PCA/PEG嵌段共聚物的合成与性能研究
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摘要
虽然在世界范围内，聚酰胺纤维的产量增长速度放慢，在合成纤维中所占的
比例也逐年下降，但是我国聚酰胺纤维在一段时期内仍有一定的发展空间。差别
化聚酰胺纤维的研究和开发对增加规格品种的多样化，提高产品的质量和档次，
提高市场占有率具有重要的意义。抗静电聚酰胺纤维是差别化聚酰胺纤维的重要
品种。在讨论合成纤维表面静电的产生和危害性的基础上，对合成纤维的抗静电
方法进行了归纳和比较，重点对抗静电聚酰胺纤维近几十年来的发展进行了综
述。
合成了PCA／PEG(聚己内酰胺／聚乙二醇)嵌段共聚物，采用先合成双端羧
基的遥爪预聚己内酰胺，再与聚乙二醇进行聚酯化反应的聚合方法。对影响
PCA／PEG嵌段共聚物的聚合度的后聚合反应条件进行了研究，得出后聚合反应最
佳的工艺条件为，反应时间2h左右，反应温度280±5℃，催化剂酞酸四丁酯的
用量为0． 35％，所得的PCA／PEG嵌段共聚物的最高相对粘度为1． 86，沸水萃取率
最低为1． 45％。
对所合成的PCA／PEG嵌段共聚物的结构和性能进行了研究，其红外光谱图
出现了PEG的-CH2-振动红外特征峰和酯官能团的羧基红外特征峰，表明了
PCA／PEG是以酯键相连的嵌段共聚物，低沸水萃取率也表明其并非PEG与PCA
的简单共混物。PCA／PEG的热重分析表明对于常规PA6的纺丝温度280℃左右，
共聚物是热稳定的，可满足共混纺丝或成型加工。随着PEG链段的增长和其百分
含量的增加，PCA／PEG的体积电阻率逐渐下降，与纯PA6的体积电阻率相比，
其体积电阻率下降5-6个数量级，最低为1． 7×107Q·cm，经水洗10次后无明
显提高，表明了PCA／PEG抗静电效果的持久性。PCA／PEG的DTA、XRD和SEM
照片的分析均表明，随着PEG链段的增长和其百分含量的增加，PCA／PEG的结
晶能力和两相间的相容性下降。
对PCA／PEG嵌段共聚物进行了小试工艺研究，由于高压釜的搅拌能力的提
高，共聚物相对粘度略有提高。初步设计了连续化中试的反应流程和反应设备。
Although the increasing rate of the produce of polyamide fibers in the world is
s1ackening and the proportion to synthetic fibers is declining year after yeaT, there will
be a deve1opment in China. The research on differential polyamide fibers is important to
increase their qua1ity and diversification and to occupy the market. Antistatic po1yamide
flber is an important tyPe of them. On the basis of the discuss of the produce and harm
of static, the afltistatic methods of synthetic fibers are summarized.
A series of PCA/PEG block polymers are synthesized by Q, to -biscarboxy
polycaProlactam and polyethylene glycol. The research on the degree ofpolymerization
show the optimal reaction conditions are timef2h, temperature: 280I5OC, catalyzer
TBTf0.35%. The highest relative viscidity of PCA/PEG is 1.86 and the lowest rate of
extraction in boiling water is 1 .45%.
The structure and properties of PCA/PEG are researched. The IR spectrogram
indicate PCA/PEG are block polymers connected with ester bonds a-nd the rate of
extraction in boiling water show they are not simple mixtures. The TG of PCA/PEG
show the block po1ymers are thermal stability in the ra-nge of processing temPerature of
PA6.The volume conductivity of PCA/PEG decreased by 5~6 orders of magnitUde to
the lowest 1.7 X l0' Q. cm. They are no apparent changes when washed by water 10
times, which indicate the lasting antistatic property The DTA,Xan and SEM figures of
PCA/PEG a11 show that the crystalline and mixed properties are harmed by the increase
of PEG.
The small test of PCA/PEG are researched. The relative viscidity of copolymers
increased because of the blend ability of high pressure reactor. The reaction process and
equipments of continued middle test are pre1iminarily designed.
比例也逐年下降，但是我国聚酰胺纤维在一段时期内仍有一定的发展空间。差别
化聚酰胺纤维的研究和开发对增加规格品种的多样化，提高产品的质量和档次，
提高市场占有率具有重要的意义。抗静电聚酰胺纤维是差别化聚酰胺纤维的重要
品种。在讨论合成纤维表面静电的产生和危害性的基础上，对合成纤维的抗静电
方法进行了归纳和比较，重点对抗静电聚酰胺纤维近几十年来的发展进行了综
述。
合成了PCA／PEG(聚己内酰胺／聚乙二醇)嵌段共聚物，采用先合成双端羧
基的遥爪预聚己内酰胺，再与聚乙二醇进行聚酯化反应的聚合方法。对影响
PCA／PEG嵌段共聚物的聚合度的后聚合反应条件进行了研究，得出后聚合反应最
佳的工艺条件为，反应时间2h左右，反应温度280±5℃，催化剂酞酸四丁酯的
用量为0． 35％，所得的PCA／PEG嵌段共聚物的最高相对粘度为1． 86，沸水萃取率
最低为1． 45％。
对所合成的PCA／PEG嵌段共聚物的结构和性能进行了研究，其红外光谱图
出现了PEG的-CH2-振动红外特征峰和酯官能团的羧基红外特征峰，表明了
PCA／PEG是以酯键相连的嵌段共聚物，低沸水萃取率也表明其并非PEG与PCA
的简单共混物。PCA／PEG的热重分析表明对于常规PA6的纺丝温度280℃左右，
共聚物是热稳定的，可满足共混纺丝或成型加工。随着PEG链段的增长和其百分
含量的增加，PCA／PEG的体积电阻率逐渐下降，与纯PA6的体积电阻率相比，
其体积电阻率下降5-6个数量级，最低为1． 7×107Q·cm，经水洗10次后无明
显提高，表明了PCA／PEG抗静电效果的持久性。PCA／PEG的DTA、XRD和SEM
照片的分析均表明，随着PEG链段的增长和其百分含量的增加，PCA／PEG的结
晶能力和两相间的相容性下降。
对PCA／PEG嵌段共聚物进行了小试工艺研究，由于高压釜的搅拌能力的提
高，共聚物相对粘度略有提高。初步设计了连续化中试的反应流程和反应设备。
Although the increasing rate of the produce of polyamide fibers in the world is
s1ackening and the proportion to synthetic fibers is declining year after yeaT, there will
be a deve1opment in China. The research on differential polyamide fibers is important to
increase their qua1ity and diversification and to occupy the market. Antistatic po1yamide
flber is an important tyPe of them. On the basis of the discuss of the produce and harm
of static, the afltistatic methods of synthetic fibers are summarized.
A series of PCA/PEG block polymers are synthesized by Q, to -biscarboxy
polycaProlactam and polyethylene glycol. The research on the degree ofpolymerization
show the optimal reaction conditions are timef2h, temperature: 280I5OC, catalyzer
TBTf0.35%. The highest relative viscidity of PCA/PEG is 1.86 and the lowest rate of
extraction in boiling water is 1 .45%.
The structure and properties of PCA/PEG are researched. The IR spectrogram
indicate PCA/PEG are block polymers connected with ester bonds a-nd the rate of
extraction in boiling water show they are not simple mixtures. The TG of PCA/PEG
show the block po1ymers are thermal stability in the ra-nge of processing temPerature of
PA6.The volume conductivity of PCA/PEG decreased by 5~6 orders of magnitUde to
the lowest 1.7 X l0' Q. cm. They are no apparent changes when washed by water 10
times, which indicate the lasting antistatic property The DTA,Xan and SEM figures of
PCA/PEG a11 show that the crystalline and mixed properties are harmed by the increase
of PEG.
The small test of PCA/PEG are researched. The relative viscidity of copolymers
increased because of the blend ability of high pressure reactor. The reaction process and
equipments of continued middle test are pre1iminarily designed.
引文
[1] 施祖培．世纪之交的聚酰胺纤维工业．合成纤维工业，2000，23(1) ：6-13
[2] 孟庆海．90年代聚酰胺纤维．合成纤维工业，1994，17(3) ：33-38
[3] 吴雷，陈志刚．聚酰胺短纤维发展概论．广东化纤，2000，(4) ：34-38
[4] 宋新，张德先．差别化聚酰胺纤维的开发．广东化纤，2001，(1) ：24-28
[5] D．T．克拉克，W．J．费斯特，聚合物表面．北京：化学工业出版社，1985
[6] 中国科学技术大学高分子物理教研室，高聚物的结构与性能．北京：科学出版 社，1981
[7] 周晓沧 肖建宇，新合成材料及其制造．北京：中国纺织出版社，1992
[8] 杨志敏，赵耀明．合成纤维永久性抗静电剂．合成纤维工业，1991，14(5) ：41-45
[9] 徐炽焕．国外抗静电剂的最新进展．化工时刊，1996，10(6) ：23-26
[10] 张亨．抗静电研究进展．精细石油化工进展，2000，1(9) ：39-43
[11] 王克智．塑料助剂的开发及应用．塑料科技，1996，(4) ：42-51
[12] 宣兆龙，易建政，杜仕国．抗静电剂的研究进展．塑料工业，1999，27(5) ：39-41
[13] 黄锐，刘劲松，张雄伟．导电塑料的进展．中国塑料，1992，6(4) ：3-11
[14] 刘美华，张正华，郭灿城．抗静电聚酰胺纤维制备方法．合成纤维工业，2002， 25(2) ：49-51
[15] 孙宇清，郑帼．涤纶锦纶用抗静电剂的结构与性能研究．合成纤维工业，1999， 22(6) ：12-14
[16] Takeshita Y., Mnsch R.A. Ultrafine synthetic fibers for antistatic flocks for flocked fabric with peach-like touch manufactured by treating the ultrafine fibers with tannins and flocked fabrics therefrom and manufacture of ultrafine fibers therefore. Jpn. Kokai Tokkyo Koho JP 2000 265 367． 2000-9-26
[17] Hirose S. Polyamide fiber products treated with finishes containing fibroins, pyrrolidonecarboxylic acid and polyamides for washfast hygroscopicity and antistatic properties. Jpn. Kokai Tokkyo Koho JP 11 279 947． 1999-10-12
[18] Otani H., Iwasaki T. Antistatic washfast nylon blend products coated with mixtures comprising antistatic agents and washfast soft binders. Jpn. Kokai Tokkyo Koho JP 2000 110078． 2000-4-18
[19] Shinozaki A., Honda H., Saito K. et al. Antistatic leg knits treated with finishes containing binders and antistatic agents with good washfastness of antistatic properties. Jpn. Kokai Tokkyo Koho JP 11 302 904． 1999-11-2
[20] Kamemaru K., Nakamura H. Manufacture of washfast antistatic water-repellent nylon and nylon blend synthetic fabrics treated with antistatic polymers and perfluoroalkyl group-containing arylic polymers. Jpn. Kokai Tokkyo Koho JP 11 152 682． 1999-6-8
[21] Kamemaru K., Hasegawa K. Antistatic water-repellent finishing nylon fabrics with good washfastness by treating the fabrics with polyoxyalylene-polyurethanes and subsequently treating the fabrics with perfluoroalkyl group-containing compounds. Jpn. Kokai Tokkyo Koho JP 2000 80 568． 2000-5-21
[22] Kamemaru K., Nakamura H. Antistatic water-repellent nylon fabrics finished with fluoropolymers with good washfastness and manufacture tjereof. Jpn. Kokai Tokkyo Koho JP 11 36 176． 1999-2-9
[23] 刘卫平．抗静电增强尼龙6的研制．现代塑料加工应用，1997，9(1) ：13-16
[24] 何汉宏．SPET离聚物与尼龙6共混纤维结构性能的研究．合成纤维，2002，31(2) ：8-10
[25] Shinozaki A., Honda H., Saito K. et al. Antistatic polyamide fiber manufacture. Jpn. Kokai Tokkyo Koho JP 61 258 019． 1977-10-5
[26] Kamemaru K., Nakamura H. Antistatic aliphatic polyester conjugated fibers with high colorfastness and easily decomposability for clothings. Jpn. Kokai Tokkyo Koho JP 2000 212 835． 2000-9-10
[27] Kanayama K., Fujii M., Abe K. Hygroscopic antistatic fabrics of polyamide fibers having the core containing modified polyoxyethylenes and the sheath comprising polyamides for inner wear having properties of windbreakers. Jpn. Kokai Tokkyo Koho JP 11 302945． 1999-11-2
[28] Akazaki K., Kijima Y. Antistatic moisture-absorbing moisture-evolving hygroscopic fabrics of mixture yams comprising polyester fibers and conjugate fibers from polyamides and polyoxyethylene-modifies compounds. Jpn. Kokai Tokkyo Koho JP 11 124755． 1999-5-11
[29] Suzuki A., Hirota M. Antistatic hydrophilic synthetic fibers treated with mixtures of anionic or cationic surfactants and amphoteric surfactants for improved antistatic properties at low humidity. Jpn. Kokai Tokkyo Koho JP 11 81 132． 1999-5-26
[30] Hikoda T. manufacture of electrically conductive flocked products having flocks treated with electrically conductive polymers and antistatic electrically conductive products therefrom. Jpn. Kokai Tokkyo Koho JP 11 229 274． 1999-8-24
[31] 金和，臧已，董纪震．抗静电聚酰胺-6纤维的制备及结构与性能研究．北京服 装学院学报，1992，12(1) ：11-18
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[49] 殷敬华，莫志深．现代高分子物理学．北京：科学出版社，2001
[2] 孟庆海．90年代聚酰胺纤维．合成纤维工业，1994，17(3) ：33-38
[3] 吴雷，陈志刚．聚酰胺短纤维发展概论．广东化纤，2000，(4) ：34-38
[4] 宋新，张德先．差别化聚酰胺纤维的开发．广东化纤，2001，(1) ：24-28
[5] D．T．克拉克，W．J．费斯特，聚合物表面．北京：化学工业出版社，1985
[6] 中国科学技术大学高分子物理教研室，高聚物的结构与性能．北京：科学出版 社，1981
[7] 周晓沧 肖建宇，新合成材料及其制造．北京：中国纺织出版社，1992
[8] 杨志敏，赵耀明．合成纤维永久性抗静电剂．合成纤维工业，1991，14(5) ：41-45
[9] 徐炽焕．国外抗静电剂的最新进展．化工时刊，1996，10(6) ：23-26
[10] 张亨．抗静电研究进展．精细石油化工进展，2000，1(9) ：39-43
[11] 王克智．塑料助剂的开发及应用．塑料科技，1996，(4) ：42-51
[12] 宣兆龙，易建政，杜仕国．抗静电剂的研究进展．塑料工业，1999，27(5) ：39-41
[13] 黄锐，刘劲松，张雄伟．导电塑料的进展．中国塑料，1992，6(4) ：3-11
[14] 刘美华，张正华，郭灿城．抗静电聚酰胺纤维制备方法．合成纤维工业，2002， 25(2) ：49-51
[15] 孙宇清，郑帼．涤纶锦纶用抗静电剂的结构与性能研究．合成纤维工业，1999， 22(6) ：12-14
[16] Takeshita Y., Mnsch R.A. Ultrafine synthetic fibers for antistatic flocks for flocked fabric with peach-like touch manufactured by treating the ultrafine fibers with tannins and flocked fabrics therefrom and manufacture of ultrafine fibers therefore. Jpn. Kokai Tokkyo Koho JP 2000 265 367． 2000-9-26
[17] Hirose S. Polyamide fiber products treated with finishes containing fibroins, pyrrolidonecarboxylic acid and polyamides for washfast hygroscopicity and antistatic properties. Jpn. Kokai Tokkyo Koho JP 11 279 947． 1999-10-12
[18] Otani H., Iwasaki T. Antistatic washfast nylon blend products coated with mixtures comprising antistatic agents and washfast soft binders. Jpn. Kokai Tokkyo Koho JP 2000 110078． 2000-4-18
[19] Shinozaki A., Honda H., Saito K. et al. Antistatic leg knits treated with finishes containing binders and antistatic agents with good washfastness of antistatic properties. Jpn. Kokai Tokkyo Koho JP 11 302 904． 1999-11-2
[20] Kamemaru K., Nakamura H. Manufacture of washfast antistatic water-repellent nylon and nylon blend synthetic fabrics treated with antistatic polymers and perfluoroalkyl group-containing arylic polymers. Jpn. Kokai Tokkyo Koho JP 11 152 682． 1999-6-8
[21] Kamemaru K., Hasegawa K. Antistatic water-repellent finishing nylon fabrics with good washfastness by treating the fabrics with polyoxyalylene-polyurethanes and subsequently treating the fabrics with perfluoroalkyl group-containing compounds. Jpn. Kokai Tokkyo Koho JP 2000 80 568． 2000-5-21
[22] Kamemaru K., Nakamura H. Antistatic water-repellent nylon fabrics finished with fluoropolymers with good washfastness and manufacture tjereof. Jpn. Kokai Tokkyo Koho JP 11 36 176． 1999-2-9
[23] 刘卫平．抗静电增强尼龙6的研制．现代塑料加工应用，1997，9(1) ：13-16
[24] 何汉宏．SPET离聚物与尼龙6共混纤维结构性能的研究．合成纤维，2002，31(2) ：8-10
[25] Shinozaki A., Honda H., Saito K. et al. Antistatic polyamide fiber manufacture. Jpn. Kokai Tokkyo Koho JP 61 258 019． 1977-10-5
[26] Kamemaru K., Nakamura H. Antistatic aliphatic polyester conjugated fibers with high colorfastness and easily decomposability for clothings. Jpn. Kokai Tokkyo Koho JP 2000 212 835． 2000-9-10
[27] Kanayama K., Fujii M., Abe K. Hygroscopic antistatic fabrics of polyamide fibers having the core containing modified polyoxyethylenes and the sheath comprising polyamides for inner wear having properties of windbreakers. Jpn. Kokai Tokkyo Koho JP 11 302945． 1999-11-2
[28] Akazaki K., Kijima Y. Antistatic moisture-absorbing moisture-evolving hygroscopic fabrics of mixture yams comprising polyester fibers and conjugate fibers from polyamides and polyoxyethylene-modifies compounds. Jpn. Kokai Tokkyo Koho JP 11 124755． 1999-5-11
[29] Suzuki A., Hirota M. Antistatic hydrophilic synthetic fibers treated with mixtures of anionic or cationic surfactants and amphoteric surfactants for improved antistatic properties at low humidity. Jpn. Kokai Tokkyo Koho JP 11 81 132． 1999-5-26
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