隐形眼镜新材料的合成研究
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摘要
自第一个角膜接触镜(PMMA)问世以来,角膜接触镜的发展日益强大。据悉,我国隐形眼镜市场在2002年增长10%,2003年增长14%。人们不仅希望角膜接触镜能够矫正视力、还能够矫正散光、防紫外线、改变眼睛的颜色等等。目前,对角膜接触镜的研究主要有角膜接触镜加工工艺和角膜接触镜材料两个方向。本论文分别从两个方向入手,一方面对目前研究较多的N-乙烯基吡咯烷酮和甲基丙烯酸β-羟乙酯(PHEMA)进行紫外聚合,并对合成产物的性能进行了分析。另一方面,以乙二醇缩水甘油醚作为交联剂制备了γ-PGA吸水树脂,对其制备工艺及性能进行了研究。
首先,以40W的紫外灯作为光源,安息香乙醚为引发剂,对N-乙烯基吡咯烷酮(NVP)和甲基丙烯酸β–羟乙酯(HEMA)的紫外聚合工艺进行研究。探讨了引发剂浓度、紫外灯距对聚合时间的影响。实验发现:当引发剂的浓度为1.6%、紫外灯距为2.6cm时,反应物完全聚合,并且吸水平衡后表面光滑。
其次,对NVP、HEMA、透明兰合成彩色角膜接触镜材料的工艺进行了研究,并探讨了其反应机理。实验发现:通过对角膜接触镜抽提前后的色泽对比可知:透明兰并没有参与聚合反应,而是吸附在角膜接触镜材料上的。通过镜片材料在NaCl溶液中浸泡24h前后的透光率对比(透光率不变),证明其与镜片材料间的作用力在泪液环境下是稳定的。
本文对合成的角膜接触镜材料性能进行了分析。通过实验获得了最佳反应条件:当m(NVP):m(HEMA)=3:2,透明兰的填加量为0.00246%时,在此条件下得到的角膜接触镜材料的含水率为66.51%、透光率为97%、镜片材料的抗张强度为916.23Pa,样品浸出液的pH在7.09～7.29之间,变化不明显,与人体泪液的pH(7.2)接近,镜片颜色与市售“清朗”镜片相近。通过IR、DSC、扫描电镜对其进行表征,证明了镜片材料具有良好的热稳定性及较强的抗张强度。
最后对以γ-PGA为原料合成角膜接触镜材料进行了研究。通过实验摸索了最佳反应条件:以乙二醇缩水甘油醚作为交联剂,在γ-PGA浓度为25%,交联剂的使用量为聚谷氨酸单体摩尔量的16.8%,pH 4.3,70℃反应35h,产物的含
The industry of contact lens has been developed rapidly since the first material—PMMA came out. As was reported, the market of contact lens in China increased 10% in 2002 and 14% in 2004. Contact lens are not only hoped to rectify eyesight but also rectify astigmatism, prevent ultraviolet radiation, change the color of eye and so on. There are two main ways to research contact lens(technology and material) in this paper. On one hand, contact lens material was prepared from NVP and HEMA by UV method and the performance of the product was studied. One the other hand, we prepared poly (γ-glutamic acid)(γ-PGA) hydrogel from glycol diglycidyl ether andγ-PGA and analysed the product also.
Poly(2-hydroxyethylmehtacrylate-N-vinylpyrrolidone)(PHEMA-NVP) was prepared by UV method(UV light :40W). Benzoin ethyl ether was used as UV sensitive initiator. The optimal conditions are as follow: the concentration of initiator is 1.6%, irradiation distance is 2.6cm, the reaction is complete. And the surface of the product is slick.
The color contact lens was prepared from NVP, HEMA and solvent blue 36. Mechanism of the reaction was studied. According to the test, the pigment did not take part in the reaction; it was just absorbed on the material. The transparency of the product which was put in the 0.9%NaCl solution for 24h was 97%, the same value as before. It proved that the product was steady in the tear.
The performance of the contact lens was analysed in this paper. The optimal conditions are as follow: the monomers(MHEMA:MNVP=3:2), the UV sensitive initiator(benzoin ethyl ether1.6%),and the pigment(solvent blue 36)( 0.00246%). the water content was 66.51%, transparency was 97%,tensile modulus was 916.23pa, and the pH range from 7.09 to 7.29, it was near to tear. IR and UV verified perfectibility of the reaction. SEM analysis suggested that the sample had higher water content and tensile modulus.
At last, A new polymer was prepared fromγ-poly(glutamic acid) (γ-PGA) and glycol diglycidyl ether. The conditions of the reaction, such as PGA concentration, crosslinking agent, pH, temperature, time were studied. The optimal conditions are as
首先,以40W的紫外灯作为光源,安息香乙醚为引发剂,对N-乙烯基吡咯烷酮(NVP)和甲基丙烯酸β–羟乙酯(HEMA)的紫外聚合工艺进行研究。探讨了引发剂浓度、紫外灯距对聚合时间的影响。实验发现:当引发剂的浓度为1.6%、紫外灯距为2.6cm时,反应物完全聚合,并且吸水平衡后表面光滑。
其次,对NVP、HEMA、透明兰合成彩色角膜接触镜材料的工艺进行了研究,并探讨了其反应机理。实验发现:通过对角膜接触镜抽提前后的色泽对比可知:透明兰并没有参与聚合反应,而是吸附在角膜接触镜材料上的。通过镜片材料在NaCl溶液中浸泡24h前后的透光率对比(透光率不变),证明其与镜片材料间的作用力在泪液环境下是稳定的。
本文对合成的角膜接触镜材料性能进行了分析。通过实验获得了最佳反应条件:当m(NVP):m(HEMA)=3:2,透明兰的填加量为0.00246%时,在此条件下得到的角膜接触镜材料的含水率为66.51%、透光率为97%、镜片材料的抗张强度为916.23Pa,样品浸出液的pH在7.09～7.29之间,变化不明显,与人体泪液的pH(7.2)接近,镜片颜色与市售“清朗”镜片相近。通过IR、DSC、扫描电镜对其进行表征,证明了镜片材料具有良好的热稳定性及较强的抗张强度。
最后对以γ-PGA为原料合成角膜接触镜材料进行了研究。通过实验摸索了最佳反应条件:以乙二醇缩水甘油醚作为交联剂,在γ-PGA浓度为25%,交联剂的使用量为聚谷氨酸单体摩尔量的16.8%,pH 4.3,70℃反应35h,产物的含
The industry of contact lens has been developed rapidly since the first material—PMMA came out. As was reported, the market of contact lens in China increased 10% in 2002 and 14% in 2004. Contact lens are not only hoped to rectify eyesight but also rectify astigmatism, prevent ultraviolet radiation, change the color of eye and so on. There are two main ways to research contact lens(technology and material) in this paper. On one hand, contact lens material was prepared from NVP and HEMA by UV method and the performance of the product was studied. One the other hand, we prepared poly (γ-glutamic acid)(γ-PGA) hydrogel from glycol diglycidyl ether andγ-PGA and analysed the product also.
Poly(2-hydroxyethylmehtacrylate-N-vinylpyrrolidone)(PHEMA-NVP) was prepared by UV method(UV light :40W). Benzoin ethyl ether was used as UV sensitive initiator. The optimal conditions are as follow: the concentration of initiator is 1.6%, irradiation distance is 2.6cm, the reaction is complete. And the surface of the product is slick.
The color contact lens was prepared from NVP, HEMA and solvent blue 36. Mechanism of the reaction was studied. According to the test, the pigment did not take part in the reaction; it was just absorbed on the material. The transparency of the product which was put in the 0.9%NaCl solution for 24h was 97%, the same value as before. It proved that the product was steady in the tear.
The performance of the contact lens was analysed in this paper. The optimal conditions are as follow: the monomers(MHEMA:MNVP=3:2), the UV sensitive initiator(benzoin ethyl ether1.6%),and the pigment(solvent blue 36)( 0.00246%). the water content was 66.51%, transparency was 97%,tensile modulus was 916.23pa, and the pH range from 7.09 to 7.29, it was near to tear. IR and UV verified perfectibility of the reaction. SEM analysis suggested that the sample had higher water content and tensile modulus.
At last, A new polymer was prepared fromγ-poly(glutamic acid) (γ-PGA) and glycol diglycidyl ether. The conditions of the reaction, such as PGA concentration, crosslinking agent, pH, temperature, time were studied. The optimal conditions are as
引文
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[6] 沈伟锋. 角膜接触镜在眼病治疗中的应用[J]. 中国实用眼科杂志,2004,9: 84～85.
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[2] 王静,谢培英.透气性硬性角膜接触镜矫治屈光不正的效果[J]. 眼视光学杂志,2002,4: 78～80.
[3] 钱进,史建明. 硬性透气性角膜接触镜对青少年近视的矫治作用[J].眼视光学杂志,2004,4:212～215.
[4] 田小波,曹晖. 硬性透气性角膜接触镜在儿童屈光不正中的应用[J].中国实用眼科杂志,2005,7: 689～690.
[5] 戴祖优,龚向明. 美容性角膜接触镜的验配探讨[J].中国实用眼科杂志,2000,12: 809～810.
[6] 沈伟锋. 角膜接触镜在眼病治疗中的应用[J]. 中国实用眼科杂志,2004,9: 84～85.
[7] 宗凤义,王玉柱. 角膜接触镜在角膜外伤治疗中的应用[J].眼外伤职业眼病杂志,2001,1:118～119.
[8] 崔亦华,崔英德,黎新明等. 角膜接触镜研究进展[J]. 广州化工,2002, 2:16～19.
[9] 陈松. 隐形眼镜纵横谈[J]. 中国眼镜科技杂志,1995, 3: 15～17.
[10] Axel Heinrich, Bernhard Seiferling, Klaus Haberstroh,etc. Contact lens manufacture using UV light [P]. EP:1314527, 2003-05-28.
[11] 蓝天. 软性角膜接触镜材料[J]. 中国眼镜科技杂志,2005,4:66-67.
[12] Sano K,Tokoro T,Imai Y.A new drug delivery system utilizing piggyback contact lenses[J]. International Contact Lens Clinic,1996,23:243～248.
[13] Qu J,Lu F. Overview of Contact Lens Development in China[J]. International Contact Lens Clinic,1995,22:102～104.
[14] Shoko I,Kunio Y. Distinct roles of maf genes during Xenopus lens development. [J]. Mechanisms of Development,2001,101:155～166.
[15] Oduntan,Alabi O,Baker,etal. Contact lenses in South Africa: an overview[J].International Contact Lens Clinic,1998,25:73-76.
[16] Lee, Cheni H T. Overview of Contact Lens Practice in Indonesia[J]. International Contact Lens Clinic,1997, 24:121-122.
[17] Briggs,Stella T,Oduntan,etal. Contact Lenses in Saudi Arabia: An Overview [J]. International Contact Lens Clinic,1996, 23:46-49.
[18] Edward G. A personal perspective on the history of contact lenses[J]. International Contact Lens Clinic,2000, 4:139-145.
[19] Girard Louis J,Sampson Whitney G.Contact lens having an index of refraction approximating that of human tears[P]. USP: 3542461,1970-11-24.
[20] Barkdoll Archie E. Soft, tough low refractive index contact lenses[P].USP: 3940207. 1976-2-24.
[21] Gaylord N. Oxygen-permeable contact lens composition,methods and article of manufacture[P]. USP: 3808178,1974-4-30.
[22] Compa? V , Guzmán J , Riande E. A potentiostatic study of oxygen transmissibility and permeability through hydrogel membranes[J]. Biomaterials. 1998,19:2139 2145.
[23] Thomas P D,Malcolm B H.Studies on copolymeric hydrogels of NVP with HEMA[J]. Macromolecules,1989,22:2824～2830.
[24] 梅满海. 实用眼镜学[M].天津:天津科学技术出版社,2000.
[25] Shah Kishore R.Water absorptive composition[P].USP:4300820,1981-11-17.
[26] Mcgrath J, Matzner M. Vinyl halide polymer-olefin copolymer alloys[P]. USP: 3798289, 1974-3-19.
[27] 郑荣领,周电根,郑一仁. 角膜接触镜研究进展[J]. 中国实用眼科杂志,2000,5:161～164.
[28] Otto W. Method of centrifugally casting layered contact lenses[P]. USP: 3557261, 1971-1-19.
[29] Otto W. Method for centrifugal casting a contact lens[P]. USP: 3408429,1968-8-29.
[30] Kunzler Jay k, Martin Ar Thur. Contact lens materials[P].USP: 6762264,2003-6-16.
[31] Dahi Ali , Chen Barry. Hybrid contact lens system and method[P]. USP:040179167,2004-10-28.
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