CN110982397A - Environment-friendly pure resin impregnated insulating paint with high paint coating amount and preparation method thereof - Google Patents
Environment-friendly pure resin impregnated insulating paint with high paint coating amount and preparation method thereof Download PDFInfo
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- CN110982397A CN110982397A CN201911295493.5A CN201911295493A CN110982397A CN 110982397 A CN110982397 A CN 110982397A CN 201911295493 A CN201911295493 A CN 201911295493A CN 110982397 A CN110982397 A CN 110982397A
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6858—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
Abstract
The invention discloses an environment-friendly high-coating-quantity pure resin impregnated insulating paint and a preparation method thereof, wherein the environment-friendly high-coating-quantity pure resin impregnated insulating paint comprises the following components in percentage by weight: 97.89-99 percent of imine modified low-viscosity self-crosslinkable unsaturated polyester resin, 0.9-2 percent of dicumyl peroxide, 0.01-0.1 percent of cobalt naphthenate and 0.05-0.2 percent of hydroquinone, wherein the imine modified low-viscosity self-crosslinkable unsaturated polyester resin is prepared from maleic anhydride, saturated dibasic acid, polyalcohol, modified monofunctional group imino alcohol, methyl methacrylate modified hydroxy diphenyl ether, tetrabutyl titanate and hydroquinone. The product of the invention does not add any micromolecule active monomer, and the imine structure and the diphenyl ether structure are introduced into the resin, so that the heat resistance, the mechanical property and the electric insulation property of the resin can be obviously improved, the invention has the advantage of high paint coating amount, and the smoke is avoided when the high-temperature baking is carried out.
Description
Technical Field
The invention relates to the technical field of insulating paint, in particular to environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint and a preparation method thereof.
Background
Vacuum pressure paint dipping (VPI) technology is widely applied to the insulation technology of electric and mechanical devices at home and abroad. VPI technology includes many elements, but the insulation performance is mainly dependent on the VPI impregnation resin. Most of the VPI impregnating resins used at home and abroad use styrene as a diluent.
The styrene has strong reactivity, good compatibility with resin, high solid content of the insulating paint, and uniform and full paint film after baking; the viscosity of the styrene is low, so that the insulating paint with high solid content has low viscosity, good permeability, easy reaching to the center and complex parts, full integral impregnation and good comprehensive insulating property. However, styrene has the disadvantages of high saturated vapor pressure, strong odor and irritation, so that unpleasant odor is emitted during paint dipping and baking, and certain influence is exerted on operators and the surrounding environment. Meanwhile, the styrene has strong volatility and strong smell, the toxicity of the styrene is equivalent to that of toluene, and the allowable concentration of the styrene and the toluene is 210mg/m3. In addition, the average maximum concentration of the environment-friendly regulated workplace within 8 hours is different from country to country, and the range is 84-420 mg/m3. When the concentration of the styrene in the air reaches 0.012mg/m3Even less, people can smell the coke, and people are sensitive to the smell of coke such as styrene, thus influencing the health of people.
Along with the development of economy, people are more and more conscious of environmental protection. Styrene has received attention because of its peculiar smell and its noxious irritant and anesthetic action at higher vapor concentrations. Many countries impose mandatory regulations on allowable styrene vapor concentrations at production sites, and the specific requirements are becoming more stringent. The average value of the measurement within 8h specified in China is 210mg/m3. Therefore, the nontoxic environment-friendly insulating paint must replace the toxic styrene solvent-free impregnating varnish. To solve the toxicity and volatility problems of styrene, many companies have begun to try to replace styrene with high-boiling, high-activity, low-toxicity, odorless reactive monomers, mainly diallyl phthalate (DAP), triallyl isocyanurate (TAIC), high-flash, high-boiling acrylates and methacrylates. But this is notDuring the use of the insulating paint prepared by the similar active monomer (such as Voltatex series products of Axalta company and Damisol-3630 of Von Roll company), the viscosity of the paint at high temperature is reduced quickly due to low volatility, the insulating paint is seriously lost during the baking process, and the paint hanging amount of a motor after the insulating paint is impregnated is small, and the insulating paint is seriously wasted. In addition, the high boiling point reactive monomer has a serious problem of "smoke" in the high temperature baking process, that is, the high boiling point monomer volatilized at high temperature condenses and liquefies in the air to generate mist, which has a great influence on the use environment.
Disclosure of Invention
The invention aims to provide an environment-friendly high-coating-capacity pure resin impregnating insulating paint and a preparation method thereof, wherein a 100% low-viscosity pure resin system is adopted, on one hand, through the ester exchange reaction of methyl methacrylate and hydroxyl diphenyl ether, the active double bond of methacrylic acid is introduced into diphenyl ether molecules, and then the structure is introduced into unsaturated polyester, so that the methacrylate double bond is brought into the unsaturated polyester molecules, and the self-crosslinking of the resin is realized; on the other hand, the unsaturated polyester resin is modified by the modified monofunctional imine alcohol and the methyl methacrylate modified hydroxyl diphenyl ether to control the molecular weight, so that the pure resin with low viscosity is synthesized, no small molecular active monomer is added into the product, and the imine structure and the diphenyl ether structure are introduced into the resin, so that the heat resistance, the mechanical property and the electrical insulation property of the resin can be obviously improved, and the problems of large loss, small paint coating amount, smoke generation in high-temperature baking and the like in the baking and curing process in the prior art are solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an environment-friendly high-coating-quantity pure resin impregnated insulating paint, which comprises the following components in percentage by weight:
the imine modified low-viscosity self-crosslinkable unsaturated polyester resin is prepared from the following raw materials in percentage by weight:
further, the modified monofunctional imine alcohol was synthesized from 61.4% of maleic anhydride, 31.3% of ethanolamine and 0.3% of catalyst of tin butoxide, in weight percent.
Further, the synthetic route of the modified monofunctional imine alcohol is shown as the reaction formula I:
reaction formula I.
Further, the methyl methacrylate modified hydroxydiphenyl ether is prepared by synthesizing 33% of methyl methacrylate, 66.7% of 4,4' -dihydroxydiphenyl ether, 0.15% of tetrabutyl titanate serving as a catalyst and 0.15% of hydroquinone serving as a polymerization inhibitor in percentage by weight. The method is characterized in that the active double bond of methacrylic acid is introduced into diphenyl ether molecules through the ester exchange reaction of methyl methacrylate and 4,4' -dihydroxy diphenyl ether, and then the structure is introduced into unsaturated polyester, so that methacrylate double bonds are introduced into the unsaturated polyester molecules, and the self-crosslinking of the resin is realized.
Further, the synthetic route of the methyl methacrylate modified hydroxyl diphenyl ether is shown as a reaction formula II:
reaction formula II.
Further, the saturated dibasic acid is one or any combination of phthalic anhydride, adipic acid and sebacic acid.
Further, the polyalcohol is one or any combination of propylene glycol, ethyl butyl propylene glycol, neopentyl glycol, bisphenol A and dipropylene glycol.
In a second aspect, the invention also provides a preparation method of any one of the environment-friendly high-varnish-content pure resin impregnated insulating varnish, which comprises the following steps:
(1) synthesis of modified monofunctional iminoalcohols: adding maleic anhydride and ethanolamine into a four-neck flask with nitrogen introduced, controlling the oil temperature to 120 ℃ for dropwise reaction, heating the ethanolamine to 210 ℃ after the ethanolamine is dropwise added for 1h, adding a catalyst of tin butoxide for dehydration reaction until the acid value is less than 2mgKOH/g, and cooling to synthesize modified monofunctional imino alcohol for later use;
(2) synthesizing methyl methacrylate modified hydroxyl diphenyl ether: sequentially adding methyl methacrylate, 4' -dihydroxy diphenyl ether, tetrabutyl titanate serving as a catalyst and hydroquinone serving as a polymerization inhibitor into a four-neck flask into which nitrogen is introduced, controlling the oil temperature to be 100 ℃, and synthesizing to obtain methyl methacrylate modified hydroxy diphenyl ether for later use when the reaction reaches the end point;
(3) synthesis of imine-modified low-viscosity self-crosslinkable unsaturated polyester resin: sequentially adding maleic anhydride, saturated dibasic acid, polyol and the modified monofunctional group imino alcohol prepared in the step (1) into a four-neck flask into which nitrogen is introduced, stirring and heating to 160 ℃, controlling the end point temperature to be 220 ℃, cooling to 130 ℃ when the acid value is less than 50mgKOH/g, adding the methyl methacrylate modified hydroxy diphenyl ether prepared in the step (2), a catalyst tetrabutyl titanate and a polymerization inhibitor hydroquinone to control the molecular weight of a product, and synthesizing to obtain the imine modified low-viscosity self-crosslinkable unsaturated polyester resin after the reaction is finished;
(4) the preparation of the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint comprises the following steps: and (3) adding the imine modified low-viscosity self-crosslinkable unsaturated polyester resin prepared in the step (3) into an initiator dicumyl peroxide, an accelerator cobalt naphthenate and a polymerization inhibitor hydroquinone, stirring and mixing uniformly, and filtering to obtain the environment-friendly high-coating-quantity pure resin impregnated insulating paint.
Further, in the step (4), the stirring speed is 100 to 200r/min, preferably 150 r/min.
Further, in the step (4), the filtering operation is performed by using a 40-mesh filter cloth.
Compared with the prior art, the invention provides the environment-friendly high-coating-quantity pure resin impregnated insulating paint and the preparation method thereof, and the environment-friendly high-coating-quantity pure resin impregnated insulating paint has the following beneficial effects:
1. the product realizes low toxicity and environmental protection by adopting a system of 100 percent of low-viscosity pure resin;
2. the coating amount is high, the coating problem of non-volatile paint is solved, and the coating thickness of the motor can be improved, so that the three-proofing and insulating properties of the motor can be improved, and the temperature rise of the motor during operation is reduced;
3. the problem of smoke generation during high-temperature baking is solved, the problem of smoke generation is mainly caused by the active diluent with high boiling point, but the invention does not need the active diluent at all, adopts a system of 100 percent of low-viscosity pure resin, does not volatilize the diluent at high temperature, and can effectively solve the problem of smoke generation during high-temperature baking;
4. compared with the common insulating paint, the invention has the advantages of long storage period, quick curing, no odor, no toxicity, convenient operation, less volatilization during curing, environmental protection and the like; compared with the common paint dipping process, the invention overcomes the problems of large loss, small paint hanging amount and smoke generation during the baking and curing process of the dipping paint, saves materials, improves the quality of products and reduces the pollution to the environment; the environment-friendly high-coating-quantity pure resin impregnated insulating paint is low-viscosity self-crosslinkable unsaturated polyester resin, does not add any small-molecule active monomer in the product, has good heat resistance and mechanical properties after being cured, and is suitable for common immersion, continuous immersion, vacuum pressure immersion and other immersion treatments of H, C-grade motors and electrical appliances.
Detailed Description
The technical solutions of the present invention will be described clearly and completely by the detailed embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment 1 provides an environment-friendly high-coating-quantity pure resin impregnated insulating paint, which comprises the following components in percentage by weight:
the imine modified low-viscosity self-crosslinkable unsaturated polyester resin is prepared from the following raw materials in percentage by weight:
the modified monofunctional imine alcohol was synthesized from 61.4% maleic anhydride, 31.3% ethanolamine and 0.3% tin butoxide as a catalyst, in weight percent.
The methyl methacrylate modified hydroxyl diphenyl ether is prepared by synthesizing 33 percent of methyl methacrylate, 66.7 percent of 4,4' -dihydroxy diphenyl ether, 0.15 percent of catalyst tetrabutyl titanate and 0.15 percent of polymerization inhibitor hydroquinone.
The preparation method of the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint comprises the following steps:
(1) synthesis of modified monofunctional iminoalcohols: introducing nitrogen into a four-neck flask provided with a thermometer, a dropping funnel, a stirring paddle and a gas-guide tube, firstly adding 61.4% of maleic anhydride, then adding 31.3% of ethanolamine into the dropping funnel, controlling the oil temperature to be 120 ℃ for dropwise addition reaction, after the ethanolamine is dropwise added for 1h, heating to 210 ℃, adding 0.3% of catalyst butoxytin for dehydration reaction until the acid value is less than 2mgKOH/g, and cooling to synthesize the modified monofunctional group imino alcohol for later use;
(2) synthesizing methyl methacrylate modified hydroxyl diphenyl ether: introducing nitrogen into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and an air guide tube, then sequentially adding 33% of methyl methacrylate, 66.7% of 4,4' -dihydroxy diphenyl ether, 0.15% of tetrabutyl titanate serving as a catalyst and 0.15% of hydroquinone serving as a polymerization inhibitor, controlling the oil temperature to be 100 ℃, judging the reaction process according to the discharge amount of methanol, and when the discharge amount of the methanol is more than 98% of a theoretical value, synthesizing to obtain methyl methacrylate modified hydroxydiphenyl ether for later use when the reaction reaches an end point;
(3) synthesis of imine-modified low-viscosity self-crosslinkable unsaturated polyester resin: introducing nitrogen into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and a gas-guide tube, then sequentially adding 28% of maleic anhydride, 6% of phthalic anhydride, 24% of propylene glycol and 22% of modified monofunctional imido alcohol prepared in the step (1), stirring and heating to 160 ℃, in order to prevent the reaction speed from being too fast, adopting a gradual heating method, controlling the end point temperature at 220 ℃, judging the reaction process by adding the change of a test acid value, when the acid value is less than 50mgKOH/g, cooling to 130 ℃, adding 19.89% of methyl methacrylate modified hydroxydiphenyl ether prepared in the step (2), 0.1% of catalyst tetrabutyl titanate and 0.01% of polymerization inhibitor hydroquinone to control the molecular weight of a product, and synthesizing to obtain the imine modified low-viscosity self-crosslinkable unsaturated polyester resin after the reaction is finished;
(4) the preparation of the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint comprises the following steps: adding 99% of the imine modified low-viscosity self-crosslinkable unsaturated polyester resin prepared in the step (3) into 0.9% of dicumyl peroxide as an initiator, 0.03% of cobalt naphthenate as an accelerator and 0.07% of hydroquinone as a polymerization inhibitor, stirring and mixing uniformly at a stirring speed of 180r/min, and filtering by using 40-mesh filter cloth to obtain the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint.
Example 2
The embodiment 2 provides an environment-friendly high-coating-quantity pure resin impregnated insulating paint, which comprises the following components in percentage by weight:
the imine modified low-viscosity self-crosslinkable unsaturated polyester resin is prepared from the following raw materials in percentage by weight:
the modified monofunctional imine alcohol was synthesized from 61.4% maleic anhydride, 31.3% ethanolamine and 0.3% tin butoxide as a catalyst, in weight percent.
The methyl methacrylate modified hydroxyl diphenyl ether is prepared by synthesizing 33 percent of methyl methacrylate, 66.7 percent of 4,4' -dihydroxy diphenyl ether, 0.15 percent of catalyst tetrabutyl titanate and 0.15 percent of polymerization inhibitor hydroquinone.
The preparation method of the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint comprises the following steps:
(1) synthesis of modified monofunctional iminoalcohols: introducing nitrogen into a four-neck flask provided with a thermometer, a dropping funnel, a stirring paddle and a gas-guide tube, firstly adding 61.4% of maleic anhydride, then adding 31.3% of ethanolamine into the dropping funnel, controlling the oil temperature to be 120 ℃ for dropwise addition reaction, after the ethanolamine is dropwise added for 1h, heating to 210 ℃, adding 0.3% of catalyst butoxytin for dehydration reaction until the acid value is less than 2mgKOH/g, and cooling to synthesize the modified monofunctional group imino alcohol for later use;
(2) synthesizing methyl methacrylate modified hydroxyl diphenyl ether: introducing nitrogen into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and an air guide tube, then sequentially adding 33% of methyl methacrylate, 66.7% of 4,4' -dihydroxy diphenyl ether, 0.15% of tetrabutyl titanate serving as a catalyst and 0.15% of hydroquinone serving as a polymerization inhibitor, controlling the oil temperature to be 100 ℃, judging the reaction process according to the discharge amount of methanol, and when the discharge amount of the methanol is more than 98% of a theoretical value, synthesizing to obtain methyl methacrylate modified hydroxydiphenyl ether for later use when the reaction reaches an end point;
(3) synthesis of imine-modified low-viscosity self-crosslinkable unsaturated polyester resin: introducing nitrogen into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and an air duct, then sequentially adding 23% of maleic anhydride, 8% of adipic acid, 10% of ethylbutylpropanediol, 6% of neopentyl glycol and 30% of the modified monofunctional imido alcohol prepared in the step (1), stirring and heating to 160 ℃, adopting a gradual temperature rise method to prevent the reaction speed from being too fast, controlling the end point temperature at 220 ℃, judging the reaction process by adding the change of a test acid value, when the acid value is less than 50mgKOH/g, cooling to 130 ℃, adding 22.45 percent of methyl methacrylate modified hydroxyl diphenyl ether prepared in the step (2), 0.5 percent of tetrabutyl titanate serving as a catalyst and 0.05 percent of hydroquinone serving as a polymerization inhibitor to control the molecular weight of the product, and synthesizing to obtain the imine modified low-viscosity self-crosslinkable unsaturated polyester resin after the reaction is finished;
(4) the preparation of the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint comprises the following steps: 97.95 percent of the imine modified low-viscosity self-crosslinkable unsaturated polyester resin prepared in the step (3) is added with 1.9 percent of dicumyl peroxide as an initiator, 0.1 percent of cobalt naphthenate as an accelerator and 0.05 percent of hydroquinone as a polymerization inhibitor, the mixture is stirred and mixed uniformly at the stirring speed of 150r/min, and then filtering is carried out by adopting 40-mesh filter cloth, thus obtaining the environment-friendly high-coating-quantity pure resin impregnating insulating paint.
Example 3
The embodiment 3 provides an environment-friendly high-coating-quantity pure resin impregnated insulating paint, which comprises the following components in percentage by weight:
the imine modified low-viscosity self-crosslinkable unsaturated polyester resin is prepared from the following raw materials in percentage by weight:
the modified monofunctional imine alcohol was synthesized from 61.4% maleic anhydride, 31.3% ethanolamine and 0.3% tin butoxide as a catalyst, in weight percent.
The methyl methacrylate modified hydroxyl diphenyl ether is prepared by synthesizing 33 percent of methyl methacrylate, 66.7 percent of 4,4' -dihydroxy diphenyl ether, 0.15 percent of catalyst tetrabutyl titanate and 0.15 percent of polymerization inhibitor hydroquinone.
The preparation method of the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint comprises the following steps:
(1) synthesis of modified monofunctional iminoalcohols: introducing nitrogen into a four-neck flask provided with a thermometer, a dropping funnel, a stirring paddle and a gas-guide tube, firstly adding 61.4% of maleic anhydride, then adding 31.3% of ethanolamine into the dropping funnel, controlling the oil temperature to be 120 ℃ for dropwise addition reaction, after the ethanolamine is dropwise added for 1h, heating to 210 ℃, adding 0.3% of catalyst butoxytin for dehydration reaction until the acid value is less than 2mgKOH/g, and cooling to synthesize the modified monofunctional group imino alcohol for later use;
(2) synthesizing methyl methacrylate modified hydroxyl diphenyl ether: introducing nitrogen into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and an air guide tube, then sequentially adding 33% of methyl methacrylate, 66.7% of 4,4' -dihydroxy diphenyl ether, 0.15% of tetrabutyl titanate serving as a catalyst and 0.15% of hydroquinone serving as a polymerization inhibitor, controlling the oil temperature to be 100 ℃, judging the reaction process according to the discharge amount of methanol, and when the discharge amount of the methanol is more than 98% of a theoretical value, synthesizing to obtain methyl methacrylate modified hydroxydiphenyl ether for later use when the reaction reaches an end point;
(3) synthesis of imine-modified low-viscosity self-crosslinkable unsaturated polyester resin: introducing nitrogen into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and a gas-guide tube, then sequentially adding 23% of maleic anhydride, 8% of sebacic acid, 6% of bisphenol A, 10% of dipropylene glycol and 30% of modified monofunctional imidol prepared in the step (1), stirring and heating to 160 ℃, adopting a gradual heating method to prevent the reaction speed from being too fast, controlling the end point temperature at 220 ℃, judging the reaction process by adding the change of a tested acid value, cooling to 130 ℃ when the acid value is less than 50mgKOH/g, adding 22.45% of methyl methacrylate modified hydroxy diphenyl ether prepared in the step (2), 0.5% of catalyst tetrabutyl titanate and 0.05% of polymerization inhibitor hydroquinone to control the molecular weight of a product, and synthesizing to obtain the imine modified low-viscosity self-crosslinkable unsaturated polyester resin after the reaction is finished;
(4) the preparation of the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint comprises the following steps: adding 98% of the imine modified low-viscosity self-crosslinkable unsaturated polyester resin prepared in the step (3) into 1.7% of dicumyl peroxide as an initiator, 0.1% of cobalt naphthenate as an accelerator and 0.2% of hydroquinone as a polymerization inhibitor, stirring and mixing uniformly at a stirring speed of 130r/min, and filtering by using 40-mesh filter cloth to obtain the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint.
Example 4
The embodiment 4 provides an environment-friendly high-coating-quantity pure resin impregnated insulating paint, which comprises the following components in percentage by weight:
the imine modified low-viscosity self-crosslinkable unsaturated polyester resin is prepared from the following raw materials in percentage by weight:
the modified monofunctional imine alcohol was synthesized from 61.4% maleic anhydride, 31.3% ethanolamine and 0.3% tin butoxide as a catalyst, in weight percent.
The methyl methacrylate modified hydroxyl diphenyl ether is prepared by synthesizing 33 percent of methyl methacrylate, 66.7 percent of 4,4' -dihydroxy diphenyl ether, 0.15 percent of catalyst tetrabutyl titanate and 0.15 percent of polymerization inhibitor hydroquinone.
The preparation method of the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint comprises the following steps:
(1) synthesis of modified monofunctional iminoalcohols: introducing nitrogen into a four-neck flask provided with a thermometer, a dropping funnel, a stirring paddle and a gas-guide tube, firstly adding 61.4% of maleic anhydride, then adding 31.3% of ethanolamine into the dropping funnel, controlling the oil temperature to be 120 ℃ for dropwise addition reaction, after the ethanolamine is dropwise added for 1h, heating to 210 ℃, adding 0.3% of catalyst butoxytin for dehydration reaction until the acid value is less than 2mgKOH/g, and cooling to synthesize the modified monofunctional group imino alcohol for later use;
(2) synthesizing methyl methacrylate modified hydroxyl diphenyl ether: introducing nitrogen into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and an air guide tube, then sequentially adding 33% of methyl methacrylate, 66.7% of 4,4' -dihydroxy diphenyl ether, 0.15% of tetrabutyl titanate serving as a catalyst and 0.15% of hydroquinone serving as a polymerization inhibitor, controlling the oil temperature to be 100 ℃, judging the reaction process according to the discharge amount of methanol, and when the discharge amount of the methanol is more than 98% of a theoretical value, synthesizing to obtain methyl methacrylate modified hydroxydiphenyl ether for later use when the reaction reaches an end point;
(3) synthesis of imine-modified low-viscosity self-crosslinkable unsaturated polyester resin: introducing nitrogen into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and a gas-guide tube, then sequentially adding 26% of maleic anhydride, 10% of phthalic anhydride, 10% of ethylbutylpropanediol and 28.67% of modified monofunctional group imino alcohol prepared in the step (1), stirring and heating to 160 ℃, in order to prevent the reaction speed from being too fast, adopting a gradual heating method, controlling the end point temperature at 220 ℃, judging the reaction process by adding the change of a tested acid value, when the acid value is less than 50mgKOH/g, cooling to 130 ℃, adding 25% of methyl methacrylate modified hydroxydiphenyl ether prepared in the step (2), 0.3% of catalyst tetrabutyl titanate and 0.03% of polymerization inhibitor hydroquinone to control the molecular weight of a product, and synthesizing to obtain the imine modified low-viscosity self-crosslinkable unsaturated polyester resin after the reaction is finished;
(4) the preparation of the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint comprises the following steps: 97.89 percent of the imine modified low-viscosity self-crosslinkable unsaturated polyester resin prepared in the step (3) is added with 2 percent of dicumyl peroxide as an initiator, 0.01 percent of cobalt naphthenate as an accelerator and 0.1 percent of hydroquinone as a polymerization inhibitor, the mixture is stirred and mixed uniformly at the stirring speed of 100r/min, and then filtering is carried out by adopting 40-mesh filter cloth, thus obtaining the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint.
Example 5
The embodiment 5 provides an environment-friendly high-coating-quantity pure resin impregnated insulating paint, which comprises the following components in percentage by weight:
the imine modified low-viscosity self-crosslinkable unsaturated polyester resin is prepared from the following raw materials in percentage by weight:
the modified monofunctional imine alcohol was synthesized from 61.4% maleic anhydride, 31.3% ethanolamine and 0.3% tin butoxide as a catalyst, in weight percent.
The methyl methacrylate modified hydroxyl diphenyl ether is prepared by synthesizing 33 percent of methyl methacrylate, 66.7 percent of 4,4' -dihydroxy diphenyl ether, 0.15 percent of catalyst tetrabutyl titanate and 0.15 percent of polymerization inhibitor hydroquinone.
The preparation method of the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint comprises the following steps:
(1) synthesis of modified monofunctional iminoalcohols: introducing nitrogen into a four-neck flask provided with a thermometer, a dropping funnel, a stirring paddle and a gas-guide tube, firstly adding 61.4% of maleic anhydride, then adding 31.3% of ethanolamine into the dropping funnel, controlling the oil temperature to be 120 ℃ for dropwise addition reaction, after the ethanolamine is dropwise added for 1h, heating to 210 ℃, adding 0.3% of catalyst butoxytin for dehydration reaction until the acid value is less than 2mgKOH/g, and cooling to synthesize the modified monofunctional group imino alcohol for later use;
(2) synthesizing methyl methacrylate modified hydroxyl diphenyl ether: introducing nitrogen into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and an air guide tube, then sequentially adding 33% of methyl methacrylate, 66.7% of 4,4' -dihydroxy diphenyl ether, 0.15% of tetrabutyl titanate serving as a catalyst and 0.15% of hydroquinone serving as a polymerization inhibitor, controlling the oil temperature to be 100 ℃, judging the reaction process according to the discharge amount of methanol, and when the discharge amount of the methanol is more than 98% of a theoretical value, synthesizing to obtain methyl methacrylate modified hydroxydiphenyl ether for later use when the reaction reaches an end point;
(3) synthesis of imine-modified low-viscosity self-crosslinkable unsaturated polyester resin: introducing nitrogen into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and a gas-guide tube, then sequentially adding 30% of maleic anhydride, 10% of phthalic anhydride, 30% of dipropylene glycol and 24.45% of modified monofunctional group imino alcohol prepared in the step (1), stirring and heating to 160 ℃, adopting a gradual heating method to prevent the reaction speed from being too fast, controlling the end point temperature at 220 ℃, judging the reaction process by adding the change of a tested acid value, cooling to 130 ℃ when the acid value is less than 50mgKOH/g, adding 5% of methyl methacrylate modified hydroxyl diphenyl ether prepared in the step (2), 0.5% of catalyst tetrabutyl titanate and 0.05% of polymerization inhibitor hydroquinone to control the molecular weight of a product, and synthesizing to obtain the imine modified low-viscosity self-crosslinkable unsaturated polyester resin after the reaction is finished;
(4) the preparation of the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint comprises the following steps: and (3) adding 98.8% of the imine modified low-viscosity self-crosslinkable unsaturated polyester resin prepared in the step (3) into 1% of dicumyl peroxide as an initiator, 0.05% of cobalt naphthenate as an accelerator and 0.15% of hydroquinone as a polymerization inhibitor, stirring and mixing uniformly at a stirring speed of 200r/min, and filtering by using 40-mesh filter cloth to obtain the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint.
Comparative example
The comparative example provides an impregnating insulating paint comprising the following components in percentage by weight:
wherein, the unsaturated polyester resin is unsaturated polyester resin which is sold in the ordinary market, and the high boiling point diluent is methacrylate reactive diluent which is sold in the ordinary market.
Adding 60% of unsaturated polyester resin into 38% of high-boiling point diluent, 1.7% of initiator dicumyl peroxide, 0.1% of accelerator cobalt naphthenate and 0.2% of polymerization inhibitor hydroquinone, stirring and mixing uniformly at a stirring speed of 150r/min, and filtering by adopting 40-mesh filter cloth to obtain the comparative impregnated insulating paint.
After the environment-friendly high-coating-quantity pure resin impregnated insulating paint prepared in the above examples 1 to 5 and the comparative example impregnated insulating paint prepared in the comparative example are respectively heated and cured, the obtained performance data are shown in table 1:
TABLE 1 Properties of the impregnating varnishes prepared in the respective examples and comparative examples
As can be seen from the data analysis in Table 1, the amount of the varnish used in examples 1 to 5 is 2.38 to 2.92 times that of the comparative example, and the volatile matter in examples 1 to 5 is only 20.7 to 28.4 percent of that in the comparative example; from the perspective of the "smoking", the problem of "smoking" does not exist in the embodiments 1 to 5; from the viewpoint of mechanical properties and electrical insulation properties, the examples 1 to 5 have significantly improved effects compared to the comparative examples; therefore, the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint can well solve the problems of large loss, small paint hanging amount, smoke generation during high-temperature baking and the like in the baking and curing process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. The environment-friendly high-coating-quantity pure resin impregnated insulating paint is characterized by comprising the following components in percentage by weight:
the imine modified low-viscosity self-crosslinkable unsaturated polyester resin is prepared from the following raw materials in percentage by weight:
2. the environmentally friendly high varnish amount pure resin impregnating insulating varnish according to claim 1, wherein said modified monofunctional imine alcohol is synthesized from 61.4% maleic anhydride, 31.3% ethanolamine, and 0.3% butoxytin, in weight percent.
3. The environmentally friendly high-varnish-content pure resin impregnating insulating varnish according to claim 2, wherein the modified monofunctional imine alcohol is synthesized according to the reaction scheme I:
4. the environment-friendly high-varnish-content pure resin impregnating insulating varnish as claimed in claim 1, wherein the methyl methacrylate modified hydroxydiphenyl ether is synthesized from 33% of methyl methacrylate, 66.7% of 4,4' -dihydroxydiphenyl ether, 0.15% of tetrabutyl titanate and 0.15% of hydroquinone in percentage by weight.
5. The environment-friendly high-coating-quantity pure resin impregnated insulating paint as claimed in claim 4, wherein the synthetic route of the methyl methacrylate modified hydroxydiphenyl ether is shown as a reaction formula II:
6. the environmentally friendly high-varnish-content pure resin impregnating insulating varnish according to claim 1, wherein the saturated dibasic acid is one or any combination of phthalic anhydride, adipic acid and sebacic acid.
7. The environmentally friendly high-varnish-content pure resin impregnating insulating varnish according to claim 1, wherein the polyol is one or any combination of propylene glycol, ethylbutylpropylene glycol, neopentyl glycol, bisphenol A and dipropylene glycol.
8. The preparation method of the environment-friendly high-varnish-content pure resin impregnated insulating varnish as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
(1) synthesis of modified monofunctional iminoalcohols: adding maleic anhydride and ethanolamine into a four-neck flask with nitrogen introduced, controlling the oil temperature to 120 ℃ for dropwise reaction, heating to 210 ℃ after the ethanolamine is dropwise added for 1h, adding tin butoxide for dehydration reaction until the acid value is less than 2mgKOH/g, and cooling to synthesize modified monofunctional imino alcohol for later use;
(2) synthesizing methyl methacrylate modified hydroxyl diphenyl ether: sequentially adding methyl methacrylate, 4' -dihydroxy diphenyl ether, tetrabutyl titanate and hydroquinone into a four-neck flask into which nitrogen is introduced, controlling the oil temperature to be 100 ℃, and synthesizing to obtain methyl methacrylate modified hydroxy diphenyl ether for later use when the reaction reaches the end point;
(3) synthesis of imine-modified low-viscosity self-crosslinkable unsaturated polyester resin: sequentially adding maleic anhydride, saturated dibasic acid, polyol and the modified monofunctional group imino alcohol prepared in the step (1) into a four-neck flask into which nitrogen is introduced, stirring and heating to 160 ℃, controlling the end point temperature to be 220 ℃, cooling to 130 ℃ when the acid value is less than 50mgKOH/g, adding the methyl methacrylate modified hydroxy diphenyl ether prepared in the step (2), tetrabutyl titanate and hydroquinone to control the molecular weight of a product, and synthesizing to obtain the imine modified low-viscosity self-crosslinkable unsaturated polyester resin after the reaction is finished;
(4) the preparation of the environment-friendly high-paint-hanging-amount pure resin impregnated insulating paint comprises the following steps: and (4) adding the imine modified low-viscosity self-crosslinkable unsaturated polyester resin prepared in the step (3) into dicumyl peroxide, cobalt naphthenate and hydroquinone, stirring and mixing uniformly, and filtering to obtain the environment-friendly high-coating-quantity pure resin impregnated insulating paint.
9. The production method according to claim 8, wherein in the step (4), the stirring speed is 100 to 200 r/min.
10. The method according to claim 8, wherein in the step (4), the filtration is performed using a 40-mesh filter cloth.
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| CN111662540A (en) * | 2020-07-31 | 2020-09-15 | 肇庆福田化学工业有限公司 | Amino modified unsaturated polyester resin |
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| CN111662540A (en) * | 2020-07-31 | 2020-09-15 | 肇庆福田化学工业有限公司 | Amino modified unsaturated polyester resin |
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