TWI549994B - A crossed siloxane macromolecule comprising polymerization functional groups and hydrophilic groups and method for manufacturing the crossed siloxane macromolecule - Google Patents
A crossed siloxane macromolecule comprising polymerization functional groups and hydrophilic groups and method for manufacturing the crossed siloxane macromolecule Download PDFInfo
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本發明係有關於一種矽氧烷高分子及其製作方法,尤指一種含可聚合官能基與親水基之十字型矽氧烷高分子及其製作方法。 The invention relates to a siloxane polymer and a preparation method thereof, in particular to a cross-type siloxane polymer containing a polymerizable functional group and a hydrophilic group, and a preparation method thereof.
由於有機矽水膠(Silicone hydrogel)具有良好的透氧性、濕潤性及生物相容性,因此被普遍應用於隱形眼鏡製作,現今用於隱形眼鏡製作的矽單體可分為直鏈型矽氧烷及十字型矽氧烷,如台灣專利公告號TWI434865中,揭露一種直鏈型且具有醯胺官能基或磷酸膽鹼官能基等親水性側鏈的聚矽氧烷,或如美國專利公告號US4463149中,揭露一種小分子十字型的矽氧烷結構。 Since Silicone hydrogel has good oxygen permeability, wettability and biocompatibility, it is widely used in the manufacture of contact lenses. Today, tantalum monomers used in contact lens manufacturing can be classified into linear type. Oxyalkane and cross-type alkane, as disclosed in Taiwan Patent Publication No. TWI434865, discloses a linear polyoxyalkylene having a hydrophilic side chain such as a guanamine functional group or a phosphorylcholine functional group, or as disclosed in the U.S. Patent Publication. No. 4,463,149 discloses a structure of a small molecular cross-type oxirane.
直鏈型矽氧烷雖可經由修飾而使其具有較好的親水性,但直鏈型矽氧烷為一維結構,其透氧率往往低於二維結構的十字型矽氧烷,而十字型矽氧烷雖具有較好的透氧率,但由於其疏水性的性質,亦會造成其含水率的下降。 Although linear linear decane can be modified to have good hydrophilicity, linear siloxane is a one-dimensional structure, and its oxygen permeability is often lower than that of a two-dimensional structure of a cross-type siloxane. Although cross-type oxane has a good oxygen permeability, due to its hydrophobic nature, it also causes a decrease in water content.
是以,如何合成一具有高透氧性及兼具高含水率之聚矽氧烷化合物,為本案欲解決的技術課題。 Therefore, how to synthesize a polyoxyxane compound having high oxygen permeability and high water content is a technical problem to be solved in the present invention.
本案一較佳作法,係提供一種含可聚合官能基與親水基之十字型矽氧烷高分子的製作方法,其中該含可聚合官能基與親水基之十字型矽氧烷高分子的製作方法包括下列步驟:(a).提供一末端具矽氫基之十字型矽氧烷;(b).對該末端具矽氫基之十字型矽氧烷進行一第一矽氫化反應,使其形成一含可聚合官能基之十字型矽氧烷小分子;(c).進行一開環聚合反應,使其形成一含矽氫基之十字型聚矽氧烷高分子;以及(d).進行一第二矽氫化反應,使其形成一含可聚合官能基與親水基之十字型矽氧烷高分子。 A preferred method of the present invention is to provide a method for preparing a cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group, wherein the method for preparing a cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group The method comprises the steps of: (a) providing a cross-type fluorinated alkane having a hydrogen group at the end; (b) performing a first hydrogenation reaction on the hydrogen-based crucible helium at the end to form a first hydrogenation reaction. a cross-type azide small molecule containing a polymerizable functional group; (c) performing a ring-opening polymerization reaction to form a ruthenium-containing hydrogen-containing cross-type polyoxyalkylene polymer; and (d). A second hydrogenation reaction is carried out to form a cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group.
於上述較佳實施方式中,如專利申請範圍第1所述之含可聚合官能基與親水基之十字型矽氧烷高分子的製作方法,其中於步驟(a)中,該末端具矽氫基之十字型矽氧烷以式(I)表示之,
於式(I)中,R0為下式表示的化學結構,
於R0中,d值介於0-20。 In R 0 , the value of d is between 0 and 20.
於上述較佳實施方式中,其中該末端具矽氫基之十字型矽氧烷為一四(二甲基矽氧基)矽烷。 In the above preferred embodiment, the cross-type oxime having a hydrogen group at the terminal is tetrakis(dimethylmethoxyoxy)decane.
於上述較佳實施方式中,其中於步驟(b)中,係添加一甲基丙烯酸烯丙酯於該末端具矽氫基之十字型矽氧烷中,並以一含鉑觸媒催化該第一矽氫化反應,使其形成一以式(II)表示之該含可聚合官能基之十字型矽氧烷小分子,
於式(II)中,可聚合官能基R具下式表示的化學結構,
於上述較佳實施方式中,其中於步驟(b)中,係於氮氣中,以溫度85-90℃及作用23小時的條件下,進行該第一矽氫化反應。 In the above preferred embodiment, in the step (b), the first hydrogenation reaction is carried out under nitrogen at a temperature of 85-90 ° C for 23 hours.
於上述較佳實施方式中,其中於步驟(c)中,係添加一強酸至一環矽氧烷、一環氫矽氧烷及該含可聚合官能基之十字型矽氧烷小分子的混合物中,進行該開環聚合反應使其形成一以式(III)表示之該含矽氫基之十字型聚矽氧烷高分子,
於式(III)中,R1為下式表示的化學結構,
於R1中,m值介於5-1000,代表矽氫基個數之n值介於0-150。 In R 1 , the m value is between 5 and 1000, and the n value representing the number of hydrogen groups is between 0 and 150.
於上述較佳實施方式中,其中於步驟(c)中,係於氮氣中,以溫度35℃及作用24小時的條件下,進行該開環聚合反應。 In the above preferred embodiment, in the step (c), the ring-opening polymerization is carried out under nitrogen at a temperature of 35 ° C for 24 hours.
於上述較佳實施方式中,其中該強酸之莫耳數為該環矽氧烷、該環氫矽氧烷及該含可聚合官能基之十字型矽氧烷小分子三者莫耳數總和之1-10%,及該強酸包括:三氟甲磺酸、硫酸中之任一者。 In the above preferred embodiment, wherein the molar number of the strong acid is the sum of the molar ratios of the cyclodecane, the cyclohydrooxane and the cross-type azide small molecule containing the polymerizable functional group. 1-10%, and the strong acid includes any one of trifluoromethanesulfonic acid and sulfuric acid.
於上述較佳實施方式中,其中該環矽氧烷包括:八甲基環四矽氧烷、六甲基環三矽氧烷中之至少一者。 In the above preferred embodiment, wherein the cyclodecane comprises at least one of octamethylcyclotetraoxane and hexamethylcyclotrioxane.
於上述較佳實施方式中,其中該環氫矽氧烷為一2,4,6,8四甲基環四矽氧烷。 In the above preferred embodiment, wherein the cyclohydrooxane is a 2,4,6,8 tetramethylcyclotetraoxane.
於上述較佳實施方式中,其中於步驟(d)中,係添加一親水性化合物至該含矽氫基之十字型聚矽氧烷高分子中,並以一含鉑觸媒催化該第二矽氫化反應,使其形成一以式(IV)表示之含可聚合官能基與親水基之十字型矽氧烷高分子,
於式(IV)中,R2為下式表示的化學結構,
於R2中,m值介於5-1000,n值介於0-150,親水基R4為一以下式表示的親水性結構,
於R4中,y值介於0-100,z值介於0-50,R3為:羥基、甲基中之任一者。 In R 4 , the y value is between 0 and 100, the z value is between 0 and 50, and R 3 is any one of a hydroxyl group and a methyl group.
於上述較佳實施方式中,其中該等R2中,至少3者具親水基R4。 In the above preferred embodiments, at least three of the R 2 have a hydrophilic group R 4 .
於上述較佳實施方式中,其中於步驟(d)中,係於氮氣中,以溫度85-90℃及作用24小時的條件下,進行該第二矽氫化反應。 In the above preferred embodiment, in the step (d), the second hydrogenation reaction is carried out under nitrogen at a temperature of 85-90 ° C for 24 hours.
於上述較佳實施方式中,其中該親水性化合物包括:3-烯丙氧基-1,2,丙二醇、2-烯丙氧基乙醇、三甲基醇丙烷烯丙基醚中之至少一者。 In the above preferred embodiment, the hydrophilic compound comprises at least one of 3-allyloxy-1,2, propylene glycol, 2-allyloxyethanol, and trimethylolpropane allyl ether. .
本案另一較佳作法,係提供一種含可聚合官能基與親水基之十字型矽氧烷高分子,係由上述含可聚合官能基與親水基之十字型矽氧烷高分子的製作方法製造而得。 Another preferred method of the present invention is to provide a cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group, which is produced by the above-mentioned method for preparing a cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group. And got it.
於上述較佳實施方式中,其中該含可聚合官能基與親水基之十字型矽氧烷高分子之氫核磁共振光譜結果如下:1H NMR(CDCl3,400MHz):δ6.1(s,4H),5.54(s,4H),4.10(t,8H),3.40-3.90(m,288H),1.94(s,12H),1.55-1.85(m,72H),0.47-0.60(m,72H),0.04-0.20(m,Si-CH3),其中3.40-3.90(m,288H)該數值代表高分子中親水性結構的形成。 In the above preferred embodiment, the hydrogen nuclear magnetic resonance spectrum of the polymer of the cross-type alkane having a polymerizable functional group and a hydrophilic group is as follows: 1 H NMR (CDCl 3 , 400 MHz): δ 6.1 (s, 4H), 5.54 (s, 4H), 4.10 (t, 8H), 3.40-3.90 (m, 288H), 1.94 (s, 12H), 1.55-1.85 (m, 72H), 0.47-0.60 (m, 72H) 0.04-0.20 (m, Si-CH3), wherein 3.40-3.90 (m, 288H) represents the formation of a hydrophilic structure in the polymer.
本案又一較佳作法,係提供一種矽水膠基材,包含上述含可聚合官能基與親水基之十字型矽氧烷高分子。 In another preferred embodiment of the present invention, a hydrophobic gel base material comprising the above-mentioned cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group is provided.
本案又一較佳作法,係提供一種矽水膠鏡片,包含上述含可聚合官能基與親水基之十字型矽氧烷高分子。 In another preferred embodiment of the present invention, there is provided a hydrophobic gel lens comprising the above-mentioned cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group.
於上述較佳實施方式中,其中該矽水膠鏡片進一步包含:三-[三(三甲基矽氧基)]甲基丙烯酸丙酯矽烷、N-乙烯基吡咯烷酮、甲基丙烯酸-2-羥基乙酯中之至少一者。 In the above preferred embodiment, the hydrophobic gel lens further comprises: tris-[tris(trimethyldecyloxy)]propyl methacrylate decane, N-vinylpyrrolidone, 2-hydroxy methacrylate At least one of the ethyl esters.
S11~S14‧‧‧步驟 S11~S14‧‧‧Steps
第1圖為本案所提供之合成含可聚合官能基與親水基之十字型矽氧烷高分子的實施步驟流程示意圖。 Fig. 1 is a schematic flow chart showing the steps of the synthesis of a cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group provided in the present invention.
由於本案所揭露之含可聚合官能基與親水基之十字型矽氧烷高分子的製作方法,其中所利用之開環聚合反應(Ring opening polymerization)及矽氫化反應(Hydrosilation),已為相關技術領域具有通常知識者所能明瞭,故以下文中之說明,不再作完整描述。 The method for preparing a crucible helioxane polymer containing a polymerizable functional group and a hydrophilic group disclosed in the present invention, wherein a ring opening polymerization reaction and a hydrogenation reaction (Hydrosilation) are used as related technologies The field is known to those of ordinary skill and will not be fully described in the following description.
本發明為提供一種含可聚合官能基與親水基之十字型矽氧烷高分子及其製作方法,此製造方法包括:第一矽氫化反應、開環聚合反應及第二矽氫化反應。 The present invention provides a cross-type azide polymer containing a polymerizable functional group and a hydrophilic group, and a process for producing the same, which comprises the first hydrogenation reaction, ring-opening polymerization reaction and second hydrogenation reaction.
請參閱第1圖,首先,提供一末端具矽氫基之十字型矽氧烷(步驟S11),該末端具矽氫基之十字型矽氧烷以下式表示之,
其中,R0為下式表示的化學結構,
於R0中,d值介於0-20。 In R 0 , the value of d is between 0 and 20.
所述末端具矽氫基之十字型矽氧烷,例如於d=0的情況下,為一四(二甲基矽氧基)矽烷(Tetrakis(dimethylsilyl)orthosilicate)。 The cross-type oxime having a hydrogen group at the end, for example, in the case of d=0, is Tetrakis (dimethylsilyl) orthosilicate.
以四(二甲基矽氧基)矽烷進行第一矽氫化反應(步驟S12),如下列化學反應式(a)所示:
步驟S12係添加甲基丙烯酸烯丙酯(Allyl methacrylate)(2)於四(二甲基矽氧基)矽烷中,於溫度85-90℃的環境下,以含鉑觸媒(Pt/C)催化第一矽氫化反應,而獲得含可聚合官能基R之十字型矽氧烷小分子(3),所述可聚合官能基R具下示之化學結構:
其中,該可聚合官能基具有Si-O-Si之結構式。 Wherein, the polymerizable functional group has a structural formula of Si—O—Si.
隨後,進行一開環聚合反應(步驟S13),如下列化學反應式(b)所示:
步驟S13係於環矽氧烷(4)、環氫矽氧烷(5)及含可聚合官能基R之十字型矽氧烷小分子(3)三者之混合物中添加一強酸(6),其中,強酸(6)之莫耳數為環矽氧烷(4)、環氫矽氧烷(5)及含可聚合官能基R之十字型矽氧烷小分子(3)混合物總莫耳數的1-10%。於常溫(約35℃)的環境下,進行開環聚合反應,使其形成含矽氫基之十字型聚矽氧烷高分子(7),所述含矽氫基之十字型聚矽氧烷高分子(7)之R1具下示之化學結構:
其中,m值介於5-1000,代表矽氫基(Si-H)個數之n值介於0-150。 Wherein, the m value is between 5 and 1000, and the number of n representing the hydrogen group (Si-H) is between 0 and 150.
於開環聚合反應(步驟S13)中,環矽氧烷(4)可為八甲基環四矽氧烷(Octamethylcyclotetrasiloxane)、六甲基環三矽氧烷(Hexamethylcyclotrisiloxane)中之至少一者;環氫矽氧烷(5)可為2,4,6,8四甲基環四矽氧烷(2,4,6,8-Tetramethylcyclotetrasiloxane);強酸(6)除化學反應式(b)所示之三氟甲磺酸(Trifluoromethane sulfonic acid)外,亦可使用硫酸(Sulfuric acid)代替。 In the ring-opening polymerization reaction (step S13), the cyclodecoxy alkane (4) may be at least one of Octamethylcyclotetrasiloxane and Hexamethylcyclotrisiloxane; The hydroquinone (5) may be 2,4,6,8 tetramethylcyclotetrasiloxane; the strong acid (6) is represented by the chemical reaction formula (b). In addition to trifluoromethane sulfonic acid, sulfuric acid (Sulfuric acid) may be used instead.
爾後,進行一第二矽氫化反應(步驟S14),如化學反應式(c)所示:
步驟S14係添加親水性化合物(8)至含矽氫基之十字型聚矽氧烷高分子(7)中,於溫度85-90℃的環境下,以含鉑觸媒(Pt/C)催化第二矽氫化反應,而獲得含可聚合官能基與親水基之十字型矽氧烷高分子(9),所述含可聚合官能基與親水基之十字型矽氧烷高分子(9)之R2具下示之化學結構:
其中,m值介於5-1000,n值介於0-150,親水基R4為以下示表示之親水性結構:
於上述親水性化合物(8)與親水基R4中,y值介於0-100,z值介於0-50,R3為:羥基(OH)、甲基(CH3)中之任一者。且親水性化合物(8)可為3-烯丙氧基-1,2,丙二醇(3-Allyloxy-1,2-propanediol)、2-烯丙氧基乙醇(2-Allyloxyethanol)、三甲基醇丙烷烯丙基醚(Trimethylolpropane allyl ether)中之至少一者。 In the above hydrophilic compound (8) and the hydrophilic group R 4 , the y value is in the range of 0 to 100, the z value is in the range of 0 to 50, and the R 3 is any one of the hydroxyl group (OH) and the methyl group (CH 3 ). By. And the hydrophilic compound (8) may be 3-Allyloxy-1,2-propanediol, 2-Allyloxyethanol, trimethylol At least one of Trimethylolpropane allyl ether.
於上述含可聚合官能基與親水基之十字型矽氧烷高分子(9)之四個R2中,至少3個R2具親水基R4。 Among the four R 2 of the above-mentioned cross-type aramid polymer (9) having a polymerizable functional group and a hydrophilic group, at least three R 2 have a hydrophilic group R 4 .
第一矽氫化反應:含可聚合官能基之十字型矽氧烷小分子之合成。 The first hydrogenation reaction: synthesis of a small molecule of a cross-type alkane having a polymerizable functional group.
將甲基丙烯酸烯丙酯(10.52g,83.39mmol)、穩定劑:4-甲氧基苯酚(4-Methoxyphenol)(9mg)與含鉑觸媒(Pt/C)(5% on carbon,0.6g)置於250mL雙頸瓶中;於該250mL雙頸瓶上裝置迴流管及血清塞,進行抽真空後再灌入氮氣三次,隨後取溶劑:無水甲苯(Toiuene)(60mL)並以玻璃針筒將之注入250mL雙頸瓶中。接著再取四(二甲基矽氧基)矽烷(6g,18.25mmol)並以針筒將之注入250mL雙頸瓶中。將250mL雙頸瓶置於油浴鍋中,加熱到85-90℃進行反應,經過23小時後,以抽氣過濾的方式收集液體(4-6次),將所收集之液體再進行重力過濾(重力過濾1次)。 Allyl methacrylate (10.52g, 83.39mmol), stabilizer: 4-methoxyphenol (9mg) and platinum-containing catalyst (Pt/C) (5% on carbon, 0.6g Place in a 250mL double-necked flask; install a reflux tube and a serum plug on the 250mL double-necked flask, vacuum and then inject nitrogen three times, then take the solvent: anhydrous toluene (60mL) and use a glass syringe Inject it into a 250 mL double neck bottle. Then, tetrakis(dimethylamyloxy)decane (6 g, 18.25 mmol) was taken and poured into a 250 mL double-necked flask with a syringe. The 250 mL double-necked flask was placed in an oil bath and heated to 85-90 ° C for reaction. After 23 hours, the liquid was collected by suction filtration (4-6 times), and the collected liquid was subjected to gravity filtration. (Gravity filtration 1 time).
以減壓濃縮方式去有機溶劑,爾後,使用乙酸乙酯(Ethyl acetate)(100mL)及飽和食鹽水(150mL)萃取上述減壓濃縮後之產物(重複萃取5次),收集有機層。使用減壓濃縮儀器進行減壓濃縮,將自有機層收集之產物以水浴加熱(約50℃)及抽真空(約3小時)的方式進行濃縮並除有機溶劑。以流管柱層析(EA/Hexane=1/20)方式收集含可聚合官能基之十字型矽氧烷小分子,產率約為37%。 The organic solvent was removed under reduced pressure. Then, ethyl acetate (ethyl acetate) (100 mL) and saturated brine (150 mL) were used to extract the product which was concentrated under reduced pressure (repeated extraction 5 times), and the organic layer was collected. The mixture was concentrated under reduced pressure using a reduced pressure concentrating apparatus, and the product collected from the organic layer was concentrated by heating in a water bath (about 50 ° C) and vacuum (about 3 hours) to remove an organic solvent. The cross-type alkane small molecule containing a polymerizable functional group was collected by flow column chromatography (EA/Hexane = 1/20) in a yield of about 37%.
含可聚合官能基之十字型矽氧烷小分子的氫核磁共振光譜結果如下:1H NMR(CDCl3,400MHz):δ6.09(s,4 H),5.54(s,4H),4.10(t,8 H),1.93(m,12H),1.63-1.79(m,8H),0.55-0.64(m,8H),0.04-0.20(m,24H),其中δ6.09(s,4 H)、5.54(s,4H)、4.10(t,8 H)及1.93(m,12H)該些數值代表含可聚合官能基之十字型矽氧烷小分子的形成。 The results of hydrogen nuclear magnetic resonance spectroscopy of a small molecule of a cross-type alkane having a polymerizable functional group are as follows: 1 H NMR (CDCl 3 , 400 MHz): δ 6.09 (s, 4 H), 5.54 (s, 4H), 4.10 ( t,8 H), 1.93 (m, 12H), 1.63-1.79 (m, 8H), 0.55-0.64 (m, 8H), 0.04-0.20 (m, 24H), where δ 6.09 (s, 4 H) 5.54 (s, 4H), 4.10 (t, 8 H) and 1.93 (m, 12H) These values represent the formation of small cross-type alkane-containing molecules containing polymerizable functional groups.
開環聚合反應:含矽氫基之十字型聚矽氧烷高分子的合成(n=8,m=43)。 Ring-opening polymerization: synthesis of a crucible-containing polyaluminoxane polymer containing a hydrogen group (n = 8, m = 43).
將八甲基環四矽氧烷(15g,50.57mmol)、2,4,6,8四甲基環四矽氧烷(3g,12.47mmol)、第一矽氫化反應產生之含可聚合官能基之十字型矽氧烷小分子(2.4g,2.88mmol)與溶劑:三氯甲烷(Chloroform)(14mL)置於250mL雙頸瓶中;於該250mL雙頸瓶上裝置血清塞與單向閥,自單向閥口通入氮氣,取三氟甲磺酸(0.1mL)並以針筒注入該250mL雙頸瓶中,於氮氣環境及室溫(約35℃)下反應24小時候,隨後打開裝置於250mL双頸瓶上之血清塞,加入飽和碳酸鈉水溶液(0.5mL),以終止開環聚合反應。 Octamethylcyclotetraoxane (15g, 50.57mmol), 2,4,6,8 tetramethylcyclotetraoxane (3g, 12.47mmol), polymerizable functional group produced by hydrogenation of the first hydrazine A small cross-type alkane small molecule (2.4 g, 2.88 mmol) and a solvent: Chloroform (14 mL) were placed in a 250 mL two-necked flask; a serum plug and a check valve were placed on the 250 mL double-necked flask. Nitrogen gas was introduced from the one-way valve port, and trifluoromethanesulfonic acid (0.1 mL) was taken and injected into the 250 mL double-necked flask with a syringe, and reacted under nitrogen atmosphere and room temperature (about 35 ° C) for 24 hours, and then the device was opened. The serum plug on a 250 mL double-necked flask was added with a saturated aqueous solution of sodium carbonate (0.5 mL) to terminate the ring-opening polymerization.
利用旋轉濃縮儀除去有機溶劑,之後進行萃取步驟,利用乙酸乙酯(200mL)與飽和食鹽水(150mL)萃取上述旋轉濃縮後之產物(重複萃取5次),收集上方有機層。再利用減壓濃 縮機進行減壓濃縮並除去有機溶劑。以丙酮(Acetone)(6mL)溶解上述減壓濃縮後之產物,將之滴入甲醇(Methanol)(27mL)中進行再沉澱;之後,再以濾紙進行重力過濾,以甲醇(250mL)清洗濾紙上層之黏稠物。收集上層黏稠物並以旋轉濃縮儀除去有機溶劑;重複進行二次前述再沉澱的步驟。收集濾紙上層黏稠物,即可得到10.9g無色黏稠之含矽氫基之十字型聚矽氧烷高分子(產率約53%)。 The organic solvent was removed by a rotary concentrator, followed by an extraction step, and the above-mentioned product after rotary concentration was extracted with ethyl acetate (200 mL) and saturated brine (150 mL) (repeated extraction 5 times), and the upper organic layer was collected. Reuse decompression The reduction machine was concentrated under reduced pressure and the organic solvent was removed. The product obtained by concentration under reduced pressure was dissolved in acetone (6 mL), and then re-precipitated by dropping into methanol (Methanol) (27 mL); then, gravity filtration was carried out with filter paper, and the upper layer of the filter paper was washed with methanol (250 mL). Sticky substance. The upper layer of the dope was collected and the organic solvent was removed by a rotary concentrator; the second reprecipitation step was repeated. The upper layer of the filter paper was collected to obtain 10.9 g of a colorless viscous hydrazine-containing cross-type polyaluminoxane polymer (yield about 53%).
含矽氫基之十字型聚矽氧烷高分子的氫核磁共振光譜結果如下:1H NMR(CDCl3,400MHz):δ6.1(s,4H),5.56(s,4H),4.70(m,32H),4.10(t,8H),1.95(s,12H),1.65-1.75(m,8H),0.50-0.65(m,8H),0.04-0.20(m,Si-CH3),其中4.70(m,32H)該數值代表矽氫基的形成。 The results of hydrogen nuclear magnetic resonance spectroscopy of a cross-type polyaluminoxane polymer containing a hydrogen group are as follows: 1 H NMR (CDCl 3 , 400 MHz): δ 6.1 (s, 4H), 5.56 (s, 4H), 4.70 (m) , 32H), 4.10 (t, 8H), 1.95 (s, 12H), 1.65-1.75 (m, 8H), 0.50-0.65 (m, 8H), 0.04-0.20 (m, Si-CH3), of which 4.70 ( m, 32H) This value represents the formation of a hydrazine group.
第二矽氫化反應:含可聚合官能基與親水基之十字型矽氧烷高分子的合成(n=8,m=50)。 The second hydrogenation reaction: synthesis of a cross-type alkane polymer containing a polymerizable functional group and a hydrophilic group (n = 8, m = 50).
將3-烯丙氧基-1,2,丙二醇(4.69g,35.49mmol)與含鉑觸媒(Pt/C)(5% on carbon,0.95g)置於250mL雙頸瓶中;接著,於該250mL雙頸瓶上裝置迴流管與滴加管,進行抽真空並灌入氮氣三次;取溶劑:無水甲苯(35mL)並以針筒注入上述250mL雙頸瓶中,將250mL雙頸瓶置入油浴鍋並加熱至85-90℃。 3-Allyloxy-1,2,propanediol (4.69 g, 35.49 mmol) and a platinum-containing catalyst (Pt/C) (5% on carbon, 0.95 g) were placed in a 250 mL double-necked flask; The 250 mL double-necked flask was equipped with a reflux tube and a dropping tube, vacuumed and filled with nitrogen three times; solvent: anhydrous toluene (35 mL) was injected into the 250 mL double-necked flask with a syringe, and a 250 mL double-necked flask was placed. Oil bath and heat to 85-90 °C.
將開環聚合反應所得之含矽氫基之十字型聚矽氧烷高分子(n=8,m=43,由NMR推算分子量約為15500)(10g,0.645mmol)置於另一100mL雙頸瓶中,於該100mL雙頸瓶上裝置血清塞與單向閥,隨後進行抽真空並灌入氮氣三次,取無水甲苯(25mL)與穩定劑:4-甲氧苯酚(6mg/20mL in toluene,4mL)並將之注入100mL雙頸瓶中,再以針筒自100mL雙頸瓶中抽出以無水甲苯溶解之含矽氫基之十字型聚矽氧烷高分子溶液;隨後,將之注入 裝置於250mL雙頸瓶上的滴加管,並由滴加管滴入250mL雙頸瓶中(滴加時間不超過4分鐘)。若100mL雙頸瓶中仍有殘餘物,可用針筒取無水甲苯(15mL)清洗100mL雙頸瓶中的殘餘物,並將洗出的殘餘物注入滴加管中,再滴入250mL雙頸瓶中。 The rhodium-containing hydrogen-containing cross-type polyaluminoxane polymer obtained by ring-opening polymerization (n=8, m=43, molecular weight estimated to be about 15500 by NMR) (10 g, 0.645 mmol) was placed in another 100 mL double neck. In the bottle, a serum plug and a check valve were placed on the 100 mL double-necked flask, followed by evacuation and nitrogen gas three times, and anhydrous toluene (25 mL) and stabilizer: 4-methoxyphenol (6 mg/20 mL in toluene, 4mL) and inject it into a 100mL double-necked flask, and then extract the hydrogen-containing hydrogen-containing cross-type polyaluminoxane polymer solution dissolved in anhydrous toluene from a 100mL double-necked flask with a syringe; then, inject it The tube was placed on a 250 mL double-necked flask and dropped into a 250 mL double-necked flask (dropping time not exceeding 4 minutes). If there is still residue in the 100mL double-necked flask, the residue in the 100mL double-necked flask can be washed with anhydrous toluene (15mL) from the syringe, and the washed residue can be injected into the dropping tube, and then dropped into the 250mL double-necked bottle. in.
將置於油浴鍋中的250mL雙頸瓶持續加熱並保持於85-90℃,使其於氮氣環境下進行第二矽氫化反應;反應作用24小時後,以抽氣過濾的方式收集液體(4-6次),再進行重力過濾(2次),使用旋轉濃縮儀去除有機溶劑,再以丙酮(15mL)溶解旋轉濃縮後之產物,將溶解於丙酮的產物加入置純水(76mL)中進行再沉澱,使用濾紙進行重力過濾,以純水(約250mL)清洗濾紙上層之產物,收集上層產物並以旋轉濃縮儀除去有機溶劑,重複進行二次上述再沉澱之步驟。收集濾紙上層之黏稠物即可得到約8.12g黃色且澄清黏稠之含可聚合官能基與親水基之十字型矽氧烷高分子(8.12g,產率63%)。 The 250 mL double-necked flask placed in the oil bath was continuously heated and maintained at 85-90 ° C, and subjected to a second hydrogenation reaction under a nitrogen atmosphere; after 24 hours of reaction, the liquid was collected by suction filtration ( 4-6 times), gravity filtration (2 times), removal of the organic solvent using a rotary concentrator, dissolution of the product after rotary concentration in acetone (15 mL), and addition of the product dissolved in acetone to purified water (76 mL) Reprecipitation was carried out, gravity filtration was carried out using a filter paper, the product of the upper layer of the filter paper was washed with pure water (about 250 mL), the upper layer product was collected, and the organic solvent was removed by a rotary concentrator, and the above-mentioned reprecipitation step was repeated. The thick layer of the upper layer of the filter paper was collected to obtain about 8.12 g of a yellow and clear viscous polymer of a cross-type alkane having a polymerizable functional group and a hydrophilic group (8.12 g, yield 63%).
含可聚合官能基與親水基之十字型矽氧烷高分子的氫核磁共振光譜結果如下:1H NMR(CDCl3,400MHz):δ6.1(s,4H),5.54(s,4H),4.10(t,8H),3.40-3.90(m,288H),1.94(s,12H),1.55-1.85(m,72H),0.47-0.60(m,72H),0.04-0.20(m,Si-CH3),其中3.40-3.90(m,288H)該數值代表高分子中親水性結構的形成。 The results of hydrogen nuclear magnetic resonance spectroscopy of a polymer of a cross-type alkane having a polymerizable functional group and a hydrophilic group are as follows: 1 H NMR (CDCl 3 , 400 MHz): δ 6.1 (s, 4H), 5.54 (s, 4H), 4.10(t,8H), 3.40-3.90(m,288H), 1.94(s,12H),1.55-1.85(m,72H),0.47-0.60(m,72H),0.04-0.20(m,Si-CH3 ), wherein 3.40 - 3.90 (m, 288H) represents the formation of a hydrophilic structure in the polymer.
分別以本案合成之含可聚合官能基與親水基之十字型矽氧烷高分子(n=8,m=50)、直鏈型矽氧烷(n=32,m=200)及美國專利公告號US4463149揭露之小分子十字型的矽氧烷製作矽水膠鏡片,其配方如下表所示:
TRIS:三-[三(三甲基矽氧基)]甲基丙烯酸丙酯矽烷(3-[Tris(trimethylsiloxy)silyl]propyl methacrylate) TRIS: 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate)
NVP:N-乙烯基吡咯烷酮(N-Vinyl-2-pyrrolidone) NVP: N-Vinyl-2-pyrrolidone
HEMA:甲基丙烯酸-2-羥基乙酯(Hydroxyethyl Methacrylate) HEMA: 2-hydroxyethyl methacrylate (Hydroxyethyl Methacrylate)
分別測試上述三種以不同矽單體配方製成之矽水膠鏡片其透氧率及含水率,測試結果如下表所示:
由上表可知,於n及m值相同的情況下,含本案合成之十字型矽氧烷高分子之矽水膠鏡片其透氧率高於含直鏈型矽氧烷之矽水膠鏡片。而含小分子十字型矽氧烷之矽水膠鏡片,由 於其為一小分子聚合物,且其中較為親水的結構是(O=C-O),故其透氧性及含水率較前述二者為低。 It can be seen from the above table that, in the case where the values of n and m are the same, the water-permeable gel lens containing the cross-type alkane polymer synthesized in the present invention has higher oxygen permeability than the hydrophobic gel lens containing linear type alkane. And a hydrophobic gel lens containing a small molecule cross-type azide It is a small molecule polymer, and the relatively hydrophilic structure is (O=C-O), so its oxygen permeability and water content are lower than the foregoing two.
此外,以本案方法合成之含可聚合官能基與親水基之十字型矽氧烷高分子除可用作矽水膠鏡片外,亦可用於製作矽水膠基材,而可應用於其他包含矽水膠材料的醫療或保健產品上。 In addition, the cross-type azide polymer containing a polymerizable functional group and a hydrophilic group synthesized by the method of the present invention can be used for making a hydrophobic rubber substrate, and can be applied to other materials including hydrazine. Water-based materials for medical or health care products.
綜上所述,本案所提供之含可聚合官能基與親水基之十字型矽氧烷高分子其同時具有高透氧及高含水率的特性;故,本案實為一極具產業價值之作。 In summary, the cross-type azide polymer containing a polymerizable functional group and a hydrophilic group provided by the present invention has high oxygen permeability and high water content at the same time; therefore, the present case is an industrial value. .
本案得由熟悉本技藝之人士任施匠思而為諸般修飾,然皆不脫如附申請專利範圍所欲保護。 This case has been modified by people who are familiar with the art, and is not intended to be protected as intended.
S11~S14‧‧‧步驟 S11~S14‧‧‧Steps
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