CN110041497A - 载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液及其制备方法 - Google Patents
载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液及其制备方法 Download PDFInfo
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- CN110041497A CN110041497A CN201910400881.9A CN201910400881A CN110041497A CN 110041497 A CN110041497 A CN 110041497A CN 201910400881 A CN201910400881 A CN 201910400881A CN 110041497 A CN110041497 A CN 110041497A
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- Prior art keywords
- acrylate
- silver
- graphene
- emulsion
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- 239000000839 emulsion Substances 0.000 title claims abstract description 44
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004945 emulsification Methods 0.000 title description 3
- 238000003848 UV Light-Curing Methods 0.000 claims abstract description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 18
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
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- 238000006243 chemical reaction Methods 0.000 claims description 23
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
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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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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Abstract
本发明公开了一种载银石墨烯水性聚氨酯‑丙烯酸酯抗菌乳液的制备方法,首先采用改进的Hummers法制得氧化石墨烯;然后用二异氰酸酯对其进行改性,再静电吸附硝酸银,用L‑抗坏血酸同时还原氧化石墨烯和硝酸银制得载银石墨烯分散液;再以载银石墨烯分散液与二异氰酸酯、低聚物二元醇、扩链剂及丙烯酸酯类单体制得的聚氨酯‑丙烯酸酯乳液在紫外光辐照下进行自由基聚合,制得UV固化型载银石墨烯/水性聚氨酯‑丙烯酸酯抗菌乳液。本发明制得的UV固化型载银石墨烯/水性聚氨酯‑丙烯酸酯抗菌乳液中的无机和有机两个组分相容性较好,并且载银石墨烯对水性聚氨酯的改性增强了其抗菌性,使其在医疗卫生及个人护理领域有着更为广泛的应用。
Description
技术领域
本发明涉及一种抗菌乳液,特别涉及一种UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液的制备方法。
背景技术
水性聚氨酯(WPU)以水为溶剂,具有绿色环保、运输安全、耐候性良好等特点,被用于制造涂料、油墨、皮革、纺织、建筑、胶粘剂、医用装置、个人护理等产品,特别的在医用装置和个人护理方面对其抗菌性能要求较高,而银离子以抗菌效果优良且对活体危险度较低等优点著称,被广泛应用于金属离子抗菌剂。2004年,英国曼彻斯特大学的研究人员借助透明胶带反复剥离制得石墨烯,石墨烯是一种由碳原子以sp2杂化轨道组成六角型呈蜂巢晶格的二维碳纳米材料,其锋利的片层会划伤细胞的细胞膜从而达到抗菌的目的。用石墨烯负载银粒子可表现出优良的缓释性,使其在医疗卫生及个人护理方面发挥长效抗菌的作用。
因此,如何将石墨烯、银离子和水性聚氨酯组合制备出具有较好抗菌性能的材料,是本领域技术人员急需解决的技术问题。
现有技术中,例如中国专利CN 106674980 A公开了一种抗菌防虫亲水性聚氨酯复合注浆及其制作方法,该专利以水性聚氨醋乳液、松香、氧化镁、氟癸基三乙氧基硅烷、尼龙纤维等为原料,但是松香低毒,且含有铅等重金属和有毒化合物会严重影响人体健康;中国专利CN 103232587 A在聚氨酯大分子侧链上连接水杨醛和植物油脂基,但是水杨醛具有中度毒性,并且具有有焦灼味及杏仁气味,可能对人体引起不适;中国专利CN 104193950 A公开了一种纳米抗菌聚氨酯组合物,但是其引入了石蜡作为防霉添加剂,导致制得的纳米抗菌聚氨酯组合物容易在光照下变黄甚至变质发臭;
因此,如何提供一种性能较优的石墨烯、银离子和水性聚氨酯组合制备出具有较好抗菌性能的材料是急需解决的问题。
发明内容
本发明的目的在于克服现有技术的不足,提供了一种载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液及其制备方法,以解决现有技术中制备的抗菌型聚氨酯毒性强、气味重和耐候性差等问题。
本发明是通过以下技术方案实现的:
本发明提供一种载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液,所述抗菌乳液按重量份的组分组成为:
进一步,所述二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯甲烷二异氰酸酯、1,6-己二异氰酸酯、二环己基甲烷二异氰酸酯和二聚酸二异氰酸酯中的一种或几种的混合物。
进一步,所述稀释剂具体为由丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸辛酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异辛酯、甲基丙烯酸十三烷基酯和甲基丙烯酸十八烷基酯中的一种或几种的混合物。
进一步,所述羟基丙烯酸酯单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯中的一种或几种的混合物。
进一步,述二元醇为聚碳酸酯二醇、聚四氢呋喃二醇、聚己二酸丁二醇酯、聚氧化丙烯二醇、聚乙二醇、聚ε-己内酯二醇、聚己二酸二醇酯二醇和聚己二酸乙二醇-丙二醇酯二醇中的一种或几种的混合物。
进一步,所述光引发剂为2-羟基-2-甲基-1-苯基丙酮、1-羟基环己基苯基甲酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、2-二甲氨基-2-苄基-1-[4-(4-吗啉基)苯基]-1-丁酮、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮和苯甲酰甲酸甲酯中的一种或几种的混合物。
进一步,步骤4中所述中和剂为三乙胺、氨水、氢氧化钾或氢氧化钠;
所述催化剂具体为辛酸亚锡。
本发明还提供一种上述抗菌乳液的制备方法,该方法包括以下步骤:
步骤1、准备材料
按照如下重量组分准备材料:
二元醇20~40份、二异氰酸酯10~30份、扩链剂3~10份、中和剂2~3份、羟基丙烯酸酯单体3~15份、稀释剂15~30份、石墨烯0.05~1份、硝酸银0.1~3份、还原剂0.25~5份、光引发剂1~5份和催化剂0.01~0.1份;
步骤2、制备固体氧化石墨烯
在冰水浴的条件下,将石墨粉、浓硫酸和硝酸钠混合均匀,缓慢加入高锰酸钾,其中:石墨粉、硝酸钠和高锰酸钾的质量比为1:0.5~1.5:3~9,浓硫酸体积与石墨粉质量的比例为20~35mL/g;冰水浴下搅拌反应0.5h,然后升温至35℃搅拌反应24h,反应结束后在冰水浴下向反应液中滴加蒸馏水搅拌0.5h,再加入蒸馏水稀释,稀释用蒸馏水的体积与石墨粉的质量的比例为30~50mL/g,然后滴加浓度为30wt%双氧水和浓度为0.5~1.5mol/L盐酸溶液,双氧水添加量为6~12mL/g石墨粉,盐酸添加量为60~100mL/g石墨粉;静置沉降,离心洗涤至pH值为5~7;再进行超声剥离后并透析,制得氧化石墨烯水分散液,冷冻干燥后得到固体氧化石墨烯;
步骤3、制备载银石墨烯
将0.05~1份固体氧化石墨烯超声分散在二甲基甲酰胺溶液中,加入0.5~5份二异氰酸酯,于60~100℃下反应24h;随后将0.1~3份硝酸银分散于混合液中,超声搅拌1h后加入0.25~5份还原剂L-抗坏血酸,再调节pH至8~12,在惰性气氛及70~90℃条件下加热回流2~6h,然后用二甲基甲酰胺洗后,再加入2~10份羟基丙烯酸酯单体,反应2~6h,制得载银石墨烯;
步骤4、制备聚氨酯-丙烯酸酯乳液
将20~40份低聚物二元醇真空脱水后和10~26份二异氰酸酯、15~30份稀释剂和辛酸亚锡在60~100℃反应0.5~4h,然后加入2~5份扩链剂A和二甲基甲酰胺,反应0.5~5h;再加入2~4份扩链剂B,反应10min~4h,然后降温至60℃,再加入1~5份羟基丙烯酸酯单体,反应2h,然后冷却至室温,然后用2~3份中和剂完全中和,然后加去离子水并高速剪切分散后,加入1~2份乙二胺,制得聚氨酯-丙烯酸酯乳液;
步骤5、制备UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液的乳胶膜;
将载银石墨烯与聚氨酯-丙烯酸酯乳液共混,再加入1~5份光引发剂,将乳液倒入模具中风干成膜后,进行紫外光固化,制得UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液的乳胶膜。
进一步,步骤2中所述超声剥离是以10000r/min的转速高速剪切0.5h后再于30℃以下,以50~100 Hz超声剥离1~2h,然后用透析袋透析7~10d。
进一步,所述扩链剂A和所述扩链剂B各自单独选自二羟甲基丙酸、二羟甲基半酯、1,4-丁二醇、1,3-丁二醇、己二醇、辛二醇、癸二醇、一缩二乙二醇和乙二醇中的一种或几种的混合物。
本发明相比现有技术具有以下优点:
1、本发明采用价格低廉的氧化石墨烯作为反应的前驱体代替昂贵的石墨烯直接作为原料,降低了成本;
2、本发明采用L-抗坏血酸作为还原剂,绿色环保,安全无毒且反应时间较短;
3、本发明用石墨烯负载银粒子再改性聚氨酯,载银石墨烯可以起到缓慢释放的作用,从而达到持久的抗菌性;
4、本发明制备的抗菌乳液,制作方法简单,原料易得。
5、本发明制备的抗菌乳液,耐候性较好,不会受外界环境影响而发黄变臭等。
附图说明
图1为实施例1制备的UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯乳液的抑菌照片,其中A、C分别为大肠杆菌和金黄色葡萄球菌的空白对照;
图2为实施例1、实施例2和实施例3制备所得UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯乳液的热重曲线;
图3为WPUA(A)、实施例1(B)、实施例2(C)、实施例3(D)制备所得UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯乳液的水接触角图。
具体实施方式
下面,举实施例说明本发明,但是,本发明并不限于下述的实施例。
本发明中选用的所有原辅材料、试剂和仪器、设备都为本领域熟知选用的,但不限制本发明的实施,其他本领域熟知的一些试剂和设备都可适用于本发明以下实施方式的实施。
实施例1
本实验按如下步骤制备UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液;
1、在冰水浴的条件下,将3.0g石墨粉、70mL浓H2SO4,1.5g硝酸钠置于250mL的锥形瓶中混合,磁力搅拌下缓慢加入9.0g高锰酸钾,继续冰水浴搅拌0.5h,然后升温至35℃搅拌反应24h,反应结束后在冰水浴下向反应液中缓慢滴加140mL蒸馏水,然后再加入约1L的蒸馏水稀释,搅拌均匀后缓慢滴加20mL30%的过氧化氢溶液,直到混合液呈金黄色后加入200mL1mol/L的盐酸溶液,静置沉淀后离心洗涤至混合液至pH值为5~7;然后在30℃以下超声剥离2h,然后用截留分子量为8000~14000的透析袋透析8d,获得氧化石墨烯水分散液,冷冻干燥后获得氧化石墨烯GO。
2、将500mg GO超声分散在DMF中,加入5g异佛尔酮二异氰酸酯,于80℃下反应24h。随后将1g硝酸银分散于混合液中,搅拌超声1h后加入2.5g L-抗坏血酸,滴加氨水直至pH=11,在N2气氛下80℃加热回流2h,反应结束后,用DMF洗后,再加入3g甲基丙烯酸羟乙酯,反应2h,制得载银石墨烯(IGAH)。
3、在配有冷凝管、温度计、搅拌器的三口烧瓶中加入25g聚乙二醇,真空脱水后加入16g异佛尔酮二异氰酸酯、10g丙烯酸乙酯、5g甲基丙烯酸甲酯和2滴辛酸亚锡,控制温度80~85℃,反应2h,向上述反应物中加入1.9g二羟甲基丙酸和少量DMF溶液,反应1.5h,随后加入1.0g1,4-丁二醇,扩链反应2h,降温至60℃再加入3g甲基丙烯酸羟乙酯,反应2h。将预聚体冷却至室温,向体系内加入三乙胺中和5min,再加入102g的去离子水,并在高速剪切分散10min后,加入适量乙二胺,制得聚氨酯-丙烯酸酯乳液(WPUA)。
4、取0.06g IGAH加入20g WPUA乳液中,再加入适量1-羟基环己基苯基甲酮,将乳液倒入模具中风干成膜后,进行紫外光固化,制得UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯乳液的乳胶膜。
实施例2
本实验按如下步骤制备UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液;
1、在冰水浴的条件下,将3.0g石墨粉、70mL浓H2SO4,1.5g硝酸钠置于250mL的锥形瓶中混合,磁力搅拌下缓慢加入9.0g高锰酸钾,继续冰水浴搅拌0.5h,然后升温至35℃搅拌反应24h,反应结束后在冰水浴下向反应液中缓慢滴加140mL蒸馏水,然后再加入约1L的蒸馏水稀释,搅拌均匀后缓慢滴加20mL30%的过氧化氢溶液,直到混合液呈金黄色后加入200mL1mol/L的盐酸溶液,静置沉淀后离心洗涤至混合液至pH值为5~7;然后在30℃以下超声剥离2h,然后用截留分子量为8000~14000的透析袋透析8d,获得氧化石墨烯水分散液,冷冻干燥后获得氧化石墨烯GO。
2、将500mg GO超声分散在DMF中,加入5g异佛尔酮二异氰酸酯,于80℃下反应24h。随后将1g硝酸银分散于混合液中,搅拌超声1h后加入2.5g L-抗坏血酸,滴加氨水直至pH=11,在N2气氛下80℃加热回流2h,反应结束后,用DMF洗后,再加入3g甲基丙烯酸羟乙酯,反应2h,制得载银石墨烯(IGAH)。
3、在配有冷凝管、温度计、搅拌器的三口烧瓶中加入25g聚碳酸酯二醇,真空脱水后加入16g异佛尔酮二异氰酸酯、10g丙烯酸丁酯、5g甲基丙烯酸甲酯和2滴辛酸亚锡,控制温度80~85℃,反应2h,向上述反应物中加入1.9g二羟甲基丙酸和少量DMF溶液,反应1.5h,随后加入1.0g1,4-丁二醇,扩链反应2h,降温至60℃再加入3g丙烯酸羟乙酯,反应2h。将预聚体冷却至室温,向体系内加入三乙胺中和5min,再加入102g的去离子水,并在高速剪切分散10min后,加入适量乙二胺,制得聚氨酯-丙烯酸酯乳液(WPUA)。
4、取0.12g IGAH加入20g WPUA乳液中,再加入适量2-羟基-2-甲基-1-苯基丙酮,将乳液倒入模具中风干成膜后,进行紫外光固化,制得UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯乳液的乳胶膜。
实施例3
本实验按如下步骤制备UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液;
1、在冰水浴的条件下,将3.0g石墨粉、70mL浓H2SO4,1.5g硝酸钠置于250mL的锥形瓶中混合,磁力搅拌下缓慢加入9.0g高锰酸钾,继续冰水浴搅拌0.5h,然后升温至35℃搅拌反应24h,反应结束后在冰水浴下向反应液中缓慢滴加140mL蒸馏水,然后再加入约1L的蒸馏水稀释,搅拌均匀后缓慢滴加20mL30%的过氧化氢溶液,直到混合液呈金黄色后加入200mL1mol/L的盐酸溶液,静置沉淀后离心洗涤至混合液至pH值为5~7;然后在30℃以下超声剥离2h,然后用截留分子量为8000~14000的透析袋透析8d,获得氧化石墨烯水分散液,冷冻干燥后获得氧化石墨烯GO。
2、将500mg GO超声分散在DMF中,加入5g异佛尔酮二异氰酸酯,于80℃下反应24h。随后将1g硝酸银分散于混合液中,搅拌超声1h后加入2.5g L-抗坏血酸,滴加氨水直至pH=11,在N2气氛下80℃加热回流2h,反应结束后,用DMF洗后,再加入3g甲基丙烯酸羟乙酯,反应2h,制得载银石墨烯(IGAH)。
3、在配有冷凝管、温度计、搅拌器的三口烧瓶中加入25g聚碳酸酯二醇,真空脱水后加入16g异佛尔酮二异氰酸酯、10g丙烯酸丁酯、5g甲基丙烯酸甲酯和2滴辛酸亚锡,控制温度80~85℃,反应2h,向上述反应物中加入1.9g二羟甲基丙酸和少量DMF溶液,反应1.5h,随后加入1.0g1,4-丁二醇,扩链反应2h,降温至60℃再加入丙烯酸羟乙酯,反应2h。将预聚体冷却至室温,向体系内加入三乙胺中和5min,再加入102g的去离子水,并在高速剪切分散10min后,加入适量乙二胺,制得聚氨酯-丙烯酸酯乳液(WPUA)。
4、取0.18g IGAH加入20g WPUA乳液中,再加入适量2-羟基-2-甲基-1-苯基丙酮,将乳液倒入模具中风干成膜后,进行紫外光固化,制得UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯乳液的乳胶膜。
将实施例1、实施例2和实施例3制备的乳液进行抗菌试验,具体结果如表1和图1
表1 水洗144小时后UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯乳液的抗菌率
表1
表2 UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯乳液的电性能
表2
现阶段对抗菌剂的抗菌耐久性研究较少,本专利用石墨烯负载银粒子,通过石墨烯所表现出的缓释性,使UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯乳液在水洗144h后的对大肠杆菌的抗菌率仍高达99.9%,对金黄色葡萄球菌的抗菌率也达到99.2以上。除此之外,在具备抗菌耐久性的前提下,复合材料也具备一定的抗静电效果。
Claims (10)
1.一种载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液,其特征在于,所述抗菌乳液按重量份的组分组成为:
2.根据权利要求1所述的一种载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液,其特征在于,所述二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯甲烷二异氰酸酯、1,6-己二异氰酸酯、二环己基甲烷二异氰酸酯和二聚酸二异氰酸酯中的一种或几种的混合物。
3.根据权利要求2所述的一种载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液,其特征在于,所述稀释剂具体为由丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸辛酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异辛酯、甲基丙烯酸十三烷基酯和甲基丙烯酸十八烷基酯中的一种或几种的混合物。
4.根据权利要求3所述的一种载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液,其特征在于,所述羟基丙烯酸酯单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯中的一种或几种的混合物。
5.根据权利要求4所述的一种载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液,其特征在于,述二元醇为聚碳酸酯二醇、聚四氢呋喃二醇、聚己二酸丁二醇酯、聚氧化丙烯二醇、聚乙二醇、聚ε-己内酯二醇、聚己二酸二醇酯二醇和聚己二酸乙二醇-丙二醇酯二醇中的一种或几种的混合物。
6.根据权利要求5所述的一种载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液,其特征在于,所述光引发剂为2-羟基-2-甲基-1-苯基丙酮、1-羟基环己基苯基甲酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、2-二甲氨基-2-苄基-1-[4-(4-吗啉基)苯基]-1-丁酮、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮和苯甲酰甲酸甲酯中的一种或几种的混合物。
7.根据权利要求6所述的一种载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液,其特征在于,步骤4中所述中和剂为三乙胺、氨水、氢氧化钾或氢氧化钠;
所述催化剂具体为辛酸亚锡。
8.一种权利要求7所述抗菌乳液的制备方法,其特征在于,该方法包括以下步骤:
步骤1、准备材料
按照如下重量组分准备材料:
二元醇20~40份、二异氰酸酯10~30份、扩链剂3~10份、中和剂2~3份、羟基丙烯酸酯单体3~15份、稀释剂15~30份、石墨烯0.05~1份、硝酸银0.1~3份、还原剂0.25~5份、光引发剂1~5份和催化剂0.01~0.1份;
步骤2、制备固体氧化石墨烯
在冰水浴的条件下,将石墨粉、浓硫酸和硝酸钠混合均匀,缓慢加入高锰酸钾,其中:石墨粉、硝酸钠和高锰酸钾的质量比为1:0.5~1.5:3~9,浓硫酸体积与石墨粉质量的比例为20~35mL/g;冰水浴下搅拌反应0.5h,然后升温至35℃搅拌反应24h,反应结束后在冰水浴下向反应液中滴加蒸馏水搅拌0.5h,再加入蒸馏水稀释,稀释用蒸馏水的体积与石墨粉的质量的比例为30~50mL/g,然后滴加浓度为30wt%双氧水和浓度为0.5~1.5mol/L盐酸溶液,双氧水添加量为6~12mL/g石墨粉,盐酸添加量为60~100mL/g石墨粉;静置沉降,离心洗涤至pH值为5~7;再进行超声剥离后并透析,制得氧化石墨烯水分散液,冷冻干燥后得到固体氧化石墨烯;
步骤3、制备载银石墨烯
将0.05~1份固体氧化石墨烯超声分散在二甲基甲酰胺溶液中,加入0.5~5份二异氰酸酯,于60~100℃下反应24h;随后将0.1~3份硝酸银分散于混合液中,超声搅拌1h后加入0.25~5份还原剂L-抗坏血酸,再调节pH至8~12,在惰性气氛及70~90℃条件下加热回流2~6h,然后用二甲基甲酰胺洗后,再加入2~10份羟基丙烯酸酯单体,反应2~6h,制得载银石墨烯;
步骤4、制备聚氨酯-丙烯酸酯乳液
将20~40份低聚物二元醇真空脱水后和10~26份二异氰酸酯、15~30份稀释剂和辛酸亚锡在60~100℃反应0.5~4h,然后加入2~5份扩链剂A和二甲基甲酰胺,反应0.5~5h;再加入2~4份扩链剂B,反应10min~4h,然后降温至60℃,再加入1~5份羟基丙烯酸酯单体,反应2h,然后冷却至室温,然后用2~3份中和剂完全中和,然后加去离子水并高速剪切分散后,加入1~2份乙二胺,制得聚氨酯-丙烯酸酯乳液;
步骤5、制备UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液的乳胶膜;
将载银石墨烯与聚氨酯-丙烯酸酯乳液共混,再加入1~5份光引发剂,将乳液倒入模具中风干成膜后,进行紫外光固化,制得UV固化型载银石墨烯/水性聚氨酯-丙烯酸酯抗菌乳液的乳胶膜。
9.根据权利要求8所述的制备方法,其特征在于,步骤2中所述超声剥离是以10000r/min的转速高速剪切0.5h后再于30℃以下,以50~100Hz超声剥离1~2h,然后用透析袋透析7~10d。
10.根据权利要求9所述的制备方法,其特征在于,所述扩链剂A和所述扩链剂B各自单独选自二羟甲基丙酸、二羟甲基半酯、1,4-丁二醇、1,3-丁二醇、己二醇、辛二醇、癸二醇、一缩二乙二醇和乙二醇中的一种或几种的混合物。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110643016A (zh) * | 2019-10-16 | 2020-01-03 | 安徽大学 | 碳纳米管负载纳米银线改性聚氨酯抗静电乳液的制备方法 |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140316073A1 (en) * | 2013-03-15 | 2014-10-23 | Mackinac Polymers Llc | Polymeric composition with electroactive characteristics |
CN104558499A (zh) * | 2013-10-23 | 2015-04-29 | 湖南岁丰新材料科技发展有限公司 | 一种可紫外光固化的弹性聚氨酯丙烯酸酯乳液及其合成方法 |
CN105170132A (zh) * | 2015-07-24 | 2015-12-23 | 河海大学 | 聚氨酯海绵负载银石墨烯二氧化钛纳米粒子复合材料、制备方法及应用 |
CN107815193A (zh) * | 2017-11-17 | 2018-03-20 | 福建宸琦新材料科技有限公司 | 石墨烯负载纳米银抗菌剂和石墨烯原位还原负载纳米银水性抗菌涂料 |
CN109096740A (zh) * | 2018-07-20 | 2018-12-28 | 山东诺威聚氨酯股份有限公司 | 抗菌抗静电tpu薄膜材料及其制备方法 |
CN109232853A (zh) * | 2018-08-27 | 2019-01-18 | 权健自然医学科技发展有限公司 | 石墨烯矫正抗菌自清洁鞋垫及其制备方法 |
CN109369964A (zh) * | 2018-09-04 | 2019-02-22 | 暨南大学 | 复合抗菌薄膜及其制备方法和应用 |
-
2019
- 2019-05-15 CN CN201910400881.9A patent/CN110041497B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140316073A1 (en) * | 2013-03-15 | 2014-10-23 | Mackinac Polymers Llc | Polymeric composition with electroactive characteristics |
CN104558499A (zh) * | 2013-10-23 | 2015-04-29 | 湖南岁丰新材料科技发展有限公司 | 一种可紫外光固化的弹性聚氨酯丙烯酸酯乳液及其合成方法 |
CN105170132A (zh) * | 2015-07-24 | 2015-12-23 | 河海大学 | 聚氨酯海绵负载银石墨烯二氧化钛纳米粒子复合材料、制备方法及应用 |
CN107815193A (zh) * | 2017-11-17 | 2018-03-20 | 福建宸琦新材料科技有限公司 | 石墨烯负载纳米银抗菌剂和石墨烯原位还原负载纳米银水性抗菌涂料 |
CN109096740A (zh) * | 2018-07-20 | 2018-12-28 | 山东诺威聚氨酯股份有限公司 | 抗菌抗静电tpu薄膜材料及其制备方法 |
CN109232853A (zh) * | 2018-08-27 | 2019-01-18 | 权健自然医学科技发展有限公司 | 石墨烯矫正抗菌自清洁鞋垫及其制备方法 |
CN109369964A (zh) * | 2018-09-04 | 2019-02-22 | 暨南大学 | 复合抗菌薄膜及其制备方法和应用 |
Non-Patent Citations (5)
Title |
---|
JIANANZHANG等: ""Anionic poly (lactic acid)-polyurethane micelles as potential biodegradable drug delivery carriers"", 《COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS》 * |
SHENG-TSUNG HSIAO等: ""Effect of Covalent Modification of Graphene Nanosheets on the Electrical Property and Electromagnetic Interference Shielding Performance of a Water-Borne Polyurethane Composite"", 《ACS APPLIED MATERIALS & INTERFACES》 * |
中国硅酸盐学会编著: "《矿物材料学科发展报告 2016-2017》", 31 March 2018, 中国科学技术出版社 * |
付长璟编著: "《石墨烯的制备、结构及应用》", 30 June 2017, 哈尔滨工业大学出版社 * |
盛锡慧焘子等: ""氨基化还原氧化石墨烯-碳纳米管/水性聚氨酯复合材料的制备及表征"", 《涂料工业》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110643016A (zh) * | 2019-10-16 | 2020-01-03 | 安徽大学 | 碳纳米管负载纳米银线改性聚氨酯抗静电乳液的制备方法 |
CN110862503A (zh) * | 2019-11-29 | 2020-03-06 | 佛山市瑞福物联科技有限公司 | 一种导电聚氨酯预聚体的制备方法及其导电胶 |
CN110862503B (zh) * | 2019-11-29 | 2022-02-11 | 佛山市瑞福物联科技有限公司 | 一种导电聚氨酯预聚体的制备方法及其导电胶 |
CN111363458A (zh) * | 2020-04-16 | 2020-07-03 | 江苏斯迪克新材料科技股份有限公司 | 抗菌防污防刮伤保护膜 |
CN116814146A (zh) * | 2023-07-05 | 2023-09-29 | 扬州市德运塑业科技股份有限公司 | 一种基于石墨烯的抗菌耐磨的汽车内饰皮革及其制备方法 |
CN116814146B (zh) * | 2023-07-05 | 2024-06-07 | 扬州市德运塑业科技股份有限公司 | 一种基于石墨烯的抗菌耐磨的汽车内饰皮革及其制备方法 |
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