阅读说明：本技术 一种有机硅树脂塑料光纤包覆层材料及使用该包覆材料的塑料光纤的制法 (Organic silicon resin plastic optical fiber cladding material and method for manufacturing plastic optical fiber using same ) 是由 曹春雷 张倩 侯依依 许源洋 于 2018-06-13 设计创作，主要内容包括：本发明的一种有机硅树脂塑料光纤包覆层材料及使用该包覆材料的塑料光纤的制法。光纤包覆材料的原料价格低廉；与纤芯结合性好,对塑料光纤纤芯包覆完整；折光指数可调；耐候性好：在-30℃条件下依然具有较好的柔韧性,在高温108-205℃条件下具有较好的电绝缘性,击穿电压可达60-80kV/mm,耐化学腐蚀性较强；包覆过程简单且易于操作。使用该包覆材料的塑料光纤的制法仅使用单螺杆挤出机将塑料光纤的纤芯挤出后再通过拉伸机将其拉伸,通过包覆层涂覆装置将涂覆材料均匀涂覆到纤芯表面,在50-70℃下包覆材料在纤芯表面形成交联的塑料光纤包覆层；加工温度低,节省能源；卷绕塑料光纤速度快,纤芯和包覆层结合性好；塑料光纤的光损耗低,最低可达165dB/km；的塑料光纤折光指数可调。(The invention relates to a coating material of organic silicon resin plastic optical fiber and a method for preparing plastic optical fiber by using the coating material. The raw material price of the optical fiber coating material is low; the bonding property with the fiber core is good, and the plastic optical fiber core is completely coated; the refractive index is adjustable; the weather resistance is good: the material still has good flexibility at the temperature of minus 30 ℃, good electrical insulation at the temperature of 108-205 ℃, breakdown voltage of 60-80kV/mm and strong chemical corrosion resistance; the coating process is simple and easy to operate. The preparation method of the plastic optical fiber using the coating material only uses a single screw extruder to extrude the fiber core of the plastic optical fiber and then stretches the fiber core through a stretcher, the coating material is uniformly coated on the surface of the fiber core through a coating device of the coating layer, and the coating material forms a cross-linked plastic optical fiber coating layer on the surface of the fiber core at 50-70 ℃; the processing temperature is low, and energy is saved; the plastic optical fiber is wound quickly, and the fiber core and the cladding layer have good associativity; the optical loss of the plastic optical fiber is low and can reach 165dB/km at least; the refractive index of the plastic optical fiber is adjustable.)

1. An organic silicon resin plastic optical fiber coating layer material is characterized by comprising the following raw materials in parts by weight: 20-60 parts of vinyl silicone oil and 80-40 parts of modified hydrogen-containing silicone oil.

2. An organic silicon resin plastic optical fiber coating layer material is characterized by comprising the following raw materials in parts by weight: 20 parts of vinyl silicone oil and 80 parts of modified hydrogen-containing silicone oil.

3. An organic silicon resin plastic optical fiber coating layer material is characterized by comprising the following raw materials in parts by weight: 45 parts of vinyl silicone oil and 40 parts of modified hydrogen-containing silicone oil.

4. An organic silicon resin plastic optical fiber coating layer material is characterized by comprising the following raw materials in parts by weight: 60 parts of vinyl silicone oil and 45 parts of modified hydrogen-containing silicone oil.

5. An organic silicon resin plastic optical fiber coating layer material is characterized by comprising the following raw materials in parts by weight: 30 parts of vinyl silicone oil and 80 parts of modified hydrogen-containing silicone oil.

6. An organic silicon resin plastic optical fiber coating layer material is characterized by comprising the following raw materials in parts by weight: 30 parts of vinyl silicone oil and 80 parts of modified hydrogen-containing silicone oil.

7. An organic silicon resin plastic optical fiber coating layer material is characterized by comprising the following raw materials in parts by weight: 60 parts of vinyl silicone oil and 50 parts of modified hydrogen-containing silicone oil.

8. A preparation method of an organic silicon resin plastic optical fiber coating layer material is characterized by comprising the following steps and conditions:

(a) preparation of modified hydrogen-containing silicone oil

The modified hydrogen-containing silicone oil comprises the following raw materials in parts by weight: 5-20 parts of modified monomer, 95-80 parts of hydrogen-containing silicone oil and 0.001-0.1 part of platinum catalyst (OK-PT-10); the modified monomer is PMMA or PS;

the preparation steps and conditions were as follows: adding the modified monomer, the hydrogen-containing silicone oil and a platinum catalyst (OK-PT-10) into a reaction kettle, uniformly mixing, removing air, reacting at 160 ℃ for 20-60min, removing unreacted monomer after hydrosilylation, and cooling to room temperature to obtain modified hydrogen-containing silicone oil;

(b) the preparation of the organic silicon resin plastic optical fiber cladding layer material comprises the following steps:

the organic silicon resin plastic optical fiber cladding layer material comprises the following raw materials in parts by weight: 20-60 parts of vinyl silicone oil, 80-40 parts of modified hydrogen-containing silicone oil and 0.001-0.1 part of catalyst; the catalyst is a platinum catalyst (OK-PT-10);

the preparation steps and conditions were as follows: uniformly mixing vinyl silicone oil, modified hydrogen-containing silicone oil and a platinum catalyst (OK-PT-10) at a temperature of between 20 and 30 ℃ according to a ratio to obtain the coating liquid material of the plastic optical fiber coating layer.

9. The method for preparing the coating material of the silicone resin plastic optical fiber according to claim 8, characterized in that the steps and conditions are as follows:

(a) preparation of modified hydrogen-containing silicone oil

Adding 20 parts by weight of PMMA (polymethyl methacrylate), 85 parts by weight of hydrogen-containing silicone oil and 0.001 part by weight of platinum catalyst (OK-PT-10) into a reaction kettle, uniformly mixing, removing air, carrying out hydrosilylation reaction, reacting at 130 ℃ for 60min, removing unreacted modified monomer, and cooling to room temperature to obtain modified hydrogen-containing silicone oil;

(b) preparation of organic silicon resin plastic optical fiber cladding layer material

The organic silicon resin plastic optical fiber cladding layer material comprises the following raw materials in parts by weight: 20 parts of vinyl silicone oil, 80 parts of modified hydrogen-containing silicone oil and 0.008 part of platinum catalyst (OK-PT-10);

the preparation steps and conditions were as follows: uniformly mixing vinyl silicone oil, modified hydrogen-containing silicone oil and a platinum catalyst (OK-PT-10) according to the proportion at the temperature of 20 ℃ to obtain the coating liquid material of the plastic optical fiber coating layer.

10. The method for preparing the coating material of the silicone resin plastic optical fiber according to claim 8, characterized in that the steps and conditions are as follows:

(a) adding 5 parts by weight of PMMA, 80 parts by weight of hydrogen-containing silicone oil and 0.005 part by weight of platinum catalyst (OK-PT-10) into a reaction kettle, uniformly mixing, removing air, carrying out hydrosilylation reaction, reacting at 120 ℃ for 20min, removing unreacted modified monomer, and cooling to room temperature to obtain modified hydrogen-containing silicone oil;

(b) the coating layer material comprises the following raw materials in parts by weight: 45 parts of vinyl silicone oil, 40 parts of modified hydrogen-containing silicone oil and 0.001 part of platinum catalyst (OK-PT-10).

The preparation steps and conditions were as follows: uniformly mixing vinyl silicone oil, modified hydrogen-containing silicone oil and a platinum catalyst (OK-PT-10) according to the proportion at the temperature of 22 ℃ to obtain the coating liquid material of the plastic optical fiber coating layer.

11. The method for preparing the coating material of the silicone resin plastic optical fiber according to claim 8, characterized in that the steps and conditions are as follows:

(a) adding 15 parts by weight of modified monomer PMMA, 95 parts by weight of hydrogen-containing silicone oil and 0.1 part by weight of platinum catalyst (OK-PT-10) into a reaction kettle, uniformly mixing, removing air, carrying out hydrosilylation reaction, reacting for 50min at 160 ℃, removing unreacted modified monomer, and cooling to room temperature to obtain modified hydrogen-containing silicone oil;

(b) the coating layer material comprises the following raw materials in parts by weight: 60 parts of vinyl silicone oil, 45 parts of modified hydrogen-containing silicone oil and 0.1 part of platinum catalyst (OK-PT-10);

the preparation steps and conditions were as follows: uniformly mixing vinyl silicone oil, modified hydrogen-containing silicone oil and a platinum catalyst (OK-PT-10) according to the proportion at 25 ℃ to obtain the coating liquid material of the plastic optical fiber coating layer.

12. The method for preparing the coating material of the silicone resin plastic optical fiber according to claim 8, characterized in that the steps and conditions are as follows:

(a) adding 10 parts by weight of modified monomer PS, 80 parts by weight of hydrogen-containing silicone oil and 0.007 part by weight of platinum catalyst (OK-PT-10) into a reaction kettle, uniformly mixing, removing air, carrying out hydrosilylation reaction, reacting at 150 ℃ for 40min, removing unreacted modified monomer, and cooling to room temperature to obtain modified hydrogen-containing silicone oil;

(b) the coating layer material comprises the following raw materials in parts by weight: 30 parts of vinyl silicone oil, 80 parts of modified hydrogen-containing silicone oil and 0.1 part of platinum catalyst (OK-PT-10);

the preparation steps and conditions were as follows: uniformly mixing vinyl silicone oil, modified hydrogen-containing silicone oil and a platinum catalyst (OK-PT-10) according to the proportion at the temperature of 27 ℃ to obtain the coating liquid material of the plastic optical fiber coating layer.

13. The method for preparing the coating material of the silicone resin plastic optical fiber according to claim 8, characterized in that the steps and conditions are as follows:

(a) adding 20 parts by weight of modified monomer PS, 90 parts by weight of hydrogen-containing silicone oil and 0.003 part by weight of platinum catalyst (OK-PT-10) into a reaction kettle, uniformly mixing, removing air, carrying out hydrosilylation reaction, reacting at 160 ℃ for 20min, removing unreacted monomer, and cooling to room temperature to obtain modified hydrogen-containing silicone oil;

(b) the coating layer material comprises the following raw materials in parts by weight: 60 parts of vinyl silicone oil, 50 parts of modified hydrogen-containing silicone oil and 0.001 part of platinum catalyst (OK-PT-10);

the preparation steps and conditions were as follows: uniformly mixing vinyl silicone oil, modified hydrogen-containing silicone oil and a platinum catalyst (OK-PT-10) at 29 ℃ according to the proportion to obtain the coating liquid material of the plastic optical fiber coating layer.

14. The method for preparing the coating material of the silicone resin plastic optical fiber according to claim 8, characterized in that the steps and conditions are as follows:

(a) adding 15 parts by weight of modified monomer PS, 90 parts by weight of hydrogen-containing silicone oil and 0.004 part by weight of platinum catalyst (OK-PT-10) into a reaction kettle, uniformly mixing, removing air, carrying out hydrosilylation reaction, reacting at 140 ℃ for 40min, removing unreacted monomer, and cooling to room temperature to obtain modified hydrogen-containing silicone oil;

(b) the coating layer material comprises the following raw materials in parts by weight: 50 parts of vinyl silicone oil, 55 parts of modified hydrogen-containing silicone oil and 0.005 part of platinum catalyst (OK-PT-10);

the preparation steps and conditions were as follows: uniformly mixing vinyl silicone oil, modified hydrogen-containing silicone oil and a platinum catalyst (OK-PT-10) according to the proportion at 30 ℃ to obtain the coating liquid material of the plastic optical fiber coating layer.

15. A method for producing a plastic optical fiber using the silicone resin plastic clad material of claim 1, the steps and conditions being as follows:

extruding PMMA or PS at the temperature of 170-220 ℃ by using a single-screw extruder, stretching the PMMA or PS into a fiber core with the diameter of 980mm by using a stretching machine, uniformly coating a coating material on the surface of the fiber core by using a coating layer coating device, forming a cross-linked plastic optical fiber coating layer on the surface of the fiber core by using the coated coating material at the temperature of 50-70 ℃ to obtain a plastic optical fiber coated by the organic silicon resin coating layer material, and winding the plastic optical fiber by using a winding cylinder for standby.

Technical Field

The invention relates to the technical field of plastic optical fiber materials, in particular to an organic silicon resin plastic optical fiber cladding material and a method for manufacturing a plastic optical fiber by using the cladding material.

Background

Plastic Optical Fiber (POF), also known as polymer optical fiber, is a light-transmitting medium prepared using a polymer material as a medium. Compared with quartz optical fiber, plastic optical fiber has the advantages of large bending radius, strong light guiding capability, large communication capacity, strong anti-interference capability, low cost, easy processing, easy installation and maintenance and the like, and is widely applied to the fields of network transmission, industrial control systems, automobile multimedia, electronic products, illumination, solar energy and the like.

The plastic optical fiber is composed of a fiber core and a cladding, wherein a high-refractive-index transparent polymer such as PS (PS) or poly PMMA (PMMA) is used as a fiber core material, a low-refractive-index fluororesin is used as a cladding material, the process is complex, a polymerization kettle is decompressed to remove residual unreacted monomers and other volatile components in the PMMA after polymerization reaction is finished, proper spinning temperature is controlled, the PMMA and the low-refractive-index fluororesin are simultaneously pressurized and fed into a co-extrusion spinning assembly and wound to obtain the plastic optical fiber with a sheath-core structure, the low-refractive-index fluororesin material is high in price and about 200 ~ 300 yuan/kg, the cladding and the fiber core are generally combined, the glass transition temperature of the cladding and the fiber core is slightly different, approximate melting temperature does not exist at a certain processing temperature, the glass transition temperature of the low-index fluororesin is 140 ℃, the glass transition temperature of the PMMA is only 105 ℃, the refractive index of the fiber core is only adjustable according to requirements, the refractive index of the cladding modified monomer material and the fiber core is fixed after the type and the refractive index is determined, the light difference value of the cladding modified material and the fiber core is fixed, the light loss can only meet the requirements of a normal weather-resistant plastic optical fiber under the conditions that the full emission of a certain total emission temperature occurring at a low-fiber core interface, the highest temperature, the highest light emission temperature can not change, the normal weather-neutral fluororesin, the normal weather-resistant optical fiber can only meet the weather-resistant environment, the weather-neutral fluororesin, the weather-;^【1】

the plastic optical fiber is mainly prepared by two processes of prefabricated rod and coextrusion. The preform process is early developed, the process is simple and easy to operate, but the optical loss of the product per unit length is large, and more importantly, the process has low productivity and is not suitable for large-scale industrial production and mainly used for laboratory research.

The co-extrusion process is developed on the basis of the prefabricated rod process, overcomes the defects of the prefabricated rod process, has the advantages of continuous process, high productivity and suitability for large-scale continuous generation, and has the defects that (1) the high extrusion temperature easily causes the degradation of polymers of a coating layer and a fiber core in the processing process, the bonding property of the materials of the coating layer and the fiber core is poor, and the performance is reduced because impurities and bubbles are easily peeled, for example, a plunger extruder is used for carrying out continuous polymerization ~ spinning operation on PMMA as the material of the fiber core to produce the plastic optical fiber^【2】The process is complicated: in order to prevent the process problems that the roundness and the surface smoothness of core fibers are damaged by a coating layer when a sheath-core material is extruded on a spinneret plate simultaneously, the process relates to a plurality of devices such as a co-extrusion spinneret assembly and the like; (2) the processing temperature is higher, and the lowest spinnable temperature also reaches 190 ℃; and (3) pressurizing and feeding the PMMA and fluororesin coating material into a co-extrusion spinning pack at the same time, and winding to obtain the plastic optical fiber. The winding speed is proportional to the winding voltage. If the plastic optical fiber is wound at a high speed, the winding voltage is high, the stretching ratio of the fiber is increased, the stretching point is not fixed, the up-and-down fluctuation is not beneficial to the extrusion of the plastic optical fiber, when the rope winding voltage only reaches 30V, the diameter fluctuation of the obtained fiber reaches 5.6 percent, and the diameter fluctuation is obvious; (3) the low-refractive-index fluororesin coating layer and the PMMA core have general associativity, the difference of the glass transition temperatures of the low-refractive-index fluororesin coating layer and the PMMA core is large, the glass transition temperature of the low-refractive-index fluororesin is 140 ℃, and the glass transition temperature of the PMMA core is only 105 ℃; the optical loss is high, and the optical loss can reach 192 dB/km under the optimal condition; the method can not be used for producing optical fibers of different models, after the fiber core and the cladding are determined, the difference value of the refractive indexes of the fiber core and the cladding is fixed, and the total emission of the light at the core-sheath interface of the fiber is fixed and cannot be changed. The above factors make it difficult for plastic optical fibers prepared by the co-extrusion method to satisfy the increasing market demand. The product has single type, limited application range and seriousThe application field of the plastic optical fiber is limited, and the development of the plastic optical fiber industry and related industries is limited.

Reference documents: (1) fluororesin coating, a Chinese novel coating net. (2) The method is used for developing a PMMA core/fluororesin clad plastic optical fiber. The plastics industry.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a coating material of a silicone resin plastic optical fiber and a method for manufacturing the plastic optical fiber by using the coating material.

The invention provides an organic silicon resin plastic optical fiber coating layer material which comprises the following raw materials in parts by weight: 20-60 parts of vinyl silicone oil and 80-40 parts of modified hydrogen-containing silicone oil;

the invention provides a preparation method of a coating material of an organic silicon resin plastic optical fiber, which comprises the following steps and conditions:

(a) preparation of modified hydrogen-containing silicone oil

The modified hydrogen-containing silicone oil comprises the following raw materials in parts by weight: 5-20 parts of modified monomer, 95-80 parts of hydrogen-containing silicone oil and 0.001-0.1 part of platinum catalyst (OK-PT-10); the modified monomer is PMMA or PS;

the preparation steps and conditions were as follows: adding the modified monomer, the hydrogen-containing silicone oil and the platinum catalyst (OK-PT-10) into a reaction kettle, uniformly mixing, removing air, reacting at 160 ℃ for 20-60min, removing unreacted monomer after hydrosilylation, and cooling to room temperature to obtain the modified hydrogen-containing silicone oil.

(b) Preparation of organic silicon resin plastic optical fiber cladding layer material

The organic silicon resin plastic optical fiber cladding layer material comprises the following raw materials in parts by weight: 20-60 parts of vinyl silicone oil, 80-40 parts of modified hydrogen-containing silicone oil and 0.001-0.1 part of catalyst; the catalyst is a platinum catalyst (OK-PT-10);

the preparation steps and conditions were as follows: uniformly mixing vinyl silicone oil, modified hydrogen-containing silicone oil and a platinum catalyst (OK-PT-10) according to the proportion at the temperature of 20-30 ℃ to obtain the coating liquid material of the plastic optical fiber coating layer.

(III) the preparation method of the plastic optical fiber using the organic silicon resin plastic cladding layer material provided by the invention comprises the following steps and conditions:

extruding PMMA or PS at the temperature of 170-220 ℃ by using a single screw extruder, stretching the PMMA or PS into a fiber core with the diameter of 980mm by using a stretching machine, uniformly coating a coating material on the surface of the fiber core by using a coating layer coating device, forming a crosslinked plastic optical fiber coating layer on the surface of the fiber core by using the coated coating material at the temperature of 50-70 ℃ to obtain the plastic optical fiber using the organic silicon resin coating layer material, and winding the plastic optical fiber by using a winding cylinder for standby.

Has the advantages that: the plastic optical fiber coating material provided by the invention and the existing fluororesin coating material have the following advantages: (1) the price of the raw materials is low, and the prices of the vinyl silicone oil and the hydrogen-containing silicone oil of the plastic optical fiber coating material are both about 50 yuan/kg. And the fluororesin coating material is about 245 yuan/kg. The former price is about 20% of the latter price.

(2) The plastic optical fiber coating material provided by the invention has good binding property with the fiber core, the coating material is in a liquid state during coating, the viscosity is 200 +/-30 mPa.s, the fluidity is good, and the plastic optical fiber core is completely coated.

(3) The refractive index of the plastic optical fiber coating material provided by the invention is adjustable, and the refractive index can be adjusted by adding different types of modified monomers with different contents. When the core material is PMMA, 5-20 parts by weight of PMMA is added as a modified monomer, and the adjustable range of the refractive index is 1.4125-1.4312; when the core material is PS, 5-20 parts by weight of PS is added as a modifying monomer, and the adjustable range of the refractive index is 1.5401-1.5636.

(4) The plastic optical fiber coating material provided by the invention has good weather resistance: the coating material still has good flexibility at the temperature of minus 30 ℃, good electrical insulation at the temperature of 108-205 ℃, breakdown voltage of 60-80kV/mm and strong chemical corrosion resistance, and the coating material is not changed when being soaked in alkali liquor with the mass concentration of 3% for 100 hours or saline water with the mass concentration of 5% for 70 hours at the temperature of 100 ℃; the high temperature resistance is good, and the organic silicon resin plastic optical fiber coating material can resist the high temperature of 108 ℃ and 205 ℃. The highest temperature resistance is improved by 37 percent compared with the fluororesin coating material.

(5) The light transmission loss ranges from 165-170 dB/km, and is 16.4% lower than the optimal light loss of 192 dB/km of the plastic optical fiber prepared by the fluororesin cladding material.

(6) The plastic optical fiber cladding material provided by the invention has a simple cladding process and is easy to operate.

Compared with the prior coextrusion process, the preparation method of the plastic optical fiber prepared by using the organic silicon resin plastic optical fiber coating layer material has the following advantages: 1) the process is simple, only one single screw extruder is used, the fiber core of the plastic optical fiber is extruded and then stretched by a stretcher, the coating material is uniformly coated on the surface of the fiber core by a coating layer coating device, hydrosilylation reaction is carried out at 50-70 ℃, so that the coated coating material forms a crosslinked plastic optical fiber coating layer on the surface of the fiber core, and the crosslinked plastic optical fiber coating layer is wound by a winding drum for standby.

2) The processing temperature is low, the fiber core of the plastic optical fiber is extruded at the temperature of 170-220 ℃, and the hydrosilylation reaction is carried out at the temperature of 50-70 ℃, so that the energy is saved.

3) The plastic optical fiber is wound at a high speed: and after the fiber core is extruded, the fiber core is stretched to the fiber core with the diameter of 980mm through a stretcher, and then the coating material is uniformly coated on the surface of the fiber core through a coating device of the coating layer and then is wound and collected by a winding drum. The extrusion speed and the drawing speed are equal to ensure that the fiber core can be smoothly extruded; the winding speed is proportional to the extrusion speed and is determined by the cord voltage. The coiling voltage can reach 35V, and compared with the prior plastic optical fiber with fluororesin as a coating layer, the diameter of the plastic optical fiber is fluctuated when the plastic optical fiber is 30V, and the performance is obviously improved; the coating material is in a liquid state, the viscosity is 200 +/-30 mPa & s, the fluidity is good, the fiber core is completely coated, air bubbles between the fiber core and the coating layer are obviously reduced, and the binding property is good.

4) The plastic optical fiber prepared by using the organic silicon resin plastic optical fiber coating layer material has low optical loss which can reach 165dB/km at least. The optical loss of the plastic optical fiber prepared by the fluororesin cladding material is 192 dB/km, which is 16.4 percent lower.

5) The plastic optical fiber prepared by the organic silicon resin plastic optical fiber coating material can produce plastic optical fibers with adjustable refractive index under different use conditions by changing the types and the contents of different modified monomers in the organic silicon resin plastic optical fiber coating material. When the core material is PMMA, 5-20 parts by weight of PMMA is added as a modified monomer, and the adjustable range of the refractive index is 1.4125-1.4312; when the core material is PS, 5-20 parts by weight of PS is added as a modifying monomer, and the adjustable range of the refractive index is 1.5401-1.5636.

Detailed Description