“第七届全国绿色环保肥料（农药）新技术、新产品交流会”专题报告——缓释腐植酸复合高吸水性树脂

1缓释腐植酸复合保水剂 高吸水性树脂不但可以大大降低生产成本，而且还具有显著吸水能力，在沙土中加入高吸水性树脂能显著提高其保水性能，30d后仍然能保持13％的水分。此外，GG-g—PAA／SH高吸水性树脂还具有较优的反复溶胀性能和SH肥料缓释功能，该树脂可用作兼具吸水、保水和肥料缓释性能的新型节水材料。     

交联度对瓜尔胶-g-聚丙烯酸／腐植酸钠高吸水性树脂性能的影响

以天然瓜尔胶（Go）,丙烯酸（AA）和腐植酸钠（SIll为原料,N,N’一亚甲基双丙烯酰胺（MBA）为交联剂,采用水溶液聚合法制备了该高吸水性接枝树脂。研究了交联度对树脂的表面形态、溶胀动力学、盐敏感度和反复溶胀性能的影响。     

GG-g-PAA/LOESS复合高吸水性树脂的制备与性能

以瓜尔胶(GG)、丙烯酸(AA)和黄土(LOESS)为原料,过硫酸铵(APS)为引发剂,N,N'-亚甲基双丙烯酰胺(MBA)为交联剂,采用水溶液聚合法制备了瓜尔胶接枝聚丙烯酸/黄土(GG-g-PAA/LOESS)复合高吸水性树脂。采用FTIR和SEM对其结构进行了表征,研究了LOESS的添加量对复合高吸水性树脂的溶胀能力和溶胀动力学的影响,考察了复合高吸水性树脂的保水性能、反复溶胀性以及在不同pH溶液中的吸水性能。结果表明,瓜尔胶、丙烯酸和LOESS发生了接枝共聚,体系中引入LOESS能够显著提高复合高吸水性树脂的吸水性能。当LOESS的质量分数为2%时,该树脂最高吸水倍率可达602 g/g,室温下6 d后,其保水率仍达28%,5次反复溶胀,吸水倍率仍能保持初始时的49%。此外,该复合高吸水性树脂还表现出优异的pH稳定性。     

聚乙烯醇/聚丙烯酸/腐植酸钠高吸水性树脂的制备及溶胀行为

以N,N＇-亚甲基双丙烯酰胺为交联剂、过硫酸铵为引发剂,采用水溶液聚合法合成了聚乙烯醇/聚丙烯酸/腐植酸钠多功能高吸水性树脂。研究了聚乙烯醇和腐植酸钠含量对树脂吸水倍率的影响,同时考察了树脂的吸水速率、溶液pH值对吸水倍率的影响及反复溶胀性能。结果表明,在体系中引入廉价的腐植酸钠,能够显著提高树脂的吸水能力。在腐植酸钠含量为10wt%时,树脂具有最高的吸水倍率,其吸蒸馏水和0.9wt%NaCl溶液分别达到1020g/g和80g/g。     

瓜尔胶基高吸水性树脂的制备、溶胀行为与保水性能

以天然瓜尔胶（GG）和丙烯酸（AA）为原料,过硫酸铵（APS）为引发剂,N,N′-亚甲基双丙烯酰胺（MBA）为交联剂,采用水溶液聚合法制备了瓜尔胶接枝聚丙烯酸（GG-g-PAA）高吸水性树脂。考察了MBA浓度对树脂溶胀动力学和溶胀能力的影响,研究了树脂在不同亲水有机溶剂/水混合溶液、不同阳离子盐（NaCl、CaCl₂和FeCl₃）和阴离子盐（KNO₃、K₂SO₄和K₃PO₄）溶液中在各浓度和离子强度下的溶胀行为,测定了高吸水性树脂在室温和高温下的保水性能。结果表明,该树脂对亲水有机溶剂较为敏感,吸水倍率随着亲水有机溶剂浓度的增加迅速减小;在各种盐溶液中的吸水倍率随着离子强度的增加而下降。     

辉光放电电解等离子体引发合成聚丙烯酸钠／腐植酸复合高吸水性树脂

以丙烯酸和腐植酸为原料,N,N-亚甲基双丙烯酰胺为交联剂,在水溶液中采用辉光放电电解等离子体引发聚合反应制备聚丙烯酸钠／腐植酸复合高吸水性树脂。研究了影响吸水性能的因素,讨论了树脂在0．9％氯化钠溶液中的溶胀速率和不同pH值溶液中的溶胀行为。用红外光谱和热重分析分别对产物进行了结构表征和稳定性测试,     

CMC-g-PAA/APT/HA复合高吸水性树脂的制备与溶胀性能

以羧甲基纤维素(CMC)为基质,丙烯酸(AA)为单体,凹凸棒黏土(APT)和腐植酸(HA)为复合组分,采用水溶液聚合法制备了羧甲基纤维素接枝聚丙烯酸/凹凸棒黏土/腐植酸(CMC-g-PAA/APT/HA)环境友好复合高吸水性树脂,用红外光谱(FTIR)进行了结构表征。考查了APT和HA含量对树脂吸水倍率和吸水速率的影响,研究了树脂在不同pH溶液中的溶胀行为以及反复吸水性能。试验结果表明,APT和HA通过其表面的活性基团参与了接枝共聚反应,在体系中引入HA和APT能够显著提高复合高吸水性树脂的吸水能力。在HA含量为5%(质量分数),APT含量为30%(质量分数)时,树脂可达到最优吸蒸馏水倍率为582g/g。该复合高吸水性树脂在pH值在4～11范围内时具有较高的吸水性能,表现出优异的pH稳定性。经过5次反复溶胀后,该复合吸水树脂仍能达到424g/g的吸水倍率,较不含APT和HA样品提高了近44%。     

腐殖酸-聚丙烯酸表面交联吸水性树脂的合成与性能

将交联剂N,N′-亚甲基双丙烯酰胺溶于甲醇溶液制成表面处理液,通过表面交联反应将磺化腐殖酸（HA）与聚丙烯酸(PAA)结合,制得一种适合于农林领域应用的腐殖酸-聚丙烯酸高吸水性树脂（HA-PAA）.研究了表面处理液浓度、交联剂用量和腐殖酸量对HA-PAA吸水性能的影响规律和吸水机理,以及产物在沙土中的保水性能,并通过扫描电镜分析了HA-PAA的表面结构.研究结果表明,当含有10% HA时,HA-PAA耐电解质性能良好,吸水性能最佳;当沙土中添加0.2%的HA-PAA时,可明显改善沙土的贮水、保水性能.HA-PAA作为农林领域用保水剂,可发挥抗旱保墒和促进植物生长的双重作用.     

腐植酸钾/丙烯酸型保水剂的合成及性能研究

以腐植酸钾(KHA)与丙烯酸(AA)为原料,N,N-亚甲基双丙烯酰胺为交联剂,过K2SO4为引发剂,进行水溶液聚合,制备得到腐植酸钾/丙烯酸高吸水性保水树脂。研究了反应物比例、反应温度、交联剂、引发剂用量、中和度等因素对产物性能的影响。考察了产物的热稳定性、保水性能、耐电解质和重复使用性能。结果表明,树脂最大吸水率为609g.g-1,耐盐性良好,50℃环境温度下9h保水树脂仍有94.2%的保水率。     

丙烯酸钠的聚合及吸水性能研究

以正己烷为连续相,司班80为分散剂,N,N‘-亚甲基双丙烯酰胺为交联剂,过硫酸钾为引发剂,采用反相悬浮聚合法合成了高吸水性聚丙烯酸钠树脂。通过调整分散剂、引发剂、交联剂的用量,制备了几种高吸水性的树脂。在制得的高吸水性聚丙烯酸钠树脂中,性能最好的树脂吸去离子水为550mL／g,吸自来水为170mL／g,吸0．9％NaCl溶液60mL／g。     

Synthesis,swelling behaviors,and slow‐release characteristics of a guar gum‐g‐poly(sodium acrylate)/sodium humate superabsorbent

Superabsorbents used in agricultural and ecological projects with low‐cost, slow‐release fertilizers and environmentally friendly characteristics have been extensively studied. The use of a natural polymer as the matrix and then further polymerization with some functional material has become the preferred method. In this work, with natural guar gum (GG), partially neutralized acrylic acid, and sodium humate (SH) as the raw materials, ammonium persulfate as the initiator, and N,N′‐methylenebisacrylamide (MBA) as the crosslinker, GG‐g‐poly(sodium acrylate) (PNaA)/SH superabsorbents were synthesized through a solution polymerization reaction and were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. The effects of the SH content and MBA concentration on the water absorbency were investigated. The results showed that the introduction of SH into the GG‐g‐PNaA system could improve the water absorbency, swelling rate, pH‐resistant property, and reswelling capability, and the superabsorbent containing 15 wt % SH had the highest water absorbency of 532 g/g of sample in distilled water and 62 g/g of sample in a 0.9 wt % NaCl solution. The slow release in water and water retention in sandy soil tests revealed that the superabsorbent could act as a fertilizer as well as an effective water‐saving material for agricultural applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Study on superabsorbent composites. XVIII. Preparation,characterization, and property evaluation of poly(acrylic acid‐co‐acrylamide)/organomontmorillonite/sodium humate superabsorbent composites

A series of novel multifunctional poly (acrylic acid‐co‐acrylamide) (PAA‐AM)/organomontmorillonite (O‐MMT)/sodium humate (SH) superabsorbent composites were synthesized by the graft copolymerization reaction of partially neutralized acrylic acid and acrylamide on O‐MMT micropowder and SH with N,N′‐methylene bisacrylamide as a crosslinker and ammonium persulfate as an initiator in an aqueous solution. The superabsorbent composites were characterized by means of Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, and thermogravimetric analysis. The effect of the relative weight ratio of SH to O‐MMT on the water absorbency was studied, and the results indicated that the best water absorbency of 591 g/g in distilled water was obtained when an O‐MMT content of 20 wt % and an SH content of 30 wt % were incorporated. The superabsorbent composite possessed a good capacity for water retention; even after 30 days, 24.4 wt % of water could still be saved by the sand soil containing 1.0 wt % superabsorbent composite. The results from this study show that the water absorbency of a superabsorbent composite is improved by the simultaneous introduction of O‐MMT and SH into a PAA‐AM network in comparison with the incorporation of only O‐MMT or SH. Also, in comparison with PAA‐AM/MMT/SH, an appropriate amount of O‐MMT can benefit the developed composites with respect to their water absorbency, salt resistance, and capacity for water retention in sand soil. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of poly(acrylic acid)/sodium humate superabsorbent composite for agricultural use

A novel poly (acrylic acid)/sodium humate superabsorbent composite was synthesized by graft copolymerization reaction of acrylic acid (AA) on sodium humate micropowder using N,N′‐methylenebisacrylamide (MBA) as a crosslinker and potassium peroxydisulfate (KPS) as an initiator in aqueous solution. The effects on water absorbency of factors such as reaction temperature, initial monomer concentration, and degree of neutralization of AA, amount of crosslinker, initiator, and sodium humate were investigated. The superabsorbent composite was characterized by scanning electron microscopy, and the graft copolymerization reaction of AA on sodium humate micropowder was characterized by IR spectroscopy. Results obtained from this study show that the water absorbency of the superabsorbent composite synthesized under optimal conditions for synthesis with a sodium humate content of 5.3% exhibited absorption of 684 g H₂O/g sample in distilled water. Water‐retention in soil is enhanced by the use of the superabsorbent composite. The effect of superabsorbent composite on the growth of corn is reported. The superabsorbent composite may be of use as water management materials for agriculture purposes in desert and drought‐prone areas. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5137–5143, 2006     

Study on superabsorbent composite. XX. Effects of cation‐exchanged montmorillonite on swelling properties of superabsorbent composite containing sodium humate

In this work, the effects of different cation‐exchanged montmorillonite on water absorbency of poly(acrylic acid‐co‐acrylamide)/montmorillonite/sodium humate (PAA‐AM/MMT/SH) superabsorbent composite were systematically investigated under the same preparation conditions. The superabsorbents doped with different cation‐exchanged montmorillonite were characterized by Fourier‐transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy technologies. Swelling behaviors of developing superabsorbent composite in various cationic saline solutions (NaCl, CaCl₂, and FeCl₃) were also investigated. The water absorbencies of superabsorbent composite with 20 wt% MMT and 30 wt% SH are 638, 723, 682, and 363 g g⁻¹ in distilled water for incorporating natural Na⁺‐MMT, Li⁺‐exchanged MMT, Ca²⁺‐exchanged MMT, and Al³⁺‐exchanged MMT, respectively. The results showed that the cation‐exchange process had some obvious influences on final water absorbency of superabsorbent composite. NaCl, CaCl₂, and FeCl₃ solutions did not alter the swelling characteristics of the superabsorbent materials at a concentration of less than 0.01 mM, however, a concentration of greater than 0.1 mM caused a collapse in the swelling curves. The excellent swelling‐reswelling‐swelling behavior and lower swelling rate testified that Al³⁺‐exchanged MMT can act as an assistant crosslinker in the polymeric network. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Preparation and slow‐release property of a poly(acrylic acid)/attapulgite/sodium humate superabsorbent composite

A novel poly(acrylic acid)/attapulgite (APT)/sodium humate (SH) superabsorbent composite was synthesized through the graft copolymerization reaction of acrylic acid on APT micropowder and SH with N,N′‐methylene bisacrylamide as a crosslinker and ammonium persulfate as an initiator in an aqueous solution. Various effects on the water absorbency, including the amounts of the crosslinker, initiator, APT, and SH, were investigated. The superabsorbent composite was characterized with Fourier transform infrared spectroscopy and scanning electron microscopy. The superabsorbent composite synthesized under optimal synthesis conditions with an APT concentration of 20% and an SH concentration of 20% exhibited absorption of 583 g of H₂O/g of sample and 63 g of H₂O/g of sample in distilled water and in a 0.9 wt % NaCl solution, respectively. The slow‐release property of SH from the superabsorbent composite into water was measured, and a test of the water retention of the superabsorbent composite in soil was also carried out experimentally with and without the superabsorbent composite. The results showed that the superabsorbent composite had not only good water retention but also an additional slow‐release property of SH. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 37–45, 2007     

Synthesis and characterization of potassium humate–acrylic acid–acrylamide hydrogel

A novel potassium humate–acrylic acid–acrylamide (KHA–AA–AM) superabsorbent polymer was prepared from the reaction among leonardite potassium humate, acrylic acid and acrylamide by free radical initiating process using ammonium persulfate as the initiator and N, N′-methylene bisacrylamide as the crosslinker. Various effects of synthesis conditions on superabsorbent polymer were studied and the optimal reaction condition was obtained with crosslinker concentration 0.44–0.74 wt%, initiator concentration 1.12–2.22 wt%, n(KOH)/n(AA) 0.51–0.70, monomer concentration 10.95–12.59 wt%, graft reaction temperature 83 ± 1°C, monomer mole ratio of acrylic acid to acrylamide 1.42–2.30, and potassium humate content 17.54 wt%. Under the optimal conditions, the solution absorbency of KHA–AA–AM superabsorbent polymer to deionized water, tap water, 0.5% carbamide solution and 0.9% NaCl solution were 733–756, 161–284, 786–825, and 76–83 g/g, respectively.     

Study on superabsorbent composite. XI. Effect of thermal treatment and acid activation of attapulgite on water absorbency of poly(acrylic acid)/attapulgite superabsorbent composite

The effect of acid activation and thermal treatment of attapulgite on water absorbency of superabsorbent composite were investigated. Under the same preparation conditions, superabsorbent composite prepared with natural attapulgite exhibited a water absorbency of 639 g/g and it merely kept 71% of its initial water absorbency after 5 times of swelling–deswelling–reswelling test. However, superabsorbent composites prepared with 2–10 M hydrochloric acid acidified attapulgite and 100–400°C thermal treated attapulgite respectively exhibited the water absorbency of 884–1,241 g/g and 701–1,515 g/g. Also, those superabsorbent composites can keep 87% and 85% of their initial water absorbency after 5 times of swelling–deswelling–reswelling test, respectively. These results showed that, compared with superabsorbent composite prepared with natural attapulgite, the comprehensive water‐absorbing properties of poly(acrylic acid)/ attapulgite superabsorbent composites were improved effectively by acid activation and thermal treatment of attapulgite. This improvement of water absorbencies and gel strength of superabsorbent composite may be due to synthetical factors such as changes in the crystalline structure and the specific surface area and improvement of the number and the activity of hydroxyl groups of attapulgite, which in turn influence the grafting efficiency of monomer, crosslinking density, and the structure of superabsorbent composite network. POLYM. COMPOS., 28:397–404, 2007. © 2007 Society of Plastics Engineers     

微波辐射APT–g-PAMPS高吸水性树脂的制备及性能

以凹凸棒黏土(APT)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为原料,过硫酸钾(KPS)为引发剂,N,N'-亚甲基双丙烯酰胺(NMBA)为交联剂,采用微波辐射法接枝共聚合成了APT-g-PAMPS耐盐性复合高吸水性树脂,用FTIR和XRD对复合吸水性树脂的结构进行了表征。考察了微波功率和时间及APT用量对树脂吸水倍率的影响,测定了不同APT用量高吸水性树脂的吸水速率、保水性能及反复吸水性能。FTIR和XRD结果显示,APT和有机单体之间发生了接枝共聚反应,其反应仅在APT的表面进行,单体并没有插入到APT的层间。结果表明,微波功率为195 W,辐射时间为2.5 min,w(APT)=5%时,树脂在去离子水和生理盐水中的吸水倍率分别为987g/g和102 g/g。该复合高吸水性树脂具有较快的吸水速率、较强的保水性能和较好的反复吸水性能。在体系中引入适量APT能够显著提高复合吸水树脂的吸水能力和耐盐性能,同时能明显加快树脂的吸水速率和提高树脂的保水性能。