CN117343491A - 一种耐高温缓释型复合材料及其制备方法和应用 - Google Patents
一种耐高温缓释型复合材料及其制备方法和应用 Download PDFInfo
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- CN117343491A CN117343491A CN202210734106.9A CN202210734106A CN117343491A CN 117343491 A CN117343491 A CN 117343491A CN 202210734106 A CN202210734106 A CN 202210734106A CN 117343491 A CN117343491 A CN 117343491A
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- release composite
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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Abstract
本发明公开了一种耐高温缓释型复合材料及其制备方法和应用。本发明的耐高温缓释型复合材料包含有可降解耐温聚合物、表面活性剂和无机颗粒;本发明的耐高温缓释型复合材料具有良好的抗温性,活性成分释放稳定,可用于高温油气井,减少频繁开井加注化学剂。
Description
技术领域
本发明涉及固体复合材料技术领域,具体是涉及一种耐高温缓释型复合材料及其制备方法和应用。
背景技术
油气开采时广泛使用多种化学剂,例如缓蚀剂,防蜡剂,防垢剂,防天然气水合物,表面活性剂等需要经常加入地层,井筒和管道中以减少地层伤害,增产油气保障井筒完好和通畅。其中的表面活性剂可以有清洗,分散、驱油、发泡的作用。产品一次性的加入量过大,产生浪费,采用慢释放技术可以减少作业次数,缓释体系还可以有效提高活性组分化学品的利用率,减少其由于环境等因素而引起的损失和挥发作用。在天然气开采中,随着开采时间增加,井下压力减少,地下水积聚于井筒中,使天然气产量减少甚至停产,其中作为发泡剂产生泡排除井筒基液。这些井筒化学剂发泡剂可以是固体或液体形状。固体发泡棒通常制成速溶固体棒,通过经常频繁开井定期投入井筒。而液体则通过泵注入井下,需要投资加装管路和泵。固体缓慢释放化学剂是减少开井和液体注入设备投入的一个有效方法。
缓慢释放技术在农业,药物,油田化学品等领域均有应用。在医药领域将药物包覆于缓释胶囊,可减少用药次数,延长药物有效作用时间几倍。在农药缓释剂方面,品种较多、其中有微胶囊剂,胶囊外壳可以是天然的、半合成的或全合成的高分子化合物,包括蛋白质类、高分子碳水化合物、纤维素类、脂肪酸及衍生物、无机高分子、乙烯基聚合物、聚酰胺、聚氨酯和聚酯等。在缓释型肥料方面,以改性聚乙烯醇分别与无机材料硅藻土、沸石粉、生物质炭、磷矿粉、硫磺进行混合作为包膜材料控释肥料,减少氮素损失,提高氮肥利用率。
缓释技术在油田中得到了很多的应用,在缓蚀阻垢方面已有现场应用。目前缓释技术还应用于油田开发其他方向如钻井固井水泥浆等,采用环氧树脂与淀粉相结合的方法制成了缓释抑盐剂等,还有微胶囊包裹技术将水泥促进剂包裹起来延缓其释放速率以改善水泥体系稠化性能等。
US20160009980A1公开了一种使用多孔氧化金属例如氧化铝,氧化锆,氧化钛为固体载体和粘合剂混合,由吸附在煅烧多孔金属氧化物上的良好处理剂的复合物或进入煅烧多孔金属氧化物的间隙中形成的形状压缩颗粒可引入采油井或产气井,将有效组分吸附于多孔材料中慢释放出来。US20180134939A1公开了将阻垢剂和缓释剂活性物质通过化学键交联在载体上,利用醇,胺和酸的反应交联,在井下交联键水解缓慢释放出活性物质。US20170058184A1公开了玉米粗砂组成的一种非水溶性载体,在油气田的增产或生产过程中将用作阻垢、表面活性剂等液体化学试剂进行吸附,利用玉米粗砂的抗压性和液体不溶性将活性化学物质缓慢释放到油气井当中,达到缓释的目的。US20120273197A1公开了一种用于水力压裂、防砂等井处理作业的一种复合材料,其允许一种或多种井处理剂缓慢释放到地下地层和/或穿透地层的井筒中,其具有高比表面积的纳米级煅烧多孔基质(吸附剂),井处理剂涂覆在其上。CN110157401A公开了一种可控长效缓释阻垢剂胶囊的制备方法,将阻垢剂与缓释组分之一的无机纳米载体以固溶体的形式组装成一个均相整体,外面包覆一层可控溶解的由羧甲基纤维素、聚乙烯醇和多孔沸石等组成的交联聚合物,当聚合物在环境介质中发生溶解时活性物质逐步释放,利用聚合物溶解和阻垢剂从无机纳米载体解吸的双重控释机制,使其可以在井筒内缓慢释放,从而延长对井筒的保护作用。CN107304078A公开了一种环保缓释型聚合物阻垢剂,以聚乙烯醇、海藻酸钠和明胶溶液混合为载体材料,硼酸为添加剂构建了缓释壁材体系对阻垢剂进行装载,在50℃的模拟油田水介质中进行缓释。
尽管缓释技术逐渐用于油田和气田的开采过程中,但是由于高温井的环境特点的复杂性,导致对缓释材料的要求异常严格。CN110564388A公开了一种油气田用温敏堵漏胶体的制备方法,由改性聚丙烯酰胺、三价交联剂、水溶性缓释剂和水相进行多相物理吸附和化学预交联,使得温敏堵漏胶体具有温敏溶胀的延迟缓释特性,但适用温度仅仅在60-90℃。CN110003875A中,开展了缓慢释放型泡沫剂的研究,将表面活性剂发泡剂与5-20%肠衣混合,使作用时间达到120小时(5天),但是该技术使用温度低于90℃,并且存在动物材料存储期小于3个月及批次质量不一致等缺点。在这些研究中,针对特定条件(例如耐酸性、耐温性)的缓释材料的选择仍然是研究的难点。
总之,现有技术中的缓释材料多采用可缓慢溶解的材料包裹表面活性剂,实现缓释作用;但是所用材料在高温下溶解分解快,表面活性剂会快速释放,缓释作用时间短。
因此,目前需要一种新型复合材料来解决现有技术中存在的油田用缓释材料缓释作用时间短,耐温性能低的问题。
发明内容
为解决现有技术中存在的问题,本发明提供了一种耐高温缓释型复合材料及其制备方法和应用。本发明的耐高温缓释型复合材料含有表面活性剂、可降解耐温聚合物和无机颗粒;本发明的复合材料具有良好的抗温性,活性成分释放稳定,可用于高温油气井,减少频繁开井加注化学剂。
本发明的目的之一是提供一种耐高温缓释型复合材料。
所述耐高温缓释型复合材料包含有可降解耐温聚合物、表面活性剂和无机颗粒。
本发明的一种优选地实施方式中,
以耐高温缓释型复合材料总重为100%计,
可降解耐温聚合物为30~80%;优选为50~75%;更优选为60~75%;
表面活性剂为1~60%;优选为5~35%;更优选为15~30%;
无机颗粒为1~50%;优选为1~40%;更优选为5~15%。
本发明中所述可降解耐温聚合物为兼具热稳定性和可生物或酸碱降解的聚合物,热稳定性可以根据应用需求适应选择。
本发明的一种优选地实施方式中,
所述可降解耐温聚合物为聚己二酸对苯二甲酸丁二醇酯(PBAT)。
聚己二酸对苯二甲酸丁二醇酯(PBAT)是由丁二醇、已二酸和对苯二甲酸反应得到,是一种可完全生物降解的高分子材料,可被环境中酸碱水解或微生物分解,最终生产二氧化碳和水,不对环境产生负面影响,并且成本不高,是具有实用价值的材料,所述PBAT优选为德国BASF公司生产的全分解塑料Ecoflex。
本发明中,本领域技术人员可以根据应用需求(例如清洗剂,发泡剂和缓蚀剂)选择所述表面活性剂的种类,可以为单一表面活性剂,也可以为复配的混合表面活性剂。
本发明的一种优选地实施方式中,
所述表面活性剂为阴离子表面活性剂、两性表面活性剂中的至少一种;
所述阴离子表面活性剂优选为烷基硫酸钠、烷基磺酸钠、烷基苯磺酸钠、烷基牛磺酸钠中的至少一种;更优选为烷基磺酸钠、烷基苯磺酸钠中的至少一种;和/或,
所述两性表面活性剂优选为烷基氧化胺、烷基甜菜碱中的至少一种,更优选为烷基酰胺丙基氧化胺、烷基酰胺丙基甜菜碱、烷基羟丙基磺基甜菜碱中的至少一种。
本发明的一种优选地实施方式中,
所述表面活性剂的烷基链长度为8~16,优选为十二烷基苯磺酸钠、十二烷基磺酸钠、十二烷基硫酸钠、椰油酰胺丙基甜菜碱、椰油酰胺丙基羟磺基甜菜碱中的至少一种。
本发明中,所述烷基链长度是指烷基主链的长度。可以理解的是,在烷基主链上可以连接或不连接支链,本发明对所述支链没有限制,例如可以为烷基支链,本领域技术人员可以自由选择,只要利于提高复合材料的抗温缓释性能即可。
本发明的一种优选地实施方式中,
所述表面活性剂中还包括非离子表面活性剂作为助剂,所述非离子表面活性剂优选为烷基聚氧乙烯和/或烷基糖苷;
所述烷基聚氧乙烯优选为烷基聚氧乙烯醚、烷基胺聚氧乙烯醚、蓖麻油聚氧乙烯醚中的至少一种;和/或,
所述烷基糖苷优选为碳链C8-14的烷基糖苷或烷基多糖苷,更优选为APG810、APG814、APG1214中的至少一种。
所述烷基聚氧乙烯的聚合度优选为4~10。
该优选实施方式下,更利于表面活性剂在复合材料中的均匀分散,耐高温缓释型复合材料的缓释作用时间更长。
本发明的一种优选地实施方式中,
所述无机颗粒为疏水蒙脱土、有机膨润土、SiO2、高岭土、CaCO3中的至少一种,优选为疏水蒙脱土、高岭土、CaCO3中的至少一种。本发明中,引入无机颗粒能够进一步增大表面活性剂的包覆密度、复合材料的强度,并延长慢释放时间。
本发明的一种优选地实施方式中,
所述无机颗粒粒径为30nm~5μm,优选为30nm~200nm。
本发明的耐高温缓释型复合材料中还可以加入本领域常用的其它助剂,如惰性无机盐等,所述惰性无机盐优选为Na2SO4或NaCl,其用量也为常规用量,本领域技术人员可以根据实际情况添加。
本发明的目的之二是提供一种本发明的目的之一的耐高温缓释型复合材料的制备方法。
所述方法包括将包括可降解耐温聚合物、表面活性剂和无机颗粒在内的组分熔融共混后注塑成型,得到所述耐高温缓释型复合材料。
以上所用的熔融共混设备和注塑成型设备可以采用现有技术常用的塑料加工领域的设备,比如转矩流变仪、螺杆挤出机、注塑机等。
本发明的一种优选地实施方式中,
熔融共混的温度为140~250℃,优选为150~250℃,更优选为150~170℃。
本发明的目的之三是提供一种本发明的目的之一的耐高温缓释型复合材料或者由本发明的目的之二的方法制备的耐高温缓释型复合材料作为泡排剂的应用。
本发明的发明人在试验过程中发现,在将活性成分(例如表面活性剂)混合熔融可降解耐温聚合物和无机颗粒中可形成耐温缓释材料,能够更好地适用于油气井,且制备方法简单、易操作。本发明优选用聚己二酸对苯二甲酸丁二醇酯(PBAT)共聚物高分子材料为原料之一,并加入无机颗粒,在热熔条件下,将活性组分均匀搅拌分散在固体材料中,形成一种具有缓释性和抗温性的固体材料,该材料兼具耐酸性和抗盐性能。本发明实现了在固体材料中包覆表面活性剂(例如发泡剂),可针对高温气井排水采气,解决频繁开井加注泡排剂的问题。而其他可降解高分子材料,例如聚乳酸(PLA),聚乙醇酸(PGA)等耐温性差、抗盐性差、与表面活性剂的相容性差。
本发明的耐高温缓释型复合材料中含有聚己二酸对苯二甲酸丁二醇酯,这种聚合物与无机颗粒和表面活性剂插层混合形成复合耐温缓释材料,具有对表面活性剂进行包覆,使得其具有良好的抗温性,同时兼具较好的缓释性,活性成分释放稳定,可在井筒高温环境下缓慢释放出活性成分-表面活性剂,可以作为清洗剂、发泡剂或缓蚀剂应用,可以应用于油气井筒清洗、发泡排水和缓蚀剂等领域。特别引入纳米无机颗粒,能够进一步提高复合材料的性能,增加缓释时间,同时提高耐温性能。
本发明提供的制备方法能够制得前述特定组成的耐高温缓释型复合材料,通过采用特定各原料配合适宜的含量,相互协同,能够形成有机无机复合结构,同时使得表面活性剂均匀的分散、被复合包覆,形成了一种兼具缓释性和抗温性的复合材料,应用时表面活性剂能够在高温(例如130℃)下缓慢释放。
在本发明的方法中,可降解聚合物和无机材料熔融共混,同时包覆表面活性剂,形成插层复合材料(即抗温缓释型复合材料),该复合材料具有良好的耐温性,可使表面活性剂缓慢释放,缓释作用时间长。其中,各原料的组分配合特定含量,能够保证在形成复合的同时对表面活性剂进行包覆,使得制得的复合材料兼具耐温性和缓释性。而在相同条件下,当采用的各原料的含量不适当时,可能不会形成复合,或者包覆表面活性剂的含量少,分层,或者释放时间短。
本发明中,可以理解的是,各原料完全转化为复合材料。
本发明中,所述熔融共混能够制备得到复合材料,在聚合物熔点以上软化混合,优选地,在聚合熔融之后,搅拌,注塑成型。该优选方案下,更利于形成复合。
本发明提供的抗温缓释型复合材料可在井筒高温(例如80-150℃)、酸性(例如pH为4-5)条件下缓慢释放出活性物-表面活性剂,作为清洗剂、发泡剂或缓蚀剂等来应用。
在本发明的抗温缓释型复合材料中携带发泡剂,便可针对高温气井排水采气,解决频繁开井加注泡排剂的问题。
附图说明
图1为对比例1的初始缓释复合材料外观图;
图2为对比例1的缓释复合材料缓释放评价实验6小时后的外观图;
图3为对比例2的缓释复合材料缓释放评价实验6小时后的外观图;
图4为对比例3的缓释复合材料缓释放评价实验20小时后的外观图;
图5为实施例4的初始耐高温缓释型复合材料外观图;
图6为实施例4的耐高温缓释型复合材料缓释放评价实验48小时后的外观图;
图7为实施例5的耐高温缓释型复合材料缓释放评价实验48小时后的外观图;
图8为实施例6的耐高温缓释型复合材料缓释放评价实验48小时后的外观图。
具体实施方式
下面结合具体实施例及附图对本发明进行具体的描述,有必要在此指出的是以下实施例只用于对本发明的进一步说明,不能理解为对本发明保护范围的限制,本领域技术人员根据本发明内容对本发明做出的一些非本质的改进和调整仍属本发明的保护范围。
实施例中所用原料均为常规市购原料。
对比例1-3
将固体表面活性剂十二烷基苯磺酸钠(SDBS,97%)分别与可降解聚合物树脂:聚乳酸(PLA)-浙江海正生物公司、聚乙醇酸(PGA)、聚己二酸对苯二甲酸丁二醇酯(PBAT)-德国巴斯夫公司(型号C1200)在转矩流变仪上选择在树脂熔融温度以上(此处选择220℃)搅拌(转速25rpm)熔融共混均匀形成预混物,再用注塑机将预混物在热熔下(220℃)注塑冷却成型(均注塑成型为复合固体棒4g)。实验用量对比数据如表1所示。
缓释放评价实验如下:将上述注塑成型的含表面活性剂的复合固体棒4g,放入含有模拟地下盐水60mL的耐压瓶中密封,盐水所含成分为:氯化钙8.37g/L,氯化镁0.42g/L,硫酸钠1.21g/L,氯化钠60.74g/L,模拟地下水通入二氧化碳直至饱和,模拟井下酸性环境。在130℃恒温中实验,期间每24小时更换一次含二氧化碳饱和的模拟地下盐水,观察样品是否维持外观成型。
表1.
组成\编号 | 对比例1 | 对比例2 | 对比例3 |
PGA | 50% | ||
PLA | 50% | ||
PBAT | 50% | ||
SDBS | 50% | 50% | 50% |
130℃盐水中溶解时间(小时) | <6 | <6 | 20 |
其典型试验开始和缓释放评价实验后外观如图1-4所示,图1显示对比例1的初始缓释复合材料为完整棒状,对比例2和对比例3的初始缓释复合材料外观类似对比例1的初始缓释复合材料外观(图1)均为完整棒状;图2显示对比例1的缓释复合材料缓释放评价实验6小时后已完全散解并溶解;图3显示对比例2的缓释复合材料缓释放评价实验6小时后已完全散解并溶解;图4显示对比例3的缓释复合材料缓释放评价实验20小时后缩小软化,但还有少量剩余。由此可以看出PBAT相对PGA和PLA维持的相对时间更长。
对比例4-6
按照对比例1的方法进行,不同的是:采用不同的可降解聚合物树脂:聚3-羟基丁酸酯/3-羟基戊酸酯(PHBV)-宁波天安公司、聚丁二酸丁二醇酯(PBS)-泰国PTT化学FZ71PB、聚己内酯(PCL)-分子量8万。
缓释放评价实验同对比例1,用量和溶解时间如表2所示。可以看出由PHBV、PBS、PCL制备的复合材料溶解时间均小于PBAT的溶解时间:20小时。
表2.
对比例7-9
按照对比例1的方法进行,不同的是:采用表面活性剂的量较高(65%),用量如表3所示。可以看出各复合材料的溶解时间相对于对比例1-3显著变短,说明表面活性剂含量过高时,不利于缓释性能。
表3
组成\编号 | 对比例7 | 对比例8 | 对比例9 |
PGA | 35% | ||
PLA | 35% | ||
PBAT | 35% | ||
SDBS | 65% | 65% | 65% |
130℃盐水中溶解时间(小时) | <2 | <2 | 10 |
对比例10和实施例1-3
按照对比例1的制备方法进行,不同的是:原料采用表面活性剂椰油酰胺丙基甜菜碱(CAB,97%固含量)和不同含量的PBAT,无机颗粒分别为高岭土、CaCO3、疏水蒙脱土进行复合,在转矩流变仪上155℃搅拌(转速25rpm)混合均匀形成预混物,再用注塑机将预混物在热熔下(150℃)注塑冷却成型(均注塑成型为复合固体棒4g),得到耐高温缓释型复合材料。耐高温缓释型复合材料的组成和溶解时间如表4所示,可以看出,与对比例10相比,添加无机材料可以增加耐高温缓释型复合材料的稳定性和延长慢释放时间。
表4
实施例4-6
按照实施例1的方法进行,不同的是,采用不同含量的表面活性剂及PBAT,和无机颗粒分别为纳米SiO2(20-30nm),5微米CaCO3和纳米CaCO3(10-100nm)进行复合,得到耐高温缓释型复合材料。耐高温缓释型复合材料的组成和溶解时间如表5所示。
表5.
组成\样品编号 | 实施例4 | 实施例5 | 实施例6 |
PBAT | 75% | 75% | 75% |
纳米SiO2 | 10% | ||
微米CaCO3 | 10% | ||
纳米CaCO3 | 10% | ||
CAB | 15% | 15% | 15% |
130℃盐水中维持时间(小时) | 48 | 72 | 96 |
其典型外观随时间变化如图5-8所示,图5显示实施例4的初始耐高温缓释型复合材料为完整棒状,实施例5和实施例6的初始耐高温缓释型复合材料外观类似实施例4的初始耐高温缓释型复合材料外观(图5)均为完整棒状;图6显示实施例4的耐高温缓释型复合材料缓释放评价实验48小时后已完全散解,形成不溶松散沉淀;图7显示实施例5的耐高温缓释型复合材料缓释放评价实验72小时后已完全散解,形成分散小块沉淀;图8显示实施例6的耐高温缓释型复合材料缓释放评价实验96小时后缩小为整块沉淀。由表5可以看出,实施例4-6制备的耐高温缓释型复合材料均可维持在2天以上,但加入无机颗粒采用微纳米CaCO3颗粒效果更好。
实施例4-6释放后表面活性剂释放效能评价
针对实施例4-6的释放后表面活性剂,通过测试其泡沫量和半衰期性能来评价其释放的效能。
取40mL释放出的溶液用水稀释配制成200mL的标准溶液进行搅拌法发泡,采用搅拌器发泡,转速设置为16000rpm,搅拌时间30秒,测得泡沫体积和半衰期(泡沫中液体体积析出一半的时间),结果如表6所示。
表6.
由表6可以看出:实施例4-6均可维持表面活性剂释放48小时以上,但含微纳米CaCO3无机颗粒的复合材料释放后表面活性剂维持泡沫性能更好,说明其缓释性能更好。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的--内容,均属于本发明的保护范围。
Claims (14)
1.一种耐高温缓释型复合材料,包含有可降解耐温聚合物、表面活性剂和无机颗粒。
2.如权利要求1所述的耐高温缓释型复合材料,其特征在于:
以耐高温缓释型复合材料总重为100%计,
可降解耐温聚合物为30~80%;
表面活性剂为1~60%;
无机颗粒为1~50%。
3.如权利要求2所述的耐高温缓释型复合材料,其特征在于:
以耐高温缓释型复合材料总重为100%计,
可降解耐温聚合物为50~75%;
表面活性剂为5~35%;
无机颗粒为1~40%。
4.如权利要求1-3任一所述的耐高温缓释型复合材料,其特征在于:
所述可降解耐温聚合物为聚己二酸对苯二甲酸丁二醇酯。
5.如权利要求1-3任一所述的耐高温缓释型复合材料,其特征在于:
所述表面活性剂为阴离子表面活性剂、两性表面活性剂中的至少一种;
所述阴离子表面活性剂优选为烷基硫酸钠、烷基磺酸钠、烷基苯磺酸钠、烷基牛磺酸钠中的至少一种;和/或,
所述两性表面活性剂优选为烷基氧化胺、烷基甜菜碱中的至少一种,更优选为烷基酰胺丙基氧化胺、烷基酰胺丙基甜菜碱、烷基羟丙基磺基甜菜碱中的至少一种。
6.如权利要求5所述的耐高温缓释型复合材料,其特征在于:
所述表面活性剂的烷基链长度为8~16。
7.如权利要求6所述的耐高温缓释型复合材料,其特征在于:
所述表面活性剂为十二烷基苯磺酸钠、十二烷基磺酸钠、椰油酰胺丙基甜菜碱、椰油酰胺丙基羟磺基甜菜碱中的至少一种。
8.如权利要求5所述的耐高温缓释型复合材料,其特征在于:
所述表面活性剂中还包括非离子表面活性剂作为助剂,所述非离子表面活性剂优选为烷基聚氧乙烯和/或烷基糖苷;
所述烷基聚氧乙烯优选为烷基聚氧乙烯醚、烷基胺聚氧乙烯醚、蓖麻油聚氧乙烯醚中的至少一种;和/或,
所述烷基糖苷优选为碳链C8-14的烷基糖苷或烷基多糖苷。
9.如权利要求8所述的耐高温缓释型复合材料,其特征在于:
所述烷基聚氧乙烯的聚合度为4~10。
10.如权利要求1-3任一所述的耐高温缓释型复合材料,其特征在于:
所述无机颗粒为疏水蒙脱土、有机膨润土、SiO2、高岭土、CaCO3中的至少一种,优选为疏水蒙脱土、高岭土、CaCO3中的至少一种。
11.如权利要求10所述的耐高温缓释型复合材料,其特征在于:
所述无机颗粒粒径为30nm~5μm,优选为30nm~200nm。
12.一种如权利要求1-11任一所述的耐高温缓释型复合材料的制备方法,包括将包括可降解耐温聚合物、表面活性剂和无机颗粒在内的组分熔融共混后注塑成型,得到所述耐高温缓释型复合材料。
13.如权利要求12所述的制备方法,其特征在于:
熔融共混的温度为140~250℃,优选为150~250℃。
14.一种如权利要求1-11任一所述的耐高温缓释型复合材料或者由权利要求12-13任一所述方法制备的耐高温缓释型复合材料作为泡排剂的应用。
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