CN111925741B - Single-side glass cloth reinforced less-glue mica tape and wire rod - Google Patents
Single-side glass cloth reinforced less-glue mica tape and wire rod Download PDFInfo
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- CN111925741B CN111925741B CN202010742265.4A CN202010742265A CN111925741B CN 111925741 B CN111925741 B CN 111925741B CN 202010742265 A CN202010742265 A CN 202010742265A CN 111925741 B CN111925741 B CN 111925741B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/28—Presence of paper
- C09J2400/283—Presence of paper in the substrate
Abstract
The invention relates to a single-side glass cloth reinforced mica tape and a wire rod with less glue, which are composed of the following components in percentage by mass of 100 percent: 9-13% of organic silicon modified epoxy resin; 0.4-2% of silicon dioxide; 22-30% of acetone; 59-68% of toluene. The adhesive for the single-sided glass cloth reinforced mica tape with less glue has larger relative molecular mass and higher viscosity at normal temperature, and is beneficial to the adhesion between the glass cloth and the mica paper; meanwhile, the adhesive has lower viscosity at high temperature, so that the adhesive is favorably permeated in the mica paper, the adhesive area of the mica paper is increased, and the adhesive force between the glass cloth and the mica paper is further increased. In addition, the adhesive has good heat resistance and good compatibility with VPI impregnating resin, meets the use requirements of current wind power generation, and has the advantages of simple preparation method and low price of raw materials.
Description
The invention relates to an adhesive for a single-sided glass cloth reinforced mica tape with less glue and a preparation method thereof, which are filed on 2016, 10 and 28 days and have the application number of 2016109612163.
Technical Field
The invention particularly relates to a single-side glass cloth reinforced less-glue mica tape and a wire rod.
Background
Wind energy is a low-carbon and environment-friendly natural resource which accords with the current sustainable development strategy and has the characteristics of reproducibility, high content, no pollution and the like. At present, wind power generation becomes a large-scale, complete-technology and optimistic-development power generation mode in the world. With the development of wind power generation gradually towards the direction of high voltage, large capacity and high performance, higher requirements are put forward on the single-sided glass cloth reinforced mica tape with less glue as a main insulating structure, particularly the heat resistance of the mica tape; the key for improving the heat resistance of the mica tape is to enhance the heat resistance of the adhesive.
Most of adhesives used for reinforcing the single-sided glass cloth of the mica tape with less glue at present adopt epoxy resin, unsaturated polyester and the like as main components; the adhesives have poor heat resistance, poor adhesion, poor compatibility with VPI impregnating resin and large dielectric loss, and are difficult to meet the development requirements of the current wind power generation.
Disclosure of Invention
The invention aims to solve the technical problem of providing an adhesive which is suitable for single-side glass cloth reinforced little-glue mica tapes, has good heat resistance and strong cohesiveness and is good in compatibility with VPI impregnated resin.
The invention also aims to provide a preparation method of the adhesive, which is simple to operate and has no special requirements on equipment.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention aims to provide an adhesive for a single-side glass cloth reinforced mica tape with less glue, which consists of the following components in percentage by mass of 100 percent:
preferably, the adhesive consists of the following components in percentage by mass of 100 percent:
according to the invention, the organosilicon modified epoxy resin is obtained by carrying out reflux reaction on an organosilicon intermediate containing styryl and bisphenol A epoxy resin in the presence of a catalyst and an organic solvent until reactants are transparent, then cooling to below 100 ℃, adding alpha, omega-dihydroxy polydimethylsiloxane and a silane coupling agent into a reaction system, and carrying out reflux reaction until a wire drawing phenomenon occurs.
Preferably, the styrene group-containing organosilicon intermediate, the bisphenol A epoxy resin, the catalyst, the organic solvent, the alpha, omega-dihydroxy polydimethylsiloxane and the silane coupling agent are fed in a mass ratio of 1: 2-3: 0.01-0.05: 4-6: 0.4-0.5: 0.05 to 0.1, and more preferably 1: 2-2.5: 0.02-0.05: 4-6: 0.4-0.5: 0.08 to 0.1.
Specifically, the specific preparation method of the organosilicon modified epoxy resin comprises the following steps: adding an organosilicon intermediate containing phenyl vinyl, bisphenol A epoxy resin, a catalyst and an organic solvent into a reactor, heating to a reflux temperature under stirring, and taking out the organic solvent and generated water in the reactor every 20-40 minutes; when the solid mass content of the reaction system is within the range of 75-95%, visually observing the transparency of the reactant by using a smear method every 10-20 minutes; when the coating is transparent, cooling to below 100 ℃, adding alpha, omega-dihydroxy polydimethylsiloxane and a silane coupling agent into a reaction system, and heating to reflux temperature under stirring; and judging the end point of the reaction by using a wire drawing method, and cooling and filtering to obtain the organic silicon modified epoxy resin when a wire drawing phenomenon occurs.
According to one embodiment, the organosilicon intermediate containing styryl is a silanol solution obtained by hydrolyzing chlorosilane in a mixed solvent system consisting of water, isopropanol and xylene at 25-60 ℃, and separating, wherein the silanol solution is obtained by performing reflux water-splitting polycondensation reaction at 100-160 ℃ under the action of a catalyst.
Preferably, the chlorosilane is a mixture of methylphenyldichlorosilane, phenyltrichlorosilane, methylvinyldichlorosilane and vinyltrichlorosilane, wherein the feeding molar ratio of the methylphenyldichlorosilane to the phenyltrichlorosilane is 1: 0.3-0.7: 1.5-1.6: 0.5-1.1.
Preferably, the feeding mass of the water is 3-5 times of the total mass of the chlorosilane feeding.
Preferably, the feeding mass of the isopropanol is 1-2 times of the total mass of the chlorosilane feeding.
Preferably, the feeding mass of the xylene is 2-3 times of the total mass of the chlorosilane.
Preferably, the catalyst is zinc isooctanoate, and the feeding mass of the catalyst is 0.5-5 per mill of the total mass of the chlorosilane feed.
More preferably, the mass fraction of the catalyst is 9%.
According to one embodiment, the bisphenol A type epoxy resin is one or more of the combinations of the trade names E44, CYD 128.
According to one embodiment, the catalyst used in the synthesis of the silicone-modified epoxy resin is tetraisopropyl titanate or tetrabutyl orthotitanate.
According to one embodiment, the organic solvent is xylene or toluene.
According to one embodiment, the α, ω -dihydroxy polydimethylsiloxane is one or a combination of more than one having a viscosity average molecular weight in the range of 2000 to 20000.
According to one embodiment, the silane coupling agent is gamma-aminopropyltriethoxysilane or gamma-glycidoxypropyltrimethoxysilane.
According to the invention, the silicon dioxide is one or more with the particle size ranging from 20nm to 20 μm.
The invention also aims to provide a preparation method of the adhesive, which is characterized in that the adhesive is obtained by uniformly mixing the organosilicon modified epoxy resin, the silicon dioxide, the acetone and the toluene according to the formula amount.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
the adhesive for the single-sided glass cloth reinforced mica tape with less glue has larger relative molecular mass and higher viscosity at normal temperature, and is beneficial to the adhesion between the glass cloth and the mica paper; meanwhile, the adhesive has lower viscosity at high temperature, so that the adhesive is favorably permeated in the mica paper, the adhesive area of the mica paper is increased, and the adhesive force between the glass cloth and the mica paper is further increased. In addition, the adhesive has good heat resistance and good compatibility with VPI impregnating resin, and meets the use requirements of current wind power generation.
The preparation method of the adhesive for the single-side glass cloth reinforced mica tape with less glue has the advantages of simple process, low price of the adopted raw materials, convenient detection and control of each parameter in the preparation process, no special requirements on preparation devices and facilities and high yield.
Detailed Description
The present invention is further illustrated by the following specific examples.
In the following examples, chlorosilane, bisphenol a type epoxy resin, α, ω -dihydroxypolydimethylsiloxane, a catalyst, a silane coupling agent, silica, and an organic solvent as raw materials were commercially available; the VPI impregnating resin is selected from TH1168 produced by Suzhou Taihu lake New electrician materials GmbH.
Example 1
The embodiment provides a preparation method of an adhesive for a single-sided glass cloth reinforced mica tape with less glue, which comprises the following steps:
A. preparation of phenyl vinyl containing organosilicon intermediates
Adding a mixed solvent of 165g of water, 55g of isopropanol and 110g of xylene into a four-neck flask, stirring and heating to 50 ℃, slowly adding 19.1g of methyl phenyl dichlorosilane, 6.4g of phenyl trichlorosilane, 21.1g of methyl vinyl dichlorosilane and 8.07g of vinyl trichlorosilane into the system, carrying out hydrolysis reaction for 6 hours, cooling to room temperature, and separating to obtain a silanol solution; and then adding 0.027g of zinc isooctanoate catalyst with the mass fraction of 9 percent into the obtained silanol solution, heating the mixture to 160 ℃ under stirring, carrying out polycondensation reaction, refluxing and water dividing, washing the mixture to be neutral when the viscosity of the system is about 3000mpa & s, vacuumizing, and removing the solvent to obtain the organosilicon intermediate containing phenyl vinyl.
B. Preparation of Silicone-modified epoxy resin
Adding 50g of phenyl vinyl-containing organosilicon intermediate, 100g of E44 epoxy resin, 1g of tetraisopropyl titanate and 200g of dimethylbenzene into a four-neck flask, heating to reflux temperature under stirring, and taking out the organic solvent and generated water in an oil-water separator every 30 minutes; when the solid content of the system is within the range of 80% + -5%, the transparency of the reactant is visually observed by using a smear method every 15 minutes; when the coating is transparent, cooling to below 100 ℃, adding 20g of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity-average molecular weight of 2000 and 4g of KH550 silane coupling agent into the system, and heating to reflux temperature under stirring; and judging the end point of the reaction by using a wire drawing method, and cooling and filtering to obtain the organic silicon modified epoxy resin when a wire drawing phenomenon occurs.
C. Adhesive for preparing single-sided glass cloth reinforced low-glue mica tape
Weighing 200g of organic silicon modified epoxy resin, 10g of 20 nm-grade silicon dioxide, 500g of acetone and 1500g of toluene, and stirring in a rubber barrel until the materials are uniformly mixed.
Weighing 100g of adhesive, drying at 120 ℃ for 3 hours, and carrying out thermal weight loss performance test; in addition, mixing the adhesive (with the solid content of 100%) and TH1168 impregnating varnish according to the mass ratio of 1:3, heating and curing to prepare a film, and determining the compatibility of the adhesive and the TH by measuring the change of the dielectric loss factor of the film; secondly, preparing a single-sided glass cloth reinforced mica tape with a thickness of 0.13mm by using the prepared adhesive, and carrying out various performance tests on the mica tape; in addition, the mica tape is used for manufacturing a wire bar, the process adopts a 6kv lapping process, and the thickness of a single side is 1.3 mm; baking the manufactured wire rod for 4 hours at 120 ℃, performing dipping treatment in a VPI (vacuum pressure impregnation) paint dipping tank by using TH1168, and performing electrical performance test on the wire rod after curing.
Example 2
The embodiment provides a preparation method of an adhesive for a single-sided glass cloth reinforced mica tape with less glue, which comprises the following steps:
A. preparation of phenyl vinyl containing organosilicon intermediates
Adding a mixed solvent of 268g of water, 105g of isopropanol and 175g of xylene into a four-neck flask, stirring and heating to 50 ℃, slowly adding 19.1g of methyl phenyl dichlorosilane, 10.6g of phenyl trichlorosilane, 21.1g of methyl vinyl dichlorosilane and 16.2g of vinyl trichlorosilane into the system, carrying out hydrolysis reaction for 8 hours, cooling to room temperature, and separating to obtain a silanol solution; and then adding 0.15g of zinc isooctanoate catalyst with the mass fraction of 9 percent into the obtained silanol solution, heating the mixture at the temperature of 100 ℃ and 160 ℃ under stirring, carrying out polycondensation reaction, refluxing and water dividing, washing the mixture to be neutral when the viscosity of the system is about 4000mpa & s, vacuumizing, and removing the solvent to obtain the organosilicon intermediate containing phenyl vinyl.
B. Preparation of Silicone-modified epoxy resin
Adding 100g of an organosilicon intermediate containing styryl, 250g of CYD128 epoxy resin, 3g of tetrabutyl orthotitanate and 500g of toluene into a four-neck flask, heating to reflux temperature under stirring, and taking out an organic solvent and generated water in an oil-water separator every 30 minutes; when the solid content of the system is in the range of 85% +/-5%, the transparency of the reactant is visually observed by using a smear method every 15 minutes; when the coating is transparent, cooling to below 100 ℃, adding 50g of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity-average molecular weight of 5000 and 10g of KH560 silane coupling agent into the system, and heating to reflux temperature under stirring; and judging the end point of the reaction by using a wire drawing method, and cooling and filtering to obtain the organic silicon modified epoxy resin when a wire drawing phenomenon occurs.
C. Adhesive for preparing single-sided glass cloth reinforced low-glue mica tape
Weighing 1000g of organic silicon modified epoxy resin, 50g of 10-micron-grade silicon dioxide, 1800g of acetone and 5000g of toluene, and stirring in a glue bucket until the materials are uniformly mixed.
Weighing 100g of adhesive, drying at 120 ℃ for 3 hours, and carrying out thermal weight loss performance test; in addition, mixing the adhesive (with the solid content of 100%) and TH1168 impregnating varnish according to the mass ratio of 1:3, heating and curing to prepare a film, and determining the compatibility of the adhesive and the TH by measuring the change of the dielectric loss factor of the film; secondly, preparing a single-sided glass cloth reinforced mica tape with a thickness of 0.13mm by using the prepared adhesive, and carrying out various performance tests on the mica tape; in addition, the mica tape is used for manufacturing a wire bar, the process adopts a 6kv lapping process, and the thickness of a single side is 1.3 mm; baking the manufactured wire rod for 4 hours at 120 ℃, performing dipping treatment in a VPI (vacuum pressure impregnation) paint dipping tank by using TH1168, and performing electrical performance test on the wire rod after curing.
Example 3
The embodiment provides a preparation method of an adhesive for a single-sided glass cloth reinforced mica tape with less glue, which comprises the following steps:
A. preparation of phenyl vinyl containing organosilicon intermediates
Adding a mixed solvent of 372g of water, 148g of isopropanol and 223g of xylene into a four-neck flask, stirring and heating to 50 ℃, slowly adding 19.1g of methyl phenyl dichlorosilane, 14.8g of phenyl trichlorosilane, 22.6g of methyl vinyl dichlorosilane and 17.8g of vinyl trichlorosilane into the system, carrying out hydrolysis reaction for 9 hours, cooling to room temperature, and separating to obtain a silanol solution; and then adding 0.372g of zinc isooctanoate catalyst with the mass fraction of 9 percent into the obtained silanol solution, heating the mixture at the temperature of 100 ℃ and 160 ℃ under stirring, carrying out polycondensation reaction, refluxing and water dividing, washing the mixture to be neutral when the viscosity of the system is about 4500mpa & s, vacuumizing, and removing the solvent to obtain the organosilicon intermediate containing phenyl vinyl.
B. Preparation of Silicone-modified epoxy resin
Adding 50g of styryl-containing organosilicon intermediate, 50g of CYD128 epoxy resin, 75g of E44 epoxy resin, 2.5g of tetrabutyl orthotitanate and 200g of toluene into a four-neck flask, heating to reflux temperature under stirring, and taking out the organic solvent and the generated water in an oil-water separator every 30 minutes; when the solid content of the system is within 90% + -5%, the transparency of the reactant is visually observed by using a smear method every 15 minutes; when the coating is transparent, cooling to below 100 ℃, adding 25g of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity average molecular weight of 20000 and 5g of KH550 silane coupling agent into the system, and heating to reflux temperature under stirring; and judging the end point of the reaction by using a wire drawing method, and cooling and filtering to obtain the organic silicon modified epoxy resin when a wire drawing phenomenon occurs.
C. Adhesive for preparing single-sided glass cloth reinforced low-glue mica tape
Weighing 1500g of organic silicon modified epoxy resin, 150g of 20-micron-level silicon dioxide, 3000g of acetone and 8000g of toluene, and stirring in a rubber barrel until the components are uniformly mixed.
Weighing 100g of adhesive, drying at 120 ℃ for 3 hours, and carrying out thermal weight loss performance test; in addition, mixing the adhesive (with the solid content of 100%) and TH1168 impregnating varnish according to the mass ratio of 1:3, heating and curing to prepare a film, and determining the compatibility of the adhesive and the TH by measuring the change of the dielectric loss factor of the film; secondly, preparing a single-sided glass cloth reinforced mica tape with a thickness of 0.13mm by using the prepared adhesive, and carrying out various performance tests on the mica tape; in addition, the mica tape is used for manufacturing a wire bar, the process adopts a 6kv lapping process, and the thickness of a single side is 1.3 mm; baking the manufactured wire rod for 4 hours at 120 ℃, performing dipping treatment in a VPI (vacuum pressure impregnation) paint dipping tank by using TH1168, and performing electrical performance test on the wire rod after curing.
Example 4
The embodiment provides a preparation method of an adhesive for a single-sided glass cloth reinforced mica tape with less glue, which comprises the following steps:
A. preparation of phenyl vinyl containing organosilicon intermediates
Adding a mixed solvent of 540g of water, 140g of isopropanol and 360g of xylene into a four-neck flask, stirring and heating to 50 ℃, slowly adding 37.5g of methyl phenyl dichlorosilane, 28.2g of phenyl trichlorosilane, 42.3g of methyl vinyl dichlorosilane and 32.0g of vinyl trichlorosilane into the system, carrying out hydrolysis reaction for 9 hours, cooling to room temperature, and separating to obtain a silanol solution; and then adding 0.2g of zinc isooctanoate catalyst with the mass fraction of 9 percent into the obtained silanol solution, heating the mixture at the temperature of 100 ℃ and 160 ℃ under stirring, carrying out polycondensation reaction, refluxing and water separation, washing the mixture to be neutral when the viscosity of the system is about 3500mpa & s, vacuumizing, and removing the solvent to obtain the organosilicon intermediate containing phenyl vinyl.
B. Preparation of Silicone-modified epoxy resin
Adding 100g of styryl-containing organosilicon intermediate, 100g of CYD128 epoxy resin, 150g of E44 epoxy resin, 3g of tetrabutyl orthotitanate and 600g of toluene into a four-neck flask, heating to reflux temperature under stirring, and taking out the organic solvent and generated water in an oil-water separator every 30 minutes; when the solid content of the system is in the range of 85% +/-5%, the transparency of the reactant is visually observed by using a smear method every 15 minutes; when the coating is transparent, cooling to below 100 ℃, adding 50g of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity-average molecular weight of 5000 and 10g of KH550 silane coupling agent into the system, and heating to reflux temperature under stirring; and judging the end point of the reaction by using a wire drawing method, and cooling and filtering to obtain the organic silicon modified epoxy resin when a wire drawing phenomenon occurs.
C. Adhesive for preparing single-sided glass cloth reinforced low-glue mica tape
1000g of organic silicon modified epoxy resin, 155g of 1 micron-grade silicon dioxide, 2000g of acetone and 4500g of toluene are weighed and stirred in a rubber barrel until the components are uniformly mixed.
Weighing 100g of adhesive, drying at 120 ℃ for 3 hours, and carrying out thermal weight loss performance test; in addition, mixing the adhesive (with the solid content of 100%) and TH1168 impregnating varnish according to the mass ratio of 1:3, heating and curing to prepare a film, and determining the compatibility of the adhesive and the TH by measuring the change of the dielectric loss factor of the film; secondly, preparing a single-sided glass cloth reinforced mica tape with a thickness of 0.13mm by using the prepared adhesive, and carrying out various performance tests on the mica tape; in addition, the mica tape is used for manufacturing a wire bar, the process adopts a 6kv lapping process, and the thickness of a single side is 1.3 mm; baking the manufactured wire rod for 4 hours at 120 ℃, performing dipping treatment in a VPI (vacuum pressure impregnation) paint dipping tank by using TH1168, and performing electrical performance test on the wire rod after curing.
Example 5
The embodiment provides a preparation method of an adhesive for a single-sided glass cloth reinforced mica tape with less glue, which comprises the following steps:
A. preparation of phenyl vinyl containing organosilicon intermediates
Adding a mixed solvent of 165g of water, 55g of isopropanol and 110g of xylene into a four-neck flask, stirring and heating to 50 ℃, slowly adding 19.1g of methyl phenyl dichlorosilane, 6.4g of phenyl trichlorosilane, 21.1g of methyl vinyl dichlorosilane and 8.07g of vinyl trichlorosilane into the system, carrying out hydrolysis reaction for 6 hours, cooling to room temperature, and separating to obtain a silanol solution; and then adding 0.027g of zinc isooctanoate catalyst with the mass fraction of 9 percent into the obtained silanol solution, heating the mixture to 160 ℃ under stirring, carrying out polycondensation reaction, refluxing and water dividing, washing the mixture to be neutral when the viscosity of the system is about 3000mpa & s, vacuumizing, and removing the solvent to obtain the organosilicon intermediate containing phenyl vinyl.
B. Preparation of Silicone-modified epoxy resin
Adding 50g of phenyl vinyl containing organosilicon intermediate, 150g of E44 epoxy resin, 0.5g of tetraisopropyl titanate and 200g of dimethylbenzene into a four-neck flask, heating to reflux temperature under stirring, and taking out the organic solvent and generated water in an oil-water separator every 30 minutes; when the solid content of the system is within the range of 80% + -5%, the transparency of the reactant is visually observed by using a smear method every 15 minutes; when the coating is transparent, cooling to below 100 ℃, adding 25g of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity average molecular weight of 20000 and 5g of KH550 silane coupling agent into the system, and heating to reflux temperature under stirring; and judging the end point of the reaction by using a wire drawing method, and cooling and filtering to obtain the organic silicon modified epoxy resin when a wire drawing phenomenon occurs.
C. Adhesive for preparing single-sided glass cloth reinforced low-glue mica tape
200g of organic silicon modified epoxy resin, 100g of 20 nm-grade silicon dioxide, 900g of acetone and 2800g of toluene are weighed and stirred in a rubber barrel until the components are uniformly mixed.
Weighing 100g of adhesive, drying at 120 ℃ for 3 hours, and carrying out thermal weight loss performance test; in addition, mixing the adhesive (with the solid content of 100%) and TH1168 impregnating varnish according to the mass ratio of 1:3, heating and curing to prepare a film, and determining the compatibility of the adhesive and the TH by measuring the change of the dielectric loss factor of the film; secondly, preparing a single-sided glass cloth reinforced mica tape with a thickness of 0.13mm by using the prepared adhesive, and carrying out various performance tests on the mica tape; in addition, the mica tape is used for manufacturing a wire bar, the process adopts a 6kv lapping process, and the thickness of a single side is 1.3 mm; baking the manufactured wire rod for 4 hours at 120 ℃, performing dipping treatment in a VPI (vacuum pressure impregnation) paint dipping tank by using TH1168, and performing electrical performance test on the wire rod after curing.
Example 6
The embodiment provides a preparation method of an adhesive for a single-sided glass cloth reinforced mica tape with less glue, which comprises the following steps:
A. preparation of phenyl vinyl containing organosilicon intermediates
Adding a mixed solvent of 372g of water, 148g of isopropanol and 223g of xylene into a four-neck flask, stirring and heating to 50 ℃, slowly adding 19.1g of methyl phenyl dichlorosilane, 14.8g of phenyl trichlorosilane, 22.6g of methyl vinyl dichlorosilane and 17.8g of vinyl trichlorosilane into the system, carrying out hydrolysis reaction for 7 hours, cooling to room temperature, and separating to obtain a silanol solution; and then adding 0.372g of zinc isooctanoate catalyst with the mass fraction of 9 percent into the obtained silanol solution, heating the mixture at the temperature of 100 ℃ and 160 ℃ under stirring, carrying out polycondensation reaction, refluxing and water separation, washing the mixture to be neutral when the viscosity of the system is about 3500mpa & s, vacuumizing, and removing the solvent to obtain the organosilicon intermediate containing phenyl vinyl.
B. Preparation of Silicone-modified epoxy resin
Adding 50g of styryl-containing organosilicon intermediate, 50g of CYD128 epoxy resin, 100g of E44 epoxy resin, 0.5g of tetrabutyl orthotitanate and 300g of toluene into a four-neck flask, heating to reflux temperature under stirring, and taking out the organic solvent and the generated water in an oil-water separator every 30 minutes; when the solid content of the system is in the range of 85% +/-5%, the transparency of the reactant is visually observed by using a smear method every 15 minutes; when the coating is transparent, cooling to below 100 ℃, adding 25g of alpha, omega-dihydroxy polydimethylsiloxane with viscosity average molecular weight of 20000 and 3g of KH550 silane coupling agent into the system, and heating to reflux temperature under stirring; and judging the end point of the reaction by using a wire drawing method, and cooling and filtering to obtain the organic silicon modified epoxy resin when a wire drawing phenomenon occurs.
C. Adhesive for preparing single-sided glass cloth reinforced low-glue mica tape
100g of organic silicon modified epoxy resin, 35g of 20-micron-grade silicon dioxide, 255g of acetone and 815g of toluene are weighed and stirred in a rubber barrel until the components are uniformly mixed.
Weighing 100g of adhesive, drying at 120 ℃ for 3 hours, and carrying out thermal weight loss performance test; in addition, mixing the adhesive (with the solid content of 100%) and TH1168 impregnating varnish according to the mass ratio of 1:3, heating and curing to prepare a film, and determining the compatibility of the adhesive and the TH by measuring the change of the dielectric loss factor of the film; secondly, preparing a single-sided glass cloth reinforced mica tape with a thickness of 0.13mm by using the prepared adhesive, and carrying out various performance tests on the mica tape; in addition, the mica tape is used for manufacturing a wire bar, the process adopts a 6kv lapping process, and the thickness of a single side is 1.3 mm; baking the manufactured wire rod for 4 hours at 120 ℃, performing dipping treatment in a VPI (vacuum pressure impregnation) paint dipping tank by using TH1168, and performing electrical performance test on the wire rod after curing.
Comparative example 1
Weighing 100g of epoxy mica tape adhesive (sold in the market), drying for 3 hours at 120 ℃, and then carrying out a thermal weight loss performance test; in addition, mixing the adhesive (with the solid content of 100%) and TH1168 impregnating varnish according to the mass ratio of 1:3, heating and curing to prepare a film, and determining the compatibility of the adhesive and the TH by measuring the change of the dielectric loss factor of the film; secondly, preparing a single-sided glass cloth reinforced mica tape with a thickness of 0.13mm by using the prepared adhesive, and carrying out various performance tests on the mica tape; in addition, the mica tape is used for manufacturing a wire bar, the process adopts a 6kv lapping process, and the thickness of a single side is 1.3 mm; baking the manufactured wire rod for 4 hours at 120 ℃, performing dipping treatment in a VPI (vacuum pressure impregnation) paint dipping tank by using TH1168, and performing electrical performance test on the wire rod after curing.
Table 1 shows the properties of the adhesives of examples 1 to 6 and comparative example 1, table 2 shows the properties of the adhesives of examples 1 to 6 and comparative example 1 for preparing mica tapes, and table 3 shows the electrical properties of the wire rod made of the mica tapes made of the adhesives of examples 1 to 6 and comparative example 1.
TABLE 1
TABLE 2
TABLE 3
As can be seen from tables 1 to 3, the adhesive for the single-sided glass cloth reinforced mica tape with less glue has good heat resistance and good compatibility with TH1168 impregnating varnish; in addition, the adhesive has good adhesion, and the glue content of the manufactured mica tape is 9-10%; in addition, the mica tape prepared by the adhesive has better tensile and dielectric properties; the bar wrapped with this mica tape also exhibited better electrical performance.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (9)
1. A single-sided glass cloth reinforced little-glue mica tape is characterized in that: the adhesive comprises an adhesive, and consists of the following components in percentage by mass of 100 percent:
the organosilicon modified epoxy resin is obtained by carrying out reflux reaction on an organosilicon intermediate containing phenyl vinyl and bisphenol A epoxy resin in the presence of a catalyst and an organic solvent until reactants are transparent, then cooling to below 100 ℃, adding alpha, omega-dihydroxy polydimethylsiloxane and a silane coupling agent into a reaction system, and carrying out reflux reaction until a wire drawing phenomenon occurs; wherein the charging mass ratio of the styryl-containing organosilicon intermediate, the bisphenol A epoxy resin, the catalyst, the organic solvent, the alpha, omega-dihydroxy polydimethylsiloxane and the silane coupling agent is 1: 2-2.5: 0.02-0.05: 4-6: 0.4-0.5: 0.08 to 0.1; the alpha, omega-dihydroxy polydimethylsiloxane is one or a combination of more than one of viscosity average molecular weight in the range of 2000-20000;
the silicon dioxide is one or more with the particle size ranging from 20nm to 20 mu m;
the organosilicon intermediate containing the styryl is a silanol solution obtained by hydrolyzing chlorosilane in a mixed solvent system consisting of water, isopropanol and xylene at 25-60 ℃ and separating, and the silanol solution is obtained by reflux water-splitting polycondensation reaction at 100-160 ℃ under the action of a catalyst; wherein the chlorosilane is a mixture of methylphenyldichlorosilane, phenyltrichlorosilane, methylvinyldichlorosilane and vinyltrichlorosilane with the feeding molar ratio of 1: 0.3-0.7: 1.5-1.6: 0.5-1.1; the feeding mass of the water is 3-5 times of the total mass of the chlorosilane feeding; the feeding mass of the isopropanol is 1-2 times of the total mass of the chlorosilane feeding; the feeding mass of the dimethylbenzene is 2-3 times of the total mass of the chlorosilane feeding; the catalyst is zinc isooctanoate, and the feeding mass of the catalyst is 0.5-5 per mill of the total mass of the chlorosilane feeding.
2. The single-sided glass cloth reinforced dry mica tape according to claim 1, wherein: the specific preparation method of the organic silicon modified epoxy resin comprises the following steps: adding the phenyl vinyl-containing organosilicon intermediate, the bisphenol A epoxy resin, the catalyst and the organic solvent into a reactor, heating to a reflux temperature under stirring, and taking out the organic solvent and generated water in the reactor every 20-40 minutes; when the solid mass content of the reaction system is within the range of 75-95%, visually observing the transparency of the reactant by using a smear method every 10-20 minutes; when the coating is transparent, cooling to below 100 ℃, adding the alpha, omega-dihydroxy polydimethylsiloxane and the silane coupling agent into a reaction system, and heating to reflux temperature under stirring; and judging the end point of the reaction by using a wire drawing method, and cooling and filtering to obtain the organic silicon modified epoxy resin when a wire drawing phenomenon occurs.
3. The single-sided glass cloth reinforced dry mica tape according to claim 1, wherein: the mass fraction of the catalyst in the preparation of the styryl-containing organosilicon intermediate is 9%.
4. The single-sided glass cloth reinforced dry mica tape according to claim 1, wherein: the bisphenol A type epoxy resin is one or a combination of more of the trade marks E44 and CYD 128.
5. The single-sided glass cloth reinforced dry mica tape according to claim 1, wherein: the catalyst for synthesizing the organic silicon modified epoxy resin is tetraisopropyl titanate or tetrabutyl orthotitanate.
6. The single-sided glass cloth reinforced dry mica tape according to claim 1, wherein: the organic solvent is xylene or toluene.
7. The single-sided glass cloth reinforced dry mica tape according to claim 1, wherein: the silane coupling agent is gamma-aminopropyl triethoxysilane or gamma-glycidoxypropyl trimethoxysilane.
8. The single-sided glass cloth reinforced dry mica tape according to claim 1, wherein: the adhesive is prepared by uniformly mixing the organosilicon modified epoxy resin, the silicon dioxide, the acetone and the toluene according to the formula ratio.
9. A wire bar, characterized by: comprising the single-sided glass cloth reinforced dry mica tape of any one of claims 1 to 8.
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| CN201610961216.3A CN106497475B (en) | 2016-10-28 | 2016-10-28 | Adhesive for single-side glass cloth reinforced mica tape with less glue and preparation method thereof |
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| CN107134328B (en) * | 2017-04-21 | 2019-01-25 | 南通中菱电力科技股份有限公司 | A kind of preparation method of few ageing-resistant mica tape of glue-type |
| CN108384479B (en) * | 2018-02-01 | 2019-12-03 | 苏州太湖电工新材料股份有限公司 | Adhesive of high thermal conductivity low resin mica tape and preparation method thereof and low resin mica tape |
| CN112778926B (en) * | 2020-12-30 | 2022-09-09 | 苏州巨峰电气绝缘系统股份有限公司 | H-grade mica tape with less glue, preparation method and application thereof |
| CN114196020A (en) * | 2021-11-12 | 2022-03-18 | 安徽沸点新材料有限公司 | Phenyl methoxy silane polymer and preparation method thereof |
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