO2的PET的Eη与纯PET相当,含质量分数2.50%TiO2的PET的Eη远低于纯PET。     

1,4环己烷二甲醇改性PBT共聚酯流变性能研究

以1, 4环己烷二甲醇（CHDM）为第三单体,对苯二甲酸（PTA）和1, 4丁二醇（BDO）为基本原料,在熔融缩聚釜中制得不同第三单体含量的聚对苯二甲酸丁二醇酯1,4环己二甲醇酯（PBTG）。通过挤出式毛细管流变仪和旋转流变仪对PBTG共聚酯的流变性能进行了分析测试。结果表明,PBTG共聚酯为假塑性非牛顿流体,其非牛顿指数均小于1;第三单体CHDM的加入增加了聚对苯二甲酸丁二酯的动态黏度。     

PET-PCT共聚酯的制备及其热性能研究

由直接酯化法制备了不同1,4-环己烷二甲醇(CHDM)含量的聚对苯二甲酸乙二醇酯-聚对苯二甲酸-1,4-环己烷二甲醇酯(PET-PCT)共聚酯;利用核磁共振表征了合成产物的实际组成及序列结构;采用差示扫描量热和热失重分析研究了共聚酯的结晶特性和热稳定性。结果表明:合成的共聚酯为无规嵌段聚合物,PCT的实际组成均高于投料比,各链段的序列长度与其含量成正比。随着CHDM含量的增加,共聚酯的玻璃化转变温度升高,退火后的试样在低温处和高温处出现了两个熔点,且熔点和焓值随PCT含量的增加而降低。合成产物热稳定性优良,起始分解温度均大于400℃,最大分解温度大于435℃。用Friedman法对热分解动力学的分析,进一步证明共聚酯的热稳定性优良。     

PET/PC复合材料的制备及其流变性能研究

利用双螺杆挤出机制备了聚对苯二甲酸乙二醇酯(PET)与聚碳酸酯(PC)共混体系,并利用毛细管流变仪对共混体系的流变性能进行了系统研究。结果表明:PET/PC共混体系为典型的假塑性流体,其表观黏度随PC含量的增加而明显降低;共混体系的非牛顿指数n随温度升高而逐渐增大;PET及PET/PC共混体系的黏流活化能较大,且随剪切速率的增加而降低,属于温敏性流体,而小分子量的PC对温度并不敏感,为切敏性流体。     

Crystallization behavior and morphology of double crystalline poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) copolymers

Double crystalline poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) copolymers (PTT/PEOT), with PTT content ranging from 16.5 to 65.5 wt%, were synthesized by melt copolycondensation. The morphological transformation of samples from microphase separation to macrophase separation was investigated by gel permeation chromatography and transmission electron microscopy. Differential scanning calorimetry and in situ wide‐angle X‐ray diffraction suggested that all copolycondensation samples displayed double crystalline behavior. The melt‐crystallization peak temperatures (T_{m, c} values) of PTT chains monotonously increased with increasing PTT content and were higher than that of homo‐PTT when the content of PTT was above 30.6 wt%. Interestingly, T_{m, c} values of PEOT chains were also increased with increasing PTT content. Polarized optical microscopy revealed that all copolycondensation samples studied could form ring‐banded spherulites and band spacing increased with increasing T_c values. In addition, band spacing decreased with increasing PTT content at a given T_c. Strangely, although PEOT was the main component in all copolycondensation samples, spherulitic morphology formed by the advance crystallization of PTT did not change after PEOT crystallization. Only a subtle change of quadrant tones was detected. © 2012 Society of Chemical Industry     

Crystallization behavior and crystal structure of poly(ethylene‐co‐trimethylene terephthalate)s

A series of random copolymers were synthesized by the bulk polycondensation of dimethyl terephthalate with ethylene glycol (EG) and propane‐1,3‐diol (PDO) in various compositions. Their composition and thermal properties were investigated. The copolymers with 57.7 mol % or more PDO or 14.4 mol % or less PDO were crystallizable, but those with 36–46.2 mol % PDO were amorphous. The nonisothermal crystallization behavior was investigated with varying cooling rates by DSC. Poly(ethylene terephthalate) (PET) and poly(trimethylene terephthalate) (PTT) homopolymers have relatively lower activation energy than their copolymers. PET‐rich copolymers (EG > 85.9%) exhibited PET crystal structure, and exhibited no PTT crystal structure; and PTT‐rich copolymers (PDO > 41.7%) exhibited PTT crystal structure, and exhibited no PET crystal structure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

PEN/PET共混物结晶行为研究

用差示扫描量热法(DSC)研究了不同共混比例PEN/PET共混物的熔体结晶行为,并进行了等温结晶动力学测定。结果表明:随着两种组分向中间比例(50/50)靠近,共混物的熔融温度越低,结晶速率也越慢。     

Blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Commercial grade poly(ethylene terephthalate), (PET, intrinsic viscosity = 0.80 dL/g) and poly(butylene terephthalate), (PBT, intrinsic viscosity = 1.00 dL/g) were melt blended over the entire composition range using a counterrotating twin‐screw extruder. The mechanical, thermal, electrical, and rheological properties of the blends were studied. All of the blends showed higher impact properties than that of PET or PBT. The 50:50 blend composition exhibited the highest impact value. Other mechanical properties also showed similar trends for blends of this composition. The addition of PBT increased the processability of PET. Differential scanning calorimetry data showed the presence of both phases. For all blends, only a single glass‐transition temperature was observed. The melting characteristics of one phase were influenced by the presence of the other. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 75–82, 2005     

聚对苯二甲酸丙二醇酯的非等温结晶动力学研究

采用DSC研究了聚对苯二甲酸丙二醇酯(PTT)在不同等速降温速率下的结晶过程,并利用由等温Avrami方程推导得到的两种不同的等速降温非等温结晶方程,研究了其结晶动力学,得出PTT的成核方式为异相成核,同时利用拟和法计算了PTT的结晶能力,发现在同等条件下PTT的结晶能力大于PET。     

Study on the macrokinetics of poly(trimethylene terephthalate) polycondensation reaction

The macrokinetics of poly(trimethylene terephthalate) (PTT) polycondensation reaction during the high‐vacuum process was studied. The results showed that PTT polycondensation reaction may be considered as a second‐order reaction and thermal degradation is negligible in mathematical handling. The intrinsic viscosity versus time undergoes two different processes according to temperature. The apparent reaction rate constants and apparent activation energy of PTT polycondensation reaction are smaller than those of PET. Under efficient stirring, PTT polycondensation reaction is still reaction‐controlled and the role of devolatilization could be neglected even during the high‐vacuum process. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1765–1770, 2004     

Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.     

聚乙交酯及聚乙丙交酯的流变性能研究

采用毛细管流变仪研究了聚乙交酯(PGA)和聚乙丙交酯(PGLA)的流变性能,分析了剪切速率、温度对聚合物流体流动曲线、非牛顿指数、流动活化能等的影响。结果表明:PGA和PGLA都属于非牛顿型假塑性流体,随着温度的提高,PGA和PGLA的表观粘度降低,非牛顿指数逐渐增大。PGA和PGLA的流动活化能均随着剪切速率的增加呈下降趋势,PGLA流体对剪切速率更敏感,而PGA流体对温度更敏感。     

Melting behavior of poly(trimethylene terephthalate)

In this study, the melting behavior of isothermally crystallized polytri‐ methylene terephthalate (PTT) was investigated. Multiple melting behaviors in DSC heating trace were found because two populations of lamellar stacks were formed during primary crystallization and the recrystallization at heating process, respectively. This fact could be also confirmed from the result of optical microscopy observation. The Hoffman–Weeks equation was applied to obtain equilibrium melting temperature (T). The T value of PTT is about 525 K, which is 10 K higher than that reported. Combining the enthalpy of fusion from the DSC result and the degree of crystallinity from WAXD result, the value of the equilibrium‐melting enthalpy ΔH was deduced to be approximately 28.8 kJ mol^?1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2426–2433, 2002     

The complicated influence of branching on crystallization behavior of poly(ethylene terephthalate)

The randomly branched poly(ethylene terephthalate) (BPET) was prepared by bulk polycondensation from dimethyl terephthalate (DMT) and ethylene glycol (EG), with 0.4–5.0 mol % (with respect to DMT) of glycerol (GL) as a branching agent. The glass transition and crystallization behavior was studied by differential scanning calorimetry (DSC). It was found that the glass transition temperature of BPET reduced with the increasing content of GL until 1.2 mol %, and then increases a little at high degrees of branching. When compared with a linear PET, the crystallization temperature of BPET from the melt shifted to higher temperature as GL content was smaller than 1.2 mol %, and then became lower while GL load was added. Nonisothermal crystallization kinetics was studied through the modified Avrami analysis. It was revealed that the overall crystallization rate parameter of BPET became larger when the GL content was less than 1.2 mol %, then turned to lower at higher branching degree. This indicated that low degree of branching could enhance the overall crystallization of poly(ethylene terephthalate) (PET), whereas high degree of branching in the range of 3.5–5.0 mol % would block the development of crystallization. On the basis of Hoffman's secondary crystallization theory, the product σσ_e of the free energy of formation per unit area of the lateral and folding surface was calculated. According to the change of the product σσ_e with the degree of branching, a possible explanation was presented to illuminate this diverse effect of different degrees of branching on crystallization. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008