CN105111407B - 一种可降解海洋防污聚氨酯杂化材料的制备方法及其应用 - Google Patents
一种可降解海洋防污聚氨酯杂化材料的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开一种可降解海洋防污聚氨酯杂化材料的制备方法及其产品。本发明采用辛酸亚锡为催化剂,利用还原石墨烯与2,2’‑双羟基苯甲醛和N‑氨基乙酸反应制备的双羟基功能化石墨烯作为引发剂,以此引发剂引发L‑丙交酯单体通过开环聚合制备石墨烯接枝聚乳酸;将1,4‑丁二醇与4,4’‑二苯基甲烷二异氰酸酯通过缩聚反应得到末端含异氰酸酯官能团的聚氨酯预聚物;利用石墨烯接枝聚乳酸端羟基与聚氨酯预聚物末端异氰酸酯官能团之间的化学反应制备出可降解海洋防污聚氨酯杂化材料。本发明通过引入石墨烯以提高目标材料的强度,并在降解过程中起到抗菌作用,通过调节石墨烯和L‑丙交酯单体的含量,以控制接枝聚丙交酯的结晶性和亲/疏水性,从而对聚氨酯的降解性能进行有效调控。本发明所制备的杂化材料具有优异的力学性能及降解速率可调,降解产物无毒且对环境无害,可应用于海洋防污涂料以及生物医用工程中药物缓释载体。
Description
技术领域
本发明属于海洋防污材料技术领域,涉及一种可降解聚氨酯杂化材料的制备及其应用。
背景技术
石墨烯(G)是一种新型二维碳质纳米材料,在材料、化学、物理、电子等领域显示了广阔的应用前景。尤其是其极高的机械强度和抗菌功能以及丰富的来源,使其成为一种理想的填料。通过在基体材料中填充石墨烯可以提高基体材料的强度,还可以赋予基体材料一定功能。有研究表明石墨烯具有优异的抗菌功能,如Francois Perreault等采用聚酰胺薄膜与氧化石墨烯的共价结合制备的功能化聚酰胺/氧化石墨烯复合膜,抗菌性能检测显示此种复合材料具有优异的抗菌活性。(Francois Perreault,Marissa E.Tousley,Menachem Elimelech.Thin-film composite polyamide membranes functionalizedwith biocidal graphene oxide nanosheets.Environmental Science and TechnologyLetters,2014,1(1),71-76.)因此,在可降解聚氨酯杂化材料中填充入一定量的石墨烯能提高材料的强度和抗菌性。
聚氨酯材料以其优异的机械性能和分子设计自由度大、性能可调控等特点,广泛的应用于各个领域。对聚氨酯进行改性可使其具有可降解功能,这种改性一般可分为物理改性和化学改性。物理改性是利用物理共混的方式将可降解的材料引入聚氨酯中;化学改性是通过在聚氨酯分子结构中引入具有生物可降解性的改性组分使其具有生物降解性。Kaibin Li等利用异佛尔酮二异氰酸酯(IPDI)、聚己内酯(PCL)和二羟甲基丁酸为主体材料制备的基于蓖麻油(CO)/季戊四醇三丙烯酸酯(PETA)的紫外固化水性聚氨酯甲基丙烯酸酯(UV-WPUA),结构和性能表征表明,聚氨酯软段抗水性、玻璃化转变温度和热学性能有所提高。(Kaibin Li,Yiding Shen,Guiqiang Fei,Haihua Wang,Jingyi Li.Preparation andproperties of castor oil/pentaerythritol triacrylate-based UV curablewaterborne polyurethane acrylate.Progress in Organic Coatings,2015,78,146–154.)聚乳酸因具有生物相容性和可降解性,可应用于各种领域,如热塑性塑料、薄膜及纤维。通过嵌段、接枝、共聚等方法对其进行改性可以形成一种可再生、可降解的环境友好型复合材料。如Young H.Lim等人利用炔基化磷杂环戊烷和L-丙交酯的一步法连续开环聚合反应制备的聚磷酸酯嵌段聚乳酸材料具有完全可降解性和生物相容性。(Young H.Lim,GyuSeong Heo,Sangho Cho,Karen L.Wooley.Construction of a reactive diblockcopolymer,polyphosphoesterblock-poly(L-lactide),as a versatile framework forfunctional materials that are capable of full degradation and nanoscopicassembly formation.ACS Macro Lett.2013,2,785-789.)常见生物降解聚氨酯材料有聚己内酯(PCL)、聚乳酸(PLA)等,但目前大多数存在结晶高、水解速度慢、对基体的粘附力差等问题,它们直接用于海洋防污材料受到限制。
发明内容
本发明的目的是提供一种可降解海洋防污聚氨酯杂化材料的制备方法及其应用。该方法以辛酸亚锡为催化剂,采用双羟基功能化石墨烯为引发剂引发L-丙交酯通过开环聚合制备石墨烯接枝聚丙交酯(G-g-PLLA);将1,4-丁二醇与4,4’-二苯基甲烷二异氰酸酯通过缩聚反应得到末端含异氰酸酯官能团的聚氨酯预聚物(PU);利用石墨烯接枝聚乳酸端羟基与聚氨酯预聚物末端异氰酸酯官能团之间的化学反应制备出可降解海洋防污聚氨酯杂化材料(G-f-PLLA-b-PU)。
本发明采用的技术方案为:
一种可降解海洋防污聚氨酯杂化材料的制备方法,包括如下步骤:
(1)将干燥好的鳞片石墨加入到硝酸钾和浓酸的混合物中,超声混合均匀,冰水浴中搅拌并缓慢加入氧化剂,然后体系升温至35~55℃,高速搅拌5~8h;再缓慢加入蒸馏水,体系升温至60~80℃反应0.4~1h;再向体系中加入蒸馏水和双氧水继续反应5~15min,得到亮黄色的氧化石墨烯母液,蒸馏水离心洗涤至中性(pH=7),得到纯净的氧化石墨烯,再向其加入分散剂,超声混合均匀,得到氧化石墨烯凝胶;
(2)取步骤(1)所得氧化石墨烯凝胶制成一定浓度的氧化石墨烯水悬浮液,搅拌下加入还原剂,70~100℃水浴中回流5~8h,反应完成后冷却至室温,过滤,无水乙醇洗涤,烘干后得到还原石墨烯;
(3)取一定量还原石墨烯、2,2’-双羟基苯甲醛、N-氨基乙酸加入到二甲基甲酰胺中,超声处理10~25min均匀分散,在100~140℃的油浴中搅拌回流4.5~6.5天,趁热离心,无水乙醇反复洗涤,烘干后得到双羟基功能化石墨烯;
(4)在无水甲苯中依次加入双羟基功能化石墨烯、L-丙交酯(LLA)、催化剂辛酸亚锡(Sn(Oct)2),超声处理10~25min混合均匀,N2保护下在100~140℃下搅拌回流24~48h,反应混合物冷却至室温,过滤,粗产物溶于甲醇中,溶液再加入到混有少量浓盐酸的甲醇溶液中除去锡残留物,过滤,分别用二氯甲烷、甲醇洗涤,过滤,产物经真空干燥,得到石墨烯接枝聚丙交酯;
(5)取一定量的扩链剂1,4-丁二醇和4,4’-二苯基甲烷二异氰酸酯加入到无水甲苯中,搅拌溶解,N2保护下使体系升温至80~110℃,反应8~15h,然后加入步骤(4)所得石墨烯接枝聚丙交酯在70~100℃下反应1.5~3h,结束反应后,将温度降至室温,将溶液滴加到100mL正己烷中沉淀,过滤,产物经真空干燥,得可降解海洋防污聚氨酯杂化材料。
进一步,步骤(1)中,所述鳞片石墨与硝酸钾和浓酸的混合物、氧化剂、双氧水、分散剂的配比为1.0g:1.2g:46mL:6.0g:6mL:0.5g。
进一步,步骤(2)中,所述还原剂为水合肼,所述氧化石墨烯与还原剂的配比为5.0g:80mL。
进一步,步骤(3)中,所述还原石墨烯、2,2’-双羟基苯甲醛、N-氨基乙酸、二甲基甲酰胺的配比为0.02g:0.2g:0.2g:50mL。
进一步,步骤(4)中,所述双羟基功能化石墨烯、L-丙交酯、辛酸亚锡和无水甲苯的配比为0.083-0.174g:2.0g:0.5-1.5mL:50-70mL。
进一步,步骤(5)中,所述石墨烯接枝聚丙交酯、4,4’-二苯基甲烷二异氰酸酯和1,4-丁二醇和无水甲苯的配比为0.13-0.51g:1.0g:0.2g:60-80mL。
上述的制备方法制备的可降解聚氨酯杂化材料可应用于海洋防污材料和生物医用工程中药物缓释载体中。
本发明的有益效果在于:
1、本发明以双羟基功能化石墨烯通过开环聚合引发LLA单体形成石墨烯接枝聚乳酸,然后将1,4-丁二醇与4,4’-二苯基甲烷二异氰酸酯通过缩聚反应得到末端含异氰酸酯官能团的聚氨酯预聚物;最后利用石墨烯接枝聚乳酸端羟基与聚氨酯预聚物末端异氰酸酯官能团之间的化学反应制备出可降解海洋防污聚氨酯杂化材料。可降解海洋防污聚氨酯杂化材料通过在海水中不断降解形成新的表面,使粘附在涂料上的污损及时脱落,从而达到防污作用。
2、将石墨烯引入到聚合物中以增强基体材料机械强度,并在降解过程中起到抗菌作用。
3、通过调节石墨烯和LLA的质量配比制备一系列不同石墨烯含量的石墨烯接枝聚乳酸,以控制接枝PLLA的结晶性和亲/疏水性,从而对聚氨酯的降解性能进行有效调控。
4、本发明所制备的聚氨酯杂化材料具有优异的力学性能及降解速率可调,降解产物无毒且对环境无害。
附图说明
图1为实施例1制备石墨烯接枝聚丙交酯(G-g-PLLA)的反应示意图。
图2为实施例1制备聚氨酯预聚物(PU)的反应示意图。
图3为实施例1制备石墨烯接枝聚丙交酯嵌段聚氨酯(G-g-PLLA-b-PU)的反应示意图。
图4为实施例1所得石墨烯接枝聚丙交酯(G-g-PLLA)的红外图谱。
图5为实施例1所得石墨烯接枝聚丙交酯嵌段聚氨酯(G-g-PLLA-b-PU)的红外图谱。
图6为实施例1所得G-g-PLLA和G-g-PLLA-b-PU的热失重对比曲线图。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明,但本发明并不限于此。
实施例1
一种可降解海洋防污聚氨酯杂化材料的制备方法,按照以下步骤进行:
(1)将1.0g干燥好的鳞片石墨加入到1.2g硝酸钾和46mL浓硫酸的混合物中,超声混合均匀,冰水浴中搅拌并缓慢加入6.0g高锰酸钾,随之体系温度升至40℃,高速搅拌6h;随之缓慢加入蒸馏水,体系升温至70℃反应0.5h;再向体系中加入80mL蒸馏水和6mL双氧水)继续反应5min,得到亮黄色的氧化石墨烯母液,蒸馏水离心洗涤pH=7,得到纯净的氧化石墨烯,在其中加入0.5g十二烷基苯磺酸钠,超声混合均匀,得到氧化石墨烯凝胶;
(2)取3.0g氧化石墨烯凝胶配成质量浓度为70%的氧化石墨烯水悬浮液于三口瓶中,剧烈搅拌下加入80mL水合肼,80℃水浴中回流6h,反应完成后冷却至室温,过滤,无水乙醇多次洗涤,烘干后得到纯净的还原石墨烯;
(3)取0.02g还原石墨烯、0.2g 2,2’-双羟基苯甲醛、0.2g N-氨基乙酸加入到50mL二甲基甲酰胺中,超声处理15min均匀分散,在120℃的油浴中搅拌回流5天,趁热离心,无水乙醇反复洗涤,烘干后得到双羟基功能化石墨烯;
(4)取50mL无水甲苯于烧瓶中,依次加入双羟基功能化石墨烯0.04g、LLA单体2.0g、催化剂辛酸亚锡0.5mL,超声处理15min混合均匀,N2保护下在120℃下搅拌回流24h。反应混合物冷却至室温,过滤,粗产物溶于甲醇中,溶液再加入到混有少量浓盐酸的甲醇溶液中除去Sn残留物,过滤,分别用二氯甲烷、甲醇洗涤,过滤,产物在真空条件下干燥。
(5)取0.2g扩链剂1,4-丁二醇(BDO)和1.0g 4,4’-二苯基甲烷二异氰酸酯加入到60mL无水甲苯,搅拌溶解,N2保护下使体系升温至90℃,反应10h,然后加入0.13g步骤(4)所得石墨烯接枝聚丙交酯在80℃下反应2h,结束反应后,将温度降至室温,将溶液滴加到100mL正己烷中沉淀,过滤,产物在真空条件下干燥。
如图4所示,处于3397cm-1处的吸收峰,这是G-g-PLLA两端羟基(-OH)的特征吸收峰。处于2970cm-1和2930cm-1处的吸收峰分别为CH3和CH2的伸缩振动吸收峰,1600cm-1处明显的吸收峰为羰基(C=O)的特征吸收峰。可以看出,已成功合成所需的物质。在图4中观测到的处于3397cm-1处的吸收峰消失,而在图5观测到在3300处有一个新的吸收峰出现,这是聚氨酯中NH的特征吸收峰。同时在1540cm-1处都出现一个强的吸收峰,这是氨基甲酸酯的特征吸收峰。可以看出,已成功合成聚氨酯。
从图6可以看出,所有物质在100℃前失重较少,大约为10%,这是吸附水和有机溶剂造成的失重;在40-800℃之间,由曲线a可算出石墨烯接枝聚丙交酯(G-g-PLLA)失重了56.1%,由曲线b可算出石墨烯接枝聚丙交酯嵌段聚氨酯(G-g-PLLA-b-PU)失重了88.1%,根据TGA数据可知,PU枝接量为32wt%。
实施例2
步骤(4)中双羟基功能化石墨烯为0.083g,辛酸亚锡为1.0mL,无水甲苯为60mL;
其它与实施例1相同。
实施例3
步骤(4)中双羟基功能化石墨烯为0.174g,辛酸亚锡为1.5mL,无水甲苯为70mL;
其它与实施例1相同。
实施例4
步骤(4)中1,4-丁二醇代替双羟基功能化石墨烯引发LLA单体,质量为0.5g,无水甲苯为50mL;
其它与实施例1相同。
实施例5
步骤(5)中石墨烯接枝聚丙交酯为0.30g,无水甲苯为70mL;
其它与实施例1相同。
实施例6
步骤(5)中石墨烯接枝聚丙交酯为0.51g,无水甲苯为80mL;
其它与实施例1相同。
实施例7
步骤(5)中石墨烯接枝聚丙交酯为0.30g,无水甲苯为70mL;
其它与实施例2相同。
实施例8
步骤(5)中石墨烯接枝聚丙交酯为0.51g,无水甲苯为80mL;
其它与实施例2相同。
实施例9
步骤(5)中石墨烯接枝聚丙交酯为0.30g,无水甲苯为70mL;
其它与实施例3相同。
实施例10
步骤(5)中石墨烯接枝聚丙交酯为0.51g,无水甲苯为80mL;
其它与实施例3相同。
Claims (8)
1.一种可降解海洋防污聚氨酯杂化材料的制备方法,其特征在于包括如下步骤:
(1)将干燥好的鳞片石墨加入到硝酸钾和浓酸的混合物中,超声混合均匀,冰水浴中搅拌并缓慢加入氧化剂,然后体系升温至34~55℃,高速搅拌5~8h;再缓慢加入蒸馏水,体系升温至60~80℃反应0.4~1h;再向体系中加入蒸馏水和双氧水继续反应5~15min,得到亮黄色的氧化石墨烯母液,蒸馏水离心洗涤至中性,得到氧化石墨烯,在其中加入分散剂,超声混合均匀,得到氧化石墨烯凝胶;
(2)取步骤(1)所得氧化石墨烯凝胶制成氧化石墨烯水悬浮液,搅拌下加入还原剂,70~100℃水浴中回流5~8h,反应完成后冷却至室温,过滤,无水乙醇洗涤,烘干后得到还原石墨烯;
(3)取一定量还原石墨烯、2,2’-双羟基苯甲醛、N-氨基乙酸加入到二甲基甲酰胺中,超声处理10~25min均匀分散,在100~140℃的油浴中搅拌回流4.5~6.5天,趁热离心,无水乙醇反复洗涤,烘干后得到双羟基功能化石墨烯;
(4)在无水甲苯中依次加入双羟基功能化石墨烯、L-丙交酯、催化剂辛酸亚锡,超声处理10~25min混合均匀,N2保护下在100~140℃下搅拌回流24~48h,反应混合物冷却至室温,过滤,粗产物溶于甲醇中,溶液再加入到混有少量浓盐酸的甲醇溶液中除去锡残留物,过滤,分别用二氯甲烷、甲醇洗涤,过滤,产物经真空干燥,得到石墨烯接枝聚丙交酯;
(5)取一定量的扩链剂1,4-丁二醇和4,4’-二苯基甲烷二异氰酸酯加入到无水甲苯中,搅拌溶解,N2保护下使体系升温至80~110℃,反应8~15h,然后加入步骤(4)所得石墨烯接枝聚丙交酯在70~100℃下反应1.5~3h,结束反应后,将温度降至室温,再将溶液滴加到正己烷中沉淀,过滤,产物经真空干燥,得到可降解海洋防污聚氨酯杂化材料。
2.根据权利要求1所述的可降解海洋防污聚氨酯杂化材料的制备方法,其特征在于:所述步骤(1)的鳞片石墨与硝酸钾、浓酸、氧化剂、双氧水、分散剂的配比为1.0g:1.2g:46mL:6.0g:6mL:0.5g。
3.根据权利要求1所述的可降解海洋防污聚氨酯杂化材料的制备方法,其特征在于:所述步骤(2)的氧化石墨烯与还原剂的配比为5.0g:80mL。
4.根据权利要求1所述的可降解海洋防污聚氨酯杂化材料的制备方法,其特征在于:所述步骤(1)的浓酸为浓硫酸,所述氧化剂为高锰酸钾,所述的分散剂为十二烷基苯磺酸钠;所述步骤(2)的还原剂为水合肼。
5.根据权利要求1至4任一项所述的可降解海洋防污聚氨酯杂化材料的制备方法,其特征在于:所述步骤(3)的还原石墨烯、2,2’-双羟基苯甲醛、N-氨基乙酸、二甲基甲酰胺的配比为0.02g:0.2g:0.2g:50mL。
6.根据权利要求5所述的可降解海洋防污聚氨酯杂化材料的制备方法,其特征在于:所述步骤(4)的双羟基功能化石墨烯、L-丙交酯、辛酸亚锡和无水甲苯的配比为0.083-0.174g:2.0g:0.5-1.5mL:50-70mL。
7.根据权利要求6所述的可降解海洋防污聚氨酯杂化材料的制备方法,其特征在于:所述步骤(5)的石墨烯接枝聚丙交酯、4,4’-二苯基甲烷二异氰酸酯和1,4-丁二醇和无水甲苯的配比为0.13-0.51g:1.0g:0.2g:60-80mL。
8.权利要求1至7任一项所述的制备方法制备的可降解聚氨酯杂化材料在于海洋防污材料或生物医用工程中药物缓释载体中的应用。
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