CN110511386A - 双性高分子及其制造方法、包含此双性高分子的隐形眼镜材料及其制造方法 - Google Patents
双性高分子及其制造方法、包含此双性高分子的隐形眼镜材料及其制造方法 Download PDFInfo
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Abstract
本发明提供一种双性高分子及其制造方法、包含此双性高分子的隐形眼镜材料及其制造方法。双性高分子包含聚二甲基硅氧烷以及与聚二甲基硅氧烷键合的双性几丁聚糖。隐形眼镜材料,包含上述双性高分子。制造双性高分子的方法包含供双性几丁聚糖;提供聚二甲基硅氧烷;以及将双性几丁聚糖与聚二甲基硅氧烷键合。制造隐形眼镜的方法包含提供上述双性高分子;提供甲基丙烯酸羟乙酯单体溶液或硅氧烷单体溶液;提供光交联剂;使用紫外光进行交联光固化。
Description
技术领域
本发明关于一种双性高分子。更具体而言,本发明关于一种可作为隐形 眼镜材料的聚二甲基硅氧烷-双性几丁聚糖共轭高分子。
背景技术
现今隐形眼镜重视高透氧、高透光度、及高亲水性,同时镜片功能化(医 疗、诊断、智慧化),已是未来发展目标。目前市售隐形眼镜的透氧率提升 主要是添加silicone成分进去隐形眼镜配方溶液内,但加入之后会产生透光 度下降及不互溶的现象。
高疏水性聚二甲基硅氧烷(poly(dimethylsiloxane),PDMS)具有高透氧 性,若能键合上含有-COOH官能基的高亲水性多糖体,其亲疏水性特性, 可增加其在亲水性水胶基材的互溶性,改善透光度及其他物理性质,例如在 隐形眼镜等水胶材料应用上,能够大幅改善例如透氧率等物性,有利于水胶 材料在功能化医材及药物方面发展及增值。
然而,已知的聚二甲基硅氧烷与高亲水性多糖体的键合,在制造过程中 大多使用有机合成技术进行纯化,通过共聚物与聚二甲基硅氧烷的极性差异 将产物进行分离,过程复杂。
发明内容
本发明的主要目的在于提供一种双性高分子,可供制作隐形眼镜。
本发明的另一目的在于提供一种制造双性高分子的方法。
本发明的另一目的在于提供一种包含双性高分子的隐形眼镜材料,其具 有良好的透光度、透氧性、保水率。
本发明的双性高分子包含聚二甲基硅氧烷以及与聚二甲基硅氧烷键合 的双性几丁聚糖。
在本发明的一实施例中,聚二甲基硅氧烷包含氨基(–NH2)。
在本发明的一实施例中,双性几丁聚糖包含羧基(-COOH)。
在本发明的一实施例中,双性高分子,具有以下结构:
本发明的隐形眼镜材料,包含上述双性高分子。
本发明制造双性高分子的方法,包含:S100、供双性几丁聚糖;S200、 提供聚二甲基硅氧烷提;以及S300、将双性几丁聚糖与聚二甲基硅氧烷键 合。
在本发明的一实施例中,步骤S300包含使用1-(3-二甲氨基丙基)-3-乙 基碳二亚胺盐酸盐(1-ethyl-3-(3-dimethylaminopropyl)carbodiimide,EDC) 作为催化剂。
在本发明的一实施例中,步骤S300包含使用N-羟基丁二酰亚胺 (N-Hydroxysuccinimide,NHS)作为催化剂。
附图说明
图1为本发明制造双性高分子的方法的实施例流程示意图。
图2为本发明制成双性高分子的核磁共振光谱仪测试结果图。
图3为本发明制成双性高分子的FT-IR测试结果图。
图4A及图4B分别为双性几丁聚糖与本发明制成的聚二甲基硅氧烷-双 性几丁聚糖共轭高分子的SEM检测结果图。
图5为透光度测试结果图。
图6为保水率测试结果图。
图7为镜片细胞毒性试验结果图。
图8为动物眼压试验结果图。
主要元件符号说明:
S100步骤
S200步骤
S300步骤
具体实施方式
本发明的双性高分子包含聚二甲基硅氧烷以及与聚二甲基硅氧烷键合 的双性几丁聚糖。其中,双性几丁聚糖包括羧甲基己酰几丁聚糖 (carboxymethyl hexanoylchitosan,CHC)、脱氧胆酸修饰羧甲基几丁聚糖 (deoxycholic acid modifiedcarboxymethylated chitosan,DCMC)、月桂酰基硫酸 几丁聚糖(lauroyl sulfatedchitosan,LSC)或甲基吡咯烷酮几丁聚糖 (methylpyrrolidone chitosan,MPC)。
在一实施例中,聚二甲基硅氧烷包含氨基(–NH2),双性几丁聚糖包 含羧基(-COOH)。更具体而言,双性高分子较佳为聚二甲基硅氧烷-双性 几丁聚糖共轭高分子(silicone-conjugated poly(dimethylsiloxane)amphiphilic chitosan co-polymer),具有以下结构:
其中,聚二甲基硅氧烷的氨基与双性几丁聚糖的羧基键合,从而使聚二 甲基硅氧烷与双性几丁聚糖键合。然而在不同实施例中,聚二甲基硅氧烷不 限于包含氨基,双性几丁聚糖不限于包含羧基,亦即聚二甲基硅氧烷与双性 几丁聚糖键合可通过氨基与羧基以外的官能基进行键合。
本发明的隐形眼镜材料,包含上述双性高分子。进一步而言,上述双性 高分子与隐形眼镜的亲水性水胶基材间具有良好的互溶性。又上述双性高分 子基于聚二甲基硅氧烷的高透氧性以及几丁聚糖的高亲水性而具有良好的 亲疏水性特性,且具备可包覆各种不同药物(功能化)的自组装能力 (self-assembly capability),故除了可以应用作为隐形眼镜材料而使其具有良 好的透光度、透氧性、保水率外,还可更广泛的应用于医材及新型药物。
如图1所示的实施例流程图,在一实施例中,本发明制造双性高分子的 方法包含例如以下步骤。
步骤S100,提供双性几丁聚糖。进一步而言,在一实施例中,步骤S100 包含将具有羧基改质亲水端(carboxyl group)和长碳链改质疏水端(hexanoyl group)的双性几丁聚糖(amphiphilic chitosan,CHC)粉末溶于水中以形成双性 几丁聚糖溶液。
步骤S200,提供聚二甲基硅氧烷。进一步而言,在一实施例中,步骤S200包含将端氨基聚二甲基硅氧烷(amine terminated poly(dimethylsiloxane))溶于异丙醇(isopropanol,IPA)中,并加入N-羟基 丁二酰亚胺(N-Hydroxysuccinimide,NHS)。
步骤S300,将双性几丁聚糖与聚二甲基硅氧烷键合。进一步而言,在 一实施例中,步骤S300包含使用1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸 盐(1-ethyl-3-(3-dimethylaminopropyl)carbodiimide,EDC)作为催化剂。
更具体而言,在一实施例中,通过以下工艺制造聚二甲基硅氧烷-双性 几丁聚糖共轭高分子。
(1)将5ml(3wt%)具有羧基改质亲水端和长碳链改质疏水端的双性几 丁聚糖粉末溶于95ml去离子水于锥形瓶内并搅拌8小时,使其完全溶解形 成双性几丁聚糖溶液(0.15wt%)。
(2)将(1)所得的双性几丁聚糖溶液加入45ml异丙醇以及分三次加 入1.0wt%N-羟基丁二酰亚胺(N-Hydroxysuccinimide,NHS)共30μl作为 催化剂。
(3)同时准备另一瓶子,加入5ml异丙醇以及200μl端氨基聚二甲基 硅氧烷(amineterminated poly(dimethylsiloxane)),缓慢搅拌均匀。
(4)4小时后,将(3)的瓶子内的溶液于搅拌下一滴一滴加到锥形瓶 中。
(5)接着提高搅拌速度,在快速地搅拌下加入1.0wt%1-(3-二甲氨基丙 基)-3-乙基碳二亚胺盐酸盐(1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, EDC),30分钟后将转速降低,缓慢地搅拌12-24小时使反应完成。
(6)将经过上述步骤所得的聚二甲基硅氧烷-双性几丁聚糖 (poly(dimethylsiloxane)amphiphilic chitosan,CHC-PDMS)共轭高分子混合 溶液利用一透析膜(分子量14000)以异丙醇进行透析12-48小时,产生一透 析物。
(7)将上述的透析产物以600℃烘箱烘干完全,以取得此聚二甲基硅 氧烷-双性几丁聚糖共轭高分子。
其中,上列1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐以及N-羟基丁二 酰亚胺作为催化剂。
将上述工艺所制造聚二甲基硅氧烷-双性几丁聚糖共轭高分子溶解在 D2O制作成3wt%的浓度,并经由核磁共振光谱仪(NMR 500,America VARIAN)测定其化学结构,结果如图2所示。由图2的结果可以看出有 -O=C-N-H-官能基存在,可证实双性几丁聚糖已与聚二甲基硅氧烷键合。
将上述工艺所制造聚二甲基硅氧烷-双性几丁聚糖共轭高分子以浓度 0.1wt%与KBr进行混掺,其中CHC-PDMS与KBr的体积量为1:8,并将其 磨成粉(需在短时间内完成,避免混和粉末吸入空气中的水气,影响信号, 最后将其压成锭并进行FT-IR(Unican MattsonMode 7000)测试(解析 度:4cm-1,扫描32次),结果如图3所示。由图3的结果可以看出有amide I、amide II、SiCH3官能基存在,可证实双性几丁聚糖已与聚二甲基硅氧烷 键合。
利用场发射扫描式电子显微镜(SEM)测定双性几丁聚糖与上述工艺所 制造聚二甲基硅氧烷-双性几丁聚糖共轭高分子的自组装型态,结果分别如 图4A及图4B所示。其中,由图4B观察出CHC-PDMS共轭高分子自组装 的颗粒大小为150~200nm左右,由此证明,将PDMS以化学键合修饰CHC 形成的CHC-PDMS共轭高分子具有与双性几丁聚糖巨分子(CHC)相同的 自组装能力,均形成纳米粒子,在大小、形状与图4A所示的CHC相似。
本发明双性高分子作为隐形眼镜材料的测试。
将不同浓度的CHC-PDMS共轭高分子、去离子水及甲基丙烯酸羟乙酯(Hydroxyethylmethacrylate,HEMA)单体溶液以如下表1的配方进行混和 作为隐形眼镜的材料,并进一步制成隐形眼镜镜片进行测试。其中,加入 10ul Darcour1173(Sigma-Aldrich,USA)作为光交联剂,经由365nm波长 紫外线交联20-40分钟后得到镜片,最后再将镜片浸泡在60%以上酒精震荡 2小时,去离子水震荡2小时,制成含CHC-PDMS共轭高分子的隐形眼镜 的镜片。在不同实施例中,甲基丙烯酸羟乙酯(Hydroxyethylmethacrylate,HEMA)单体溶液可替换为硅氧烷单体溶液,单体可以加热方式交联固化。
表1总体积1ml的预聚合溶液的组成
透光度测试
将上述镜片以UV-Visible spectrometer(Evolution 300,Thermo)进行测试。 如图5所示,添加较多的共聚高分子制成镜片会导致透光度稍微下降(90% →80%),但与市售镜片并无太大差距,其穿透度都相当良好。
透氧性测试
将上述镜片进行透氧量的测试,其中含CHC-PDMS共轭高分子的 poly-HEMA水胶镜片,其Dk值分别为10.2(0%CHC-PDMS)、 14.3(1.0%CHC-PDMS)、及17.3(2.0%CHC-PDMS),增幅明显。由此可证, 使用本发明双性高分子作为材料的隐形眼镜,具有较佳的透氧性。
保水率测试
将上述镜片于烘箱中烘干,称重(Wd),待其饱和状态,将表面水分擦干, 称重(Ww);之后将此镜片置于一密闭容器内,每隔一段时间,称重(Wt)。
保水率(Water Retention)可由下式计算:
Water Retention(%)=100%×(Wt-Wd)/(Ww-Wd)
如图6所示,在保水率测试中,添加较多的CHC-PDMS共轭高分子的 镜片的waterretention增加,推测可能是由于在双性几丁聚糖分子内的 -COOH官能基影响,因为其属于高亲水性基团。
镜片细胞毒性试验
将上述镜片以牛角皮内膜细胞bovine cornea endothelial cell(BCE)进 行MTT细胞毒性测试。如图7所示,经由24小时细胞培养后,此纳米复合 材料镜片展现出高达90%以上的细胞相容性(cell viability)。
根据上述测试结果,本发明双性高分子作为隐形眼镜材料,兼具良好的 透光度、透氧性、保水率、细胞相容性,改善了市售隐形眼镜为了提升透氧 率添加silicone成分但会产生透光度下降及不互溶的现象的问题。
动物眼压(IOP)试验
为了评估此载药型眼镜疗效,使用青光眼兔(眼压大于21mmHg)进行青 光眼治疗测试。(右眼为实验组(高眼压:27~30mmHg),左眼为对照组(正常眼 压))。
将含有青光眼药物(latanoprost;药物浓度10μg)载入上述镜片,进 行一天配戴八小时的实验,并长达七天。如图8所示,实线箭头表示每日更 换含药镜片时间点,经由载药镜片治疗后,动物眼压(Intraocular pressure, IOP)有明显且快速的下降(由30mmHg降至20mmHg以下)。由此可知前述 镜片具备可包覆药物的能力,能进行药物释放。在不同实施例中,药物不限 于青光眼药物,还可包含例如抗过敏性药物、红眼症药物等。其中,在制造上述镜片时,药物与CHC-PDMS共轭高分子、去离子水及甲基丙烯酸羟乙 酯(Hydroxyethylmethacrylate,HEMA)单体溶液混和一起作为隐形眼镜的 材料,并进一步制成隐形眼镜镜片,由以将药物载入镜片。
虽然前述的描述及附图已公开本发明的较佳实施例,必须了解到各种增 添、许多修改和取代可能使用于本发明较佳实施例,而不会脱离如所附申请 专利范围所界定的本发明原理的精神及范围。本领域技术人员将可体会,本 发明可使用于许多形式、结构、布置、比例、材料、元件和组件的修改。因 此,本文于此所公开的实施例应被视为用以说明本发明,而非用以限制本发 明。本发明的范围应由权利要求范围所界定,并涵盖其合法均等物,并不限 于先前的描述。
Claims (11)
1.一种双性高分子,其特征在于,包含:
一聚二甲基硅氧烷;以及
一双性几丁聚糖,与该聚二甲基硅氧烷键合。
2.根据权利要求1所述的双性高分子,其特征在于,该聚二甲基硅氧烷包含氨基。
3.根据权利要求1所述的双性高分子,其特征在于,该双性几丁聚糖包含羧基。
4.根据权利要求1所述的双性高分子,其特征在于,具有以下结构:
5.一种隐形眼镜材料,其特征在于,包含根据权利要求1至4任一项所述的双性高分子。
6.一种制造双性高分子的方法,其特征在于,包含:
S100、提供一双性几丁聚糖;
S200、提供一聚二甲基硅氧烷;
以及
S300、将该双性几丁聚糖与该聚二甲基硅氧烷键合。
7.根据权利要求6所述的方法,其特征在于,该双性几丁聚糖包含羧基。
8.根据权利要求6所述的方法,其特征在于,该聚二甲基硅氧烷包含氨基。
9.根据权利要求6所述的方法,其特征在于,步骤S300包含使用1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐作为催化剂。
10.根据权利要求6所述的方法,其特征在于,步骤S300包含使用N-羟基丁二酰亚胺作为催化剂。
11.一种制造隐形眼镜的方法,其特征在于,包含:
T100、提供根据权利要求1至4任一项所述的双性高分子;
T200、提供甲基丙烯酸羟乙酯单体溶液或硅氧烷单体溶液;
T300、提供光交联剂;
T400、使用紫外光或加热进行交联光固化。
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