CN87101695A - 具有芯——套层结构的光学波导 - Google Patents
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Abstract
本文介绍了一种塑料光学波导，它通常由芯和套层组成。芯材料的折光指数比套层材料的折光指数高。适宜的芯材料为不含氟的聚合物，而适宜的套层材料为含氟聚合物(可含氘原子)。用使聚合物线材通过套层聚合物溶液，然后除掉溶剂的方法可制得该光学波导。该光学波导尤其适用于传递信息(借助于波长为500至750毫微米的光波)。
Description
本发明涉及具有芯-套层结构的光学波导。该波导的芯由透明的、不含氟的聚合物组成，其套层由透明的含氟聚合物组成。其相对折光指数差
(n芯－n套层)/(n芯)
为至少0.2%。本发明还涉及这种导管的制法及应用。
众所周知，由塑料制成的光导纤维具有一个由以聚甲基丙烯酸甲酯为基的不含氟的聚合物所构成的芯和一个由含氟的聚合物（例如由氟代醇与甲基丙烯酸生成的酯类的聚合物）构成的、包覆着芯的套层（见欧洲专利申请公开号第0，155，567号）。在此，套层聚合物的折光指数须比芯聚合物的折光指数低至少1%，而且芯聚合物和套层聚合物的玻璃化转变温度须高于80℃。可以用拉丝方法（Spinnprozeβ）制造该光导纤维（在该方法中用一种特殊的模具把芯聚合物和套层聚合物挤出）;也可以用涂敷方法制造该光导纤维（在该方法中用套层聚合物的溶液涂敷芯聚合物纤维，然后除去溶剂）。
本发明的目的是提供一种有芯-套层结构的光学波导，其中芯和套层由不同的聚合物所构成，而且芯与套层之间的附着力却不因此而减弱。
本发明涉及具有芯-套层结构的光学波导，其芯由透明的、不含氟的聚合物构成，其套层由透明的含氟聚合物构成，其相对折光指数差
(n芯－n套层)/(n芯)
为至少0.2%，其中芯聚合物基本上是甲基丙烯酸甲酯的聚合物或聚碳酸酯，而套层聚合物基本上是含有由式（1）的化合物衍生出的单体单元的聚合物
（1）H2C＝CF-CO-O-C（CF3）2-X
式中X代表氢或氘原子。
本发明还涉及具有芯-套层结构的光学波导的制造方法。该光学波导的芯由透明的、不含氟的聚合物构成，而其套层由透明的含氟聚合物构成，其相对折光指数差
(n芯－n套层)/(n芯)
为至少0.2%。该方法是一种用一层套层聚合物包覆线状芯聚合物的方法，它包括牵引一种基本上由甲基丙烯酸甲酯的聚合物或聚碳酸酯构成的线材，使其通过一种聚合物的溶液，该聚合物含有由式（1）的化合物衍生的单体单元，
（1）H2C＝CF-CO-O-C（CF3）2-X
式中X代表氢或氘原子，所用溶剂为基本不溶解芯聚合物的无水有机溶剂，然后除去溶剂。
芯聚合物基本上是甲基丙烯甲酯的聚合物，也就是说，是一种甲基丙烯酸甲酯的均聚物，或是甲基丙烯甲酯与另一种乙烯基单体（如1，1-二氟乙烯）的共聚物，或是聚碳酸酯，且以由碳酸和二羟基二苯基-2，2-丙烷所形成的聚酯为宜。芯聚合物的平均分子量（用光散射法测定）为8×104至25×104，且以1×105至2×105为宜;其玻璃化转变温度为100至170℃，且以110至150℃为宜;其折光指数（n23 D）为1.4至1.6，且以1.44至1.59为宜。芯聚合物也可以是甲基丙烯酸甲酯的聚合物与聚碳酸酯的混合物。
套层聚合物基本上是含由式（1）的化合物
（1）H2C＝CF-CO-O-C（CF3）2-X
衍生的单体单元的聚合物（式中X代表氢或氘原子）。可用的单体有α-氟代丙烯酸六氟异丙酯和α-氟代丙烯酸含氘六氟异丙酯。套层聚合物的平均分子量（光散射法测定）为8000至5，000，000，且以10，000至200，000为宜;其玻璃化转变温度为95至150℃，且以100至145℃为宜;其折光指数（n23 D）为1.34至1.46，且以1.348至1.400为宜。套层聚合物也可以是一种聚合物混合物。
通常在温度为60至150℃、在有游离基引发剂存在的条件下，通过使α-氟代丙烯酸六氟异丙酯或α-氟代丙烯酸含氘六氟异丙酯单体聚合（最好是本体聚合），可制得套层聚合物。
这些单体可按下述方法制备：
a）将150克（1摩尔）α-氟代丙二酸二甲酯〔见《氟化学杂志》（Journal of Fluorine Chemistry）第25卷（1984），第203至212页〕在1小时之内滴入到由96克浓度为35%（重量）的甲醛水溶液（1.1摩尔）和10克（0.1摩尔）碳酸氢钾组成的混合物中，温度为25℃。然后将反应溶液与4倍体积的氯化铵饱和水溶液相混合，再将此混合物用二氯甲烷萃取三次，每次用150毫升二氯甲烷。把各次萃取液混在一起，用硫酸钠干燥。将二氯甲烷蒸发掉之后，得到无色固态的α-羟甲基-α-氟代丙二酸二甲酯。
将180克（1摩尔）α-羟甲基-α-氟代丙二酸二甲酯在1.5升6N盐酸中、加热沸腾2.5小时，脱水脱羧。停止产生气体之后，将反应混合物在压力为700毫巴的条件下蒸馏，并用***萃取馏出液三次，每次用150毫升***。将混在一起的各次萃取液用硫酸钠干燥。在向该***溶液中通入19克（1.1摩尔）氨气之后，得到无色固态的α-氟代丙烯酸的铵盐。
将107克（1摩尔）该α-氟代丙烯酸的铵盐与14.5克（0.2摩尔）二甲基甲酰胺和0.6升二甲苯相混合，并在1小时之内向该混合物中滴加131克（1.1摩尔）亚硫酰氯。将该混合物在温度为80℃的条件下加温两个小时。在冷却至温度为0℃之后，在30分钟之内向该反应混合物中加入由204克（1.1摩尔）三丁胺和185克（1.1克）六氟异丙醇所组成的混合物。将此混合物在温度为30℃的条件下再搅拌1小时，最后过滤。将滤液在压力为270毫巴的条件下蒸馏，得到无色液态的α-氟代丙烯酸六氟异丙酯。
b）如果在第三步中用二氘代六氟异丙醇代替六氟异丙醇，那么按与a）相似的操作方法可制得α-氟代丙烯酸含氘六氟异丙酯。
本发明的光学波导是通过把一根芯聚合物包覆在一层套层聚合物中的方法制得的。为此，将芯聚合物线材拉过一种套层聚合物的溶液（该溶液中所用溶剂为一种基本上不溶解芯聚合物的无水有机溶剂），然后，除掉溶剂。
所用的基本不溶解芯聚合物的溶剂（这就是说，根本不溶解或仅少量溶解）具体地讲是低级醇（以甲醇为宜）、低级酮（以丙酮为宜）、或者是低级醇的醋酸酯（以醋酸乙酯为宜）。如果合适的话，所用溶剂可以是几种上述溶剂的混合物。套层聚合物在溶液中的浓度为2%至15%（重量）。且以6%至10%（重量）为宜。
芯聚合物线材的直径为0.1至2毫米，且以0.5至1毫米为宜。为了用套层聚合物将其包覆，使其通过盛于一个容器中的套层聚合物的溶液。在该容器的底部有一个截面为圆形的毛细管通道，其直径比所用的特定的线材的直径大10%至40%。从毛细管通道出来之后，应立即驱除掉附着在已包覆了的线材上的溶剂。举例来说，这可以通过在温度为30℃至120℃（以50℃至100℃为宜）、压力为200至1000毫巴（以800至1000毫巴为宜）的条件下进行蒸发来实现。由此得到的套层的厚度为0.003至0.05毫米，且以0.005至0.02毫米为宜。
本发明的光学波导适用于传递信息（借助于波长为500至750毫微米的光波，尤其是600至670毫微米的光波）。其衰减为不大于每千米1500分贝（A）〔dB（A）/Km〕，一般不大于1000dB（A）/Km。
下面的例子进一步说明了本发明。其中的百分率数据都以重量计。
实施例
将浓度为10%的聚α-氟代丙烯酸六氟异丙酯的无水乙醇溶液加入到一个容器中。所用的聚α-氟代丙烯酸六氟异丙酯的平均分子量为150，000（用光散射法测定），其玻璃化转变温度为109℃，其折光指数n23 D为1.355。所用的容器的底部有一个毛细管通道。该通道的截面为圆形，直径为1毫米。牵拉一根平均分子量为180，000（光散射法测定）、玻璃化转变温度为107℃、折光指数n23 D为1.49的聚甲基丙烯酸甲酯线材，使其通过该溶液，并通过毛细管通道。线材的直径为0.8毫米。使涂敷好的线材在从毛细管通道出来之后立即通过一个恒温在70℃的空气浴（该空气浴借助于两个辐射式加热器恒温）。这样，便蒸发掉了甲醇，并得到了牢固地附在芯线上的、厚度为0.02毫米的一层聚α-氟代丙烯酸六氟异丙酯。所得到的具有芯-套层结构的光学波导在作为信息的传递介质时（借助于波长为670毫微米的光波），其衰减为800dB（A）/Km。
Claims (5)
1、一种具有芯-套层结构的光学波导，其芯由透明的、不含氟的聚合物构成，其套层由透明的含氟聚合物构成，其相对折光指数差
(n芯－n套层)/(n芯)
为至少0.2%，其中芯聚合物基本上是甲基丙烯酸甲酯的聚合物或聚碳酸酯，套层聚合物基本上是含由式(1)的化合物衍生的单体单元的聚合物(1)H2C=CF-CO-O-C(CF3)2-X
式中X代表氢或氘原子。
2、一种具有芯-套层结构的光学波导的制造方法，该光学波导的芯由透明的、不含氟的聚合物构成，其套层由透明的含氟聚合物构成，其相对折光指数差
(n芯－n套层)/(n芯)
为至少0.2%，该方法是一种用一层套层聚合物包覆线状芯聚合物的方法，该方法包括：牵引基本上由甲基丙烯酸甲酯的聚合物或聚碳酸酯构成的线材，使其通过一种聚合物的溶液，该聚合物含有由式（1）的化合物衍生的单体单元
（1）CH2＝CF-CO-O-C（CF3）2-X
式中X代表氢或氘原子，聚合物溶液中所用溶剂为基本上不溶解芯聚合物的无水有机溶剂;然后除掉溶剂。
3、根据权利要求2的方法，其中用低级醇、低级酮或低级醇的醋酸酯作为溶剂。
4、根据权利要求2的方法，其中在温度为30至120℃的条件下，用蒸发的方法来除掉溶剂。
5、权利要求1所要求的光学波导的应用，借助于波长为500至750毫微米的光波传递信息。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3607301.6 | 1986-03-06 | ||
| DEP3607301 | 1986-03-06 | ||
| DE19863607301 DE3607301A1 (de) | 1986-03-06 | 1986-03-06 | Lichtleitfaser mit kern-mantel-struktur |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87101695A true CN87101695A (zh) | 1987-09-23 |
| CN1021137C CN1021137C (zh) | 1993-06-09 |
Family
ID=6295609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87101695A Expired - Fee Related CN1021137C (zh) | 1986-03-06 | 1987-03-05 | 具有芯-套层结构的光学波导 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4863236A (zh) |
| EP (1) | EP0236881B1 (zh) |
| JP (1) | JP2573203B2 (zh) |
| CN (1) | CN1021137C (zh) |
| AT (1) | ATE75427T1 (zh) |
| AU (1) | AU582954B2 (zh) |
| CA (1) | CA1290176C (zh) |
| DE (2) | DE3607301A1 (zh) |
| ES (1) | ES2031840T3 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347573C (zh) * | 1996-03-28 | 2007-11-07 | 三菱丽阳株式会社 | 分布的折光指数型光导纤维及其制作方法 |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5319131A (en) * | 1985-05-25 | 1994-06-07 | Hoechst Aktiengesellschaft | α-fluoroacrylic acid esters and polymers thereof |
| US5198925A (en) * | 1985-05-25 | 1993-03-30 | Hoechst Aktiengesellschaft | α-fluoroacrylic acid esters and polymers thereof |
| JPH0778564B2 (ja) * | 1988-03-09 | 1995-08-23 | 日立電線株式会社 | プラスチック光ファイバの製造方法 |
| EP0333083A3 (en) * | 1988-03-16 | 1990-05-30 | Daikin Industries, Limited | Water- and oil-repellent antifouling finishing agent |
| DE3912151A1 (de) * | 1989-04-13 | 1990-10-18 | Hoechst Ag | Transparente thermoplastische formmasse aus 2,3-difluoracrylsaeureestern |
| CA2026042C (en) * | 1989-09-27 | 1996-02-27 | Saburo Imamura | Plate plastics optical waveguide |
| US5187769A (en) * | 1991-02-26 | 1993-02-16 | Hoechst Aktiengesellschaft | Transparent thermoplastic molding composition, process for its preparation and its use |
| US5223593A (en) * | 1991-08-08 | 1993-06-29 | Minnesota Mining And Manufacturing Company | Fluorine containing plastic optical fiber cores |
| DE4310866A1 (de) * | 1993-04-02 | 1994-10-06 | Kernforschungsz Karlsruhe | Meßanordnung mit einer optischen Meßsonde |
| US6614977B2 (en) | 2001-07-12 | 2003-09-02 | Little Optics, Inc. | Use of deuterated gases for the vapor deposition of thin films for low-loss optical devices and waveguides |
| US7043133B2 (en) * | 2001-07-12 | 2006-05-09 | Little Optics, Inc. | Silicon-oxycarbide high index contrast, low-loss optical waveguides and integrated thermo-optic devices |
| JP2004341489A (ja) * | 2003-04-25 | 2004-12-02 | Fuji Photo Film Co Ltd | 保護層付き光学部材並びに製造方法及び製造装置 |
| WO2015108529A1 (en) * | 2014-01-17 | 2015-07-23 | Empire Technology Development Llc | Optical fibers without cladding |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE31868E (en) * | 1977-10-14 | 1985-04-16 | Mitsubishi Rayon Co., Ltd. | Low attenuation optical fiber of deuterated polymer |
| DE2909198A1 (de) * | 1979-03-08 | 1980-09-11 | Basf Ag | Phenylcarbamidsaeurechloride und verfahren zu ihrer herstellung |
| US4568146A (en) * | 1982-10-21 | 1986-02-04 | Sumitomo Electric Industries, Ltd. | Plastic optical fiber and production thereof |
| IT1153311B (it) * | 1982-10-27 | 1987-01-14 | Montedison Spa | Processo di fabbricazione di manufatti conduttori di luce |
| JPS59116702A (ja) * | 1982-12-24 | 1984-07-05 | Mitsubishi Rayon Co Ltd | 光伝送性繊維 |
| JPS59227908A (ja) * | 1983-06-10 | 1984-12-21 | Daikin Ind Ltd | 光学繊維プラスチック系さや材 |
| DE3485903T2 (de) * | 1983-06-10 | 1993-04-15 | Daikin Ind Ltd | Optisches material. |
| DE3470127D1 (en) * | 1983-11-02 | 1988-05-05 | Sumitomo Chemical Co | Optical fiber |
| CA1247415A (en) * | 1984-03-02 | 1988-12-28 | Isao Sasaki | Light-transmitting fiber |
| JPS60250310A (ja) * | 1984-05-28 | 1985-12-11 | Daikin Ind Ltd | 光学繊維鞘材 |
| JPS61190511A (ja) * | 1985-02-20 | 1986-08-25 | Central Glass Co Ltd | 含ふつ素重合体の製造法 |
| EP0243605B1 (en) * | 1986-02-27 | 1993-06-16 | Dainippon Ink And Chemicals, Inc. | Fluorine-containing resin composition having a low refractive index |
-
1986
- 1986-03-06 DE DE19863607301 patent/DE3607301A1/de not_active Withdrawn
-
1987
- 1987-02-27 EP EP87102847A patent/EP0236881B1/de not_active Expired - Lifetime
- 1987-02-27 ES ES198787102847T patent/ES2031840T3/es not_active Expired - Lifetime
- 1987-02-27 AT AT87102847T patent/ATE75427T1/de not_active IP Right Cessation
- 1987-02-27 DE DE8787102847T patent/DE3778571D1/de not_active Expired - Fee Related
- 1987-03-04 JP JP62047885A patent/JP2573203B2/ja not_active Expired - Lifetime
- 1987-03-04 US US07/021,469 patent/US4863236A/en not_active Expired - Lifetime
- 1987-03-05 CA CA000531281A patent/CA1290176C/en not_active Expired - Fee Related
- 1987-03-05 CN CN87101695A patent/CN1021137C/zh not_active Expired - Fee Related
- 1987-03-05 AU AU69759/87A patent/AU582954B2/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347573C (zh) * | 1996-03-28 | 2007-11-07 | 三菱丽阳株式会社 | 分布的折光指数型光导纤维及其制作方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE75427T1 (de) | 1992-05-15 |
| EP0236881A3 (en) | 1990-05-30 |
| DE3778571D1 (de) | 1992-06-04 |
| AU6975987A (en) | 1987-09-10 |
| US4863236A (en) | 1989-09-05 |
| DE3607301A1 (de) | 1987-09-10 |
| CA1290176C (en) | 1991-10-08 |
| JPS62254106A (ja) | 1987-11-05 |
| CN1021137C (zh) | 1993-06-09 |
| EP0236881B1 (de) | 1992-04-29 |
| AU582954B2 (en) | 1989-04-13 |
| EP0236881A2 (de) | 1987-09-16 |
| JP2573203B2 (ja) | 1997-01-22 |
| ES2031840T3 (es) | 1993-01-01 |
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