CN103952079A - Photo-cured fluorine-containing organosilicone optical fiber coating and preparation method thereof - Google Patents
Photo-cured fluorine-containing organosilicone optical fiber coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a photo-cured fluorine-containing organosilicone optical fiber coating and a preparation method thereof. The photo-cured fluorine-containing organosilicone optical fiber coating comprises the following active ingredients in parts by weight: 30-60 parts of polytrifluoropropylvinylmethylsiloxane and 5-30 parts of thiopropyl silicon oil, as well as photoinitiator the weight of which is 1-5wt% of the total weight of active ingredients. The preparation method of the coating comprises the following steps: preparing polytrifluoropropylvinylmethylsiloxane, thiopropyl silicon oil and the photoinitiator (the weight of which is 1-5wt% of the total weight of active ingredients) according to the formula, and evenly mixing to obtain the photo-cured fluorine-containing organosilicone optical fiber coating. Compared with the prior art, the photo-cured fluorine-containing organosilicone optical fiber coating has lower refractive index, and low additional losses, as well as higher mechanical strength.
Description
Technical field
The present invention relates to a kind of fibre coating material, be specifically related to a kind of photo-cured fluorine-containing organosilicon optical fiber coatings and preparation method thereof.
Background technology
Along with the develop rapidly of optical fiber communication technology, increasing as the optical fiber coatings consumption of fiber optic protection, performance is also had higher requirement.Existing fiber coating mainly be take acrylic acid or the like or acrylic resin as main, because resin viscosity is very large, need to add thinner to reduce dope viscosity, and for the ease of construction, the general acrylic ester monomer that adopts is as reactive thinner at present.But these monomer molecule amounts are little, have shrinkage phenomenon after film-forming, increased optical fiber coatings internal stress, cause optical fiber coatings to become fragile; In addition, no matter be acrylic acid or the like performed polymer or acrylic ester monomer, all contain certain toxicity and pungency, and volatile, the health that not only endangers operator, and contaminate environment.
It is high that organosilicon optical fiber coatings has the transparency, and good fluidity does not discharge small molecules when sulfuration, has good physical strength, and heat-resisting, cold-resistant, weather-proof, moistureproof, shockproof, nontoxic corrosion-free, is the ideal chose as optical fiber coatings.The refractive index of organosilicon polymer is 1.43 left and right, lower than quartzy refractive index 1.46, and the light (being the angle that is less than 17 ° with mandrel) that is incident upon quartzy core wall can be reflected back toward core and pass waveguide.Therefore, use it as after fibre coating, can reduce light and reveal from optical fiber, the unlikely generation of protection optical fiber causes microbend and the little kink phenomenon of fiber loss, has increased light path.
Ultraviolet-curing paint (UVCC) is a kind of energy saving and environment friendly coating of being developed by Germany the sixties in 20th century, and this coating, after being subject to UV-irradiation, photochemical reaction occurs, and makes coating rapid polymerization, crosslinked, thereby reaches solidifying of coating.The organosilicon optical fiber coatings of the employing ultraviolet light polymerization of having reported is a lot, as Xu Jun (Fudan University's academic dissertation, the study on the synthesis of UV-light fixed line optical fiber internal layer coating material, 2004) disclose a kind of by methyl vinyl MQ silicone resin, mercapto propyl group silicone oil, methyl vinyl silicon oil, through the containing hydrogen silicone oil of acrylic ester monomer modification and the optical fiber internal layer coating material of light trigger composition, the coating effect of this material is better, but its added losses are higher, 1550mn wavelength place light added losses 0.198dB/km wherein, 1310nm wavelength place light added losses are 0.337dB/km.And for example, Yang Yanan (Shanghai Communications University's academic dissertation, the applied research of high-performance UV-cured optical fiber buffer coating, 2003) a kind of buffer fiber coating of the ultraviolet light polymerization being comprised of methyl vinyl MQ silicone resin, mercapto propyl group silicone oil, thiazolinyl end-blocking methyl-silicone oil, stablizer and initiator is disclosed.But the specific refractory power of above method gained optical fiber coatings higher (be 1.43, be greater than 1.41), tensile strength lower (< 0.5MPa), elongation at break less (< 60%).In addition, publication number is the patent of invention of CN102031030A, a kind of low refractive index photocureable coating is disclosed, it is on the segment of methyl vinyl silicon oil, to introduce vinylformic acid fluorine monomer to obtain vinylformic acid silicon-fluorine polymer thing oligopolymer, mix with methyl vinyl silicon oil, mercapto propyl group silicone oil again, and add acrylate containing fluorine reactive thinner, stablizer and initiator and make.Described coating makes coating have lower specific refractory power (1.38～1.41) by introducing vinylformic acid fluorine monomer; higher Young's modulus (1.02～1.56MPa) and higher tensile strength (elasticity is 102～158%), be applicable to external protection in optical fiber.But, wherein raw materials used vinylformic acid silicon-fluorine polymer thing oligopolymer is to adopt low viscous methyl vinyl silicon oil and three kinds of above vinylformic acid fluorine monomers through heated polymerizable, to obtain under the effect of initiator, in this polyreaction because there is raw material self-polymerization and mutually polymerization, by product is many, cause its product composition, structure, molecular weight distribution to be difficult to control, too much small molecules amount vinylformic acid silicon-fluorine polymer thing more can cause the optical fiber coatings that obtains excessive because of cross-linking density, produces stress and reduces the resistance to low temperature of gained optical fiber coatings; In addition, this optical fiber coating composite has adopted vinylformic acid fluorine monomer as reactive thinner, although can play the effect that reduces optical fiber coatings viscosity and reduce specific refractory power, but, the vinylformic acid fluorine monomer of small molecules amount is after polymerization, can cause optical fiber coatings shrinking percentage high, have in addition environmental issue; Moreover although the hydrophobicity of product is improved because introducing fluorin radical, the low temperature resistant and uv-radiation of acrylate is poor, the variation of more difficult adaptation severe environment.
Summary of the invention
The technical problem to be solved in the present invention is to provide photo-cured fluorine-containing organosilicon optical fiber coatings that a kind of specific refractory power is low, added losses are low and physical strength is high and preparation method thereof.
Photo-cured fluorine-containing organosilicon optical fiber coatings of the present invention, by weight, comprises the trifluoro propyl methylvinyl-polysiloxane of 30～60 parts, the mercapto propyl group silicone oil of 5～30 parts, and the light trigger that accounts for the weight 1～5wt% that always feeds intake.
The present invention is by introducing the trifluoro propyl methylvinyl-polysiloxane of straight chain type, wherein fluorine-containing and methyl functional group and straight chain skeleton can greatly reduce the specific refractory power of coating, simultaneously, straight chain skeleton polymer is flexible large, when being subject to stress, can, by the motion of chain, change conformation, reach stress relaxation, there is larger elongation at break; On the other hand, the vinyl of end reacts with mercapto propyl group, has increased the molecular chain of polymkeric substance, makes polymkeric substance more pliable and tougher, thereby further improves elongation at break; Vinyl on molecular chain reacts with mercapto propyl group silicone oil, forms network structure, has increased cross-linking density, thereby improves the breaking tenacity of polymkeric substance; In addition, vinyl and mercapto propyl group generation addition reaction realize paint solidification, process is deviate from without small molecules, has avoided the problem of environmental pollution bringing because of small molecules amount fluorinated acrylate monomer in prior art, has improved resistance to low temperature and the ultraviolet radiation of acrylate simultaneously; Moreover, add-on type reaction has reduced the volumetric shrinkage before and after paint solidification to a certain extent, reduced the generation of stress, even if coating is subject to various External Force Actings, its long linear also can be along the direction motion of external force, to eliminate or to reduce stress, its faster stress relaxation characteristics reduced largely the added losses of coating; Finally, utilize unreactiveness, hydrophobicity and the special interior oilness of fluorinated polysiloxane itself, also played the object that reduces optical fiber coatings frictional coefficient, facilitates the quick production of optical fiber.
In the composition of above-mentioned photo-cured fluorine-containing organosilicon optical fiber coatings, the viscosity of described trifluoro propyl methylvinyl-polysiloxane is preferably controlled at 1000～6000mPas.Described trifluoro propyl methylvinyl-polysiloxane can directly be purchased (Ru Cong Hangzhou Pedagogic University organosilicon chemistry and key lab of the material technology the Ministry of Education from the market, Hebei Guigu Chemical Co., Ltd, Tianjin Zhi Tai Chemical Co., Ltd., the companies such as Chengdu Sen Fa rubber and plastic company limited buy), also can obtain by existing ordinary method is synthetic, preferably be prepared by the following method: get the octamethylcyclotetrasiloxane of 10～20 parts, the tetramethyl-tetrem thiazolinyl cyclotetrasiloxane of 2～5 parts and the trifluoro propyl methyl cyclotrisiloxane of 60～80 parts are placed in reaction vessel, drying and dehydrating under vacuum condition, then the catalyzer Tetramethylammonium hydroxide that adds 0.5～1.5 part, pass into nitrogen or rare gas element bubbling, be warming up to 70 ℃, maintain 0.5～1h, the tetramethyl divinyl disiloxane that adds again 0.5～1.5 part, is slowly warming up to 95～105 ℃, insulation reaction 1～3h, finally temperature is increased to 180～190 ℃, maintains 1～2h, with decomposition catalyst Tetramethylammonium hydroxide, cooling, vacuumize and remove low molecular weight substance, obtain trifluoro propyl methylvinyl-polysiloxane.The viscosity of the trifluoro propyl methylvinyl-polysiloxane being made by aforesaid method meets the requirement of above-mentioned 1000～6000mPas, wherein the viscosity of gained trifluoro propyl methylvinyl-polysiloxane, molecular weight, fluorine content, contents of ethylene etc. all can carry out by the addition of raw material free adjustment, and the trifluoro propyl methylvinyl-polysiloxane that adopts above-mentioned raw materials proportioning to make all can obtain the photo-cured fluorine-containing organosilicon optical fiber coatings that specific refractory power is low, added losses are low and physical strength is high while being applied in the application with other component proportion.
In the composition of above-mentioned photo-cured fluorine-containing organosilicon optical fiber coatings, described mercapto propyl group silicon oil viscosity is 1000～5000mPas.Described mercapto propyl group silicone oil can directly be purchased from the market (as being polymerized to million industry organosilicon donor centers from Guangzhou, the companies such as Zhejiang profit standing grain chemical industry organosilicon novel material company limited or upper Haidian triumphant silicon materials company limited buy), also can obtain by existing ordinary method is synthetic, preferably be prepared by the following method: get the octamethylcyclotetrasiloxane of 30～60 parts, the methyltrimethoxy silane of 5～20 parts, the KH590 of 5～15 parts (silane coupling agent KH590), the KH970 of 5～15 parts (silane coupling agent KH970), the acid catalyst of the water of 0.5～2 part and 0.4～1 part is placed in reaction vessel, under nitrogen or protection of inert gas, in 80～90 ℃ of reaction 2～4h, cooling, be washed to neutrality, vacuum decompression is removed small-molecule substance and water, obtains mercapto propyl group silicone oil.In the method, described acid catalyst can be to be selected from any one in concentrated hydrochloric acid, the vitriol oil and strong phosphoric acid.The mercapto propyl group silicon oil viscosity being made by aforesaid method all meets the requirement of above-mentioned 1000～6000mPas, wherein gained mercapto propyl group silicon oil viscosity all can be carried out free adjustment by the addition of raw material, and the mercapto propyl group silicone oil that adopts above-mentioned raw materials proportioning to make all can obtain the photo-cured fluorine-containing organosilicon optical fiber coatings that specific refractory power is low, added losses are low and physical strength is high while being applied in the application with other component proportion.
In the composition of above-mentioned photo-cured fluorine-containing organosilicon optical fiber coatings, described light trigger is same as the prior art, it can be any one or a few the mixing in Alpha-hydroxy ketone, benzophenone, alkylbenzene ketone and bitter almond oil camphor and derivative etc., preferably, light trigger is for being selected from Alpha-hydroxy-α, any three kinds of above combinations in alpha, alpha-dimethyl methyl phenyl ketone, benzophenone, benzoin isobutyl ether and 2,2-diethoxy acetophenone.
The preparation method of above-mentioned photo-cured fluorine-containing organosilicon optical fiber coatings is: get the trifluoro propyl methylvinyl-polysiloxane of 30～60 parts, the mercapto propyl group silicone oil of 5～30 parts, and the light trigger that accounts for the weight 1～5wt% that always feeds intake mixes, obtain.Wherein, the viscosity of described trifluoro propyl methylvinyl-polysiloxane is preferably 1000～6000mPas, and described mercapto propyl group silicon oil viscosity is preferably 1000～5000mPas.
Preparation method more specifically, comprises the following steps:
1) prepare trifluoro propyl methylvinyl-polysiloxane: get the octamethylcyclotetrasiloxane of 10～20 parts, the tetramethyl-tetrem thiazolinyl cyclotetrasiloxane of 2～5 parts and the trifluoro propyl methyl cyclotrisiloxane of 60～80 parts and be placed in reaction vessel, drying and dehydrating under vacuum condition, then the catalyzer Tetramethylammonium hydroxide that adds 0.5～1.5 part, pass into nitrogen or rare gas element bubbling, be warming up to 70 ℃, maintain 0.5～1h; The tetramethyl divinyl disiloxane that adds again 0.5～1.5 part, is slowly warming up to 95～105 ℃, insulation reaction 1～3h; Finally temperature is increased to 180～190 ℃, maintains 1～2h, with decomposition catalyst Tetramethylammonium hydroxide, cooling, vacuumize and remove low molecular weight substance, obtain trifluoro propyl methylvinyl-polysiloxane;
2) prepare mercapto propyl group silicone oil: get the octamethylcyclotetrasiloxane of 30～60 parts, methyltrimethoxy silane, the KH590 of 5～15 parts, the KH970 of 5～15 parts, the water of 0.5～2 part and the acid catalyst of 0.4～1 part of 5～20 parts is placed in reaction vessel, under nitrogen or protection of inert gas, in 80～90 ℃ of reaction 2～4h; Cooling, be washed to neutrality, vacuum decompression is removed small-molecule substance and water, obtains mercapto propyl group silicone oil;
3) mix: get 30～60 parts of steps 1) the trifluoro propyl methylvinyl-polysiloxane making, the step 2 of 5～30 parts) the mercapto propyl group silicone oil that makes, and the light trigger that accounts for the weight 1～5wt% that always feeds intake mixes, obtain described photo-cured fluorine-containing organosilicon optical fiber coatings.
The step 3 of aforesaid method) in, conventionally adopt homogenizer to mix, the rotating speed of preferably controlling homogenizer is 200～800rpm.The viscosity of the photo-cured fluorine-containing organosilicon optical fiber coatings being made by aforesaid method is 1000～5000mPas, and peeling force is 4～6N, and gained coating answers shading sealing to preserve.
The buffer layer coating that photo-cured fluorine-containing organosilicon optical fiber coatings of the present invention is especially suitable as on the optical fiber after Primary coating is used.
Compared with prior art, feature of the present invention is:
1, the present invention is by introducing the fluorine-containing of straight chain type and containing vinyl segment polysiloxane, make gained optical fiber coatings when having compared with low-refraction (specific refractory power is 1.38～1.40), (wherein tensile strength is more than 3Mpa also to have higher intensity modulus and elongation at break, elongation at break is more than 150%), and lower water-intake rate and added losses (wherein water-intake rate is less than 0.25%, 1550mn wavelength place light added losses are less than 0.05dB/km, 1310nm wavelength place light added losses are less than 0.1dB/km), and without small molecules, deviate from before and after paint solidification, avoided the problem of environmental pollution bringing because of small molecules amount fluorinated acrylate monomer in prior art, resistance to low temperature and the ultraviolet radiation of acrylate have been improved simultaneously, in addition, add-on type reaction has reduced the volumetric shrinkage before and after paint solidification to a certain extent, reduced the generation of stress, even if coating is subject to various External Force Actings, its long linear also can be along the direction motion of external force, to eliminate or to reduce stress, its faster stress relaxation characteristics reduced largely the added losses of coating, moreover, utilize unreactiveness, hydrophobicity and the special interior oilness of fluorinated polysiloxane itself, also played the object that reduces optical fiber coatings frictional coefficient, facilitates the quick production of optical fiber.
2, the method for the invention is simple to operation, greatly reduces the pollution to environment.
Embodiment
With specific embodiment, the invention will be further described below, but the present invention is not limited to these embodiment.
Embodiment 1
1) by 10g octamethylcyclotetrasiloxane, 4g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and 60g trifluoro propyl methyl cyclotrisiloxane vacuum-drying dehydration 0.5h at 40 ℃, add 0.74g Tetramethylammonium hydroxide, pass into nitrogen bubble (being equivalent to stir), be warming up to 70 ℃, maintain 0.5h, add 0.8g tetramethyl divinyl disiloxane, be slowly warming up to 100 ℃ of reactions 2 hours; Finally temperature is increased to 190 ℃, maintains 1h, Tetramethylammonium hydroxide is decomposed, vacuumize (vacuum tightness is-0.09MpaKPa) and remove low molecular weight substance, obtain water white trifluoro propyl methylvinyl-polysiloxane, viscosity is 2800mPas.
2) by the 85 ℃ little reactions 3 hours under nitrogen gas protection of 38g octamethylcyclotetrasiloxane, 10g methyltrimethoxy silane, 5g KH590,7gKH970,0.7g water and 0.42g concentrated hydrochloric acid, be cooled to room temperature, adopt deionized water wash to neutral, vacuum decompression (vacuum tightness is-0.09MpaKPa) removes small molecules and water obtains mercapto propyl group silicone oil, and viscosity is 2400mPas;
3) by 40g trifluoro propyl methylvinyl-polysiloxane obtained above, 5g mercapto propyl group obtained above silicone oil, 0.7g Alpha-hydroxy-α, alpha, alpha-dimethyl methyl phenyl ketone, 0.7g benzophenone, 0.7g benzoin isobutyl ether, through homogenizer (rotating speed is 200～800rpm/minrpm), mix, obtain photo-cured fluorine-containing organosilicon optical fiber coatings, shading sealing is preserved.
After testing, the fluorine-containing organic silicon optical fiber coatings viscosity that the present embodiment makes is 2600mPas, specific refractory power is 1.39, tensile strength is 3.85MPa, elongation at break is 210%, peeling force is 4.2N, and water-intake rate is that the added losses at 0.18%, 1310nm and 1550nm place are respectively 0.03dB/km and 0.01dB/km.
Embodiment 2
(1) by 18g octamethylcyclotetrasiloxane, 3g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and 75g trifluoro propyl methyl cyclotrisiloxane vacuum-drying dehydration 0.5h at 40 ℃, add 0.97g Tetramethylammonium hydroxide, pass into nitrogen bubble (being equivalent to stir), be warming up to 70 ℃, maintain 0.5h, add 1g tetramethyl divinyl disiloxane, be slowly warming up to 105 ℃ of reactions 2 hours; Finally temperature is elevated to 190 ℃, maintains 1h, Tetramethylammonium hydroxide is decomposed, vacuumize (vacuum tightness is-0.09MpaKPa) and remove low molecular weight substance, obtain water white trifluoro propyl methylvinyl-polysiloxane, viscosity is 3200mPas.
(2) by the 80 ℃ little reactions 3 hours under nitrogen gas protection of 45g octamethylcyclotetrasiloxane, 10g methyltrimethoxy silane, 10g KH590,15g KH970,1.5g water and 0.72g concentrated hydrochloric acid, be cooled to room temperature, adopt deionized water wash to neutral, vacuum decompression (vacuum tightness is-0.09MpaKPa) removes small molecules and water obtains mercapto propyl group silicone oil, and viscosity is 3100mPas;
(3) by 30g trifluoro propyl methylvinyl-polysiloxane obtained above, 10g mercapto propyl group obtained above silicone oil, 0.3g Alpha-hydroxy-α, alpha, alpha-dimethyl methyl phenyl ketone, 0.2g benzophenone, 0.5g benzoin isobutyl ether, 0.2g2,2-diethoxy acetophenone, through homogenizer (rotating speed is 200～800rpm/min), mix, obtain photo-cured fluorine-containing organosilicon optical fiber coatings, shading sealing is preserved.
After testing, the fluorine-containing organic silicon optical fiber coatings viscosity that the present embodiment makes is 3100mPas, specific refractory power is 1.39, tensile strength is 4.49MPa, elongation at break is 193%, peeling force is 4.9N, and water-intake rate is that the added losses at 0.20%, 1310nm and 1550nm place are respectively 0.05dB/km and 0.03dB/km.
Embodiment 3
(1) by 10g octamethylcyclotetrasiloxane, 2g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and 70g trifluoro propyl methyl cyclotrisiloxane vacuum-drying dehydration 0.5h at 40 ℃, add 0.83g Tetramethylammonium hydroxide, pass into nitrogen bubble (being equivalent to stir), be warming up to 70 ℃, maintain 0.5h, add 1.2g tetramethyl divinyl disiloxane, be slowly warming up to 95 ℃ of reactions 2 hours; Finally temperature is elevated to 190 ℃, maintains 1h, Tetramethylammonium hydroxide is decomposed, vacuumize (vacuum tightness is-0.09MpaKPa) and remove low molecular weight substance, obtain water white trifluoro propyl methylvinyl-polysiloxane, viscosity is 1200mPas;
(2) by the 85 ℃ little reactions 3 hours under nitrogen gas protection of 60g octamethylcyclotetrasiloxane, 5g methyltrimethoxy silane, 10g KH590,10g KH970,2.4g water and the 0.64g vitriol oil, be cooled to room temperature, adopt deionized water wash to neutral, vacuum decompression (vacuum tightness is-0.09Mpa) removes small molecules and water obtains mercapto propyl group silicone oil, and viscosity is 4500mPas;
(3) by 50g trifluoro propyl methylvinyl-polysiloxane obtained above, 15g mercapto propyl group obtained above silicone oil, 0.6g Alpha-hydroxy-α, alpha, alpha-dimethyl methyl phenyl ketone, 0.7g benzophenone, 0.6g2,2-diethoxy acetophenone, through homogenizer (rotating speed is 200～800rpm/minrpm), mix, obtain photo-cured fluorine-containing organosilicon optical fiber coatings, shading sealing is preserved.
After testing, the fluorine-containing organic silicon optical fiber coatings viscosity that the present embodiment makes is 2200mPas, specific refractory power is 1.39, tensile strength is 4.03MPa, elongation at break is 202%, peeling force is 4.8N, and water-intake rate is that the added losses at 0.20%, 1310nm and 1550nm place are respectively 0.05dB/km and 0.02dB/km.
Embodiment 4
(1) by 15g octamethylcyclotetrasiloxane, 4.5g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and 70g trifluoro propyl methyl cyclotrisiloxane vacuum-drying dehydration 0.5h at 40 ℃, add 0.92g Tetramethylammonium hydroxide, pass into nitrogen bubble (being equivalent to stir), be warming up to 70 ℃, maintain 0.5h, add 1.5g tetramethyl divinyl disiloxane, be slowly warming up to 105 ℃ of reactions 2 hours; Finally temperature is elevated to 190 ℃, maintains 1h, Tetramethylammonium hydroxide is decomposed, vacuumize (vacuum tightness is-0.09MpaKPa) and remove low molecular weight substance, obtain water white trifluoro propyl methylvinyl-polysiloxane, viscosity is 4500mPas;
(2) by the 90 ℃ little reactions 3 hours under nitrogen gas protection of 30g octamethylcyclotetrasiloxane, 20g methyltrimethoxy silane, 15g KH590,5g KH970,2g water and the 0.8g vitriol oil, be cooled to room temperature, adopt deionized water wash to neutral, vacuum decompression (vacuum tightness is-0.09MpaKPa) removes small molecules and water obtains mercapto propyl group silicone oil, and viscosity is 3700mPas;
(3) by 35g trifluoro propyl methylvinyl-polysiloxane obtained above, 20g mercapto propyl group obtained above silicone oil, 0.6g Alpha-hydroxy-α, alpha, alpha-dimethyl methyl phenyl ketone, 0.5g benzoin isobutyl ether, 0.5g2,2-diethoxy acetophenone, through homogenizer (rotating speed is 200～800rpm/minrpm), mix, obtain photo-cured fluorine-containing organosilicon optical fiber coatings, shading sealing is preserved.
After testing, the fluorine-containing organic silicon optical fiber coatings viscosity that the present embodiment makes is 4000mPas, specific refractory power is 1.40, tensile strength is 4.77MPa, elongation at break is 186%, peeling force is 4.7N, and water-intake rate is that the added losses at 0.21%, 1310nm and 1550nm place are respectively 0.07dB/km and 0.03dB/km.
Embodiment 5
(1) by 20g octamethylcyclotetrasiloxane, 2.5g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and 80g trifluoro propyl methyl cyclotrisiloxane vacuum-drying dehydration 0.5h at 40 ℃, add 1g Tetramethylammonium hydroxide, pass into nitrogen bubble (being equivalent to stir), be warming up to 70 ℃, maintain 0.5h, add 0.5g tetramethyl divinyl disiloxane, be slowly warming up to 100 ℃ of reactions 2 hours; Finally temperature is elevated to 180 ℃, maintains 1h, Tetramethylammonium hydroxide is decomposed, vacuumize (vacuum tightness is-0.09MpaKPa) and remove low molecular weight substance, obtain water white trifluoro propyl methylvinyl-polysiloxane, viscosity is 6000mPas;
(2) by the 85 ℃ little reactions 3 hours under nitrogen gas protection of 50g octamethylcyclotetrasiloxane, 10g methyltrimethoxy silane, 5g KH590,10g KH970,1.5g water and 0.52g strong phosphoric acid, be cooled to room temperature, adopt deionized water wash to neutral, vacuum decompression (vacuum tightness is-0.09MpaKPa) removes small molecules and water obtains mercapto propyl group silicone oil, and viscosity is 4100mPas;
(3) by 60g trifluoro propyl methylvinyl-polysiloxane obtained above, 25g mercapto propyl group obtained above silicone oil, 0.4g benzophenone, 0.8g benzoin isobutyl ether, 1.0g2,2-diethoxy acetophenone, through homogenizer (rotating speed is 200～800rpm/minrpm), mix, obtain photo-cured fluorine-containing organosilicon optical fiber coatings, shading sealing is preserved.
After testing, the fluorine-containing organic silicon optical fiber coatings viscosity that the present embodiment makes is 5000mPas, specific refractory power is 1.39, tensile strength is 5.21MPa, elongation at break is 180%, peeling force is 5.2N, and water-intake rate is that the added losses at 0.20%, 1310nm and 1550nm place are respectively 0.05dB/km and 0.03dB/km.
Embodiment 6
(1) by 15g octamethylcyclotetrasiloxane, 5g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and 80g trifluoro propyl methyl cyclotrisiloxane vacuum-drying dehydration 0.5h at 40 ℃, add 0.9g Tetramethylammonium hydroxide, pass into nitrogen bubble (being equivalent to stir), be warming up to 70 ℃, maintain 0.5h, add 0.8g tetramethyl divinyl disiloxane, be slowly warming up to 100 ℃ of reactions 2 hours; Finally temperature is elevated to 185 ℃, maintains 1h, Tetramethylammonium hydroxide is decomposed, vacuumize (vacuum tightness is-0.09MpaKPa) and remove low molecular weight substance, obtain water white trifluoro propyl methylvinyl-polysiloxane, viscosity is 4800mPas;
(2) by the 85 ℃ little reactions 3 hours under nitrogen gas protection of 30g octamethylcyclotetrasiloxane, 16g methyltrimethoxy silane, 10g KH590,5g KH970,2g water and 1g strong phosphoric acid, be cooled to room temperature, adopt deionized water wash to neutral, vacuum decompression (vacuum tightness is-0.09MpaKPa) removes small molecules and water obtains mercapto propyl group silicone oil, and viscosity is 1200mPas;
(3) by 48g trifluoro propyl methylvinyl-polysiloxane obtained above, 30g mercapto propyl group obtained above silicone oil, 1g benzophenone, 0.7g benzoin isobutyl ether, 0.6g2,2-diethoxy acetophenone, through homogenizer (rotating speed is 200～800rpm/min), mix, obtain photo-cured fluorine-containing organosilicon optical fiber coatings, shading sealing is preserved.
After testing, the fluorine-containing organic silicon optical fiber coatings viscosity that the present embodiment makes is 2900mPas, specific refractory power is 1.40, tensile strength is 4.83MPa, elongation at break is 191%, peeling force is 4.5N, and water-intake rate is that the added losses at 0.21%, 1310nm and 1550nm place are respectively 0.08dB/km and 0.04dB/km.
Claims (10)
1. a photo-cured fluorine-containing organosilicon optical fiber coatings, by weight, comprises the trifluoro propyl methylvinyl-polysiloxane of 30～60 parts, the mercapto propyl group silicone oil of 5～30 parts, and the light trigger that accounts for the weight 1～5wt% that always feeds intake.
2. photo-cured fluorine-containing organosilicon optical fiber coatings according to claim 1, is characterized in that: the viscosity of described trifluoro propyl methylvinyl-polysiloxane is 1000～6000mPas.
3. photo-cured fluorine-containing organosilicon optical fiber coatings according to claim 1 and 2, is characterized in that: described trifluoro propyl methylvinyl-polysiloxane makes by the following method:
Get the octamethylcyclotetrasiloxane of 10～20 parts, the tetramethyl-tetrem thiazolinyl cyclotetrasiloxane of 2～5 parts and the trifluoro propyl methyl cyclotrisiloxane of 60～80 parts and be placed in reaction vessel, drying and dehydrating under vacuum condition, then the catalyzer Tetramethylammonium hydroxide that adds 0.5～1.5 part, pass into nitrogen or rare gas element bubbling, be warming up to 70 ℃, maintain 0.5～1h; The tetramethyl divinyl disiloxane that adds again 0.5～1.5 part, is slowly warming up to 95～105 ℃, insulation reaction 1～3h; Finally temperature is increased to 180～190 ℃, maintains 1～2h, with decomposition catalyst Tetramethylammonium hydroxide, cooling, vacuumize and remove low molecular weight substance, obtain trifluoro propyl methylvinyl-polysiloxane.
4. photo-cured fluorine-containing organosilicon optical fiber coatings according to claim 1, is characterized in that: described mercapto propyl group silicon oil viscosity is 1000～5000mPas.
5. according to the photo-cured fluorine-containing organosilicon optical fiber coatings described in claim 1 or 4, it is characterized in that: described mercapto propyl group silicone oil makes by the following method:
Get the octamethylcyclotetrasiloxane of 30～60 parts, methyltrimethoxy silane, the KH590 of 5～15 parts, the KH970 of 5～15 parts, the water of 0.5～2 part and the acid catalyst of 0.4～1 part of 5～20 parts is placed in reaction vessel, under nitrogen or protection of inert gas, in 80～90 ℃ of reaction 2～4h; Cooling, be washed to neutrality, vacuum decompression is removed small-molecule substance and water, obtains mercapto propyl group silicone oil.
6. photo-cured fluorine-containing organosilicon optical fiber coatings according to claim 5, is characterized in that: described acid catalyst is to be selected from any one in concentrated hydrochloric acid, the vitriol oil and strong phosphoric acid.
7. photo-cured fluorine-containing organosilicon optical fiber coatings according to claim 1, it is characterized in that: described light trigger is for being selected from Alpha-hydroxy-α, any three kinds of above combinations in alpha, alpha-dimethyl methyl phenyl ketone, benzophenone, benzoin isobutyl ether and 2,2-diethoxy acetophenone.
8. the preparation method of photo-cured fluorine-containing organosilicon optical fiber coatings claimed in claim 1, it is characterized in that: get the trifluoro propyl methylvinyl-polysiloxane of 30～60 parts, the mercapto propyl group silicone oil of 5～30 parts, and the light trigger that accounts for the weight 1～5wt% that always feeds intake mixes, obtain.
9. the preparation method of photo-cured fluorine-containing organosilicon optical fiber coatings claimed in claim 8, is characterized in that: the viscosity of described trifluoro propyl methylvinyl-polysiloxane is 1000～6000mPas, and described mercapto propyl group silicon oil viscosity is 1000～5000mPas.
10. the preparation method of the photo-cured fluorine-containing organosilicon optical fiber coatings described in claim 8 or 9, is characterized in that: comprise the following steps:
1) prepare trifluoro propyl methylvinyl-polysiloxane: get the octamethylcyclotetrasiloxane of 10～20 parts, the tetramethyl-tetrem thiazolinyl cyclotetrasiloxane of 2～5 parts and the trifluoro propyl methyl cyclotrisiloxane of 60～80 parts and be placed in reaction vessel, drying and dehydrating under vacuum condition, then the catalyzer Tetramethylammonium hydroxide that adds 0.5～1.5 part, pass into nitrogen or rare gas element bubbling, be warming up to 70 ℃, maintain 0.5～1h; The tetramethyl divinyl disiloxane that adds again 0.5～1.5 part, is slowly warming up to 95～105 ℃, insulation reaction 1～3h; Finally temperature is increased to 180～190 ℃, maintains 1～2h, with decomposition catalyst Tetramethylammonium hydroxide, cooling, vacuumize and remove low molecular weight substance, obtain trifluoro propyl methylvinyl-polysiloxane;
2) prepare mercapto propyl group silicone oil: get the octamethylcyclotetrasiloxane of 30～60 parts, methyltrimethoxy silane, the KH590 of 5～15 parts, the KH970 of 5～15 parts, the water of 0.5～2 part and the acid catalyst of 0.4～1 part of 5～20 parts is placed in reaction vessel, under nitrogen or protection of inert gas, in 80～90 ℃ of reaction 2～4h; Cooling, be washed to neutrality, vacuum decompression is removed small-molecule substance and water, obtains mercapto propyl group silicone oil;
3) mix: get 30～60 parts of steps 1) the trifluoro propyl methylvinyl-polysiloxane making, the step 2 of 5～30 parts) the mercapto propyl group silicone oil that makes, and the light trigger that accounts for the weight 1～5wt% that always feeds intake mixes, obtain described photo-cured fluorine-containing organosilicon optical fiber coatings.
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