CN114437730B - 兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料 - Google Patents
兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料 Download PDFInfo
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Abstract
本发明涉及一种兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料,其由兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料与可生物降解高分子材料织物组成,其中兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料包裹在可生物降解高分子材料织物表面并嵌合于该织物网格中,两者之间存在分子间氢键相互作用。本发明的固沙材料在水和微生物的作用下,会逐步水解、降解为小分子营养物质并被植物吸收,降解产物无有害物质,绿色环保。此外,力学性能优异,可防固风沙、吸水保水并含有植物生长发育所需要的氮、磷、钾等营养元素,从而为沙漠中植物的生长提供良好的水肥环境。
Description
技术领域
本发明属于生物降解高分子材料技术领域,具体为一种兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料。
背景技术
土地荒漠化已成为二十一世纪人类面临的最大威胁。目前,全世界约有1/4的土地面积、上百个国家和地区受到荒漠化的危害。荒漠化不仅造成巨大的经济损失,而且导致土地生产力剧降、自然环境恶化等一系列威胁人类生存和发展的严重问题。我国荒漠化面积大,分布广,危害严重。因此,是最重视荒漠化治理的国家之一,对荒漠化防治技术与固沙材料的制备一直非常关注。
现有固沙技术主要分为工程固沙、化学固沙以及植物固沙。各种固沙技术各有其优缺点,工程固沙挡风效果明显,但不可降解的材料会导致沙漠污染;化学固沙有利于保水保肥,但喷洒方式导致其的广泛应用受到限制;植物固沙有利于沙漠的长久治理,但沙漠种植难度较大。因此,只有将三种固沙方式有效结合,才能够使沙漠治理更为有效。
因具有使用方便、见效快、造价低等方面优势,目前,高分子材料制品被广泛应用于公路边坡防护等交通体系建设和特定地域的防沙治沙。但是,这些石化衍生品在发挥较大防护效益的同时也给环境带来了不同程度的二次污染,限制了它们的广泛应用。因此,可生物降解固沙材料的开发与应用引起了人们的广泛关注。使用可生物降解高分子材料编织物制作的沙障,具有操作简单并易于运输的特点。此外,寿命长、防护作用持久且失效后不会对环境造成二次污染。因此,目前可生物降解高分子材料已作为一种新型的沙障材料应用于防风治沙领域。
沙漠化土壤因贫瘠、土质疏松、保水保肥能力差而不利于植物的生长。具有良好吸水保水以及粘附性能的高吸水性聚合物被广泛应用于固沙剂的制备,其可固结沙土并为植株生长提供水分。
发明内容
本发明针对现有固沙技术存在的问题,提供了一种兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料,不仅能够防风固沙,而且还兼具养分缓控释和吸水保水功能,可为沙漠中植物的生长提供良好的水肥环境。
本发明是通过以下技术方案实现的:一种兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料,由兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料与可生物降解高分子材料织物组成,其中兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料包裹在可生物降解高分子材料织物表面并嵌合于该织物网格中,两者之间存在分子间氢键相互作用。
作为本发明尿素醛基可生物降解高分子固沙材料技术方案的进一步改进,兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料与可生物降解高分子材料织物之间的界面结合强度大于可生物降解高分子材料织物自身的断裂强度。
本发明进一步提供了一种兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料的制备方法,将所述兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料涂覆于可生物降解高分子材料织物表面,加热固化至一定程度后,辊压并进一步加热固化,则得到兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料。
作为本发明制备方法技术方案的进一步改进,所述辊压压力为0~1MPa且不为0。
作为本发明制备方法技术方案的进一步改进,所述兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料的具体制备工艺为:
往反应容器中分别加入计算量的甲醛和尿素,调节体系pH=8,设定温度下反应;之后加入含磷钾的无机肥料以及高吸水性聚合物或高吸水性聚合物的单体并在一定温度下反应,则得到粘稠状的兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料。
本发明还提供了一种兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料在保水防风固沙中的应用。
与现有固沙材料相比,本发明具有如下所述的优越性:
(1)本发明制备的兼具养分缓控释以及吸水保水的生物降解高分子固沙材料工艺简单,涂覆辊压工艺配合加热固化就可以制备得到。
(2)本发明中,涂覆在可生物降解高分子材料织物上的粘稠状尿素醛基生物降解聚合物复合材料会嵌入到生物降解高分子材料织物的网格中,两者之间存在分子间氢键相互作用且两种材料紧密结合,难以分离。
(3)制备的兼具养分缓控释和吸水保水功能的尿素醛基生物降解高分子固沙材料具有吸水保水的功能,可在下雨时存储水分,从而减少水土流失。
(4)所述兼具养分缓控释和吸水保水功能的尿素醛基生物降解高分子固沙材料使用后,在水和微生物的作用下,会逐步水解、降解为小分子营养物质并被植物吸收,降解产物无有害物质,绿色环保。
(5)本发明的兼具养分缓控释和吸水保水功能的尿素醛基生物降解高分子固沙材料的力学性能优异,可防固风沙、吸水保水并含有作物生长发育所需要的氮、磷、钾等营养元素,从而为沙漠中植物的生长提供良好的水肥环境。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术的技术方案,下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图是本发明的一些实施方式,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为实施例2制备的固沙材料与对比例1制备的复合材料将PAACS(秸秆改性聚丙烯酸)/KH2PO4(磷酸二氢钾)/UF(尿素醛)-1从PLA(聚乳酸)织物表面剥离后所得到的PLA织物的红外光谱图。
图2为实施例1-3制备的固沙材料以及对比例1和2制备的复合材料的拉伸强度。
图3为实施例1-3制备的固沙材料以及对比例1和2制备的复合材料的吸水率曲线。
图4为实施例1、2和3制备的兼具养分缓控释和吸水保水功能的尿素醛基生物降解高分子固沙材料吸水后的SEM照片。图中(A)为实施例1,(B)为实施例2,(C)为实施例3。
图5为铺设由实施例2的固沙材料缝制的圆柱形沙障与未铺设沙障的风蚀曲线图。
图6为实施例1-3制备的固沙材料以及对比例1和2制备的复合材料的N、P养分缓控释曲线。图中(A)为N养分缓控释曲线,(B)为P养分缓控释曲线。
图7为添加有实施例1-3制备的固沙材料以及对比例1和2制备的复合材料的沙土的持水率曲线。
图8为添加有实施例1-3以及对比例1和2的尿素醛基生物降解高分子固沙材料的沙土保水率曲线。
由图1可知,与对比例1相比,实施例2中PLA织物分子链中的羰基(-C=O)的伸缩振动峰出现明显的红移,表明在实施例2中,PAACS/KH2PO4/UF-1与PLA织物之间存在分子间氢键作用,从而提升了二者的界面结合强度。
由图2可知,实施例2因具有合适的AA(丙烯酸)/MU(羟甲基脲)比值,因而具有最高的拉伸强度,为2.66MPa,其次为实施例1的2.42MPa,实施例3的拉伸强度最低,为0.7MPa,表明AA/MU对制备的尿素醛基生物降解高分子固沙材料的力学性能有显著的影响。与对比例相比,实施例1和2中的拉伸强度均显著提升,这归因于兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料与可生物降解高分子材料织物之间较高的结合强度,二者之间的结合强度超过了可生物降解高分子材料织物的断裂强度0.3MPa。
由图3可知,实施例2具有最优的吸水倍率,可达41.59g/g。这归因于各组分之间合适的配比,表明各组分的不同加入比例对尿素醛基生物降解高分子固沙材料的吸水性能具有显著的影响。对比例1与实施例2的吸水曲线几乎一致,但实施例2略高于对比例1的。这可以归因于兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料与可生物降解高分子材料织物之间存在分子间氢键相互作用,提升了二种材料之间的界面结合强度,从而使实施例2能够在吸水溶胀时更加完整,不散落。
由图4可知,实施例1、2和3制备的三种尿素醛基生物降解高分子固沙材料均存在孔隙结构,且表面粗糙,有利于吸收水分。其中实施例2的网孔更加均匀且更强键,这使其具有最好的吸水性能。
图5为铺设沙障与未铺设沙障的风蚀曲线图。该沙障是将实施例2的固沙材料缝制为圆柱形沙障,在其中内装沙土而制成。铺设兼具养分缓控释以及吸水保水功能的尿素醛基可生物降解高分子固沙材料,可明显减少风蚀损失。在风蚀后沙土的保持率由不铺设沙障的7%提高到55%,因此由该固沙材料制备成的沙袋沙障,有很高的沙土保持率。
由图6可知,各实施例制备的尿素醛基可生物降解高分子固沙材料所含有的N、P营养元素均具有良好的缓释性能。其中实施例2具有最好的N、P缓释性能,在沙土中放置30天,N释放了67.12%,P释放了81.98%。实施例2比对比例1具有更好的养分缓释效果。原因在于:实施例2中的兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料与可生物降解高分子材料织物之间存在分子间氢键作用,提升了两种材料之间的界面结合强度,使兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料的养分缓释性能更优。
由图7可知,实施例2因具有合适的AA/MU比例,因此其沙土持水率最高,可达到103.87%。在实施例3中,加入的吸水组分AA过少,因此其沙土持水率最低,为73.61%。对比例1的沙土持水率低于实施例2的,原因在于:对比例1制备的复合材料中的PAACS/KH2PO4/UF-1与PLA织物之间的界面结合强度很弱,因此,一部分尿素醛基生物降解聚合物会被水流带走。以上实施例以及对比例均可说明,本发明所制备的兼具养分缓控释以及吸水保水功能的尿素醛基可生物降解高分子固沙材料具有良好的持水性能。
由图8可知,实施例2具有最长的保水期,在室温30内,所含水分仍未完全挥发,剩余约0.21%的水分。但对比例1在第27天已经失去所含有的全部水分。以上实施例以及对比例均可说明,本发明所制备的兼具养分缓控释以及吸水保水功能的尿素醛基可生物降解高分子固沙材料具有良好的保水性能。因此本发明可以实现在下雨时吸收并存储水分的目的。
具体实施方式
下面将结合附图对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明中各实验的测定标准:
1)红外测试:将兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料从可生物降解高分子材料织物表面剥离后,对可生物降解高分子材料织物表面进行红外测试。
2)拉伸性能:将材料裁成30*100mm2的宽条,使用高低温万能拉伸试验机测试其拉伸强度。夹具距离50mm,标定距离25mm,拉伸速度为30mm/min。每个处理重复测试5次。
3)吸水性能:室温下,将制备的样品称重,装入已知重量的300目尼龙网袋中,然后放入装有300ml蒸馏水的烧杯中,每隔10分钟取出样品并用脱脂棉擦干,称重,连续测量120分钟。样品吸水率Qeq(g/g)的计算公式如式(1)所示,其中M和M0分别表示吸水后和吸水前样品的质量。
4)N和P养分释放性能:将材料装于300目尼龙网袋中,在花盆中装入500g沙土,将尼龙网袋埋于沙土下3cm处,保持沙土水分湿度为20%,在第5、10、15、20、25、30天时进行破坏性取样,对尼龙网袋内的材料称重,并测试其N、P含量。
5)抗风蚀性能:在塑料板上将500g沙土堆成直径10cm、高5cm的沙丘,在迎风面铺设由材料编织的长10cm、宽5cm的袋并在其中装入40g沙土,使用15m/s(对应于7级疾风)的风速对沙堆进行风蚀实验,测试不同时间沙土的重量。
6)沙土持水率:将材料编织成5cm*10cm的袋,然后往其中装入40g沙土。将制成的沙袋放入直径4.5cm的PVC管(底部用300目尼龙网袋封底)中并称重(M1),然后将其固定在铁架台上,从顶部缓缓加入自来水,直至袋底有水渗出为止。静置一段时间后,待管底部无自来水渗出后,再次称重尼龙网袋并记为M2,沙土持水率(WH%)的计算公式如式(2)所示:
7)沙土保水率:将材料编织成5cm*10cm的袋,往其中装入40g沙土制成沙袋。将所制沙袋置于500ml塑料瓶中,并称重(M0),然后用自来水逐步润湿至沙土饱和(依据沙土持水率确定自来水的添加量),再次称量塑料瓶的重量(M1),每天同一时间测量塑料瓶重量(Mi),直至塑料瓶至恒重为止。保水率根据以下公式计算:
下面通过具体实施例来对本发明的技术方案进行详细的说明。
实施例1至3
一种吸水保水高分子材料为玉米秸秆(CS)改性聚丙烯酸(PAACS)、无机肥料为磷酸二氢钾(KH2PO4)和可生物降解高分子材料织物选用聚乳酸(PLA)织物的兼具养分缓控释以及吸水保水功能的尿素醛基生物降解固沙材料的制备方法,包括以下步骤:
(1)羟甲基脲(MU)溶液的制备:往密闭的反应容器中加入甲醛和尿素,两者的摩尔比为1:2,然后调节溶液pH=8,在40℃下反应2h,得到MU溶液。
(2)使用KOH调节丙烯酸AA的中和度至80%,然后依次将中和度为80%的AA溶液、预处理的CS、KH2PO4和过硫酸铵加入到步骤(1)制备的MU溶液中,其中AA/CS/过硫酸铵的质量比为100:10:0.3,KH2PO4与MU溶液的质量比为1:20;设定温度下通氮气反应2h,得到粘稠状的秸秆改性聚丙烯酸(PAACS)/磷酸二氢钾(KH2PO4)/尿素醛(UF)-n复合材料PAACS/KH2PO4/UF-n,其中n=AA/MU(质量比)。
(3)将步骤(2)制备的PAACS/KH2PO4/UF-n复合材料按照0.2g/cm2均匀涂覆到PLA织物表面,55℃固化2h后,使用轧车在0.6MPa下辊压;
(4)将步骤(3)辊压完成的涂覆有PAACS/KH2PO4/UF-n的PLA织物继续于55℃固化至恒重,则得到兼具养分缓控释和吸水保水功能的尿素醛基生物降解高分子固沙材料。表1AA和MU溶液加入质量表
实施例1
得到本发明的由涂覆有PAACS/KH2PO4/UF-1.5的PLA织物制备的兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料,拉伸强度为2.42MPa,吸水倍率为21.67g/g,营养元素氮的含量6.55wt%,以P2O5计的营养元素P的含量为0.61wt%,以K2O计的营养元素K的含量为24.97wt%。
实施例2
得到本发明的由涂覆有PAACS/KH2PO4/UF-1的PLA织物制备的兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料,拉伸强度为2.66MPa,吸水倍率为41.59g/g,营养元素氮的含量11.03wt%,以P2O5计的营养元素P的含量为1.03wt%,以K2O计的营养元素K的含量为21.37wt%。
实施例3
得到本发明的由涂覆有PAACS/KH2PO4/UF-0.5的PLA织物制备的兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料,拉伸强度为0.7MPa,吸水倍率为10.06g/g,营养元素氮的含量16.76wt%,以P2O5计的营养元素P的含量为1.57wt%,以K2O计的营养元素K的含量为16.77wt%。
对比例1
(1)羟甲基脲(MU)溶液的制备:往密闭的反应容器中加入甲醛和尿素,两者的摩尔比为1:2,然后调节溶液pH=8,在40℃下反应2h,得到MU溶液。
(2)使用KOH调节AA的中和度至80%,然后依次将中和度为80%的AA溶液、预处理的CS、KH2PO4和过硫酸铵加入到步骤(1)制备的MU溶液中,其中MU溶液/AA/CS/过硫酸铵/KH2PO4的质量比为100:100:10:0.3:5。设定温度下通氮气反应2h,得到粘稠状的PAACS/KH2PO4/UF-1。
(3)将步骤(2)制备的PAACS/KH2PO4/UF-1复合材料按照0.2g/cm2均匀涂覆到聚四氟乙烯板上,55℃固化2h后,将其从聚四氟乙烯板上揭下。
(4)将步骤(3)得到的PAACS/KH2PO4/UF-1复合材料与PLA织物叠合在一起并使用轧车在0.6MPa下辊压,将辊压后的复合材料继续于55℃固化至恒重,则得到PLA+(PAACS/KH2PO4/UF-1)复合材料。
该PLA+(PAACS/KH2PO4/UF-1)复合材料的拉伸强度为1.73MPa,吸水倍率为38.62g/g,营养元素氮的含量11.03wt%,以P2O5计的营养元素P的含量为1.03wt%,以K2O计的营养元素K的含量为21.37wt%。
对比例2
(1)磷酸二氢钾/尿素醛(KH2PO4/UF)粉末的制备:往密闭的第一反应容器中加入摩尔比为1:2的甲醛和尿素,调节溶液pH=8,在40℃下反应2h,生成MU溶液,再加入与MU溶液质量比为1:20的KH2PO4,升温至60℃反应至生成白色固体,捏合挤出,80℃干燥,磨碎至300目得到KH2PO4/UF粉末。
(2)往密闭的第二反应容器中加入AA,利用KOH调节其中和度至80%,加入预处理过的CS以及过硫酸铵溶液,其中AA/CS/过硫酸铵的质量比为100:10:0.3;升温至55℃下反应2h后,得到粘稠的PAACS。
(3)将步骤(2)得到的粘稠PAACS与KH2PO4/UF粉末混合,其中所加入的AA与MU溶液质量比为1:1,机械搅拌至均匀,得到(PAACS+KH2PO4/UF)-1。
(4)将步骤(3)得到的(PAACS+KH2PO4/UF)-1按照0.2g/cm2均匀涂抹到PLA织物表面,55℃固化2h后,使用轧车在0.6MPa下辊压,然后继续于55℃固化至恒重,得到PLA/PAACS+KH2PO4/UF-1复合材料。
该复合材料的拉伸强度为1.95MPa,吸水倍率为18.6g/g,营养元素氮的含量11.03wt%,以P2O5计的营养元素P的含量为1.03wt%,以K2O计的营养元素K的含量为21.37wt%。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (3)
1.一种兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料的制备方法,其特征在于,所述兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料由兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料与可生物降解高分子材料织物组成,其中兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料包裹在可生物降解高分子材料织物表面并嵌合于该织物网格中,两者之间存在分子间氢键相互作用;
所述制备方法为:将所述兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料涂覆于可生物降解高分子材料织物表面,加热固化至一定程度后,辊压并再次加热固化,则得到兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料;
所述兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料的具体制备工艺为:
往反应容器中分别加入计算量的甲醛和尿素,调节体系pH=8,设定温度下进行反应;之后加入含磷钾的无机肥料以及高吸水性聚合物或高吸水性聚合物的单体并在一定温度下反应,则得到粘稠状的兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料。
2.根据权利要求1所述的一种兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料的制备方法,其特征在于,兼具养分缓控释和吸水保水功能的尿素醛基生物降解聚合物复合材料与可生物降解高分子材料织物之间的界面结合强度大于可生物降解高分子材料织物自身的断裂强度。
3.根据权利要求1所述的一种兼具养分缓控释和吸水保水功能的尿素醛基可生物降解高分子固沙材料的制备方法,其特征在于,所述辊压压力为0~1MPa且不为0。
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