高分子基环境响应性肥料的研究进展
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摘要
随着农业现代化进程的不断推进和高分子材料的不断发展,环境响应性肥料作为一种新型的功能化肥料正受到越来越多研究者的关注.环境响应性肥料是指能够根据温度和土壤环境中特定的刺激响应信号来改变吸水、保水和养分释放等行为,从而达到智能调控土壤中水分和养分的新型多功能肥料.本文首先简要介绍了肥料的发展阶段,然后根据外界刺激信号的不同和肥料实际的应用效果,将环境响应性肥料分为温度响应性肥料、pH响应性肥料和盐敏感性肥料,并对其制备方法、刺激响应行为和应用领域进行了综述.可以预期,天然高分子基环境响应性肥料、多重响应性智能肥料和生物响应性肥料的制备及其应用研究将会成为今后肥料科学的发展趋势.
Mineral nutrients from environment are required for plants growing, but the natural nutrients from soil can not completely meet the need. Therefore, use of fertilizers is the simple, effective and fast method to increase the yield and to improve the quality of the grains. However, only a small amount of the fertilizers used can be effectively absorbed by crops, and most of them are lost by volatilizing into the atmosphere or leaching into the ground, which leads to a serious waste of the fertilizers with severe environmental pollution(e.g. acidic rain, soil salinization and greenhouse gas release etc.). To solve these problems, polymer-based slow-release fertilizers were developed by functional modification to control the release of the nutrients and to prolong the effective use of the fertilizer. However, the release behavior of these slow-release fertilizers is always influenced by some factors such as temperature, humidity, pH and salinization of soil in practical applications. To address this issue, intelligent fertilizer, i.e. fertilizer with functional controlled-release, has been developed to regulate the release of various nutrients in accordance with the change of soil environment and the different stages of plant growth. Especially, polymer-based environment-responsive fertilizer, as an intelligent fertilizer, can change water absorbency, water-holding capacity and nutrient release behavior, by intelligently regulating water and nutrients in soil according to specific stimulus response signals of soil environment, such as temperature, humidity, pH value and ion concentration. This review briefly introduces the development stages of the fertilizer and their classification. On the basis of different stimulation signals from the environment and actual application, these environment-responsive fertilizers are classified as temperature-responsive, pH-responsive and salt-sensitive fertilizers. Their preparations, properties, stimulus-responsive behaviors and application are introduced in detail. Intelligentialization of the fertilizer is an important tendency in agriculture and horticulture field, and the polymer-based environment-responsive fertilizer has great potential in fertilizer development and application. With the development of agricultural modernization and polymer science, it can be expected that the preparation and application of the natural polymer-based responsive fertilizer, the multiple-responsive fertilizer and the biologically responsive fertilizer will be research trends in the fertilizer fields.
Mineral nutrients from environment are required for plants growing, but the natural nutrients from soil can not completely meet the need. Therefore, use of fertilizers is the simple, effective and fast method to increase the yield and to improve the quality of the grains. However, only a small amount of the fertilizers used can be effectively absorbed by crops, and most of them are lost by volatilizing into the atmosphere or leaching into the ground, which leads to a serious waste of the fertilizers with severe environmental pollution(e.g. acidic rain, soil salinization and greenhouse gas release etc.). To solve these problems, polymer-based slow-release fertilizers were developed by functional modification to control the release of the nutrients and to prolong the effective use of the fertilizer. However, the release behavior of these slow-release fertilizers is always influenced by some factors such as temperature, humidity, pH and salinization of soil in practical applications. To address this issue, intelligent fertilizer, i.e. fertilizer with functional controlled-release, has been developed to regulate the release of various nutrients in accordance with the change of soil environment and the different stages of plant growth. Especially, polymer-based environment-responsive fertilizer, as an intelligent fertilizer, can change water absorbency, water-holding capacity and nutrient release behavior, by intelligently regulating water and nutrients in soil according to specific stimulus response signals of soil environment, such as temperature, humidity, pH value and ion concentration. This review briefly introduces the development stages of the fertilizer and their classification. On the basis of different stimulation signals from the environment and actual application, these environment-responsive fertilizers are classified as temperature-responsive, pH-responsive and salt-sensitive fertilizers. Their preparations, properties, stimulus-responsive behaviors and application are introduced in detail. Intelligentialization of the fertilizer is an important tendency in agriculture and horticulture field, and the polymer-based environment-responsive fertilizer has great potential in fertilizer development and application. With the development of agricultural modernization and polymer science, it can be expected that the preparation and application of the natural polymer-based responsive fertilizer, the multiple-responsive fertilizer and the biologically responsive fertilizer will be research trends in the fertilizer fields.
引文
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2 Liu W,Qiu R.J Chem Technol Biot,2007,82(9):781-786
3 Conley D J,Paerl H W,Hwarth R W,Boesch D F,Seitzinger S P,Havens K E,Lancelot C,Likens G E.Science,2009,323(5917):1014-1015
4 Matson P A,Naylor R,Ortiz-Monasterio I I.Science,1998,280(5360):112-115
5 Chien S H,Prochnow L I,Tu S,Snyder C.Nutr Cycl Agroecosyst,2011,89(2):229-255
6 Shavit U,Shaviv A,Shalit G,Zaslavsky D.J Control Release,1997,43(2):131-138
7 Li Shengxiu(李生秀).J Plant Nutr Fertilizer(植物营养与肥料学报),1999,(3):193-205
8 Liang R,Liu M Z.J Agr Food Chem,2006,54(4):1392-1398
9 Wu L,Liu M Z,Liang R.Bioresource Technol,2008,99(3):547-554
10 Wu L,Liu M Z.Carbohyd Polym,2008,72(2):240-247
11 Liang R,Liu M Z.Ind Eng Chem Res,2006,45(25):8610-8616
12 Guo M Y,Liu M Z,Zhan F L,Wu L.Ind Eng Chem Res,2005,44(12):4206-4211
13 Ni B L,Liu M Z,LüS Y.Chem Eng J,2009,155(3):892-898
14 Ni B L,Liu M Z,LüS Y,Xie L H,Zhang X,Wang Y F.Ind Eng Chem Res,2010,49(10):4546-4552
15 Ni B L,Liu M Z,LüS Y,Xie L H,Wang Y F.J Agr Food Chem,2010,58(23):12373-12378
16 Azeem B,Ku Shaari K Z,Man Z B,Basit A,Thanh T H.J Control Release,2014,181:11-21
17 Husby C E,Niemiera A X,Harris J R,Wright R D.Hortscience,2003,38(3):387-389
18 Tlustos P,Blackmer A M.Soil Sci Soc Am J,1992,56(6):1807-1810
19 Ewen H,Jahns T.Recent Res Dev Microbiol,2000,4(2):537-546
20 Bao Xianyang(鲍先扬),Amjad A,Qiao Dongling(乔冬玲),Liu Hongsheng(刘宏生),Chen Ling(陈玲),Yu Long(余龙).Acta Polymerica Sinica(高分子学报),2015,(9):1010-1019
21 Yin X,Hoffman A S,Stayton P S.Biomacromolecules,2006,7(5):1381-1385
22 Zhang Haixuan(张海璇),Meng Xun(孟旬),Li Ping(李平).Progress in Chemistry(化学进展),2008,20(5):657-672
23 Roy D,Cambre J N,Sumerlin B S.Prog Polym Sci,2010,35(1):278-301
24 Wang X G,LüS Y,Gao C M,Xu X B,Wei Y,Bai X,Feng C,Gao N N,Liu M Z,Wu L.RSC Adv,2014,4(35):18382-18390
25 Wang X G,LüS Y,Gao C M,Xu X B,Zhang X J,Bai X,Liu M Z,Wu L.Chem Eng J,2014,252:404-414
26 LüS Y,Gao C M,Wang X G,Xu X B,Bai X,Gao N N,Feng C,Wei Y,Wu L,Liu M Z.RSC Adv,2014,4(93):51208-51214
27 LüS Y,Feng C,Gao C M,Wang X G,Xu X B,Bai X,Gao N N,Liu M Z.J Agr Food Chem,2016,64(24):4965-4974
28 Wang Y F,Liu M Z,Ni B L,Xie L H,Zhang X.J Macromol Sci A,2011,48(10):806-815
29 Xie L H,LüS Y,Liu M Z,Gao C M,Wang X G,Wu L.J Agr food Chem,2013,61(14):3382-3388
30 Xie L H,Liu M Z,Ni.L,Wang Y F.J Agr Food Chem,2012,60(28):6921-6928
31 Daly E,Saunders B R.Langmuir,2000,16(13):5546-5552
32 Pan Gaoxiang(潘高翔),Feng Ze(冯泽),Wei Jia(韦嘉),Yu Yanlei(俞燕蕾).Acta Chimica Sinica(化学学报),2013,71(5):733-738
33 Bradley M,Vincent B,Warren N,Eastoe J,Vesperinas A.Langmuir,2006,22(1):101-105
34 Dalmont H,Pinprayoon O,Saunders B R.Langmuir,2008,24(6):2834-2840
35 Liu Shouxin(刘守信),Fang Yu(房喻),Liu Mingzhu(柳明珠),Wang Mingzhen(王明珍),Wang Zhuanrong(王转绒).Acta Chimica Sinica(化学学报),2006,64(15):1575-1580
36 Wang Zhen(王振),Guo Dongsheng(郭东升),Zhang Jie(张捷),Liu Yu(刘育).Acta Chimica Sinica(化学学报),2012,70(16):1709-1715
37 Ma Z Y,Jia X,Hu J M,Liu Z Y,Wang H Y,Zhou F.J Agric Food Chem,2013,61:12232-12237
38 Zhang Y,Liang X Y,Yang X G,Liu H Y,Yao J M.ACS Sustain Chem Eng,2014,2(7):1871-1878
39 Cheng Dongdong(程冬冬),Zhao Guizhe(赵贵哲),Liu Yaqing(刘亚青),Hao Shuaiqun(郝率群).J Soil Water Conservation(水土保持学报),2013,27(6):216-220
40 Zou Hongtao(邹洪涛),Han Yanyu(韩艳玉),Zhang Yuling(张玉玲),Huang Yi(黄毅),Cao Minjian(曹敏建),Zhang Yulong(张玉龙).Chinese J Soil Sci(土壤通报),2009,(2):321-324
41 Jarosiewicz A,Tomaszewska M.J Agr Food Chem,2003,51(2):413-417
42 Ni B L,Liu M Z,LüS Y,Xie L H,Wang Y F.J Agr Food Chem,2011,59(18):10169-10175
43 Du C W,Zhou J M,Shaviv A.J Polym the Environ,2006,14(3):223-230
44 Adams C,Frantz J,Bugbee B.J Plant Nutr Soil Sci,2013,176(1):76-88
45 Guo J H,Liu X J,Zhang Y,Shen J L,Han W X,Zhang W F.Science,2010,327(5968):1008-1010
46 Lal R.Soil Till Res,1997,42:145
47 Wang M,Zhang G L,Zhou L L,Wang D F,Zhong N Q,Cai D Q,Wu Z Y.ACS Sustain Chem Eng,2016,4(12):6800-6808
48 Hill M R,Mac Krell E J,Forsthoefel C P,Jensen S P,Chen M S,Moore G A,He Z L,Sumerlin B S.Biomacromolecules,2015,16:1276-1280
49 Ma Z Y,Jia X,Zhang G X,Hu J M,Zhang X L,Liu Z Y,Wang H Y,Zhou F.J Agric Food Chem,2013,61:5474-5482
50 Feng C,LüS Y,Gao C M,Wang X G,Xu X B,Bai X,Gao N N,Liu M Z,Wu L.ACS Sustain Chem Eng,2015,3(12):3157-3166
51 Cheng D D,Zhao G Z,Bai T,Liu Y Q.J Chem Soc Pakistan,2014,36(4):647-653
52 Cheng Dongdong(程冬冬),Dou Wuhong(窦午红),Zhao Guizhe(赵贵哲),Liu Yaqing(刘亚青).J Basic Sci Eng(应用基础与工程科学学报),2015,(3):484-492
53 Wen P,Wu Z S,He Y H,Ye B C,Han Y J,Wang J,Guan X Y.ACS Sustain Chem Eng,2016,4:6572-6579
54 Wang X G,LüS Y,Gao C M,Feng C,Xu X B,Bai X,Gao N N,Yang J L,Liu M Z,Wu L.ACS Sustain Chem Eng,2016,4:2068-2079
55 Dai H J,Huang H H.J Agr Food Chem,2017,65:565-574
56 Wang W,Wang A.Carbohydr Polym,2010,80:1028-1036
57 Mahdavinia G R,Zohuriaan-Mehr M J,Pourjavadi A.Polym Adv Technol,2004,15:173-180
58 Li X D,Li Q,Su Y,Yue Q Y,Gao B Y,Su Y J.Taiwan Inst Chem Eng,2015,55:170-179
59 Ghassemi F,Jakeman A J,Nix H A.Salinisation of Land and Water Rresources:Human Causes,Extent,Management and Case Studies.Australia:Univ New South Wales Press,1995.1-3
60 Qian Yibing(钱亦兵),Zhou Huarong(周华荣).J Soil Water Conservation(水土保持学报),2004,18(2):186-188
61 Xu X H,Su X Y,Bai B,Wang H L,Suo Y R.RSC Adv,2016,6:103199-103209
62 Giri T K,Pradhan M,Tripathi D K.Turk J Chem,2016,40(2):283-295
63 El Salmawi K M,Ibrahim S M.Macromol Res,2011,19(10):1029-1034
2 Liu W,Qiu R.J Chem Technol Biot,2007,82(9):781-786
3 Conley D J,Paerl H W,Hwarth R W,Boesch D F,Seitzinger S P,Havens K E,Lancelot C,Likens G E.Science,2009,323(5917):1014-1015
4 Matson P A,Naylor R,Ortiz-Monasterio I I.Science,1998,280(5360):112-115
5 Chien S H,Prochnow L I,Tu S,Snyder C.Nutr Cycl Agroecosyst,2011,89(2):229-255
6 Shavit U,Shaviv A,Shalit G,Zaslavsky D.J Control Release,1997,43(2):131-138
7 Li Shengxiu(李生秀).J Plant Nutr Fertilizer(植物营养与肥料学报),1999,(3):193-205
8 Liang R,Liu M Z.J Agr Food Chem,2006,54(4):1392-1398
9 Wu L,Liu M Z,Liang R.Bioresource Technol,2008,99(3):547-554
10 Wu L,Liu M Z.Carbohyd Polym,2008,72(2):240-247
11 Liang R,Liu M Z.Ind Eng Chem Res,2006,45(25):8610-8616
12 Guo M Y,Liu M Z,Zhan F L,Wu L.Ind Eng Chem Res,2005,44(12):4206-4211
13 Ni B L,Liu M Z,LüS Y.Chem Eng J,2009,155(3):892-898
14 Ni B L,Liu M Z,LüS Y,Xie L H,Zhang X,Wang Y F.Ind Eng Chem Res,2010,49(10):4546-4552
15 Ni B L,Liu M Z,LüS Y,Xie L H,Wang Y F.J Agr Food Chem,2010,58(23):12373-12378
16 Azeem B,Ku Shaari K Z,Man Z B,Basit A,Thanh T H.J Control Release,2014,181:11-21
17 Husby C E,Niemiera A X,Harris J R,Wright R D.Hortscience,2003,38(3):387-389
18 Tlustos P,Blackmer A M.Soil Sci Soc Am J,1992,56(6):1807-1810
19 Ewen H,Jahns T.Recent Res Dev Microbiol,2000,4(2):537-546
20 Bao Xianyang(鲍先扬),Amjad A,Qiao Dongling(乔冬玲),Liu Hongsheng(刘宏生),Chen Ling(陈玲),Yu Long(余龙).Acta Polymerica Sinica(高分子学报),2015,(9):1010-1019
21 Yin X,Hoffman A S,Stayton P S.Biomacromolecules,2006,7(5):1381-1385
22 Zhang Haixuan(张海璇),Meng Xun(孟旬),Li Ping(李平).Progress in Chemistry(化学进展),2008,20(5):657-672
23 Roy D,Cambre J N,Sumerlin B S.Prog Polym Sci,2010,35(1):278-301
24 Wang X G,LüS Y,Gao C M,Xu X B,Wei Y,Bai X,Feng C,Gao N N,Liu M Z,Wu L.RSC Adv,2014,4(35):18382-18390
25 Wang X G,LüS Y,Gao C M,Xu X B,Zhang X J,Bai X,Liu M Z,Wu L.Chem Eng J,2014,252:404-414
26 LüS Y,Gao C M,Wang X G,Xu X B,Bai X,Gao N N,Feng C,Wei Y,Wu L,Liu M Z.RSC Adv,2014,4(93):51208-51214
27 LüS Y,Feng C,Gao C M,Wang X G,Xu X B,Bai X,Gao N N,Liu M Z.J Agr Food Chem,2016,64(24):4965-4974
28 Wang Y F,Liu M Z,Ni B L,Xie L H,Zhang X.J Macromol Sci A,2011,48(10):806-815
29 Xie L H,LüS Y,Liu M Z,Gao C M,Wang X G,Wu L.J Agr food Chem,2013,61(14):3382-3388
30 Xie L H,Liu M Z,Ni.L,Wang Y F.J Agr Food Chem,2012,60(28):6921-6928
31 Daly E,Saunders B R.Langmuir,2000,16(13):5546-5552
32 Pan Gaoxiang(潘高翔),Feng Ze(冯泽),Wei Jia(韦嘉),Yu Yanlei(俞燕蕾).Acta Chimica Sinica(化学学报),2013,71(5):733-738
33 Bradley M,Vincent B,Warren N,Eastoe J,Vesperinas A.Langmuir,2006,22(1):101-105
34 Dalmont H,Pinprayoon O,Saunders B R.Langmuir,2008,24(6):2834-2840
35 Liu Shouxin(刘守信),Fang Yu(房喻),Liu Mingzhu(柳明珠),Wang Mingzhen(王明珍),Wang Zhuanrong(王转绒).Acta Chimica Sinica(化学学报),2006,64(15):1575-1580
36 Wang Zhen(王振),Guo Dongsheng(郭东升),Zhang Jie(张捷),Liu Yu(刘育).Acta Chimica Sinica(化学学报),2012,70(16):1709-1715
37 Ma Z Y,Jia X,Hu J M,Liu Z Y,Wang H Y,Zhou F.J Agric Food Chem,2013,61:12232-12237
38 Zhang Y,Liang X Y,Yang X G,Liu H Y,Yao J M.ACS Sustain Chem Eng,2014,2(7):1871-1878
39 Cheng Dongdong(程冬冬),Zhao Guizhe(赵贵哲),Liu Yaqing(刘亚青),Hao Shuaiqun(郝率群).J Soil Water Conservation(水土保持学报),2013,27(6):216-220
40 Zou Hongtao(邹洪涛),Han Yanyu(韩艳玉),Zhang Yuling(张玉玲),Huang Yi(黄毅),Cao Minjian(曹敏建),Zhang Yulong(张玉龙).Chinese J Soil Sci(土壤通报),2009,(2):321-324
41 Jarosiewicz A,Tomaszewska M.J Agr Food Chem,2003,51(2):413-417
42 Ni B L,Liu M Z,LüS Y,Xie L H,Wang Y F.J Agr Food Chem,2011,59(18):10169-10175
43 Du C W,Zhou J M,Shaviv A.J Polym the Environ,2006,14(3):223-230
44 Adams C,Frantz J,Bugbee B.J Plant Nutr Soil Sci,2013,176(1):76-88
45 Guo J H,Liu X J,Zhang Y,Shen J L,Han W X,Zhang W F.Science,2010,327(5968):1008-1010
46 Lal R.Soil Till Res,1997,42:145
47 Wang M,Zhang G L,Zhou L L,Wang D F,Zhong N Q,Cai D Q,Wu Z Y.ACS Sustain Chem Eng,2016,4(12):6800-6808
48 Hill M R,Mac Krell E J,Forsthoefel C P,Jensen S P,Chen M S,Moore G A,He Z L,Sumerlin B S.Biomacromolecules,2015,16:1276-1280
49 Ma Z Y,Jia X,Zhang G X,Hu J M,Zhang X L,Liu Z Y,Wang H Y,Zhou F.J Agric Food Chem,2013,61:5474-5482
50 Feng C,LüS Y,Gao C M,Wang X G,Xu X B,Bai X,Gao N N,Liu M Z,Wu L.ACS Sustain Chem Eng,2015,3(12):3157-3166
51 Cheng D D,Zhao G Z,Bai T,Liu Y Q.J Chem Soc Pakistan,2014,36(4):647-653
52 Cheng Dongdong(程冬冬),Dou Wuhong(窦午红),Zhao Guizhe(赵贵哲),Liu Yaqing(刘亚青).J Basic Sci Eng(应用基础与工程科学学报),2015,(3):484-492
53 Wen P,Wu Z S,He Y H,Ye B C,Han Y J,Wang J,Guan X Y.ACS Sustain Chem Eng,2016,4:6572-6579
54 Wang X G,LüS Y,Gao C M,Feng C,Xu X B,Bai X,Gao N N,Yang J L,Liu M Z,Wu L.ACS Sustain Chem Eng,2016,4:2068-2079
55 Dai H J,Huang H H.J Agr Food Chem,2017,65:565-574
56 Wang W,Wang A.Carbohydr Polym,2010,80:1028-1036
57 Mahdavinia G R,Zohuriaan-Mehr M J,Pourjavadi A.Polym Adv Technol,2004,15:173-180
58 Li X D,Li Q,Su Y,Yue Q Y,Gao B Y,Su Y J.Taiwan Inst Chem Eng,2015,55:170-179
59 Ghassemi F,Jakeman A J,Nix H A.Salinisation of Land and Water Rresources:Human Causes,Extent,Management and Case Studies.Australia:Univ New South Wales Press,1995.1-3
60 Qian Yibing(钱亦兵),Zhou Huarong(周华荣).J Soil Water Conservation(水土保持学报),2004,18(2):186-188
61 Xu X H,Su X Y,Bai B,Wang H L,Suo Y R.RSC Adv,2016,6:103199-103209
62 Giri T K,Pradhan M,Tripathi D K.Turk J Chem,2016,40(2):283-295
63 El Salmawi K M,Ibrahim S M.Macromol Res,2011,19(10):1029-1034