CN117126081A - 一种尿素与有机酸的共晶及其制备方法、应用 - Google Patents
一种尿素与有机酸的共晶及其制备方法、应用 Download PDFInfo
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- CN117126081A CN117126081A CN202311101434.6A CN202311101434A CN117126081A CN 117126081 A CN117126081 A CN 117126081A CN 202311101434 A CN202311101434 A CN 202311101434A CN 117126081 A CN117126081 A CN 117126081A
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- Prior art keywords
- urea
- eutectic
- preparing
- organic acid
- acid
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
- C07C273/14—Separation; Purification; Stabilisation; Use of additives
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- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
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- A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
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- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
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- C07C273/14—Separation; Purification; Stabilisation; Use of additives
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
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- C11D3/2086—Hydroxy carboxylic acids-salts thereof
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Abstract
本发明公开了一种尿素与有机酸的共晶及其制备方法、应用,属于共晶技术领域。本发明通过混合有机酸与尿素,将固体混合物加热至并搅拌直至得到液态混合物,并对液态混合物进一步超声,反应完冷却,得到尿素与有机酸的共晶。本发明公开的有机酸与尿素形成的共晶其原料中不含任何有毒有害物质,没有任何对人体不利的潜在危害;在提高尿素单体的稳定性的同时基本不改变助溶效果与洗涤效果,是更加稳定的共晶系。
Description
技术领域
本发明公开了一种尿素与有机酸的共晶及其制备方法、应用,属于共晶技术领域。
背景技术
尿素在多个方面均有广泛的应用:在化妆品和皮肤医学领域,尿素是一种很好用的保湿成分,它存在于肌肤的角质层当中,是天然保湿因子(natural moisturizingfactor,NMF)的组成部分,对角质层的充分水合作用和完整性至关重要。
尿素在皮肤上层结合水分,减少经皮失水率,并有助于提高皮肤弹性,人体可通过特异性尿素转运蛋白和水-甘油跨膜运输蛋白通道机制吸收尿素,在健康的角质层中,尿素占据7%的NMF,这个比例会随着年龄的增长而下降。缺乏尿素会导致各种皮肤病,例如,干性皮肤中尿素缺乏比例高达50%,而在银屑病中这一比例达到了60%。尿素具有柔软角质的功效,所以也能够防止角质层阻塞毛细孔,藉此改善粉刺的问题,尿素可以作为面膜、护肤水、膏霜、护手霜等化妆品中保湿成份添加。
在现有技术中,尿素能够通过与溶质直接相互作用、改变溶质水化层、改变水分子体积结构或其综合作用增加极性和非极性溶质在水溶液中的溶解性。溶液中添加适量尿素能够方便地调控分子间的相互作用,大量学者研究了添加尿素对极性分子和非极性分子在水中溶解性和溶液性质的影响,包括非极性的芳烃、脂肪烃,两亲性的表面活性剂,蛋白质以及一些极性分子,因此常被作为助溶剂应用在洗涤产品当中。在农业领域,尿素是我国农业生产上应用最普遍、用量最大的高浓度氮肥,属中性速效肥料,也可用于生产多种复合肥料,在土壤中不残留任何有害物质,长期施用没有不良影响,施入土壤后,小部分以分子态溶于土壤溶液中,并通过氢键作用被土壤吸附。另外,尿素可用作反刍动物的饲料,但由于其稳定性差、易分解,在长期的储存或高温条件下会产生挥发性胺,释放出难闻的气味,容易造成化妆品、肥料、饲料等产品不稳定、不易保存、降低产品功能效果等问题,造成严重的资源浪费,很多研究者力图通过各种手段来提高尿素的稳定性:有研究者通过改变化学成分或在尿素表面包涂半透水性或不透水性物质来制备缓释尿素,使其有效成分缓慢释放,来增强尿素的稳定性,提高其利用率。也有科学家通过腐殖酸活化的方式,抑制脲酶活性,减缓尿素的分解速度,增强尿素的稳定性,进而提高尿素的利用效率并减少对环境的污染。但上述研究仍存在一些问题与不足,缓释尿素的生产成本较高,限制了其应用和推广,而腐植酸主要来源于草炭、风化煤和褐煤等低阶煤,分子量较大,制得的尿素产品存在难溶且难直接发挥作用的问题,因此,现有技术对尿素的改良还有待于改进和发展。
发明内容
共晶是指两种或两种以上的前驱体,在一定条件下,通过氢键、其他非共价键、静电作用或疏水作用等力的作用下结合而成的晶体,是一种具有生物活性的全新固体原料,可以很好的改善共晶前驱体的稳定性、水溶性、分散速率和生物利用度等理化性质。
共晶技术在化妆品领域中最大的应用价值就是能够在保持两种及两种以上共晶形成物官能团的同时改善其理化性质。共晶化合物可以将原料性质得到更大程度的改善,在化妆品领域拥有巨大的应用价值,对化妆品配方研究和设计具有积极影响。
针对上述问题,本发明公开了一种尿素与有机酸的共晶及其制备方法、应用,目的在于解决现有技术中尿素稳定性差的问题。
本发明的第一个目的是提供一种尿素与有机酸共晶的制备方法,包括步骤:
(1)取尿素和有机酸混匀,在80~120℃条件下反应,得到尿素-有机酸的熔融共晶;
(2)将熔融状态的共晶趁热超声,之后放置冷却,得到尿素-有机酸的共晶。
优选的,所述加热的温度为100℃。
在一种实施方式中,所述有机酸包括柠檬酸、乳酸、水杨酸、壬二酸、没食子酸、透明质酸、聚丙烯酸、聚谷氨酸中的一种或多种。
优选的,所述有机酸为柠檬酸、乳酸、聚丙烯酸、没食子酸、壬二酸中的一种或多种。
在一种实施方式中,所述步骤(1)的反应是在搅拌状态下进行,搅拌的时间为1~3h。
优选的,所述搅拌的时间为1~2h。
在一种实施方式中,所述超声时间为5~100min。
优选的,所述超声时间为10min。
在一种实施方式中,所述尿素和所述有机酸的摩尔比为1:1~10:1。
优选的,所述尿素和有机酸的摩尔比为2~5:1。
在一种实施方式中,不额外添加第三物质得到二元共晶系;或加入少量水促进共晶系的形成,所述水的添加质量分数为0.1%~10%。
优选的,所述水的添加质量分数为5%。
本发明的第二个目的是提供一种尿素与有机酸共晶,所述共晶由上述任一方法制备得到。
本发明的第三个目的在于提供一种提高尿素稳定性的方法,所述方法为制备尿素-有机酸共晶,包括步骤:
(1)取尿素和有机酸混匀,在80~120℃条件下反应,得到尿素-有机酸的熔融共晶;
(2)将熔融状态的共晶趁热超声,之后放置冷却,得到尿素-有机酸的共晶。
本发明的第四个目的是提供尿素-有机酸共晶的应用,所述应用包括:制备化妆品,或制备洗涤剂,或制备温敏材料,或制备饲料,或制备肥料,或制备农药,或制备药物制剂,或制备药物输送载体,或制备食品添加剂,或制备助溶剂,或制备催化剂,或制备化学涂料,或制备电池材料,或制备燃料添加剂,或制备纺织品加工剂。
有益效果:
本发明力图通过开发一种尿素与有机酸共晶的新的制备方法,在基本不改变尿素原有优良性质的基础上,降低尿素的分解速率,增强尿素的稳定性,提高尿素的利用效率,并将其推广到化妆品、洗涤剂、肥料、药物、饲料等实际应用中去。本发明的有益效果具体如下:
(1)本发明通过采用尿素与有机酸形成共晶,得到的尿素与有机酸的共晶的稳定性比尿素单体的稳定性更高,且采用加热熔融的方法形成尿素与有机酸的共晶,得到的尿素与有机酸的共晶的助溶效果与洗涤效果基本不变。
(2)本发明提供的新型共晶的制备方法,不仅能够提高尿素单体的稳定性,抑制其分解,其作为原料还同时具备了尿素单体和有机酸原有的功能效果,在应用功效上能够产生叠加效应,不仅满足了尿素在洗涤剂和化妆品领域中的应用要求,还提供了一种集多种功效于一身的多功能新原料晶体。
(3)本发明提供的共晶,所用原料不含任何有毒有害物质,没有任何对人体不利的潜在危害。
(4)共晶的本质是原子、离子或分子自组装过程中各组分和相态达到了热力学和动力学平衡,是一个物理过程。本发明在加热搅拌至熔融的基础上,引入了超声的手段,同时充分满足热力学条件与动力学条件,以形成更加稳定的共晶系。
(5)本发明的一种共晶,其应用范围更广泛,可添加到洗涤剂中其到助溶效果,也可添加到化妆品中作保湿剂,使产品功效开发最大化。
附图说明
为了更清楚地说明本发明实施例中的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,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为柠檬酸:尿素=1:5制得共晶与柠檬酸单体和尿素单体红外对比;
图2为柠檬酸:尿素=1:5制得共晶与柠檬酸单体和尿素单体热重曲线对比;
图3为尿素(共晶)对饱和硫酸钠溶液的助溶效果;
图4为制得共晶与柠檬酸单体和尿素单体对JB-01污布(碳黑油)去污能力测试数据分析;
图5为制得共晶与柠檬酸单体和尿素单体对JB-02污布(蛋白)去污能力测试数据分析;
图6为制得共晶与柠檬酸单体和尿素单体对JB-03污布(皮脂)去污能力测试数据分析;
图7为柠檬酸:尿素=1:2制得共晶与柠檬酸单体和尿素单体红外对比;
图8为乳酸:尿素=1:5制得共晶与乳酸单体和尿素单体红外对比;
图9为柠檬酸:乳素=1:5制得共晶与乳酸单体和尿素单体热重曲线对比;
图10为尿素(共晶)对饱和硫酸钠溶液的助溶效果;
图11为乳酸:尿素=1:2制得共晶与乳酸单体和尿素单体红外对比;
图12为尿素(共晶)对饱和硫酸钠溶液的助溶效果。
具体实施方式
为使本发明的目的、技术方案及优点更加清楚、明确,以下参照附图并举实施例和对比例对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
请同时参阅所附图表,本发明提供了一种尿素与有机酸的共晶的制备方法的一些实施实例。由于尿素的稳定性差,在制备和储存过程中很容易分解,容易造成产品不稳定、不易保存等问题,其助溶性和保湿性也有所降低影响产品功能效果。因此,需要采取一定的措施来提高尿素的稳定性。
本发明的一种尿素与有机酸的共晶的制备方法,包括以下步骤:
步骤S100、提供尿素与有机酸,将尿素和所述有机酸混匀得到混合物;
步骤S200、搅拌且加热熔融所述混合物,得到共晶液体;
步骤S210、将所述加热熔融后的共晶液体在超声仪中超声处理;
步骤S220、将所述超声后的共晶液体冷却结晶得到尿素-有机酸共晶。
具体地,有机酸是指分子中含有羧基的有机化合物。可以采用柠檬酸、乳酸、聚丙烯酸、聚谷氨酸。
柠檬酸和乳酸都是α-羟基酸,α-羟基酸是指在α位有羟基的羧酸,因其最初是从苹果、柠檬、甘蔗等水果和植物中提取的,也称果酸,α-羟基酸是一类小分子物质,可迅速被吸收,具有较好的保湿作用;其浓度高时可引起角质脱落和角质溶解,对皮肤干燥、细微皱纹、斑点有显著的改善作用,可使皮肤变得光滑、柔软、富有弹性,因此倍受化妆品厂商的青睐,现在已广泛用于化妆品中,因此本方法柠檬酸、乳酸等为共晶形成物,与尿素形成有机酸-尿素共晶,以此来提高尿素的稳定性,满足其在洗涤剂和化妆品领域中的应用要求。
本发明通过采用有机酸与尿素形成共晶,以提高尿素单体的稳定性。尿素呈晶体或粉末状,有机酸通常呈粉末状或液态,在将尿素和有机酸混合时,可以进行搅拌以充分混合,得到混合物。当然,也可以进行对晶体或粉末状的反应物进行研磨并混合。
实施例1:柠檬酸与尿素(1:5)的共晶及其共晶性质测定
共晶的制备:
(1)称取0.0l mol的柠檬酸和0.05mol的尿素,置于反应器中,在100℃条件下搅拌并反应1h,得到尿素-柠檬酸的熔融共晶。
(2)将熔融状态的共晶趁热放入超声仪中进行超声处理10min,之后将产品取出放置室温冷却,得到尿素-柠檬酸的共晶。
共晶的性质检测:
(1)红外分析:取制备得到的尿素-柠檬酸共晶用红外光谱仪进行表征,得到的红外谱图如图1所示。由图1可以看出在频率柠檬酸和尿素在3000-3500cm-1处出现尖峰,这与O-H键的存在有关,而在共晶中,在3000-3500cm-1处出现更宽的峰,说明组分之间形成了更多的O-H键,同时C=O带从1622cm-1转移到1626cm-1.这是由于碳基氧中电子密度的增加造成的,进一步说明组分之间形成了更多的氢键。
(2)热重分析:取制备得到的尿素-柠檬酸共晶用TGA热重分析仪进行表征,得到热重分析如图2所示。由图2可以看出尿素的第一失重温度点在130℃左右,而柠檬酸的第一失重温度点与160℃接近,这是因为尿素和柠檬酸的熔点分别在133℃和159℃左右,这一温度范围的质量损失主要是尿素和柠檬酸的挥发损失,而制得共晶产品的第一失重温度点在90℃左右,这进一步说明了尿素与柠檬酸之间形成了大量氢键,导致共晶的熔点降低,第一失重点提前出现。而第一次失重点之后,共晶的热解损失速率远小于柠檬酸和尿素单体,说明共晶的热稳定性大于柠檬酸和尿素单体。
(3)热稳定性研究:取烧杯8只,分成两组,分别放入尿素单体和所制尿素共晶,置电热恒温干燥箱中,再分40℃、50℃、60℃、70℃四个温度组进行高温加速试验,定时取出,测尿素含量。尿素含量的测定方法:本专利采用高效液相色谱法测定尿素含量,流动相为乙腈-水(90:10,V/V);流速为1.0mL/min;检测波长为190nm;柱温为25℃;进样量为10μL。取尿素单体30.7mg,精密称定,置50mL棕色容量瓶中,加流动相溶解并定容,摇匀,即得质量浓度为0.614mg/mL的对照品贮备液;取5mL,10mL容量瓶中,用流动相稀释并定容,摇匀,得质量浓度为0.307mg/mL的对照品溶液。取样品(尿素单体0.5g和制得共晶0.8g),分别精密称定,置50mL烧杯中,加流动相20mL,水浴加热使溶解,放至室温,冰浴30min,滤过,滤液转移至50mL棕色容量瓶中,放至室温,用流动相稀释并定容,摇匀;精密吸取2mL,置10mL容量瓶中,以流动相稀释并定容,摇匀,得供试品溶液。精密吸取对照品溶液、供试品溶液各10μL,按上述色谱条件进样分析,40℃、50℃、60℃、70℃四个温度各做一次,记录色谱图,分析尿素含量。
表1尿素单体高温加速试验结果
表2尿素柠檬酸共晶高温加速试验结果
根据表1和表2可对各温度组的尿素单体和制得共晶的尿素质量和相对百分量进行分析,可以明显看到所制得共晶相比尿素单体分解速率下降许多,稳定性有大幅度提高。
(4)助溶性研究:取多组10mL的饱和硫酸钠溶液,以尿素和制得共晶分别为助溶剂,充分溶解,分别加入1.00g的硫酸钠固体,运用超声振荡溶解,抽滤得未溶解的硫酸钠固体,烘干,称量,计算助溶率如图3所示。
从图3可以看出,相较与尿素单体,共晶对饱和硫酸钠的助溶率有所下降,不过这是由于尿素共晶中尿素含量不为100%导致的,尿素共晶的助溶率可达到尿素单体的60%左右,这与共晶中尿素的质量分数基本相符,说明形成共晶在提高尿素稳定性的基础上,基本上没有影响尿素的助溶效果。
(5)去污能力测试:洗涤试验中配制洗涤剂溶液采用250mg/kg(以碳酸钙表示,下同)硬水,钙离子与镁离子摩尔比为6:4,配制方法如下:称16.70g氯化钙(5.1)和20.37g氯化镁,配制10.0L,即为2500mg/kg硬水。使用时取1.0L冲至10.0L即为250mg/kg硬水。根据洗涤剂性能测试的要求,参考《中华人民共和国国家标准-衣料用洗涤剂去污力及循环洗涤性能的测定》,制备JB-01污布(碳黑油)、JB-02污布(蛋白)、JB-03污布(皮脂)。
将试片按同一类别相叠,用白度计在457nm下逐一读取洗涤前后的白度值:洗前白度以试片正反两面各取两个点(每一面的两点应中心对称),测量白度值,以四次测量的平均值为该试片的洗前白度F1;洗后白度则在试片的正反两面各取两个点(每一面的两点应中心对称)测量白度值,以四次测量的平均值为该试片的洗后白度F2(当对不同污渍采用分别测试洗涤剂去污力的方式时,每组试片至少为6片)。
试验时用250mg/kg硬水(事先应预热至约30℃时使用)分别将试样与标准洗衣粉配制成一定浓度(未特别说明时,标准洗衣粉与试样溶液浓度均为0.2%)的测试溶液1L倒入对应的去污浴缸内,将浴缸放入所对应的位置并装好搅拌叶轮,调节仪器使洗涤试验温度保持在30℃±1℃,准备测定。以一一对应的方式,计算每个试片洗涤前后的白度差(F2-F1),并对每组试片,分别在置信度90%下,进行Q值检验,对可疑值进行取舍。确认有效的白度差和试片数量n后,按公式:计算去污力,结果如图4-6所示。
由图4-6可知上述四种洗衣液其去污比值均大于1,其中所制得共晶在增强去污能力上表现优异,共晶和尿素更有利于碳黑油和蛋白的洗涤,而共晶和柠檬酸更有利于皮脂的洗涤,而且共晶含量越多,其增强去污能力的效果越明显。
实施例2:柠檬酸与尿素=1:2,添加质量百分比5%的去离子水的共晶性质测定
共晶的制备:
(1)称取0.0l mol的柠檬酸和0.02mol的尿素,置于反应器中,添加质量百分比5%的去离子水在100℃条件下搅拌并反应1h,得到尿素-柠檬酸的熔融共晶。
(2)将熔融状态的共晶趁热放入超声仪中进行超声处理10min,之后将产品取出放置室温冷却,得到尿素-柠檬酸的共晶。
共晶的性质检测:
红外分析:取本发明尿素-柠檬酸共晶用红外光谱仪进行表征,得到的红外谱图如7所示。
由图7可以看出在频率柠檬酸和尿素在3000-3500cm-1处出现尖峰,这与O-H键的存在有关,而在共晶中,在3000-3500cm-1处出现更宽的峰,说明组分之间形成了更多的O-H键,而实施例2中的峰相较于实施例1宽些,这是尿素占比较少导致的。
实施例3:乳酸与尿素=1:5共晶性质测定
共晶的制备:
(1)称取0.0l mol的乳酸和0.05mol的尿素,置于反应器中,在100℃条件下搅拌并反应1h,得到尿素-乳酸的熔融共晶。
(2)将熔融状态的共晶趁热放入超声仪中进行超声处理10min,之后将产品取出放置室温冷却,得到尿素-乳酸的共晶。
共晶的性质检测:
(1)红外分析:取本发明尿素-柠檬酸共晶用红外光谱仪进行表征,得到的红外谱图如图8所示。由图8可以看出尿素在频率3000-3500cm-1处出现尖峰,这与O-H键的存在有关,而在共晶中,3000-3500cm-1处的峰变得更宽了,说明组分之间形成了更多的O-H键,同时C=O带从1621cm-1转移到1625cm-1.这是由于碳基氧中电子密度的增加造成的,进一步说明组分之间形成了更多的氢键。
(2)热重分析:取本发明尿素-乳酸共晶用TGA热重分析仪进行表征,得到热重分析图如图9所示。由图9可以看出所制得共晶在热解温度范围内的热解损失重量始终位于两种单体之间,其中主要的重量损失来自乳酸的挥发。
(3)热稳定性研究:按照实施例1中的做法,在此对尿素-乳酸共晶进行高温加速试验:
表3尿素单体高温加速试验结果
表4尿素乳酸共晶高温加速试验结果
根据表3和表4可对各温度组的尿素单体和制得共晶的尿素质量和相对百分量进行分析,可以明显看到所制得共晶相比尿素单体分解速率下降许多,稳定性有大幅度提高。
(4)助溶性研究:取多组10mL的饱和硫酸钠溶液,以尿素和制得共晶为助溶剂,充分溶解,分别加入1.00g的硫酸钠固体,运用超声振荡溶解,抽滤得未溶解的硫酸钠固体,烘干,称量,计算助溶率,结果如图10所示。
由图10可知,相较与尿素单体,共晶对饱和硫酸钠的助溶率有所下降,不过这是由于尿素共晶中尿素含量不为100%导致的,尿素共晶的助溶率可达到尿素单体的77%左右,这与共晶中尿素的质量分数基本相符,说明形成共晶在提高尿素稳定性的基础上,基本上没有影响尿素的助溶效果。
实施例4:乳酸与尿素=1:2共晶性质测定
共晶的制备:
(1)称取0.0l mol的乳酸和0.02mol的尿素,置于反应器中,在100℃条件下搅拌并反应1h,得到尿素-乳酸的熔融共晶。
(2)将熔融状态的共晶趁热放入超声仪中进行超声处理10min,之后将产品取出放置室温冷却,得到尿素-乳酸的共晶。
共晶的性质检测:
红外分析:取本发明尿素-乳酸共晶用红外光谱仪进行表征,得到红外谱图如图11所示。从图11可以看出尿素在频率3000-3500cm-1处出现尖峰,这与O-H键的存在有关,而在共晶中,3000-3500cm-1处的峰变得更宽了,说明组分之间形成了更多的O-H键。
实施例5:不同种类有机酸与尿素形成共晶的稳定性
共晶的制备:
(1)分别称取0.0l mol的聚丙烯酸、没食子酸、壬二酸和0.02mol的尿素,分别置于反应器中,在100℃条件下反应1h,得到尿素与不同有机酸的熔融共晶。
(2)将熔融状态的共晶趁热放入超声仪中进行超声处理10min,之后将产品取出放置室温冷却,得到尿素与不同有机酸的共晶。
共晶的性质检测:
热稳定性研究:按照实施例1中的做法,在此对尿素与不同有机酸的共晶进行高温加速试验(70℃),将几种制得的尿素与不同有机酸共晶的热稳定性进行比较分析:
表5尿素与各种有机酸共晶高温加速试验结果
根据表5可对70℃下尿素单体和制得共晶的尿素质量和相对百分量进行分析,可以明显看到所制得共晶相比尿素单体分解速率下降许多,说明所列几种有机酸与尿素制得共晶均可提高稳定性,但不同有机酸形成的共晶其稳定性有所不同,其中柠檬酸-尿素共晶的稳定性最高。
对比例1:柠檬酸与尿素=1:5在70℃下形成的共晶性质测定
共晶的制备:
(1)称取0.0l mol的柠檬酸和0.05mol的尿素,置于反应器中,在70℃条件下搅拌并反应1h,得到尿素-柠檬酸的熔融共晶。
(2)将熔融状态的共晶趁热放入超声仪中进行超声处理10min,之后将产品取出放置室温冷却,得到尿素-柠檬酸的共晶。
共晶的性质检测:
热稳定性研究:按照实施例1中的做法,在此对尿素-柠檬酸共晶进行高温加速试验:
表6尿素与柠檬酸共晶高温加速试验结果
根据表6可对各温度组的尿素单体和制得共晶的尿素质量和相对百分量进行分析,可以明显看到所制得共晶相比尿素单体分解速率几乎持平,稳定性基本不变,与同比例下100℃的实施例1相比,效果相差甚远,这是由于共晶形成的本质是原子、离子或分子自组装过程中各组分和相态达到了热力学和动力学平衡,热力学有利是形成共晶的必要前提,在满足动力学条件有利的条件下,还要满足热力学条件。即,即使我们在共晶制备过程中,给予了充分的搅拌甚至是超声处理,但达不到一定的温度,依然形不成共晶,得不到相应的结果。
对比例2:柠檬酸与尿素=1:5在130℃下形成的共晶性质测定
共晶的制备:
(1)称取0.0l mol的柠檬酸和0.05mol的尿素,置于反应器中,在130℃条件下搅拌并反应1h,得到尿素-柠檬酸的熔融共晶。
(2)将熔融状态的共晶趁热放入超声仪中进行超声处理10min,之后将产品取出放置室温冷却,得到尿素-柠檬酸的共晶。
共晶的性质检测:
助溶性研究:取多组10mL的饱和硫酸钠溶液,以尿素和制得共晶为助溶剂,充分溶解,分别加入1.00g的硫酸钠固体,运用超声振荡溶解,抽滤得未溶解的硫酸钠固体,烘干,称量,计算助溶率,结果如图12所示。由图12可以看出,相较与尿素单体,共晶对饱和硫酸钠的助溶率大幅度下降,与100℃同比例下的实施1相比,助溶效果也是大相径庭,这是由于在制备共晶过程中,反应温度过高,达到了130℃,在共晶尚未完全形成前,大量的尿素已经分解挥发,因此助溶效果变差。
对比例3:柠檬酸与尿素=1:5在100℃下但不超声形成共晶性质测定
共晶的制备:
称取0.0l mol的柠檬酸和0.05mol的尿素,置于反应器中,在100℃条件下搅拌并反应1h,得到尿素-柠檬酸的熔融共晶。
共晶的性质检测:
热稳定性研究:按照实施例1中的做法,在此对尿素-柠檬酸共晶进行高温加速试验:
表7尿素与柠檬酸共晶高温加速试验结果
根据表7可对各温度组的尿素单体和制得共晶的尿素质量和相对百分量进行分析,可以明显看到所制得共晶相比尿素单体虽然分解速率有所下降,稳定性在一定程度上提高了,但与同比例下经过超声过的实施例1相比,有一定差异,这是由于在对比例3中,共晶形成未经过超声,其动力学条件和热力学条件未经过充分满足,这使得形成的共晶不是很稳定,效果较实施例1相比,共晶稳定性低。
本发明实施例中的部分步骤,可以利用软件实现,相应的软件程序可以存储在可读取的存储介质中,如光盘或硬盘等。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种尿素与有机酸共晶的制备方法,其特征在于,包括步骤:
(1)取尿素和有机酸混匀,在80~120℃条件下反应,得到尿素-有机酸的熔融共晶;
(2)将熔融状态的共晶趁热超声,之后放置冷却,得到尿素-有机酸的共晶。
2.根据权利要求1所述的尿素与有机酸共晶的制备方法,其特征在于,所述有机酸包括柠檬酸、乳酸、水杨酸、壬二酸、没食子酸、透明质酸、聚丙烯酸、聚谷氨酸中的一种或多种。
3.根据权利要求1所述的尿素与有机酸的共晶的制备方法,其特征在于,所述步骤(1)的反应温度为100℃。
4.根据权利要求1所述的尿素与有机酸的共晶的制备方法,其特征在于,所述超声时间为5~100min。
5.根据权利要求1所述的尿素与有机酸的共晶的制备方法,其特征在于,所述尿素和所述有机酸的摩尔比为1:1~10:1。
6.根据权利要求1所述的尿素与有机酸的共晶的制备方法,其特征在于,不额外添加第三物质得到二元共晶系;或加入少量水促进共晶系的形成,所述水的添加质量分数为0.1%~10%。
7.一种尿素与有机酸共晶,其特征在于,所述共晶由权利要求1~6任一所述的方法制备得到。
8.一种提高尿素稳定性的方法,其特征在于,所述方法为制备尿素-有机酸共晶,包括步骤:
(1)取尿素和有机酸混匀,在80~120℃条件下反应,得到尿素-有机酸的熔融共晶;
(2)将熔融状态的共晶趁热超声,之后放置冷却,得到尿素-有机酸的共晶。
9.权利要求7所述的尿素与有机酸共晶在化学领域,或农业领域,或食品领域,或医药领域,或材料领域,或纺织领域中的应用。
10.根据权利要求9所述的应用,其特征在于,所述应用包括:制备化妆品,或制备洗涤剂,或制备温敏材料,或制备饲料,或制备肥料,或制备农药,或制备药物制剂,或制备药物输送载体,或制备食品添加剂,或制备助溶剂,或制备催化剂,或制备化学涂料,或制备电池材料,或制备燃料添加剂,或制备纺织品加工剂。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160130496A1 (en) * | 2013-09-04 | 2016-05-12 | Halliburton Energy Services, Inc. | Scale-inhibiting cocrystals for treatment of a subterranean formation |
CN105696066A (zh) * | 2015-10-26 | 2016-06-22 | 西北大学 | 一种压片法制备共晶的方法 |
CN106659693A (zh) * | 2014-07-02 | 2017-05-10 | 布拉德福德大学 | 包含酸部分的共晶的泡腾组合物 |
-
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- 2023-08-29 CN CN202311101434.6A patent/CN117126081A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160130496A1 (en) * | 2013-09-04 | 2016-05-12 | Halliburton Energy Services, Inc. | Scale-inhibiting cocrystals for treatment of a subterranean formation |
CN106659693A (zh) * | 2014-07-02 | 2017-05-10 | 布拉德福德大学 | 包含酸部分的共晶的泡腾组合物 |
CN105696066A (zh) * | 2015-10-26 | 2016-06-22 | 西北大学 | 一种压片法制备共晶的方法 |
Non-Patent Citations (2)
Title |
---|
GERMAN L. PERLOVICH: "Two-component molecular crystals: relationship between the entropy term and the molecular volume of co-crystal formation", CRYSTENGCOMM, vol. 20, 31 December 2018 (2018-12-31), pages 3634 * |
李晓锐: "小分子共晶制备方法的研究", 中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑), no. 4, 15 April 2021 (2021-04-15), pages 1 - 2 * |
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