纺织学报 ›› 2018, Vol. 39 ›› Issue (11): 1-7.doi: 10.13475/j.fzxb.20180105307

• 纤维材料 •    下一篇

高分子量聚对苯二甲酸乙二醇酯中低聚物的提取及其表征

    

  1.  
  • 收稿日期:2018-01-23 修回日期:2018-08-01 出版日期:2018-11-15 发布日期:2018-11-19
  • 基金资助:

     

Extraction and characterization of oligomers from high molecular weight poly(ethylene terephthalate)

  • Received:2018-01-23 Revised:2018-08-01 Online:2018-11-15 Published:2018-11-19
  • Supported by:

     

摘要:

为研究高分子量聚对苯二甲酸乙二醇酯(HMW-PET)中低聚物的成分和含量及其对HMW-PET结晶和热学性能的影响,通过萃取法和沉淀法对纤维级PET、液相增黏和固相增黏HMW-PET产品及过程样中的低聚物进行提取,并借助超高效聚合物色谱和差示扫描量热仪对低聚物进行表征。结果表明:沉淀法可快速分离不同工艺产品中的低聚物,得到的低聚物种类较齐全;而萃取法准确性较高,重复提取偏差控制在3% 以内;不同工艺制备的HMW-PET产品低聚物含量存在明显差异;萃取的低聚物在246.6、310.7 ℃附近出现吸热峰,其中环状三聚体含量最高;纤维级PET 及HMW-PET经提取后冷结晶温度均升高,但纤维级PET 熔融焓降低,而HMW-PET熔融焓升高。

关键词: 聚对苯二甲酸乙二醇酯, 低聚物, 超高效聚合物色谱, 固相增黏, 液相增黏

Abstract:

In order to study the composition and content of oligomers extracted from high molecular weight poly(ethylene terephthalate) (HMW-PET) and its invluence on the properties of HMW-PET, the extraction and precipitation of oligomers were performed on fiber-grade PET, solid-state polycondensation (SSP) and liquid-state polycondensation (LSP). The obtained oligomers were characterized by advanced polymer chromatography and differential scanning calorimetry. The results show that the precipitation process could separate oligomers quickly and completely. The extraction process can obtain oligomers with a good accuracy and less than 3%. The difference of oligomers content and  component is significant between SSP product and LSP products. The oligomers extracted show endothermic peaks at about 246.6 and 310.7 °C, respectively, and cyclic trimer accounts for the highest proportion in oligomers for all products. The cold crystallization temperature of fiber-grade PET and HMW-PET treated by extraction is increased. The melt enthalpy of fiber grade PET decreases by the extraction, while the enthalpy of HMW-PET become higher.

Key words: poly(ethylene terephthalate), oligomer, advanced polymer chromatography, solid-statepolycondensation, liquid-state polycondensation

[1] MILENA Z, Structure-Mechanical properties relationship of poly(ethylene terephthalate) fibers[J]. Journal of Applied Polymer Science, 2003, 89(12): 3383-3389.
[2] SCHEIR J,LONG TE. Modern polyesters: Chemistry and technology of polyesters and copolyesters[M]. West Sussex: Wiley, 2003, 31-104.
[3] 江渊,潘菊芳,徐憬等.涤纶纤维筒子染色过程中白色粉末性质的探讨[J].纺织学报,2010,31(5):24-29.
JIANG Yuan, PAN Jufang, XU Jing, et al. A discussion on properties of white powders yielded during package dyeing of polyester yarns[J]. Journal of Textile Research, 2010, 31(5): 24-29.
[4] YOSHIOKA T, TSUJI M, KAWAHARA Y, et al. Morphological study by TEM on uniaxially oriented thin films of PBT[J]. Polymer, 2005, 46(14): 4987-4990.
[5] HOLLAND B J, Hay J N. Analysis of comonnomer content and cyclic oligomers of poly(ethyleneterephthalate)[J]. Polymer, 2002, 43(6): 1797-1804
[6] HARRISON A G, Taylor M. Analysis of cyclic oligomers of poly(ethylene terephthalate) by liquid chromatography/massspectrometry[J]. Polymer, 1997, 38(10): 2549-2555.
[7] CIMECIOGLU A L, ZERONIAN S, ALGER K W, et al. Properties of oligomers present in poly(ethylene terephthalate)[J]. Journal of Applied Polymer Science, 1986, 32(4): 4719-4733.
[8] GOODMAN I, NESBITT B F. The structures and reversible polymerization of cyclic oligomers from poly(ethylene terephthalate)[J]. Polymer, 1960, 1(150): 384-396.
[9] 徐台顺.PET中齐聚物总量及环三聚体含量测定法[J].纺织学报,1985,6(3): 7-11.
XU Taishun. Determination of oligomer content and trimer content in PET[J]. Journal of Textile Research, 1985, 6(03): 7-11.
[10] TRAN J C, DOUCETTE A A. Cyclic polyamide oligomers extracted from Nylon 66 membrane filter disks as a source of contamination in liquid chromatography/mass spectrometry[J]. Journal of the American Society for Mass Spectrometry, 2006, 17(5): 652-656.
[11] NASSER A L, Lopes L M X, Eberlin M N, et al. Identfication of oligomers in poy(ethylene terephthalate) bottles for mineral water and fruit juice[J]. Journal of chromatography A, 2005, 1097(1): 130-137.
[12] SHIONO S. Separation and identification of poly(ethylene terephthalate) oligomers by gel permeation chromatography[J]. Polymer Science Polymer Chemistry Edition, 2003, 17(12): 4123-4127.
[13] MANSOURI H, YAGOUBI N, SCHOLLER D, et al. Propylene oligomers: extraction methods and characterization by FTIR, HPLC, and SEC[J]. Journal of Applied Polymer Science, 2015, 71(3): 371-375.
[14] KIM D J, LEE K T. Determination of monomers and ologomers in polyethylene terephthalate trays and bottles for food use by using high performance liquid chromatography-electrospray ionization-mass spectrometry[J]. Polymer Testing, 2012, 31(3): 490-499.
[15] 刘梅,陈世昌,陈文兴等.超高效聚合物色谱-激光光散射联用测定聚酯绝对分子质量及其分布[J].纺织学报,2016,37(05): 11-16.
LIU Mei, CHEN Shichang, CHEN Wenxing, et al. Determination of polymester molecular weight and its
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