CN1087749C - Polyacrylate type high water absorption resin - Google Patents

Polyacrylate type high water absorption resin Download PDF

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CN1087749C
CN1087749C CN 97104129 CN97104129A CN1087749C CN 1087749 C CN1087749 C CN 1087749C CN 97104129 CN97104129 CN 97104129 CN 97104129 A CN97104129 A CN 97104129A CN 1087749 C CN1087749 C CN 1087749C
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water
sodium
weight
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acrylic acid
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CN1165152A (en )
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梅秀泉
邓世平
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梅秀泉
邓世平
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本发明阐述一种具有吸水能力强、凝胶强度高、吸水速度快的高吸水树脂。 The present invention describes a strong water absorption capacity, high gel strength, high water absorption rate superabsorbent. 它是由丙烯酸、丙烯酸钠以及其它至少一种功能性单体经交联共聚合反应,然后通过表面化学处理而改善其应用性能。 It is made of acrylic acid, sodium acrylate, and at least one other functional monomer crosslinked copolymerization reaction, and improve application performance by chemical conversion treatment.

Description

一种聚丙烯酸盐类高吸水树脂 Polyacrylates one kind of water-absorbent resin

本发明是关于一种交联聚丙烯酸盐类高吸水树脂的合成方法,以及通过表面化学处理方法而改进其应用性能。 The present invention is a method for synthesizing a crosslinked polyacrylate-based superabsorbent, and improved by a chemical surface treatment performance with respect to its application. 具体地说,是用丙烯酸、丙烯酸钠以及其它至少一种功能性单体为主要原料,经过交联共聚合反应,然后用亲水性表面交联剂和小分子有机溶剂配制而成的混合溶液进行表面化学处理,最终得到吸水能力强、凝胶强度高、吸水速度快的高吸水树脂。 Specifically, with acrylic acid, sodium acrylate, and at least one other functional monomer as main raw materials, crosslinked copolymerization reaction, and then formulated with a hydrophilic surface crosslinking agent and a small molecule organic solvent mixed solution chemical surface treatment to finally obtain strong water absorption capacity, high gel strength, high water absorption rate superabsorbent.

吸水树脂最先是由美国农业部北方研究所于1969年研制成功的,方法是用玉米淀粉与丙烯腈接枝共聚,再用氢氧化钠水解。 Water-absorbent resin was first successfully developed in 1969 by the USDA Northern Research, it is graft copolymerized with acrylonitrile corn starch, hydrolyzed with caustic soda. 由于此法采用毒性很强的丙烯腈单体,后来日本用丙烯酸代替丙烯腈,再与淀粉直接接枝聚合。 Since this method uses highly toxic acrylonitrile monomer, acrylonitrile and later replaced with an acrylic Japan, and then graft polymerized with the starch directly. 此后,美国、日本、欧洲相继开发了各种各样的吸水树脂(例如美国专利3980663号、4093776号、4954562号、4880858号以及欧洲专利申请公开467073号、478150号、454497号等)。 Thereafter, the United States, Japan and Europe have developed a wide variety of water-absorbing resin (e.g., U.S. Patent No. 3,980,663, No. 4,093,776, No. 4,954,562, No. 4,880,858 and European Patent Application Publication No. 467,073, No. 478,150, No. 454,497, etc.). 吸水树脂在生理卫生用品,医用材料,农林与园艺、农药、化肥、石油化工、日用化工、保鲜制品、食品工业、土木建筑、纺织品等领域获得了广泛的应用。 Absorbent resin has been widely applied in the fields of physical health supplies, medical materials, agriculture, forestry and horticulture, pesticides, fertilizers, petrochemicals, household chemicals, fresh products, food industry, civil construction, textiles and so on.

目前,吸水树脂最大的应用领域是个人卫生用品,比如:儿童尿布、妇女卫生巾等各种不同的吸水用品。 Currently, the largest application areas are water-absorbent resin personal hygiene items, such as: children's diapers, sanitary napkins and other various water-absorbent articles. 通过添加少量的吸水树脂,可以改进其液体保留特性,并减少液体渗漏量,而且可以使卫生巾或尿布变得更薄、更轻,使用起来更方便舒适。 By adding small amounts of water-absorbent resin, which can improve liquid retention properties, and to reduce the leakage of liquid, but also can make the diaper or sanitary napkin becoming thinner, lighter, easier to use and comfortable. 其次,吸水树脂可在农林园艺上用作土壤保水剂,例如:向土壤中加入0.1%(重量)的吸水树脂,可使土壤在较长时间有足够的水分供植物所需,提高农作物产量。 Secondly, the water-absorbing resin may be used in agriculture, forestry, horticulture soil water retaining agent, for example: 0.1% (by weight) of water-absorbent resin to the soil, soil can have a longer time for the desired plant sufficient moisture, increase crop yields. 在植树造林、荒山改造、沙漠绿化中,可利用吸水树脂来保持土壤水分,提高植物发芽和成活率。 In the afforestation of barren hills transformation, greening the desert, the water-absorbing resin can be used to maintain soil moisture, improve plant germination and survival. 此外,在建筑方面,吸水树脂可用作防渗堵漏剂、防结露剂;在石油化工上用作油水分离剂;在纺织品待业,用于制作防汗衫、防汗鞋垫等;在日用化工领域,可用作制造缓释药物、缓释化肥、除臭剂以及化状品等。 Further, in the construction, the water absorbing resin may be used as impermeable sealing agent, anti-condensation agent; agent used in the oil-water separation petrochemical; unemployed in the textiles, for the production of anti-shirts, sweat proof insole; the daily chemical industry, can be used as sustained-release pharmaceutical manufacture, release fertilizers, deodorants and the like of the shaped article.

当使用普通的吸水树脂后,人们发现,吸水用品吸收诸如尿液、血液、分泌物等体液后,所形成的凝胶易破碎而使该用品变形,从而导致该用品的液体保留特性降低和液体渗漏量增加,使戴用者感到不舒适。 When using ordinary water absorbent resin, it was found that the water-absorbent articles for absorbing body fluids such as urine, blood, secretions and the like, the formed gel so that the article deform easily broken, thereby causing the liquid retention characteristics of the article and reduce the liquid leakage increased, so that those who wear uncomfortable. 因此,需研制一种对体液具有较高凝胶稳定性的吸水树脂。 Therefore, the need to develop a water-absorbent resin having a high gel stability to body fluids. 此外,通常使用的吸水树脂,当其吸水或吸湿后易出现“鱼眼”,即凝胶阻塞效应,因而阻碍了其进一步吸水,从而降低了吸水速度。 Further, the water absorbing resin is generally used, when its water or moisture prone to "fish eyes," i.e. gel-blocking effect, thus hindering further water absorption, thereby reducing the water absorption rate. 因此,有必要研制出一种吸水速度快的吸水树脂。 Thus, there is a need to develop a fast absorption rate of water absorbing resin.

鉴于上述情况,本发明者深入地进行了研究。 In view of the above circumstances, the present inventors have deeply studied. 通常,纯粹的聚丙烯酸盐型吸水树脂具有较高的吸水倍数,但其凝胶强度不高。 Typically, pure polyacrylate water absorbent resin has a high water absorption ratio, but not high gel strength. 研究发现,当加入另外一种功能性单体,如马来酸酐参与共聚合反应后得到的吸水树脂,不仅有很高的吸水倍数,而且吸水后凝胶强度得到改善。 The study found that when the addition of another functional monomer, such as maleic anhydride co-participate-absorbent resin obtained after the polymerization reaction, not only has a high water absorption ratio, and the gel strength after water absorption is improved. 此外,当用亲水性表面交联剂与亲水性小分子有机溶剂配制而成的溶液对吸水树脂进行表面化学处理后,吸水速度明显提高,从而改进了其应用性能。 In addition, when formulated with a hydrophilic surface crosslinking agent and hydrophilic small molecule organic solvent solution of the water-absorbent resin to surface chemical treatment, absorption rate significantly improved, thereby improving the application performance.

也就是说,本发明的第一个目的是提供一种吸水能力强的新型交联聚丙烯酸盐型吸水树脂。 That is, a first object of the present invention is to provide a strong water absorbing ability novel crosslinked polyacrylate type water absorbing resin. 经测试,本发明提供的吸水树脂吸收0.9%生理盐水的能力超过70倍,而日本触媒化学公司提供的同类样品吸收0.9%生理盐水的能力仅为47倍。 After testing, the water-absorbing resin of the present invention provides a 0.9% physiological saline absorption capacity exceeds 70 times, capacity of 0.9% saline of the same sample by Nippon Shokubai Chemical Company absorbed only 47 times.

本发明的第二个目的是提供一种对诸如尿液、血液、分泌物等体液具有高的凝胶稳定性的吸水树脂。 A second object of the present invention is to provide a water-absorbent resin having a high gel stability to body fluids such as urine, blood, secretions and the like.

本发明的另一个目的是提供一种具有吸水速度快的吸水树脂。 Another object of the present invention is to provide a water-absorbent resin fast absorption rate.

下面详细说明本发明的这些目的:在本发明的第一个目的中,提供了一种新型的聚丙烯酸盐类高吸水树脂的合成方法。 The following detailed description of the present invention, these objects: the first object of the present invention, there is provided a method of synthesizing a new class of highly absorbent polyacrylate resin. 这种新型的聚丙烯酸盐类高吸水树脂是由丙烯酸、丙烯酸钠以及其它至少一种功能性单体进行交联共聚合反应而得到的。 This new class of highly absorbent polyacrylates are crosslinked by a resin of acrylic acid, sodium acrylate, and at least one other copolymerizable functional monomer obtained by reacting. 具体工艺过程是:首先将丙烯酸配制成一定的水溶液,然后用碱液进行中和。 Specific process is: firstly formulated into a certain aqueous acrylic acid, followed by neutralization with lye. 中和完毕,加入另外一种功能性单体,再加入交联剂,升温至一定反应温度,在氮气保护下,加入引发剂进行交联共聚合反应。 Complete neutralization, addition of another functional monomer, a crosslinking agent was added, the reaction warmed to a certain temperature, under nitrogen, was added a crosslinking initiator copolymerization reaction. 上述反应体系中丙烯酸浓度为15~40%(重量),丙烯酸中和度为70~85%。 Acrylic acid concentration in the reaction system is 15 to 40% (by weight), acrylic acid and of 70 to 85%. 中和剂选用氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠或氨水。 Neutralizers of using sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate or aqueous ammonia. 另外一种功能性单体选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酰胺、衣康酸、富马酸、甲基丙烯酸、马来酸(酐)、乙烯基磺酸等。 Another functional monomer selected from methyl acrylate, ethyl acrylate, butyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylamide, itaconic acid, fumaric acid, methacrylic acid, maleic acid (anhydride), vinylsulfonic acid and the like. 这种功能性单体的加入量为丙烯酸用量的0.5~50%(重量)。 This amount of functional acrylic monomer in an amount from 0.5 to 50% (by weight).

上述交联共聚合反应中,所用的交联剂选自N,N′-亚甲基双丙烯酰胺、乙二醇双丙烯酸酯、一缩乙二醇双丙烯酸酯、二缩乙二醇双丙烯酸酯、1,3-丙二醇双丙烯酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、甲基丙烯酸缩水甘油酯、聚乙二醇双丙烯酸酯。 The crosslinking copolymerization reaction, the crosslinking agent is selected from N, N'- methylene bisacrylamide, ethylene glycol diacrylate, dipropylene glycol diacrylate, dipropylene glycol diacrylate ester, 1,3-propanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, glycidyl methacrylate, polyethylene glycol diacrylate. 交联剂的用量对最终产物的吸水率有显著的影响。 The amount of the crosslinking agent has a significant effect on the water absorption of the final product. 这是因为当交联剂用量过少时,聚合物未能形成三维网络结构,宏观上表面为水溶性的,故吸水率不高。 This is because when the amount of the crosslinking agent is too small, the polymer failed to form a three dimensional network structure, macroscopic surface water soluble, so that water absorption rate is not high. 但当交联剂用量过高时,聚合物离子网络结构中交联点增多,交联密度过大,致使网络结构中微孔变小,故吸水率下降。 But when the amount of crosslinker is too high, the network structure of the polymer ionic crosslinking points increases, the crosslinking density is too large, resulting in a network structure of micropores becomes small, so the water absorption decreased. 交联剂的适宜用量为丙烯酸用量的0.05~2.0%(重量)。 Suitable crosslinking agents are used in an amount of acrylic amount of 0.05 to 2.0% (by weight).

在上述吸水树脂的合成方法中,所用的引发剂包括氧化剂和还原剂两种。 In the synthesis method above water-absorbent resin, used initiators include oxidizing and reducing two kinds. 氧化剂选自过硫酸铵、过硫酸钾、过硫酸钠。 The oxidizing agent is selected from ammonium persulfate, potassium persulfate, sodium persulfate. 还原剂选自亚硫酸钠、亚硫酸氢钠、连二亚硫酸钠、硫代硫酸钠、甲醛合次亚硫酸钠。 The reducing agent is selected from sodium sulfite, sodium bisulfite, sodium dithionite, sodium thiosulfate, sodium sulfite formaldehyde sulfoxylate. 引发剂的用量对吸水树脂的吸水率也有较显著的影响,因为其用量直接关系到聚合物的分子量和交联密度。 The water absorption amount of the initiator to the water-absorbing resin also have a more significant effect, because it is directly related to the amount of polymer molecular weight and crosslink density. 研究发现,氧化剂的适宜用量为丙烯酸用量的0.01~0.5%(重量),还原剂的适宜用量为丙烯酸用量的0.02~0.75%(重量)。 The study found that a suitable amount of oxidizing agent is used in an amount of acrylic acid 0.01 to 0.5% (by weight), acrylic acid appropriate amount of reducing agent is used in an amount of 0.02 to 0.75% (by weight).

在上述交联共聚合反应过程中,聚合温度控制在35~65℃,聚合反应时间为10~60分钟,干燥时间为1~4小时,干燥温度为100~190℃。 In the copolymerization reaction of the crosslinking process, the polymerization temperature was controlled at 35 ~ 65 ℃, the polymerization reaction time is 10 to 60 minutes, the drying time is 1-4 hours, the drying temperature is 100 ~ 190 ℃.

在本发明的第二个目的中,提供了一种对人体的体液具有高的凝胶稳定性的吸水树脂。 In the second object of the present invention, there is provided a water-absorbent resin having a high gel stability to the body fluids. 为了提高凝胶强度,通常的做法是提高吸水树脂的交联点密度。 In order to increase the gel strength, the usual practice is to increase the crosslink density of the water-absorbent resin. 但是,当交联点密度增大时,吸水倍数也会相应降低。 However, when the crosslink density increases, the water absorption will be reduced multiples. 因此,实际使用时,需要增加吸水树脂的用量,因而是不经济的。 Thus, the actual use, the need to increase the amount of the water-absorbing resin, and thus is not economical. 本发明研制的高吸水树脂,通过加入另外一种功能性单体参与共聚合反应,不仅吸水倍数高,而且提高了凝胶强度,因而对诸如尿液、血液、分泌物等体液具有高的凝胶稳定性。 The present inventors have developed a high water-absorbent resin, by adding another functional monomers involved in the copolymerization, not only the high water absorption ratio, but also improves the gel strength, and thus have a high pour bodily fluids such as urine, blood, secretions, etc. glue stability.

本发明的另一个目的是提供一种具有吸水速度快的吸水树脂。 Another object of the present invention is to provide a water-absorbent resin fast absorption rate. 通常使用的吸水树脂,当其吸水或吸湿后,易产生“鱼眼”,即凝胶阻塞效应,从而阻碍了其进一步吸水,因此吸水速度较慢。 Commonly used water-absorbent resin, when its water or moisture, is easy to produce "fish eye", i.e., gel-blocking effect, thus preventing further water absorption, and therefore a slower absorption rate. 本发明通过对吸水树脂进行表面化学处理而提高其吸水速度,其中用于表面化学处理的试剂包括:亲水性表面交联剂和亲水性小分子有机溶剂。 The present invention water-absorbing resin by the surface chemical treatment to improve the absorption rate, wherein the reagent for the chemical treatment of the surface comprising: a hydrophilic surface crosslinking agent and hydrophilic small molecule organic solvent. 亲水性表面交联剂选自下列至少一种化合物:多羟基醇类、多羟基胺类、聚缩水甘油醚类、多元胺类以及多价金属化合物类。 Hydrophilic surface crosslinking agent is at least one compound selected from the following: polyhydric alcohols, polyhydroxy amines, polyglycidyl ethers, polyvalent amines, and polyvalent metal compounds. 亲水性小分子有机溶剂是选自如下之一的化合物:甲醇、乙醇、异丙醇、正丁醇、丙酮、正丁酮、2-丁酮。 Hydrophilic small molecule organic solvent is selected as one of the compounds: methanol, ethanol, isopropanol, n-butanol, acetone, n-butyl ketone, 2-butanone. 对吸水树脂进行表面处理的具体过程为,首先将一定比例的亲水性表面交联剂和小分子有机溶剂与适量的水混合均匀,即得到表面交联剂混合溶液。 The specific process of the water absorbing resin for the surface treatment, a proportion of the first surface crosslinking agent and a hydrophilic organic solvent, a small molecule with a suitable amount of water were mixed uniformly to obtain a mixed solution of surface crosslinking agent. 然后称取定量的前述制备的吸水树脂粉末,并将配制好的表面交联剂混合溶液在搅拌下慢慢滴入吸水树脂粉末中。 And said water absorbing resin powder prepared to take the amount of, and the prepared solution was mixed a surface crosslinking agent was slowly added dropwise with stirring under water-absorbent resin powder. 使得树脂粉末颗粒表面均匀覆盖一层表面交联剂,其中亲水性表面交联剂和小分子有机溶剂的适宜用量分别为吸水树脂的0.005~5%和0.01~10%(按重量计)。 Such that the resin powder particle surfaces covered with a uniform surface-crosslinking agent, wherein the appropriate amount of surface crosslinking agent and a hydrophilic small molecule organic solvent is 0.005 to 5% and 0.01 to 10%, respectively, water absorbent resin (by weight). 然后,将如此处理过的吸水树脂置于150~190℃烘箱中进行表面交联反应,时间控制在20~45分钟。 Then, the thus treated water-absorbent resin was placed in a surface crosslinking reaction in an oven at 150 ~ 190 ℃, time control in 20 to 45 minutes. 取出后冷却,并粉碎成粒度为5~15μm吸水树脂粉末。 After removing the cooling, and pulverized to a particle size of 5 ~ 15μm water-absorbent resin powder.

通过上述方法得到的吸水树脂,用茶袋法测试其吸水倍数和吸水速度,吸水倍数用下式计算: By water-absorbent resin obtained as described above, and tested for their absorption rate by multiple absorbent tea bag method, the water absorbing multiple calculated by: 吸水速度则用树脂吸收液体达到饱和时所用的时间表示。 Absorption rate of the resin is saturated when the time of the liquid absorbent used in FIG.

凝胶强度则用树脂吸水后凝胶所承受的最大压力来表示。 The maximum gel strength after water-absorbing gel resin pressure to afford expressed.

下面结合实施例详细说明本发明:实施例一:称取100g丙烯酸,置于带有温度计的三口反应瓶中,然后加入180g去离子水。 In conjunction with the following detailed description of embodiments of the present invention: Example I: 100g acrylic acid was weighed, placed in three reaction flask equipped with a thermometer, and then added 180g of deionized water. 搅拌下在30分钟内加入100g浓度为30%(重量)的氢氧化钠溶液。 100g was added with stirring over 30 minutes to a concentration of 30% (by weight) sodium hydroxide solution. 升温到60℃,加入6g丙烯酰胺和0.5g一缩乙二醇双丙烯酸酯,通氮气10分钟以逐出溶解氧。 Warmed to 60 ℃, was added 6g of acrylamide and 0.5g of dipropylene glycol diacrylate, nitrogen for 10 minutes to expel dissolved oxygen. 然后加入0.1g过硫酸铵。 Then add 0.1g of ammonium persulfate. 2分钟后,再加入0.15g硫代硫酸钠,继续搅拌反应30分钟后,将反应混合物置于130℃真空烘箱中,干燥3小时。 After two minutes, then 0.15g of sodium thiosulfate was added, the reaction was continued stirring for 30 minutes, the reaction mixture was placed in a vacuum oven at 130. deg.] C, for 3 hours. 然后冷却、粉碎,得到吸水树脂粉末。 Then cooled and pulverized to obtain water-absorbing resin powder.

取上述吸水树脂粉末50g,进行表面化学处理。 Take the above water-absorbent resin powder 50g, surface chemical treatment. 首先将0.5g丙三醇、1.0g丙酮以及5g去离子水混合均匀,即得到表面交联剂混合溶液。 First, 0.5g of glycerol, acetone, 1.0 g of deionized water and 5g uniformly mixed to obtain a mixed solution of surface crosslinking agent. 将此混合溶液在搅拌下慢慢滴入上述50g吸水树脂粉末中,使得树脂粉末颗粒表面均匀覆盖一层表面交联剂。 The mixed solution was slowly added dropwise with stirring at the above-described water-absorbing resin powder 50g, so that the resin powder particle surfaces uniformly covered with a surface crosslinking agent. 然后将其置于150℃真空烘箱中进行表面交联反应,时间为30分钟。 Then placed in a vacuum oven at 150 deg.] C for surface crosslinking reaction time of 30 minutes. 冷却、粉碎成粒度为5~15μm的吸水树脂。 Cooled and pulverized into a particle size of 5 ~ 15μm of the water absorbing resin. 分别测试其吸收0.9%生理食盐水的能力、吸水速度以及凝胶强度,结果列于附表。 Were tested for 0.9% physiological saline absorption capacity, water-absorption rate and gel strength results are shown in Table.

实施例二:称取100g丙烯酸,置于带有温度计的三口反应瓶中,然后加入200g去离子水。 Example Two: 100g acrylic acid was weighed, placed in three reaction flask equipped with a thermometer, and then added 200g of deionized water. 搅拌下在30分钟内加入90g浓度为30%(重量)的氢氧化钠溶液。 90g was added with stirring over 30 minutes to a concentration of 30% (by weight) sodium hydroxide solution. 升温至55℃,加入4g马来酸酐和4g丙烯酸乙酯以及1.0g三羟甲基丙烷三丙烯酸酯。 Warmed to 55 ℃, maleic anhydride and 4g 4g of ethyl acrylate and 1.0g of trimethylol propane triacrylate. 通氮气10分钟以逐出溶解氧。 Nitrogen for 10 minutes to expel dissolved oxygen. 然后加入0.14g过硫酸钾。 Then added 0.14g potassium persulfate. 3分钟后,再加入0.18g亚硫酸氢钠。 After 3 minutes, then added 0.18g sodium hydrogen sulfite. 搅拌反应45分钟后,将反应混合物置于150℃真空烘箱中,干燥2.5小时。 After the reaction stirred for 45 minutes, the reaction mixture was placed in a vacuum oven at 150 deg.] C, and dried for 2.5 hours. 然后冷却、粉碎,得到吸水树脂粉末。 Then cooled and pulverized to obtain water-absorbing resin powder.

取上述吸水树脂粉末50g,进行表面化学处理。 Take the above water-absorbent resin powder 50g, surface chemical treatment. 首先将0.3g乙醇胺、1.5g正丁酮以及4g去离子水混合均匀,即得到表面交联剂混合溶液。 First, 0.3g of diethanolamine, 1.5 g n-butyl ketone and 4g deionized water were mixed uniformly to obtain a mixed solution of surface crosslinking agent. 将此混合溶液在搅拌下慢慢滴入上述50g吸水树脂粉末中,使得树脂粉末颗粒表面均匀覆盖一层表面交联剂。 The mixed solution was slowly added dropwise with stirring at the above-described water-absorbing resin powder 50g, so that the resin powder particle surfaces uniformly covered with a surface crosslinking agent. 然后将其置于170℃真空烘箱中进行表面交联反应,时间为25分钟。 Then placed in a vacuum oven at 170 ℃ surface crosslinking reaction time of 25 minutes. 冷却、粉碎成粒度为5~15μm的吸水树脂。 Cooled and pulverized into a particle size of 5 ~ 15μm of the water absorbing resin. 分别测试其吸收0.9%生理食盐水的能力、吸水速度以及凝胶强度,结果列于附表。 Were tested for 0.9% physiological saline absorption capacity, water-absorption rate and gel strength results are shown in Table. 附表:吸水树脂性能测试结果 Schedule: water absorbing resin performance test results

[注]:1.吸水倍数用茶袋法测试。 [Note]: 1 ratio by the absorbent tea bag test method. 吸收介质为0.9%生理食盐水。 Absorbing medium is 0.9% physiological saline.

2.吸水速度用树脂吸收液体达到饱和时所用的时间表示。 2. When the liquid reaches a saturated water absorption rate of the absorbent resin used in the time representation.

3.凝胶强度是指树脂充分吸水后的凝胶所承受的最大压力。 3. The gel strength is the maximum pressure of the resin is sufficiently water-absorbing gel is subjected.

Claims (9)

  1. 1.一种聚丙烯酸盐类高吸水树脂的制备方法,其特征是首先将丙烯酸配制成重量浓度为15-40%的水溶液,然后用碱液进行中和;中和完毕,加入另外一种功能性单体,再加入交联剂后升温,在氮气保护下,加入引发剂进行交联共聚合反应;其中,所述另外一种功能性单体选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酰胺、衣康酸、富马酸、甲基丙烯酸、马来酸(酐)、乙烯基磺酸;所述交联剂选自N,N'-亚甲基双丙烯酰胺、乙二醇双丙烯酸酯、一缩乙二醇双丙烯酸酯、二缩乙二醇双丙烯酸酯、1,3-丙二醇双丙烯酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、甲基丙烯酸缩水甘油酯、聚乙二醇双丙烯酸酯;所述引发剂包括氧化剂和还原剂两种,氧化剂选自过硫酸铵、过硫酸钾、过硫酸钠;还原剂选 1. A method for preparing polyacrylate-based super absorbent resin, wherein the first acrylic formulated to a concentration of 15-40% by weight of an aqueous solution, followed by neutralization with lye; complete neutralization, addition of another function monomer, and then adding a crosslinking agent after heated, under nitrogen, was added a crosslinking initiator copolymerization reaction; wherein said another functional monomer selected from methyl acrylate, ethyl acrylate, butyl acrylate, acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methacrylamide, itaconic acid, fumaric acid, methacrylic acid, maleic acid (anhydride), vinylsulfonic acid; the crosslinking agent selected from N, N'- methylene bisacrylamide, ethylene glycol diacrylate, dipropylene glycol diacrylate, dipropylene glycol diacrylate, 1,3-propanediol diacrylate, trihydroxy methyl propane triacrylate, pentaerythritol triacrylate, glycidyl methacrylate, polyethylene glycol diacrylate; the initiator comprises oxidizing and reducing two kinds of the oxidizing agent is selected from ammonium persulfate, potassium persulfate, sodium persulfate; reducing agent is selected from 自亚硫酸钠、亚硫酸氢钠、连二亚硫酸钠、硫代硫酸钠、甲醛合次亚硫酸钠。 Since sodium sulfite, sodium bisulfite, sodium dithionite, sodium thiosulfate, sodium sulfite formaldehyde sulfoxylate.
  2. 2.如权利要求1所述的制备方法,其特征是所述功能性单体的加入量为丙烯酸所用重量的0.5-50%。 2. The method as recited in claim 1, characterized in that the functional monomer added in an amount of 0.5-50% by weight of acrylic acid used.
  3. 3.如权利要求1所述的制备方法,其特征是所述交联剂的用量为丙烯酸所用重量的0.05-2.0%。 The production method as claimed in claim 1, characterized in that the amount of the crosslinking agent is 0.05 to 2.0% by weight of acrylic acid used.
  4. 4.如权利要求1所述的制备方法,其特征是氧化剂的用量为丙烯酸所用重量的0.01-0.5%,还原剂的用量为丙烯酸所用重量的0.02-0.75%。 4. The method as recited in claim 1, wherein the oxidizing agent is used in an amount from 0.01 to 0.5% by weight of acrylic acid used, the reducing agent in an amount of 0.02 to 0.75% by weight of acrylic acid used.
  5. 5.如权利要求1所述的制备方法,其特征是丙烯酸中和度为70-85%。 5. The method as recited in claim 1, characterized in that the acrylic acid and of 70-85%.
  6. 6.如权利要求1所述的制备方法,其特征是中和剂选用氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠或氨水。 The production method as claimed in claim 1, wherein the neutralizing agent of using sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate or aqueous ammonia.
  7. 7.如权利要求1所述的制备方法,其特征是交联共聚合反应过程中,聚合温度控制在35-65℃,聚合反应时间为10-60分钟。 7. The method as recited in claim 1, wherein the crosslinking during the copolymerization reaction, the polymerization temperature is controlled at 35-65 deg.] C, the polymerization reaction time is 10-60 minutes.
  8. 8.如权利要求1所述的制备方法,其特征是还包括将聚合反应后的物质进行干燥。 The production method as claimed in claim 1, characterized by further comprising the polymerization reaction material was dried.
  9. 9.如权利要求8所述的制备方法,其特征是干燥时间为1-4小时,干燥温度为100-190℃。 The production method as claimed in claim 8, characterized in that the drying time of 1-4 hours, a drying temperature of 100-190 ℃.
CN 97104129 1997-04-22 1997-04-22 Polyacrylate type high water absorption resin CN1087749C (en)

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JP5374793B2 (en) * 2006-04-21 2013-12-25 エボニック デグサ ゲーエムベーハーEvonik Degussa GmbH Water-absorbing polymer structures transmittance and under pressure absorption rate is improved
CN1317307C (en) * 2005-04-29 2007-05-23 清华大学 Method for preparing high water adsorbing resin by sun light radiation polymerization
CN100549100C (en) 2005-08-12 2009-10-14 中国矿业大学(北京) Humate compound water retaining agent and its preparation method
US20100120940A1 (en) 2007-04-05 2010-05-13 Nippon Shokubai Co., Ltd. Particulate water-absorbing agent having water-absorbing resin as main component
CN101434667B (en) 2008-12-15 2010-10-13 中国科学院长春应用化学研究所 Method for preparing organic polymer absorbent material using post treatment
CN102408505B (en) * 2011-10-12 2014-04-23 浙江卫星石化股份有限公司 Method for preparing super absorbent resin by inverse suspension polymerization
CN103665411B (en) * 2012-09-24 2018-08-24 浙江卫星石化股份有限公司 Superabsorbent kinds of high salt and a preparation method of a high water absorption ratio
CN103102443B (en) * 2012-12-28 2015-12-23 南通科益化工有限公司 A physiological sanitary absorbent resin polymer
CN103203089B (en) * 2013-03-20 2016-04-06 北京工业大学 One kind of extinguishing coal mine material and method
CN103254335B (en) * 2013-05-31 2014-05-14 晋江汇森高新材料科技有限公司 Method for preparing polyacrylate super absorbent resin from composite alkaline liquid
CN103554375A (en) * 2013-11-19 2014-02-05 宜兴丹森科技有限公司 Preparation method of polyacrylate type super absorbent resin
CN104341545A (en) * 2014-11-08 2015-02-11 邦丽达(福建)新材料股份有限公司 Method for preparing cross-linked polyelectrolyte

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