CN111205912B - 一种智能存储型纳米颗粒的制备方法 - Google Patents
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Abstract
本发明公开了属于新型纳米材料制备技术领域的一种智能存储型纳米颗粒的制备方法。步骤如下:1)将含有润滑介质和单体的分散相加入含有表面活性剂的连续相中,搅拌使之乳化;2)然后通过高强度均化器的均化作用,获得含有纳米尺寸液滴的细乳液;3)将细乳液移至反应器中引发聚合,反应结束后冷冻干燥获得纳米颗粒。本发明所制备的智能存储型纳米颗粒,可用于自润滑领域复合材料的制备,比现有的自润滑微胶囊材料尺寸更小,易于分散,可通过共聚对颗粒进行表面改性或引入活性官能团增强颗粒与基体材料的相互作用力,有利于解决含微胶囊自润滑复合材料力学性能显著降低的问题,且尺寸优势使其在自润滑涂层领域有较大应用潜力和市场价值。
Description
技术领域
本发明属于新型纳米材料制备技术领域,尤其涉及一种智能存储型纳米颗粒的制备方法。
背景技术
随着纳米封装技术的发展,利用中空纳米容器隔离封装活性成分的存储型纳米材料已广泛应用于食品科学、生物医药、电子技术和农业等领域,由于其尺寸小、分散性好、易与其他材料结合制备复合材料或直接进行材料改性与修饰,当前已成为一项引人瞩目的高新技术。
近年来,研究者为解决油敏感环境下的摩擦磨损问题,提出了多种自润滑微胶囊材料的制备方法,微胶囊壳材常为有机或无机聚合物材料,内部包覆润滑介质。目前所报道的大部分自润滑微胶囊直径为上百微米,随着微胶囊尺寸和含量的增加,虽然摩擦性能有所提高,但是由于大尺寸微胶囊在基体中作为缺陷更容易引发和传播裂纹,材料力学性能显著下降。微胶囊本身的大尺寸和脆性不仅会降低基体的力学性能,还容易在加工合成过程中发生破裂。对于涂层制备来说,微胶囊的尺寸极大的限制了其添加量和涂层厚度。制备高强度壁材微胶囊可以改善这一缺陷,但此种方法会牺牲微胶囊对外界刺激的敏感性,降低材料在低载条件下的润滑效果。目前溶剂挥发技术可以用于制备微胶囊,但其在实际应用中仍存在局限性:1)胶囊粒度分布宽。由于溶剂挥发技术的产物尺寸和形貌受搅拌条件影响很大,通常难以获得单分散胶囊,需要额外筛分处理;2)一般采用单一聚合物作为壁材,多种聚合物共混时存在兼容性问题。溶剂挥发技术制备聚合物胶囊基本为物理过程,不改变聚合物原料的分子量和固有性质,多种聚合物参与时易发生相分离,影响整体性能;3)不易与表面改性及功能化等技术结合,限制了胶囊的性能拓展。在胶囊形成过程中,聚合物链之间基本不发生键合反应,难以进行高分子结构设计。
发明内容
针对上述问题,本发明提出了一种智能存储型纳米颗粒的制备方法,包括以下步骤:
a. 将润滑介质、聚合单体和正十六烷混合作为分散相;将去离子水和表面活性剂混合作为连续相,分别在常温下搅拌均匀;
b. 将步骤a中的分散相加入连续相中,常温搅拌得到乳液;
c. 将步骤b中所得乳液用超声粉碎机细乳化,得到细乳液;
d. 将步骤c中所得细乳液倒入三口烧瓶,随后加入偶氮二异丁氰,在惰性气体氛围下搅拌反应,得到产物;
e. 将步骤d产物冷冻使其凝固后进行冷冻干燥制得纳米颗粒。
所述步骤d中一种或几种单体发生聚合反应形成纳米颗粒,避免多种聚合物组分的兼容性问题,同时提供了直接进行表面改性及功能化的合成条件。
所述步骤a的分散相中,润滑介质与聚合单体的质量比为1:0.5~3;正十六烷的质量分数为0~0.04;在连续相中,去离子水和表面活性剂的质量比为120:0.4~1;分散相和连续相的搅拌时间均为30 min;搅拌速度为500~700 rpm。
所述步骤a中润滑介质为基础油或含各种油溶性添加剂的润滑油,包括聚α-烯烃合成油、硅油、聚醚;聚合单体为甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、丙烯酸丁酯、苯乙烯任意一种或几种;表面活性剂为十二烷基硫酸钠、曲拉通x114、OP-10乳化剂任意一种或几种。
所述步骤b中,搅拌时间为1 h;搅拌速度为500~700 rpm。
所述步骤c中超声功率为100W~800W;超声处理时间为5~25 min;超声使用脉冲方式为工作3 s,间歇2 s。
所述步骤d中偶氮二异丁氰与聚合单体质量比为0.022:1;反应温度为60~90oC;反应时间为1~24 h;搅拌速度为500~700 rpm;所述惰性气氛为氮气、氩气或氦气。
所述步骤e中冷冻干燥时间为48 h。
一种智能存储型纳米颗粒,所述纳米颗粒在去离子水中稳定分散,形貌为完整球形,粒径小于300 nm。
一种智能存储型纳米颗粒的应用,所述智能存储型纳米颗粒用于制备自润滑复合材料或自润滑涂层。
本发明的有益效果在于:
1.本发明所制备的智能存储型纳米颗粒尺寸小且粒度分布窄,在水溶液中或干燥后均具有良好的分散性,可用于制备自润滑复合材料或涂层。
2.本发明采用细乳液聚合法,在不同润滑介质和聚合单体条件下均成功合成存储型纳米颗粒,说明该制备方法具有一定普适性,可推广到其他材料体系及应用领域。
3.本发明所制备的智能存储型纳米颗粒易于进行高分子结构设计,颗粒表面可通过多种单体共聚合成,避免了多种聚合物组分的兼容性问题,同时提供了直接进行表面改性及功能化的合成条件,颗粒结构和表面性能可根据具体需求进行设计。
4.本发明利用纳米封装技术制备含有润滑介质的智能存储型纳米颗粒,机械触发或热触发可引起内部活性成分释放,实现智能润滑目的,同时其在基体材料中可大大降低尺寸、分散性和结合性引起的性能损失。
附图说明
图1为本发明实施例1制备的智能存储型纳米颗粒SEM图;
图2为本发明实施例1制备的智能存储型纳米颗粒粒径分布图;
图3为本发明实施例2制备的智能存储型纳米颗粒SEM图;
图4为本发明实施例2与对比例1制备的智能存储型纳米颗粒自润滑材料与微胶囊自润滑材料应力应变曲线对比图;
图5为本发明实施例3制备的智能存储型纳米颗粒SEM图;
图6为本发明实施例4制备的智能存储型纳米颗粒SEM图。
具体实施方式
以下结合附图和具体实施例对本发明作进一步的详细说明:
实施例1
按照下述步骤制备智能存储型纳米颗粒:
1)称取6 g聚α-烯烃合成油、12 g甲基丙烯酸甲酯和0.75 g正十六烷作为溶液A;在溶液A中,润滑介质与聚合单体的质量比为1:2;正十六烷的质量分数为0.04;常温搅拌30min;称取0.75 g十二烷基硫酸钠加入90 g去离子水作为溶液B;在溶液B中,去离子水和表面活性剂的质量比为120:1;常温搅拌30 min,搅拌速度为600 rpm。
2)将溶液A加入溶液B,常温搅拌1 h,搅拌速度为600 rpm,得到乳液C。
3)将步骤2)中的乳液C用超声粉碎机细乳化,超声功率为300W,处理时间为25min,超声使用脉冲方式为工作3 s,间歇2 s,得到细乳液D。
4)将步骤3)中所得细乳液D倒入三口烧瓶,随后加入0.264 g偶氮二异丁氰,偶氮二异丁氰与聚合单体质量比为0.022:1;保持体系温度为75oC,采用氮气保护,搅拌速度为600 rpm,继续反应5 h,得到产物E。
5)将步骤4)中产物E在冰箱中冷冻一夜,凝固后冷冻干燥48 h制得纳米颗粒,SEM照片如图1所示,粒径分布如图2所示,纳米颗粒粒径为20-260nm。
实施例2
按照下述步骤制备智能存储型纳米颗粒:
1)称取6 g聚α-烯烃合成油、6 g甲基丙烯酸甲酯、6 g甲基丙烯酸缩水甘油酯和0.75 g正十六烷作为溶液A,在溶液A中,润滑介质与聚合单体的质量比为1:2;正十六烷的质量分数为0.04;常温搅拌30 min;称取0.75 g十二烷基硫酸钠加入90 g去离子水作为溶液B,在溶液B中,去离子水和表面活性剂的质量比为120:1;常温搅拌30 min,搅拌速度为600 rpm。
2)将溶液A加入溶液B,常温搅拌1 h,搅拌速度为600 rpm,得到乳液C。
3)将步骤2)中的乳液C用超声粉碎机细乳化,超声功率为420W,处理时间为25min,超声使用脉冲方式为工作3 s,间歇2 s,得到细乳液D。
4)将步骤3)中所得细乳液D倒入三口烧瓶,随后加入0.264 g偶氮二异丁氰,偶氮二异丁氰与聚合单体质量比为0.022:1;保持体系温度为75oC,采用氮气保护,搅拌速度为600 rpm,继续反应5 h,得到产物E。
5)将步骤4)中产物E在冰箱中冷冻一夜,凝固后冷冻干燥48 h制得纳米颗粒,SEM照片如图3所示,粒度分布集中,粒径约为50nm,甲基丙烯酸甲酯与甲基丙烯酸缩水甘油酯共聚反应式如反应式1,该反应将环氧官能团引入纳米颗粒表面。
反应式1
对比例1
将实施例1制备的0.8 g纳米颗粒与7.2 g含胺类固化剂的环氧树脂液体混合,室温搅拌40 min随后超声10 min使纳米颗粒充分分散,在真空干燥箱中去除气泡后倒入硅胶模具,常温干燥7天后得到自润滑复合材料,将自润滑材料在电子万能试验机上进行拉伸测试,拉伸速率为2 mm/min,应力应变曲线如图4所示,由于环氧基可与胺类固化剂反应,最终形成交联网络,反应式如反应式2,共价键的形成将有效增加颗粒与基体的结合性,提高复合材料力学性能。
反应式2
为对比含本发明纳米颗粒自润滑材料与现有技术微胶囊自润滑材料力学性能差异,利用溶剂挥发法制备微胶囊:将4 g聚α-烯烃合成油、8 g聚甲基丙烯酸甲酯与50 ml二氯甲烷混合,常温搅拌均匀,得到溶液A;将0.2 g阿拉伯树胶、1 g聚乙烯醇与200 ml去离子水混合,125oC下搅拌均匀,得到溶液B。将上述溶液A和B混合倒入烧瓶,保持机械搅拌速度为600 rpm,在40oC下反应30 min,随后45oC下继续反应2 h。产物用去离子水冲洗后过滤,常温干燥得到微胶囊。SEM测试表明,所制备微胶囊粒径为10-30 μm。将0.8 g微胶囊与7.2 g含胺类固化剂的环氧树脂液体混合制备微胶囊自润滑复合材料,具体制备方法与对比例1中纳米颗粒自润滑材料相同。将自润滑材料在电子万能试验机上进行拉伸测试,拉伸速率为2 mm/min,应力应变曲线如图4所示,与微胶囊自润滑材料相比,纳米颗粒自润滑材料的强度和韧性分别提高2.6倍和7.0倍。
在本实施例中,通过对纳米颗粒进行表面改性,颗粒与基体之间形成共价键,增强了二者的结合性,同时提高了复合材料的强度和韧性。
实施例3
按照下述步骤制备智能存储型纳米颗粒:
1)称取6 g硅油、12 g甲基丙烯酸甲酯和0.75 g正十六烷作为溶液A,在溶液A中,润滑介质与聚合单体的质量比为1:2;正十六烷的质量分数为0.04;常温搅拌30 min;称取0.75 g十二烷基硫酸钠加入90 g去离子水作为溶液B,在溶液B中,去离子水和表面活性剂的质量比为120:1;常温搅拌30 min,搅拌速度为600 rpm。
2)将溶液A加入溶液B,常温搅拌1 h,搅拌速度为600 rpm,得到乳液C。
3)将步骤2)中的乳液C用超声粉碎机细乳化,超声功率为300W,处理时间为25min,超声使用脉冲方式为工作3 s,间歇2 s,得到细乳液D。
4)将步骤3)中所得细乳液D倒入三口烧瓶,随后加入0.264 g偶氮二异丁氰,偶氮二异丁氰与聚合单体质量比为0.022:1;保持体系温度为75oC,采用氮气保护,搅拌速度为600 rpm,继续反应5 h,得到产物E。
5)将步骤4)中产物E在冰箱中冷冻一夜,凝固后冷冻干燥48 h制得纳米颗粒,SEM照片如图5所示,粒径约为100nm。
实施例4
按照下述步骤制备智能存储型纳米颗粒:
1)称取5 g聚α-烯烃合成油、12 g苯乙烯和3 g甲基丙烯酸甲酯作为溶液A,在溶液A中,润滑介质与聚合单体的质量比为1:3;常温搅拌30 min;称取0.2 g十二烷基硫酸钠和0.2 g曲拉通x114加入120 g去离子水作为溶液B,在溶液B中,去离子水和表面活性剂的质量比为120:0.4;常温搅拌30 min,搅拌速度为600 rpm。
2)将溶液A加入溶液B,常温搅拌1 h,搅拌速度为600 rpm,得到乳液C。
3)将步骤2)中的乳液C用超声粉碎机细乳化,超声功率为300W,处理时间为25min,超声使用脉冲方式为工作3 s,间歇2 s,得到细乳液D。
4)将步骤3)中所得细乳液D倒入三口烧瓶,随后加入0.33 g偶氮二异丁氰,偶氮二异丁氰与聚合单体质量比为0.022:1;保持体系温度为85oC,采用氮气保护,搅拌速度为600rpm,继续反应6 h,得到产物E。
5)将步骤4)中产物E在冰箱中冷冻一夜,凝固后冷冻干燥48 h制得纳米颗粒,SEM照片如图6所示,粒径约为100nm。
Claims (1)
1.一种采用智能存储型纳米颗粒制备成的自润滑复合材料,其特征在于,所述自润滑复合材料包括纳米颗粒和环氧树脂;
所述自润滑复合材料的具体制备方法为,将智能存储型纳米颗粒、环氧树脂和胺类固化剂混合后,在室温搅拌40 min随后超声10 min使纳米颗粒充分分散,在真空干燥箱中去除气泡后倒入硅胶模具,常温干燥7天后得到自润滑复合材料;
智能存储型纳米颗粒的制备方法包括以下步骤:
1)称取6 g聚α-烯烃合成油、6 g甲基丙烯酸甲酯、6 g甲基丙烯酸缩水甘油酯和0.75 g正十六烷作为溶液A,在溶液A中,润滑介质与聚合单体的质量比为1:2;正十六烷的质量分数为4%;常温搅拌30 min;称取0.75 g十二烷基硫酸钠加入90 g去离子水作为溶液B,在溶液B中,去离子水和表面活性剂的质量比为120:1;常温搅拌30 min,搅拌速度为600 rpm;
2)将溶液A加入溶液B,常温搅拌1 h,搅拌速度为600 rpm,得到乳液C;
3)将步骤2)中的乳液C用超声粉碎机细乳化,超声功率为420W,处理时间为25 min,超声使用脉冲方式为工作3 s,间歇2 s,得到细乳液D;
4)将步骤3)中所得细乳液D倒入三口烧瓶,随后加入0.264 g偶氮二异丁氰,偶氮二异丁氰与聚合单体质量比为0.022:1;保持体系温度为75oC,采用氮气保护,搅拌速度为600rpm,继续反应5 h,得到产物E;
5)将步骤4)中产物E在冰箱中冷冻一夜,凝固后冷冻干燥48 h制得纳米颗粒,所述纳米颗粒的粒度分布集中,粒径为50nm,环氧官能团被引入纳米颗粒表面。
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