高性能淀粉基接枝共聚物的制备及性能研究
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摘要
采用反相乳液聚合法,以硝酸铈铵为引发剂、用Span-80和Op-4复合乳化剂,选用可溶性淀粉基材分别与丙烯酰胺和二甲基二烯丙基氯化铵单体进行接枝共聚。制备出了性能优越的淀粉乙烯基单体接枝共聚物。
用傅立叶变换红外光谱和核磁共振波谱对产品进行了结构表征。通过接枝率、接枝效率、单体转化率、阳离子度和特性粘数等指标,研究了反应条件对接枝共聚产品性能的影响。通过单因素及正交试验确定的最佳工艺参数分别为:搅拌速度为450rpm,引发剂浓度为1.5mmol/L,pH值为3-4,HLB值为6.0,乳化剂用量为8%,油水体积比为1.4:1,单体与淀粉配比为1.5:1,单体浓度为35%,丙烯酰胺:二甲基二烯丙基氯化铵为3:7,反应温度为45℃,反应时间为4h。最佳条件下制得的聚合物接枝率达到122.31%,接枝效率为92.19%,转化率为87.84%,阳离子度为21.45,特性粘数为628.73 ml/g。所得产品作絮凝剂处理硅藻土模拟水样及造纸厂废水研究表明,其具有良好的絮凝效果。絮凝效果明显优于市售聚丙烯酰胺。
对可生物降解的淀粉接枝共聚物和其工业应用的研究,对于改善淀粉加工性能,提高力学性能,增强低温水分散性和渗透力,从深度和广度上开发应用淀粉资源,充分发挥我国资源丰富的优势,促进工业发展及减少合成材料对环境的污染等多个方面具有一定的理论与实际应用价值。
The graft copolymers of starch, acrylamide, diallyl dimethyl ammonium chloride were synthesized by inversed emulsion copolymerization using ceric ammonium nitrate as initiator and the compounds of Span-80 and Op-4 as emulsifier. The excellent performance of starch-ethylene monomers graft copolymerization was prepared.
The graft copolymers were characterized and analyzed by IR and1H-NMR. The affection of synthesis conditions on the graft copolymers were discussed based on graft percentage、graft efficiency、monomers conversion ratio、cationic degree and intrinsic viscosity. The optimum experimentation parameters were determined by single factor experiments and orthogonal experiments as that: stir speed was 450rpm, initiator concentration was 1.5mmol/L,pH was 3-4, HLB was 6.0, emulsifier percentage was 8%, oil:water was 1.4:1(the ration of volume), monomers:starch was 1.5:1 (the ration of weight), monomers concentration was 35%, AM:DMDAAC was 3:7,reaction temperature was 45℃, reaction time was 4h. The product prepared during this condition graft percentage was 122.31%,graft efficiency was92.19 %, monomers conversion ratio was 87.84%, cationic degree was 21.45 and intrinsic viscosity was 628.73 mL/g.
When the copolymers were used in treatment for infusorial earth and papermaking waste water, it had high effect of flocculation. It had better effect on flocculation than commercial PAM.
The research of biodegradable starch graft copolymerization and its industry application has some theory and practice application value in meliorating starch machining performance, improving its mechanics capability, increasing its dispersion in water in low temperature and penetrability, exploiting and applying starch resource both in breadth and depth, exerting the resourceful advantage in our country in the most extent, advancing industry development and reducing environment pollution from synthesized material.
用傅立叶变换红外光谱和核磁共振波谱对产品进行了结构表征。通过接枝率、接枝效率、单体转化率、阳离子度和特性粘数等指标,研究了反应条件对接枝共聚产品性能的影响。通过单因素及正交试验确定的最佳工艺参数分别为:搅拌速度为450rpm,引发剂浓度为1.5mmol/L,pH值为3-4,HLB值为6.0,乳化剂用量为8%,油水体积比为1.4:1,单体与淀粉配比为1.5:1,单体浓度为35%,丙烯酰胺:二甲基二烯丙基氯化铵为3:7,反应温度为45℃,反应时间为4h。最佳条件下制得的聚合物接枝率达到122.31%,接枝效率为92.19%,转化率为87.84%,阳离子度为21.45,特性粘数为628.73 ml/g。所得产品作絮凝剂处理硅藻土模拟水样及造纸厂废水研究表明,其具有良好的絮凝效果。絮凝效果明显优于市售聚丙烯酰胺。
对可生物降解的淀粉接枝共聚物和其工业应用的研究,对于改善淀粉加工性能,提高力学性能,增强低温水分散性和渗透力,从深度和广度上开发应用淀粉资源,充分发挥我国资源丰富的优势,促进工业发展及减少合成材料对环境的污染等多个方面具有一定的理论与实际应用价值。
The graft copolymers of starch, acrylamide, diallyl dimethyl ammonium chloride were synthesized by inversed emulsion copolymerization using ceric ammonium nitrate as initiator and the compounds of Span-80 and Op-4 as emulsifier. The excellent performance of starch-ethylene monomers graft copolymerization was prepared.
The graft copolymers were characterized and analyzed by IR and1H-NMR. The affection of synthesis conditions on the graft copolymers were discussed based on graft percentage、graft efficiency、monomers conversion ratio、cationic degree and intrinsic viscosity. The optimum experimentation parameters were determined by single factor experiments and orthogonal experiments as that: stir speed was 450rpm, initiator concentration was 1.5mmol/L,pH was 3-4, HLB was 6.0, emulsifier percentage was 8%, oil:water was 1.4:1(the ration of volume), monomers:starch was 1.5:1 (the ration of weight), monomers concentration was 35%, AM:DMDAAC was 3:7,reaction temperature was 45℃, reaction time was 4h. The product prepared during this condition graft percentage was 122.31%,graft efficiency was92.19 %, monomers conversion ratio was 87.84%, cationic degree was 21.45 and intrinsic viscosity was 628.73 mL/g.
When the copolymers were used in treatment for infusorial earth and papermaking waste water, it had high effect of flocculation. It had better effect on flocculation than commercial PAM.
The research of biodegradable starch graft copolymerization and its industry application has some theory and practice application value in meliorating starch machining performance, improving its mechanics capability, increasing its dispersion in water in low temperature and penetrability, exploiting and applying starch resource both in breadth and depth, exerting the resourceful advantage in our country in the most extent, advancing industry development and reducing environment pollution from synthesized material.
引文
[1] Takeda Y, Hizukuri S, Juliano B O. Purification and structure of amylase from rice starch. Carbohydrate Research, 1986, 148:299~308
[2] Takeda Y, Shirasaka K, Hizukuri S. Examination of the purity and structure of amylase by gel-permeation chromatography. Carbohydrate Research, 1984, 132:83~92
[3]邓宇编.淀粉化学品及其应用.北京:化学工业出版社,2002:6.
[4] Kuakpetoon D, Wang Y J. Characterization of different starches oxidized by hypochlorite. Starch-Starke, 2001 (5): 211-218
[5]郭敏杰,刘振.我国淀粉接枝共聚改性的研究进展.化工生产与技术,2003,10(2):22~28
[6]王涛,葛福芃.羧甲基淀粉钠工业品的生产工艺研究.安徽理工大学学报(自然科学版),2003,23(2):57~60
[7] 王 香 爱 , 张 洪 利 . 低 取 代 度 阳 离 子 淀 粉 的 制 备 及 在 造 纸 上 的 应 用 . 化 工 科技,2007,15(2):20~23
[8]吕延文,吾国强,谢建伟.不溶性淀粉黄原酸酯的合成.天津化工,2002(5):8~9
[9]Stuart A S.Craig, Clodualdoc C.Maningat.el.al.Starch Paste Clarity.Cereal Chemistry, 1989, 66(3):173~182.
[10]张力田.变性淀粉.广州:华南理工大学出版社,1999:1~2; 6~11; 190~200.
[11] 王 刚 , 殷 立 雄 . 氧 化 锆 超 细 粉 体 及 其 制 备 技 术 综 述 . 西 北 轻 工 业 学 院 学报,2000,18(1):99~103
[12]张庆杰,张建军,周艳霞.二氧化锆的稳定化.无机盐工业,1998,30(6):21~23
[13] 张 明 杰 , 李 和 平 . 吸 水 性 淀 粉 接 枝 共 聚 树 脂 的 研 究 进 展 及 应 用 . 辽 宁 化工,2006,35(11):652~655
[14]Mino G, Kaizerman S. Synthesis and characterization of graft copolymer of starch with acrylic acid and acryl amide.Sci, 1985,25,1287
[15]Swapna Rao P. Subrahmanya S. Sathyanarayana. D N. Inverse emulsion polymerization: a new route for the synthesis of conduction polyaniline. Synthetic metals, 2002.128:311~316
[16] Athawale, V D.Vidyagauri L. Graft copolymerization onto starch. II. Grafting of acrylic acid and preparation of its hydrogels .Carbohydrate Polymers, 1998, 35(1-2):21~27
[17]马永生,邱化玉,王友才.淀粉接枝反应引发剂的进展.造纸化学品,2005, (1):19~24
[18]陈密封,朱琳晖,吉彦.引发剂在淀粉接枝反应中的研究与应用.化学世界,2001, (3):153~156
[19]Brockway, C E. Moser, K B. Grafting of polymath methacrylate to granular corn starch.Applied Polymer Sciecne.1963, Part A (1):1025-1039
[20] Trimnell D.Fanta G F, Salch J H. Graft polymerization of methyl acrylate onto granular starch: Comparison of the Fe2+/H2O2 and ceric initiating systems. Journal of Applied Polymer Science, 1996, 60(3):285~292
[21]李永红,蔡永红,张普玉.淀粉接枝改性的研究进展.河北化工,2005, (6):5~8
[22]何卫东.高分子化学实验.合肥:中国科学技术大学出版社,2003,141
[23]刘盈海,张劲松,李卫平. 二过碘酸合铜(III)钾引发丙烯酸甲酯在淀粉上接枝共聚合反应的研究.河北大学学报(自然科学版),2001, 21(1):57~60
[24] Jian-ping GAO, Ru-chuan Tian, Jiu-gao Yu, et al.Graft copolymers of methyl methacrylate onto canna starch using maganic pyrophosphate as a initiator.Applied polymer science, 1994, 53(8):1091-1102
[25]葛学武,徐相凌,张志成. 淀粉接枝丙烯酰胺制备絮凝剂的研究方法.高分子材料科学与工程,1999, 15(4):130~132
[26]Athawale V D, Lele V.Graft copolymerization of acryl amide onto starch initiated by ceric ammonium nitrate. Starch/Starke, 1998, 50(10):426~431
[27]易昌凤,周枝群,徐祖顺. Starch - g - PAM 絮凝剂的反相乳液合成及应用研究.湖北大学学报(自然科学版),2006, 28(2):172~175
[28]喻发全,黄世英,张宝真等. 紫外光引发淀粉接枝丙烯腈的研究(Ⅱ).高分子材料科学与工程,1999, 15(1):142~144
[29] Ming- zhu LIU, Shu- fu PENG. A novel method to prepare super absorbent polymers. Journal of Lanzhou University (Natural science), 2002, 38(3): 63- 66.
[30] Vilas D, Athawale, Vidyagaufi Lele. Recent trends in hydrgels based on starch- graft- acrylic: a review. Starch/Starke, 2001, 53(1): 7- 13.
[31]陈卓,范宏,洪涤.Fe2+-H2O2引发淀粉-二甲基二烯丙基氯化铵接枝共聚的研究.高分子材料科学与工程,2002, 18(4):81~84
[32]王立刚,李安东,杨杨.淀粉接枝MA共混LLDP可降解薄膜研究.塑料科技,2007,35 (12):54~57
[33] Athawale V D,Rathi S C. Effect of chain length of the alkyl group of alkyl methacrylates on graft polymerization onto starch using ceric ammonium nitrate as initiator.Eur Polym J,1997,33(7):1067~1071.
[34] Cho C G, Lee K H. Preparation of starch-g-polystyrene copolymer by emulsion polymerization. Carbohydrate Polymers, 2001(48):125~130.
[35]董延茂,路建美,鲍治宇.淀粉接枝聚合物的合成与性能研究.哈尔滨工业大学学报,2004,36(9):1161~1163.
[36]宋辉,马希晨. NaF对S-DMDAAC-AM合成及其絮凝性能的影响. LEATHER CHEMICALS, 2003, 20(1):34~38
[37]杨锦宗,曹亚峰,刘兆丽等.超高分子量淀粉接枝丙烯酰胺-丙烯酸共聚物的合成.高分子材料科学与工程,2004,20(5):89~92.
[38]陈苏,唐果东.淀粉与苯乙烯/甲基丙烯酸甲酯乳液共聚合.南京化工大学学报 ,2001, 23(6):92~94.
[39]葛玉斌,吴永革,孙文田等.多孔球状淀粉接枝共聚物的合成及其性质研究.高等学校化学学报,1997,18(6):978~985.
[40]马希晨,曹亚峰,邰玉蕾.以淀粉为基材的两性天然高分子絮凝剂的合成.大连轻工业学院学报,2002,21(3):157~160.
[41] Wong Sin Yeng, Paridah Md Tahir, Liew Kang Chiang, et al. Sago starch and its acrylamide modified products as coating material on hand sheets made from recycled pulp fibers. Journal Applied Polymer Science, 2004, 94:154~158.
[42] Youming, CAO. Xiaosun, QING, et al. Graft copolymerization of acrylamide onto carboxymethyl starch. European Polymer Journal, 2002, 38:1921~1924.
[43]惠泉,刘福胜,于丽明等.阳离子聚丙烯酰胺合成工艺研究进展.化工生产与技术, 2007,14(5):31~33
[44]孙衍宁,马希晨.淀粉改性阳离子絮凝剂的合成及应用.大连轻工业学院学报, 2006,25(2):114~117
[45]张洪涛,黄锦霞编著.乳液聚合新技术及应用.北京:化学工业出版社,2006:102.
[46]李淋,刘秉钺,曹亚峰.反相乳液聚合制备阳离子改性接枝淀粉.造纸化学品,2005, (1):59~62
[47] Leong Y S, Candau F. Inverse micro emulsion polymerization. Phys Chem., 1982, 86(12): 2269.
[48] Candau F, Pabon M, Anquetil J Y. Polymerizable micro emulsions: some criteria to achieve an optimalformulation.Colloids and Surfaces, 1999, 153: 47~59.
[49] Puig L J, Sanchez D, Villacampa M, et al. Micro structured Polyacrylamide Hydro gels Prepared Via Inverse Micro emulsion Polymerization. J Colloid Inter Sci, 2001, 235(2): 278~ 282.
[50] Jian-ping GAO, Jiu-gao YU, Wei WANG, et al. Graft copolymerization of Starch-AN Initiated by Potassium Permanganate. Applied polymer science, 1998, 68 (12): 1965-1972
[51]李淑红,俞敦义,罗逸等.淀粉改性絮凝剂的制备及其在高矿化度油田水处理中的应用.水处理技术,2002, 28(4):220~223
[52]刘祥义,徐晓军.改性淀粉絮凝剂的制备与应用研究进展.胶体与聚合物,2004, 22(2):38~40
[53]陆敏.高吸水性树脂的合成方法及应用前景.高师理科学刊,2000, (2):45~47
[54]曹会兰,李雅丽.吸水性淀粉接枝共聚树脂的研究进展及应用.应用化工,2003, 32(1):12~14
[55]乔长安.淀粉接枝共聚技术及应用.西部粮油科技,1999, 24(3):33~34
[56]王康健,唐琴琼,王芸.淀粉接枝共聚物应用研究进展.胶体与聚合物,2005, 23(1):43~44
[57]赵建国,徐进.淀粉高吸水性树脂的制备与应用.淀粉与淀粉糖. 1997, 2(34):18~21
[58] Fanta F., Frederick C. Felker, John H. Salch. Graft polymerization of acrylonitrile onto starch-coated polyethylene film surfaces. Applied Polymer science, 2003, 89(12):3 323~3328.
[59] 武 海 良 , 顾 振 亚 . 经 纱 上 浆 用 淀 粉 接 枝 共 聚 物 的 开 发 与 展 望 . 棉 纺 织 技术,2003,31(3):17~20.
[60] Hany El-Hamshary, Samia Al-Sigeny. Catalytic activities of amino acid modified starch-grafted acryl amide for the decomposition of hydrogen peroxide.Appl Polym Sci, 2004, 93 (1): 630~636
[61] Manolache S, Samadi M, et al. Synthesis of starch copolymers by silicon tetrachloride plasma-induced graft polymerization.Starch-starke, 2004, 56 (2):47~57
[62]宋辉,马希晨, NaF 对 S ? DMDAAC ? AM合成及其絮凝性能的影响,LEATHER CHEMICALS,No.1, Vol.20, 34~38.
[63]徐勉懿,方国春,潘祖亭等.无机及分析化学实验.武汉大学出版社,1991:84~86.
[2] Takeda Y, Shirasaka K, Hizukuri S. Examination of the purity and structure of amylase by gel-permeation chromatography. Carbohydrate Research, 1984, 132:83~92
[3]邓宇编.淀粉化学品及其应用.北京:化学工业出版社,2002:6.
[4] Kuakpetoon D, Wang Y J. Characterization of different starches oxidized by hypochlorite. Starch-Starke, 2001 (5): 211-218
[5]郭敏杰,刘振.我国淀粉接枝共聚改性的研究进展.化工生产与技术,2003,10(2):22~28
[6]王涛,葛福芃.羧甲基淀粉钠工业品的生产工艺研究.安徽理工大学学报(自然科学版),2003,23(2):57~60
[7] 王 香 爱 , 张 洪 利 . 低 取 代 度 阳 离 子 淀 粉 的 制 备 及 在 造 纸 上 的 应 用 . 化 工 科技,2007,15(2):20~23
[8]吕延文,吾国强,谢建伟.不溶性淀粉黄原酸酯的合成.天津化工,2002(5):8~9
[9]Stuart A S.Craig, Clodualdoc C.Maningat.el.al.Starch Paste Clarity.Cereal Chemistry, 1989, 66(3):173~182.
[10]张力田.变性淀粉.广州:华南理工大学出版社,1999:1~2; 6~11; 190~200.
[11] 王 刚 , 殷 立 雄 . 氧 化 锆 超 细 粉 体 及 其 制 备 技 术 综 述 . 西 北 轻 工 业 学 院 学报,2000,18(1):99~103
[12]张庆杰,张建军,周艳霞.二氧化锆的稳定化.无机盐工业,1998,30(6):21~23
[13] 张 明 杰 , 李 和 平 . 吸 水 性 淀 粉 接 枝 共 聚 树 脂 的 研 究 进 展 及 应 用 . 辽 宁 化工,2006,35(11):652~655
[14]Mino G, Kaizerman S. Synthesis and characterization of graft copolymer of starch with acrylic acid and acryl amide.Sci, 1985,25,1287
[15]Swapna Rao P. Subrahmanya S. Sathyanarayana. D N. Inverse emulsion polymerization: a new route for the synthesis of conduction polyaniline. Synthetic metals, 2002.128:311~316
[16] Athawale, V D.Vidyagauri L. Graft copolymerization onto starch. II. Grafting of acrylic acid and preparation of its hydrogels .Carbohydrate Polymers, 1998, 35(1-2):21~27
[17]马永生,邱化玉,王友才.淀粉接枝反应引发剂的进展.造纸化学品,2005, (1):19~24
[18]陈密封,朱琳晖,吉彦.引发剂在淀粉接枝反应中的研究与应用.化学世界,2001, (3):153~156
[19]Brockway, C E. Moser, K B. Grafting of polymath methacrylate to granular corn starch.Applied Polymer Sciecne.1963, Part A (1):1025-1039
[20] Trimnell D.Fanta G F, Salch J H. Graft polymerization of methyl acrylate onto granular starch: Comparison of the Fe2+/H2O2 and ceric initiating systems. Journal of Applied Polymer Science, 1996, 60(3):285~292
[21]李永红,蔡永红,张普玉.淀粉接枝改性的研究进展.河北化工,2005, (6):5~8
[22]何卫东.高分子化学实验.合肥:中国科学技术大学出版社,2003,141
[23]刘盈海,张劲松,李卫平. 二过碘酸合铜(III)钾引发丙烯酸甲酯在淀粉上接枝共聚合反应的研究.河北大学学报(自然科学版),2001, 21(1):57~60
[24] Jian-ping GAO, Ru-chuan Tian, Jiu-gao Yu, et al.Graft copolymers of methyl methacrylate onto canna starch using maganic pyrophosphate as a initiator.Applied polymer science, 1994, 53(8):1091-1102
[25]葛学武,徐相凌,张志成. 淀粉接枝丙烯酰胺制备絮凝剂的研究方法.高分子材料科学与工程,1999, 15(4):130~132
[26]Athawale V D, Lele V.Graft copolymerization of acryl amide onto starch initiated by ceric ammonium nitrate. Starch/Starke, 1998, 50(10):426~431
[27]易昌凤,周枝群,徐祖顺. Starch - g - PAM 絮凝剂的反相乳液合成及应用研究.湖北大学学报(自然科学版),2006, 28(2):172~175
[28]喻发全,黄世英,张宝真等. 紫外光引发淀粉接枝丙烯腈的研究(Ⅱ).高分子材料科学与工程,1999, 15(1):142~144
[29] Ming- zhu LIU, Shu- fu PENG. A novel method to prepare super absorbent polymers. Journal of Lanzhou University (Natural science), 2002, 38(3): 63- 66.
[30] Vilas D, Athawale, Vidyagaufi Lele. Recent trends in hydrgels based on starch- graft- acrylic: a review. Starch/Starke, 2001, 53(1): 7- 13.
[31]陈卓,范宏,洪涤.Fe2+-H2O2引发淀粉-二甲基二烯丙基氯化铵接枝共聚的研究.高分子材料科学与工程,2002, 18(4):81~84
[32]王立刚,李安东,杨杨.淀粉接枝MA共混LLDP可降解薄膜研究.塑料科技,2007,35 (12):54~57
[33] Athawale V D,Rathi S C. Effect of chain length of the alkyl group of alkyl methacrylates on graft polymerization onto starch using ceric ammonium nitrate as initiator.Eur Polym J,1997,33(7):1067~1071.
[34] Cho C G, Lee K H. Preparation of starch-g-polystyrene copolymer by emulsion polymerization. Carbohydrate Polymers, 2001(48):125~130.
[35]董延茂,路建美,鲍治宇.淀粉接枝聚合物的合成与性能研究.哈尔滨工业大学学报,2004,36(9):1161~1163.
[36]宋辉,马希晨. NaF对S-DMDAAC-AM合成及其絮凝性能的影响. LEATHER CHEMICALS, 2003, 20(1):34~38
[37]杨锦宗,曹亚峰,刘兆丽等.超高分子量淀粉接枝丙烯酰胺-丙烯酸共聚物的合成.高分子材料科学与工程,2004,20(5):89~92.
[38]陈苏,唐果东.淀粉与苯乙烯/甲基丙烯酸甲酯乳液共聚合.南京化工大学学报 ,2001, 23(6):92~94.
[39]葛玉斌,吴永革,孙文田等.多孔球状淀粉接枝共聚物的合成及其性质研究.高等学校化学学报,1997,18(6):978~985.
[40]马希晨,曹亚峰,邰玉蕾.以淀粉为基材的两性天然高分子絮凝剂的合成.大连轻工业学院学报,2002,21(3):157~160.
[41] Wong Sin Yeng, Paridah Md Tahir, Liew Kang Chiang, et al. Sago starch and its acrylamide modified products as coating material on hand sheets made from recycled pulp fibers. Journal Applied Polymer Science, 2004, 94:154~158.
[42] Youming, CAO. Xiaosun, QING, et al. Graft copolymerization of acrylamide onto carboxymethyl starch. European Polymer Journal, 2002, 38:1921~1924.
[43]惠泉,刘福胜,于丽明等.阳离子聚丙烯酰胺合成工艺研究进展.化工生产与技术, 2007,14(5):31~33
[44]孙衍宁,马希晨.淀粉改性阳离子絮凝剂的合成及应用.大连轻工业学院学报, 2006,25(2):114~117
[45]张洪涛,黄锦霞编著.乳液聚合新技术及应用.北京:化学工业出版社,2006:102.
[46]李淋,刘秉钺,曹亚峰.反相乳液聚合制备阳离子改性接枝淀粉.造纸化学品,2005, (1):59~62
[47] Leong Y S, Candau F. Inverse micro emulsion polymerization. Phys Chem., 1982, 86(12): 2269.
[48] Candau F, Pabon M, Anquetil J Y. Polymerizable micro emulsions: some criteria to achieve an optimalformulation.Colloids and Surfaces, 1999, 153: 47~59.
[49] Puig L J, Sanchez D, Villacampa M, et al. Micro structured Polyacrylamide Hydro gels Prepared Via Inverse Micro emulsion Polymerization. J Colloid Inter Sci, 2001, 235(2): 278~ 282.
[50] Jian-ping GAO, Jiu-gao YU, Wei WANG, et al. Graft copolymerization of Starch-AN Initiated by Potassium Permanganate. Applied polymer science, 1998, 68 (12): 1965-1972
[51]李淑红,俞敦义,罗逸等.淀粉改性絮凝剂的制备及其在高矿化度油田水处理中的应用.水处理技术,2002, 28(4):220~223
[52]刘祥义,徐晓军.改性淀粉絮凝剂的制备与应用研究进展.胶体与聚合物,2004, 22(2):38~40
[53]陆敏.高吸水性树脂的合成方法及应用前景.高师理科学刊,2000, (2):45~47
[54]曹会兰,李雅丽.吸水性淀粉接枝共聚树脂的研究进展及应用.应用化工,2003, 32(1):12~14
[55]乔长安.淀粉接枝共聚技术及应用.西部粮油科技,1999, 24(3):33~34
[56]王康健,唐琴琼,王芸.淀粉接枝共聚物应用研究进展.胶体与聚合物,2005, 23(1):43~44
[57]赵建国,徐进.淀粉高吸水性树脂的制备与应用.淀粉与淀粉糖. 1997, 2(34):18~21
[58] Fanta F., Frederick C. Felker, John H. Salch. Graft polymerization of acrylonitrile onto starch-coated polyethylene film surfaces. Applied Polymer science, 2003, 89(12):3 323~3328.
[59] 武 海 良 , 顾 振 亚 . 经 纱 上 浆 用 淀 粉 接 枝 共 聚 物 的 开 发 与 展 望 . 棉 纺 织 技术,2003,31(3):17~20.
[60] Hany El-Hamshary, Samia Al-Sigeny. Catalytic activities of amino acid modified starch-grafted acryl amide for the decomposition of hydrogen peroxide.Appl Polym Sci, 2004, 93 (1): 630~636
[61] Manolache S, Samadi M, et al. Synthesis of starch copolymers by silicon tetrachloride plasma-induced graft polymerization.Starch-starke, 2004, 56 (2):47~57
[62]宋辉,马希晨, NaF 对 S ? DMDAAC ? AM合成及其絮凝性能的影响,LEATHER CHEMICALS,No.1, Vol.20, 34~38.
[63]徐勉懿,方国春,潘祖亭等.无机及分析化学实验.武汉大学出版社,1991:84~86.