CN117511212B - High-temperature-resistant silicone glass fiber sleeve and preparation method thereof - Google Patents
High-temperature-resistant silicone glass fiber sleeve and preparation method thereof Download PDFInfo
- Publication number
- CN117511212B CN117511212B CN202311488771.5A CN202311488771A CN117511212B CN 117511212 B CN117511212 B CN 117511212B CN 202311488771 A CN202311488771 A CN 202311488771A CN 117511212 B CN117511212 B CN 117511212B
- Authority
- CN
- China
- Prior art keywords
- glass fiber
- fiber sleeve
- adamantane
- temperature
- resistant silicone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003365 glass fiber Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920001296 polysiloxane Polymers 0.000 title claims description 31
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000010445 mica Substances 0.000 claims abstract description 21
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 21
- 229920002050 silicone resin Polymers 0.000 claims abstract description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 21
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 20
- 229920001558 organosilicon polymer Polymers 0.000 claims description 20
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- -1 adamantane diphenol silicon Chemical compound 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 17
- 239000000839 emulsion Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- QQAMHHZQONQBFZ-UHFFFAOYSA-N 1-(5-bromo-2-methoxyphenyl)adamantane Chemical compound COC1=CC=C(Br)C=C1C1(C2)CC(C3)CC2CC3C1 QQAMHHZQONQBFZ-UHFFFAOYSA-N 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 8
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- LGTIILMXIZRZQU-UHFFFAOYSA-N dichloro(dimethyl)silane;silicon Chemical compound [Si].C[Si](C)(Cl)Cl LGTIILMXIZRZQU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 9
- 229910052710 silicon Inorganic materials 0.000 abstract description 9
- 239000010703 silicon Substances 0.000 abstract description 9
- 238000009413 insulation Methods 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- 239000010410 layer Substances 0.000 abstract description 4
- 238000003763 carbonization Methods 0.000 abstract description 3
- 229910021385 hard carbon Inorganic materials 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000011241 protective layer Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 229910004298 SiO 2 Inorganic materials 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005336 cracking Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910018557 Si O Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OGFYGJDCQZJOFN-UHFFFAOYSA-N [O].[Si].[Si] Chemical compound [O].[Si].[Si] OGFYGJDCQZJOFN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of glass fiber bushings, and discloses a high-temperature-resistant silicone resin glass fiber bushing and a preparation method thereof, wherein a rigid and high-symmetry cage-shaped adamantane structure is introduced into silicone resin, so that the degradation of side chain groups is avoided, and the thermal stability of the organic silicone resin is effectively improved; under the action of high temperature, the crosslinked network structure of the phenyl siloxane bond leads the surface of the material to form a compact SiO 2 The protective layer effectively prevents the inward diffusion of external air, and simultaneously, adamantane and benzene rings can form a hard carbon layer after carbonization, so that the damage to the inside of the material is reduced; the silicate metal of the mica powder can form a network structure with S i-O bond in the organic silicon resin, so that the problem of insufficient viscosity of the existing silicon resin is solved; the material is coated on the surface of the glass fiber sleeve, so that the sleeve has the characteristic of stability in a range with larger temperature change, thereby having excellent voltage resistance, high temperature resistance and heat insulation performance.
Description
Technical Field
The invention relates to the technical field of glass fiber bushings, in particular to a high-temperature-resistant silicone glass fiber bushing and a preparation method thereof.
Background
The fiber sleeve is a sleeve formed by reinforcing and braiding glass fibers, has higher electrical insulation property, corrosion resistance, ageing resistance and heat dissipation property, can keep soft and bending resistance at low temperature and cannot damage the electrical insulation property because of excellent softness and elasticity, and is widely applied to various fields of national economy such as electrical insulation materials, heat insulation materials, circuit substrates and the like; however, when the existing glass fiber sleeve is prepared, the loosening amount of glass fibers is large, the quality of the formed glass fiber sleeve is affected, and meanwhile, the glass fiber sleeve has defects in the preparation process, so that the high temperature resistance and the voltage resistance of the glass fiber sleeve are affected.
In the prior art, in order to ensure the high temperature resistance of the glass fiber insulating sleeve, the glass fiber insulating sleeve is generally arranged into a multi-layer structure during production, so that the performance of the glass fiber insulating sleeve can be improved, but the integral high temperature resistance and heat insulation performance of the existing sleeve are poor, so that unsafe factors exist in a circuit in the use process, and certain hidden danger is caused to electronic components in normal operation; the silicone glass fiber sleeve is formed by dip-coating organic silicone resin after being woven into a tube shape by alkali-free glass fibers and being heated and cured, has strong dielectric property, high heat resistance, good self-extinguishing property and softness, and is widely used for insulating protection of products such as household appliances, lamp decorations, electric heating products, electric equipment, heat-resistant appliances and the like.
However, in the existing silicone glass fiber sleeve, the viscosity of silicone is still insufficient in the processing process, so that the subsequent sizing operation is affected, the silicone glass fiber sleeve is easy to break in the deformation process, and the high temperature resistance of the glass fiber sleeve is adversely affected, so that a novel silicone glass fiber sleeve needs to be prepared to solve the problems. The invention synthesizes a novel silicon resin containing adamantane and benzene ring heat-resistant groups, and coats the surface of the glass fiber sleeve, so that the glass fiber sleeve has high temperature resistance, voltage resistance and heat insulation performance.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a high-temperature-resistant silicone glass fiber sleeve and a preparation method thereof, and solves the problem that the existing glass fiber sleeve is poor in high-temperature resistance.
(II) technical scheme
The preparation method of the high-temperature-resistant silicone glass fiber sleeve comprises the following steps:
(1) And (3) adding adamantane diphenol silicon and diethylene glycol dimethyl ether into a three-mouth bottle with a dropping funnel, dropwise adding dichlorodimethylsilane, cooling, filtering, and washing a filter cake with deionized water after the reaction is finished to obtain the adamantane organosilicon polymer.
(2) Adding mica powder and adamantane organosilicon polymer into silicone, stirring and dissolving to obtain organosilicon modified emulsion, coating the emulsion on a glass fiber sleeve with the diameter of 8-10mm, heating at 40-60 ℃ for 10-20min and then baking at 90-110 ℃ for 5-15min, and heating at 140-160 ℃ for 8-18min to obtain the high-temperature-resistant silicone glass fiber sleeve.
Further, the mass ratio of each reactant in the step (1) is as follows: adamantanediphenol silicon dichlorodimethylsilane = 1g:0.55-0.75g.
Further, the reaction process in the step (1) is to raise the temperature to 60-80 ℃ for reaction for 1-3 hours, and raise the temperature to 100-120 ℃ for reaction for 3-6 hours.
Further, the mass ratio of each reactant in the step (2) is as follows: silicone resin: mica powder: adamantane silicone polymer = 1g:0.02-0.1g:0.15-0.35g.
Further, the preparation method of the adamantane diphenol silicon in the step (1) comprises the following steps:
s1, adding magnesium powder and tetrahydrofuran into a dry three-mouth bottle with a condenser tube and a constant pressure dropping funnel, adding elemental iodine, heating to 40-50 ℃, and dropping tetrahydrofuran and 2- (1-adamantyl) -4-bromoanisole (formula C) 17 H 21 BrO, CAS number: 104224-63-7), refluxing at 70-85deg.C for 2-5 hr, cooling to 0-10deg.C, adding dropwise mixed solution of tetrahydrofuran and dichlorodimethylsilane, reacting at 40-50deg.C for 8-16 hr, cooling, filtering, and concentrating the filtrate to obtain intermediate 1. The preparation process comprises the following steps:
s2, adding the intermediate 1 and methylene dichloride into a three-mouth bottle with a thermometer and a dropping funnel, uniformly stirring, controlling the system temperature to be about minus 50 ℃, slowly dropping boron tribromide, stirring for reaction after the dropping is finished, adding methanol for quenching, pouring the reaction liquid into deionized water, precipitating, filtering, and recrystallizing a filter cake with ethanol to obtain adamantane diphenol silicon. The preparation process comprises the following steps:
further, in the step S1, the mass ratio of each reactant is as follows: magnesium powder, elemental iodine, 2- (1-adamantyl) -4-bromoanisole, dichlorodimethylsilane=0.09-0.11 g, 0.005-0.01g, 1g, and 0.16-0.2g.
Further, in the step S2, the mass ratio of each reactant is as follows: intermediate 1: boron tribromide = 1g:1.8-2.6g.
Further, the reaction temperature in the step S2 is 0-10 ℃ and the reaction time is 12-24 hours.
(III) beneficial technical effects
2- (1-adamantyl) -4-bromoanisole reacts with dichlorodimethylsilane under the initiation of magnesium powder and elemental iodine to obtain an intermediate 1, and then the intermediate reacts with BBr 3 The reaction of cracking ether and demethylation are carried out to obtain adamantane diphenol silicon which contains bisphenol hydroxyl and dichloro dimethyl silaneAnd (3) carrying out reaction on Si-Cl bonds of the glass fiber sleeve, polymerizing to obtain adamantane organosilicon polymer containing siloxane bonds, finally adding silicone resin and mica powder to prepare organosilicon modified emulsion, and then coating the organosilicon modified emulsion on the surface of the glass fiber sleeve to obtain the high-temperature-resistant silicone resin glass fiber sleeve.
The organic silicon resin has a unique Si-O bond structure, and has higher bond energy compared with C-O bonds and C-C bonds, and the Si-O bonds are difficult to break by simple thermal movement, so that the organic silicon resin has higher stability to heat and oxygen than common organic polymers and excellent high-temperature resistance; the adamantane organosilicon polymer prepared by the invention introduces a rigid and highly symmetrical cage-shaped adamantane structure into the organosilicon side chain, avoids the degradation of the side chain group, and effectively improves the thermal stability of the organosilicon resin; the polymer contains rigid heat-resistant benzene ring and crosslinking network structure of phenyl siloxane bond, so that the material forms a compact SiO on the surface under the action of high temperature 2 The protective layer can effectively prevent the outside air from diffusing inwards, and simultaneously, adamantane and benzene ring can form a hard carbon layer after carbonization, thereby reducing the damage to the inside of the material.
The silicate mica powder material containing Al and Mg is added, the metal of the silicate can form a network structure with Si-O bonds in the organic silicon resin, the problem of insufficient viscosity of the silicon resin is solved, and the material is coated on the surface of the glass fiber sleeve, so that the glass fiber sleeve has the characteristic of stability in a larger temperature change range, and has excellent voltage resistance, high temperature resistance and heat insulation performance.
Detailed Description
The following describes the technical scheme in the embodiment of the present invention in detail. It should be noted that variations and modifications can be made by those skilled in the art without departing from the principles of the present invention, which are also considered to be within the scope of the present invention.
Example 1
(1) To a dry three-necked flask with a condenser and a constant pressure dropping funnel, 1.61g of magnesium powder and tetrahydrofuran were added, 0.12g of elemental iodine was added, then the flask was heated to 45℃and tetrahydrofuran and 15g of 2- (1-adamantyl) -4-bromoanisole were added dropwise, refluxing was carried out at 75℃for 4 hours, then the flask was cooled to 5℃and a mixture of tetrahydrofuran and 2.7g of dichlorodimethylsilane was added dropwise, reacted at 40℃for 12 hours, cooled, filtered and the filtrate was concentrated to obtain intermediate 1.
(2) Adding 12g of intermediate 1 and methylene dichloride into a three-port bottle with a thermometer and a dropping funnel, uniformly stirring, controlling the system temperature to be about minus 50 ℃, slowly dropping 30g of boron tribromide, after the dropping is finished, reacting for 20 hours at 0 ℃, adding methanol for quenching, then pouring the reaction solution into deionized water, precipitating and filtering, and recrystallizing a filter cake with ethanol to obtain the adamantane diphenol silicon.
(3) 6.5g of adamantane diphenol silicon and diethylene glycol dimethyl ether are added into a three-mouth bottle with a dropping funnel, 3.9g of dichlorodimethyl silane is added dropwise, the temperature is firstly increased to 75 ℃ for reaction for 2 hours, then the temperature is increased to 105 ℃ for reaction for 4 hours, cooling is carried out, filtration is carried out, and a filter cake is washed by deionized water, so that the adamantane organosilicon polymer is obtained.
(4) Adding 2g of mica powder and 15g of adamantane organosilicon polymer into 100g of silicone, stirring and dissolving to obtain organosilicon modified emulsion, coating the emulsion on a glass fiber sleeve with the diameter of 9mm, heating the glass fiber sleeve at the coating thickness of 55 mu m for 15min at 50 ℃, then baking the glass fiber sleeve at 100 ℃ for 10min, and then heating the glass fiber sleeve at 155 ℃ for 12min to obtain the high-temperature-resistant silicone glass fiber sleeve.
Example 2
(1) To a dry three-necked flask with a condenser and a constant pressure dropping funnel, 0.85g of magnesium powder and tetrahydrofuran were added, 0.076g of elemental iodine was added, then the flask was heated to 50℃and tetrahydrofuran and 8.5g of 2- (1-adamantyl) -4-bromoanisole were added dropwise, reflux was conducted at 80℃for 5 hours, then the flask was cooled to 0℃and a mixture of tetrahydrofuran and 1.61g of dichlorodimethylsilane was added dropwise, reacted at 50℃for 10 hours, cooled, filtered and the filtrate was concentrated to obtain intermediate 1.
(2) Adding 4.2g of intermediate 1 and methylene dichloride into a three-port bottle with a thermometer and a dropping funnel, uniformly stirring, controlling the temperature of the system to be about minus 50 ℃, slowly dropping 10.5g of boron tribromide, after the dropping is finished, reacting for 15 hours at 5 ℃, adding methanol for quenching, pouring the reaction solution into deionized water, precipitating, filtering, and recrystallizing a filter cake with ethanol to obtain adamantane diphenol silicon.
(3) 2.3g of adamantane diphenol silicon and diethylene glycol dimethyl ether are added into a three-mouth bottle with a dropping funnel, 1.49g of dichlorodimethyl silane is added dropwise, the temperature is firstly increased to 80 ℃ for reaction for 1h, then the temperature is increased to 110 ℃ for reaction for 6h, cooling is carried out, filtration is carried out, and a filter cake is washed by deionized water, so that the adamantane organosilicon polymer is obtained.
(4) Adding 2g of mica powder and 20g of adamantane organosilicon polymer into 100g of silicone, stirring and dissolving to obtain organosilicon modified emulsion, coating the emulsion on a glass fiber sleeve with the diameter of 10mm, heating the glass fiber sleeve at the temperature of 45 ℃ for 10min, then baking the glass fiber sleeve at the temperature of 95 ℃ for 5min, and then heating the glass fiber sleeve at the temperature of 145 ℃ for 9min to obtain the high-temperature-resistant silicone glass fiber sleeve.
Example 3
(1) To a dry three-necked flask with a condenser and a constant pressure dropping funnel, 2.47g of magnesium powder and tetrahydrofuran were added, 2.02g of elemental iodine was added, then heated to 50 ℃, tetrahydrofuran and 22.5g of 2- (1-adamantyl) -4-bromoanisole were added dropwise, refluxing was performed at 85 ℃ for 2 hours, then cooling was performed to 10 ℃, a mixture of tetrahydrofuran and 4.5g of dichlorodimethylsilane was added dropwise, reacted at 50 ℃ for 16 hours, cooled, filtered, and the filtrate was concentrated to obtain intermediate 1.
(2) Adding 16.8g of intermediate 1 and methylene dichloride into a three-port bottle with a thermometer and a dropping funnel, uniformly stirring, controlling the temperature of the system to be about minus 50 ℃, slowly dropping 36.9g of boron tribromide, after the dropping is finished, reacting for 24 hours at 8 ℃, adding methanol for quenching, pouring the reaction solution into deionized water, precipitating, filtering, and recrystallizing a filter cake with ethanol to obtain adamantane diphenol silicon.
(3) 12.6g of adamantane diphenol silicon and diethylene glycol dimethyl ether are added into a three-mouth bottle with a dropping funnel, 8.25g of dichlorodimethyl silane are added dropwise, the temperature is firstly increased to 60 ℃ for reaction for 3 hours, then the temperature is increased to 120 ℃ for reaction for 6 hours, cooling is carried out, filtration is carried out, and filter cakes are washed by deionized water, thus obtaining the adamantane organosilicon polymer.
(4) Adding 2g of mica powder and 25g of adamantane organosilicon polymer into 100g of silicone, stirring and dissolving to obtain organosilicon modified emulsion, coating the emulsion on a glass fiber sleeve with the diameter of 10mm, heating the glass fiber sleeve at 60 ℃ for 12min, then baking the glass fiber sleeve at 100 ℃ for 9min, and then heating the glass fiber sleeve at 150 ℃ for 18min to obtain the high-temperature-resistant silicone glass fiber sleeve.
Example 4
(1) To a dry three-necked flask with a condenser and a constant pressure dropping funnel, 3.15g of magnesium powder and tetrahydrofuran were added, 0.175g of elemental iodine was added, then the flask was heated to 40 ℃, tetrahydrofuran and 35g of 2- (1-adamantyl) -4-bromoanisole were added dropwise, reflux was conducted at 85℃for 5 hours, then the flask was cooled to 2℃and a mixture of tetrahydrofuran and 5.95g of dichlorodimethylsilane was added dropwise, the flask was reacted at 50℃for 10 hours, cooled, filtered, and the filtrate was concentrated to obtain intermediate 1.
(2) Adding 28g of intermediate 1 and methylene dichloride into a three-port bottle with a thermometer and a dropping funnel, uniformly stirring, controlling the system temperature to be about minus 50 ℃, slowly dropping 67.2g of boron tribromide, after the dropping is finished, reacting for 12 hours at 0 ℃, adding methanol for quenching, then pouring the reaction solution into deionized water, precipitating, filtering, and recrystallizing a filter cake with ethanol to obtain the adamantane diphenol silicon.
(3) 18g of adamantane diphenol silicon and diethylene glycol dimethyl ether are added into a three-mouth bottle with a dropping funnel, 13.5g of dichloro dimethyl silane is added dropwise, the temperature is firstly increased to 70 ℃ for reaction for 3 hours, then the temperature is increased to 120 ℃ for reaction for 3 hours, cooling and filtering are carried out, and a filter cake is washed by deionized water, so that the adamantane organosilicon polymer is obtained.
(4) Adding 2g of mica powder and 30g of adamantane organosilicon polymer into 100g of silicone, stirring and dissolving to obtain organosilicon modified emulsion, coating the emulsion on a glass fiber sleeve with the diameter of 8mm, heating the glass fiber sleeve at the temperature of 50 ℃ for 20min, then baking the glass fiber sleeve at the temperature of 110 ℃ for 5min, and then heating the glass fiber sleeve at the temperature of 155 ℃ for 18min to obtain the high-temperature-resistant silicone glass fiber sleeve.
Example 5
(1) To a dry three-necked flask with a condenser and a constant pressure dropping funnel, 0.57g of magnesium powder and tetrahydrofuran were added, 0.05g of elemental iodine was added, then heated to 50 ℃, tetrahydrofuran and 5.2g of 2- (1-adamantyl) -4-bromoanisole were added dropwise, reflux was carried out at 75 ℃ for 3 hours, then the temperature was lowered to 0 ℃, a mixture of tetrahydrofuran and 0.83g of dichlorodimethylsilane was added dropwise, reaction was carried out at 50 ℃ for 16 hours, cooling, filtration and concentration of the filtrate were carried out, and intermediate 1 was obtained.
(2) 3.5g of intermediate 1 and methylene dichloride are added into a three-mouth bottle with a thermometer and a dropping funnel, the mixture is stirred uniformly, the system temperature is controlled to be about minus 50 ℃, 9.1g of boron tribromide is slowly added dropwise, after the dropwise addition is finished, the mixture is reacted for 20 hours at 5 ℃, methanol is added for quenching, then the reaction solution is poured into deionized water, precipitation is separated out, filtration is carried out, and a filter cake is recrystallized by ethanol, thus obtaining adamantane diphenol silicon.
(3) 1.8g of adamantane diphenol silicon and diethylene glycol dimethyl ether are added into a three-mouth bottle with a dropping funnel, 0.99g of dichlorodimethyl silane is added dropwise, the temperature is firstly increased to 60 ℃ for reaction for 2 hours, then the temperature is increased to 115 ℃ for reaction for 5 hours, cooling is carried out, filtration is carried out, and a filter cake is washed by deionized water, so that the adamantane organosilicon polymer is obtained.
(4) Adding 2g of mica powder and 35g of adamantane organosilicon polymer into 100g of silicone, stirring and dissolving to obtain organosilicon modified emulsion, coating the emulsion on a glass fiber sleeve with the diameter of 10mm, heating the glass fiber sleeve at the coating thickness of 50 mu m at 40 ℃ for 16min, then baking the glass fiber sleeve at 105 ℃ for 12min, and then heating the glass fiber sleeve at 160 ℃ for 15min to obtain the high-temperature-resistant silicone glass fiber sleeve.
Example 6
This example differs from example 1 in that the amount of mica powder used in step (4) is 4g, with other conditions remaining the same.
Example 7
This example differs from example 1 in that the amount of mica powder used in step (4) was 6g, and the other conditions were kept the same.
Example 8
This example differs from example 1 in that the amount of mica powder used in step (4) was 8g, with other conditions remaining the same.
Example 9
This example differs from example 1 in that the amount of mica powder used in step (4) was 10g, and the other conditions were kept the same.
Comparative example 1
This comparative example differs from example 1 in that the adamantane silicone polymer was not added in step (4), and the other conditions were kept identical.
Comparative example 2
This comparative example differs from example 1 in that no mica powder was added in step (4), and other conditions were kept consistent.
High and low temperature resistance test: and placing the coated glass fiber sleeve at different temperatures for 24 hours, and observing whether the appearance of the sleeve is yellowing or cracking.
| 180℃ | -10℃ | |
| Example 1 | Does not turn yellow and has no change in appearance | No cracking |
| Example 2 | Does not turn yellow and has no change in appearance | No cracking |
| Example 3 | Does not turn yellow and has no change in appearance | No cracking |
| Example 4 | Does not turn yellow and has no change in appearance | No cracking |
| Example 5 | Does not turn yellow and has no change in appearance | No cracking |
| Comparative example 1 | Slightly yellow | Slightly crack |
As shown by the test results of the table, the high temperature resistance and the low temperature resistance of the glass fiber sleeve are greatly enhanced along with the increase of the content of the adamantane organosilicon polymer in the coating, and the adamantane organosilicon polymer is added in examples 1 to 5, and the sleeve has no change in appearance, no yellowing and no cracking after being placed for 24 hours at 180 ℃, and has better high temperature resistance, because the adamantane organosilicon polymer contains a crosslinked network structure of heat-resistant phenyl siloxane bonds, and the main chain structure is a structure of silicon-oxygen-silicon bondsThe silicon-oxygen bond is stable and is not easy to break, and when the silicon-oxygen bond is subjected to high temperature, a compact SiO is formed on the surface 2 The protective layer can effectively prevent the external air from diffusing inwards, and is combined with the rigid heat-resistant structure of adamantane, so that the coating material has the characteristic of being more stable in a range with larger temperature change, and can simultaneously play roles of high temperature resistance and low temperature resistance. Whereas comparative example 1, in which adamantane silicone polymer was not added, exhibited a slight yellowing and a slight cracking phenomenon, indicating that the temperature resistance was to be further improved.
Breakdown voltage test: the test is carried out by adopting a withstand voltage tester, a bare copper rod with the wire gauge of 3.35mm multiplied by 8.5mm is sleeved with a prepared glass fiber sleeve with the length of 300mm, and an alternating current power frequency voltage breakdown experiment is carried out after a sample is coated with an aluminum foil.
From the test data in the table above, as the adamantane organosilicon polymer content in the coating layer increases, the breakdown voltage value is increased, example 5 reaches 9.2kV, and compared with comparative example 1, the breakdown voltage is improved by 113.9%, which shows that the voltage resistance of the glass fiber bushing coated with the modified organosilicon is effectively improved.
Thermal insulation performance test: the outer wall of the glass sleeve is heated by using the outer flame of the alcohol burner, a thermometer is placed in the center of the sleeve, the time required for heating the center of the sleeve to 150 ℃ is recorded, and the longer the time is, the better the heat insulation performance of the sleeve is.
| Heating to 150 ℃ for a desired time(s) | |
| Example 1 | 6.2 |
| Example 6 | 6.8 |
| Example 7 | 7.5 |
| Example 8 | 7.9 |
| Example 9 | 8.1 |
| Comparative example 2 | 5.8 |
The mica powder is silicate containing Al and Mg and is of a flaky filler structure; as shown in the test data of the table above, as the content of mica powder in the coating material increases, the time required for the center temperature of the glass fiber sleeve to reach 150 ℃ increases, 8.1s is required in example 9, 5.8s is required in comparative example 2 without adding mica powder, and the addition of mica powder obviously improves the heat insulation performance of the glass fiber sleeve, because under the high temperature effect, the silicon-oxygen bond in the organic silicon resin can form a cross-linked network structure with the metal of silicate, thereby playing the roles of a framework, also playing the roles of high temperature resistance and heat insulation, improving the problem of insufficient viscosity of the silicon resin, and simultaneously, the adamantane and benzene ring structure can form a hard carbon layer after carbonization, thereby reducing the damage to the inside of the material.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The preparation method of the high-temperature-resistant silicone glass fiber sleeve is characterized by comprising the following steps of:
(1) Adding adamantane diphenol silicon and diethylene glycol dimethyl ether into a three-mouth bottle with a dropping funnel, dropwise adding dichlorodimethylsilane, cooling, filtering, and washing a filter cake with deionized water to obtain an adamantane organosilicon polymer;
(2) Adding mica powder and adamantane organosilicon polymer into silicone, stirring and dissolving to obtain organosilicon modified emulsion, coating the emulsion on a glass fiber sleeve with the diameter of 8-10mm, wherein the thickness of the coating is 50-60 mu m, heating for 10-20min at 40-60 ℃, then baking for 5-15min at 90-110 ℃, and then heating for 8-18min at 140-160 ℃ to obtain a high-temperature-resistant silicone glass fiber sleeve;
the preparation method of the adamantane diphenol silicon in the step (1) comprises the following steps:
s1, adding magnesium powder and tetrahydrofuran into a dry three-mouth bottle with a condensing tube and a constant-pressure dropping funnel, adding elemental iodine, heating to 40-50 ℃, dropwise adding tetrahydrofuran and 2- (1-adamantyl) -4-bromoanisole, refluxing at 70-85 ℃ for 2-5h, cooling to 0-10 ℃, dropwise adding a mixed solution of tetrahydrofuran and dichlorodimethylsilane, reacting at 40-50 ℃ for 8-16h, cooling, filtering, and concentrating the filtrate to obtain an intermediate 1;
s2, adding the intermediate 1 and methylene dichloride into a three-mouth bottle with a thermometer and a dropping funnel, uniformly stirring, controlling the temperature of the system to be minus 50 ℃, slowly dropping boron tribromide, stirring for reaction after dropping, adding methanol for quenching, pouring the reaction liquid into deionized water, precipitating, filtering, and recrystallizing a filter cake with ethanol to obtain the adamantane diphenol silicon.
2. The method for preparing a high temperature resistant silicone glass fiber sleeve according to claim 1, wherein the mass ratio of each reactant in the step (1) is as follows: adamantanediphenol silicon dichlorodimethylsilane = 1g:0.55-0.75g.
3. The method for preparing the high temperature resistant silicone glass fiber sleeve according to claim 1, wherein the reaction process in the step (1) is to raise the temperature to 60-80 ℃ for 1-3 hours and raise the temperature to 100-120 ℃ for 3-6 hours.
4. The method for preparing a high temperature resistant silicone glass fiber sleeve according to claim 1, wherein the mass ratio of each reactant in the step (2) is as follows: silicone resin: mica powder: adamantane silicone polymer = 1g:0.02-0.1g:0.15-0.35g.
5. The method for preparing a high temperature resistant silicone glass fiber sleeve according to claim 4, wherein the mass ratio of each reactant in the step S1 is: magnesium powder, elemental iodine, 2- (1-adamantyl) -4-bromoanisole, dichlorodimethylsilane=0.09-0.11 g, 0.005-0.01g, 1g, and 0.16-0.2g.
6. The method for preparing a high temperature resistant silicone glass fiber sleeve according to claim 4, wherein the mass ratio of each reactant in the step S2 is: intermediate 1: boron tribromide = 1g:1.8-2.6g.
7. The method for preparing a high temperature resistant silicone glass fiber sleeve according to claim 4, wherein the reaction temperature in the step S2 is 0-10 ℃ and the reaction time is 12-24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311488771.5A CN117511212B (en) | 2023-11-09 | 2023-11-09 | High-temperature-resistant silicone glass fiber sleeve and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311488771.5A CN117511212B (en) | 2023-11-09 | 2023-11-09 | High-temperature-resistant silicone glass fiber sleeve and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117511212A CN117511212A (en) | 2024-02-06 |
| CN117511212B true CN117511212B (en) | 2024-04-12 |
Family
ID=89750730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311488771.5A Active CN117511212B (en) | 2023-11-09 | 2023-11-09 | High-temperature-resistant silicone glass fiber sleeve and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117511212B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008080993A2 (en) * | 2006-12-28 | 2008-07-10 | Ivars Kalvinsh | A method for preparation of substituted adamantylarylmagnesium halides |
| CN112712945A (en) * | 2021-01-04 | 2021-04-27 | 深圳市顺博绝缘材料制造有限公司 | Silicon resin glass fiber sleeve and processing method |
| CN113667167A (en) * | 2021-08-24 | 2021-11-19 | 老河口市维杰电子材料有限公司 | Processing method of silicone resin glass fiber sleeve |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7807012B2 (en) * | 2004-10-25 | 2010-10-05 | Dow Corning Corporation | Moldable compositions containing carbinol functional silicone resins or anhydride functional silicone resins |
| EP1985616A1 (en) * | 2006-01-27 | 2008-10-29 | Idemitsu Kosan Co., Ltd. | Adamantane derivative, resin composition containing same, and optoelectronic member and sealing agent for electronic circuit using those |
-
2023
- 2023-11-09 CN CN202311488771.5A patent/CN117511212B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008080993A2 (en) * | 2006-12-28 | 2008-07-10 | Ivars Kalvinsh | A method for preparation of substituted adamantylarylmagnesium halides |
| CN112712945A (en) * | 2021-01-04 | 2021-04-27 | 深圳市顺博绝缘材料制造有限公司 | Silicon resin glass fiber sleeve and processing method |
| CN113667167A (en) * | 2021-08-24 | 2021-11-19 | 老河口市维杰电子材料有限公司 | Processing method of silicone resin glass fiber sleeve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117511212A (en) | 2024-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102161860B (en) | Preparation method of organic silicon modified polyester wire enamel | |
| KR100382702B1 (en) | Method for preparing organic silicate polymer | |
| CN107459652B (en) | Heat-resistant silicone resin capable of being cured at room temperature and preparation method thereof | |
| CN117511212B (en) | High-temperature-resistant silicone glass fiber sleeve and preparation method thereof | |
| CN116082843A (en) | Heat-resistant addition type silicone rubber composition and preparation method thereof | |
| CN113845840A (en) | Epoxy modified organic silicon flame-retardant coating and application thereof | |
| CN113045902A (en) | Corrosion-resistant self-curing insulating material and preparation method thereof | |
| KR20140010730A (en) | Hydrogen oligosiloxane resin and preparing method thereof | |
| JP2019099788A (en) | Epoxy resin composition and transformer containing the same | |
| CN110204900B (en) | Flame-retardant organopolysiloxane composition and preparation method thereof | |
| CN111748178A (en) | Epoxy resin composition and preparation method and application thereof | |
| CN115746306A (en) | Modified polysiloxane and preparation method thereof | |
| CN114334262A (en) | Fluoroplastic insulating silicon rubber sheath high-temperature-resistant control cable | |
| CN111087621B (en) | Fluorine modified organosilicon material and preparation method and application thereof | |
| CN113637325A (en) | Long-life ceramic silicon rubber material for wire distribution and preparation method thereof | |
| CN112795370A (en) | Organic pouring sealant and device containing same | |
| CN112159624B (en) | Organic silicon-based polymer coating and preparation process thereof | |
| CN115926468B (en) | Interpenetrating network type organic silicon resin and preparation method thereof | |
| CN109003723A (en) | A kind of insulated compound aluminium enamel-covered wire | |
| KR100343552B1 (en) | A method of preparing for polymethylsilsesquioxane copolymer with well dispersed dimethysiloxane unit | |
| CN116874785A (en) | High-heat-conductivity high-temperature-resistant insulating layer for instant metal electric heating tube and preparation method thereof | |
| CN114133574B (en) | Bridged naphthene toughened silicone resin and preparation method thereof | |
| CN117304802A (en) | High-content silicone rubber insulating paint containing fluorosilicone | |
| TWI820493B (en) | Corona-resistant enamel wire and preparation method thereof | |
| KR950000995B1 (en) | Solid silicone resin material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |