CN112759966B - Halogen-free flame-retardant insulating paint and preparation method thereof - Google Patents
Halogen-free flame-retardant insulating paint and preparation method thereof Download PDFInfo
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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
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- 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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- C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/22—Halogen free composition
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Abstract
The invention discloses a halogen-free flame-retardant insulating paint and a preparation method thereof, wherein the insulating paint comprises the following raw materials: phosphorus-containing unsaturated polyester resin, silicon-containing epoxy resin, bifunctional methacrylate, a curing agent, an accelerator, an initiator and an optional flame retardant; the insulating paint is prepared by the following method: adding the prepared phosphorus-containing unsaturated polyester resin and silicon-containing epoxy resin into a reaction kettle, heating, vacuumizing, reacting, gradually cooling, sequentially adding bifunctional methacrylate, an accelerator, a flame retardant, a curing agent and an initiator, filtering and packaging to obtain the insulating paint. According to the invention, the specific phosphorus-containing unsaturated polyester resin and silicon-containing epoxy resin are adopted and combined with bifunctional methacrylate, and the insulating layer formed after the insulating paint is cured has good flame retardant property, and the insulating paint not only can control proper viscosity, but also can realize rapid curing at a lower temperature, and has good application manufacturability.
Description
Technical Field
The invention belongs to the field of insulating paint, and particularly relates to halogen-free flame-retardant insulating paint and a preparation method thereof.
Background
The insulating varnish is an important insulating material which is based on high molecular polymer and is cured into an insulating film or an insulating whole under certain conditions, and generally consists of materials such as resin, curing agent and the like. With the enhancement of international environmental awareness and the establishment of relevant legislation, various restrictions are applied to the emission of volatile organic solvents of insulating paint in various countries in the world, and solvent-free insulating paint is widely developed. However, a large amount of benzene-type active solvents such as styrene and vinyl toluene are still used in the conventional solvent-free insulating paint at present, and the solvents have pungent odor and are volatilized into the atmosphere in a large amount in the baking process to pollute the environment.
Meanwhile, with the continuous improvement of safety consciousness of people, flame retardant requirements are also put forward on the insulating paint, flame retardants such as phosphorus-containing compounds and halogenated compounds are mainly added in the traditional flame retardant technology, but when a fire disaster happens, a large amount of smoke and toxic corrosive hydrogen halide gas can be generated by halogen-containing flame retardant materials, and secondary harm is caused.
The environment-friendly flame-retardant insulating impregnating varnish has been produced and put into the market by a large number of manufacturers at home and abroad, but the products which are really halogen-free and benzene-free are rarely produced, so that the research in the field is still in the blank stage at home, and therefore, the technical personnel in the field need to find a benzene-free and halogen-free environment-friendly flame-retardant insulating varnish to solve the problems.
Chinese patent application CN201810890493.9, Chinese patent application CN201610963290.9 and the like disclose halogen-free flame-retardant insulating paint, but vinyl toluene and other reactive diluents are used in the halogen-free flame-retardant insulating paint, and the diluents have pungent smell, high toxicity and high volatile, and do not meet the requirement of environmental protection.
The applicant filed earlier patent application for halogen-free flame-retardant high-temperature-resistant insulating paint for motors (patent No. 201210024926.5), wherein the halogen-free flame-retardant high-temperature-resistant insulating paint comprises 20-40 parts of phosphorus-containing epoxy resin, 30-60 parts of silicon-containing skeleton epoxy resin, 100 parts of glycidyl ether type epoxy resin, 5-20 parts of curing agent and 0.1-1 part of curing accelerator, and after the paint is cured and reacted at 80-100 ℃ for 0.8-1.2 hours, the paint is cured and reacted at 120-140 ℃ for 1.8-2.2 hours, and then the curing and reaction are performed at 150-170 ℃ for 2.0-3.0 hours to obtain the insulating material with the oxygen index of more than 30%. The insulating paint disclosed by the patent has excellent performances, does not use vinyl toluene reactive diluents, and is a real environment-friendly insulating paint. However, the said insulating varnish also has the disadvantages of high viscosity, poor workability, long curing time (4.6-6.4h) and high production cost due to the use of pure epoxy system.
Disclosure of Invention
The invention aims to provide the environment-friendly halogen-free flame-retardant insulating paint which has excellent performances and good construction manufacturability.
In order to achieve the purpose, the invention adopts the technical scheme that:
a halogen-free flame-retardant insulating paint is characterized in that: the insulating paint comprises the following raw materials: phosphorus-containing unsaturated polyester resin, silicon-containing epoxy resin, bifunctional methacrylate, a curing agent, an accelerator, an initiator and an optional flame retardant;
the structural formula of the phosphorus-containing unsaturated polyester resin is as follows:
the number average molecular weight of the phosphorus-containing unsaturated polyester resin is 750-1500;
the mass ratio of the phosphorus-containing unsaturated polyester resin to the silicon-containing epoxy resin to the bifunctional methacrylate is 1: 0.6-1.5: 0.6 to 1.25.
Preferably, the mass ratio of the phosphorus-containing unsaturated polyester resin, the silicon-containing epoxy resin and the bifunctional methacrylate is 1: 1.2-1.5: 0.8 to 0.9.
Preferably, the difunctional methacrylate is one or more selected from the group consisting of triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, and trimethylolpropane trimethacrylate.
Preferably, the silicon-containing epoxy resin is prepared by reacting a silane coupling agent KH550, dihydroxy polydimethylsiloxane and epoxy resin, and the number average molecular weight is 3500-7500.
Preferably, the epoxy resin is one or more selected from the group consisting of novolac epoxy resin, bisphenol a epoxy resin, bisphenol F epoxy resin and aliphatic epoxy resin.
Preferably, the flame retardant is one or more selected from the group consisting of tricresyl phosphate, triphenyl phosphite, triisopropylphenyl phosphate, cresyldiphenyl phosphate, and cyclic phosphate.
Preferably, the curing agent is one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, tung oil anhydride and dodecenyl succinic anhydride.
Preferably, the curing accelerator is one or more selected from aluminum acetylacetonate, chromium acetylacetonate, zinc isooctanoate and zinc naphthenate.
Preferably, the initiator is selected from one of benzoyl oxide, benzoyl butyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide or a combination thereof.
Preferably, the raw materials comprise, by mass, 20-30 parts of phosphorus-containing unsaturated polyester resin, 20-30 parts of silicon-containing epoxy resin, 20-25 parts of bifunctional methacrylate, 10-20 parts of curing agent, 0.5-1 part of accelerator, 0.5-1 part of initiator and 15-20 parts of flame retardant.
Preferably, the curing conditions of the insulating varnish are as follows: firstly, curing for 1-2 hours at 100-120 ℃, and then curing for 1-2 hours at 140-150 ℃.
The invention also aims to provide a preparation method of the halogen-free flame-retardant insulating paint, which comprises the following steps:
(1) preparing the phosphorus-containing unsaturated polyester resin: adding resorcinol into xylene, heating to melt resorcinol, adding phenyl phosphoryl dichloride under the condition of stirring, and reacting for 8-12 hours at 120-130 ℃; after the reaction is finished, adding maleic anhydride and neopentyl glycol, heating to 160-190 ℃, reacting, keeping the temperature until the acid value is less than or equal to 30mg KOH/g, and carrying out reduced pressure distillation to obtain the phosphorus-containing unsaturated polyester resin;
(2) preparing insulating paint: adding phosphorus-containing unsaturated polyester resin and silicon-containing epoxy resin into a reaction kettle, heating to 110-130 ℃, vacuumizing and reacting, cooling to 75-85 ℃, adding bifunctional methacrylate, and stirring while keeping the temperature; cooling to 65-75 ℃, adding an accelerant aluminum acetylacetonate, and stirring while keeping the temperature; cooling to 55-65 ℃, adding a flame retardant, and stirring while keeping the temperature; cooling to 45-55 ℃, adding a curing agent, and stirring while keeping the temperature; and cooling to 35-45 ℃, adding an initiator, keeping the temperature, stirring, filtering and packaging to obtain the insulating paint.
Preferably, in the step (1), the feeding molar ratio of the maleic anhydride to the neopentyl glycol is 1:0.6-1: 1; the feeding molar ratio of the phenyl phosphoryl dichloride to the resorcinol is 1:2-1: 3.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, specific phosphorus-containing unsaturated polyester resin and silicon-containing epoxy resin are adopted and combined with bifunctional methacrylate, so that on one hand, an insulating layer formed after the insulating paint is cured has good flame retardant property through a silicon-phosphorus synergistic effect; on the other hand, both the control of the appropriate viscosity and the achievement of rapid curing at lower temperatures (2-4 hours) are possible. Compared with the real halogen-free flame-retardant insulating paint in the prior art, the construction manufacturability is improved on the premise of ensuring the same excellent performance and even improving the performance, the paint can be conveniently suitable for various paint dipping processes such as immersion, dripping immersion, rolling immersion and the like, and meanwhile, the curing time can be obviously shortened and the curing temperature can be reduced.
The invention also provides a preparation process of the insulating paint, the process is simple, the cost of the adopted main raw materials is relatively lower, and the obtained insulating paint has excellent performances and good construction manufacturability.
Detailed Description
The invention aims to provide an environment-friendly halogen-free insulating paint with excellent flame retardant property and other properties and good construction process and a preparation method thereof. The insulating paint mainly adopts the combination of phosphorus-containing unsaturated polyester resin (with the number average molecular weight of 750-1500), silicon-containing organic resin and bifunctional methacrylate, wherein the phosphorus-containing unsaturated polyester resin has the following structure:
the phosphorus-containing resin can be prepared by a simple preparation process, and the raw materials are cheap. On one hand, unsaturated double bonds in the resin and bifunctional methacrylate can be quickly added, so that the purpose of low-temperature quick curing of the insulating paint is realized (the curing time is 2-4 hours, and the highest curing temperature is 150 ℃). The difunctional methacrylate can effectively adjust the viscosity of the insulating paint system to 88-130 seconds (4 cups coated at 23 ℃), has good application manufacturability, and can be suitable for various paint dipping processes such as dipping, dripping dipping, rolling dipping and the like. The oxygen index of the insulating material obtained after curing is more than 33 percent.
In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below, 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.
It is noted that the terms "comprises" and "comprising," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a composition, process, method, apparatus, article, or apparatus that comprises a list of elements, steps, or components is not necessarily limited to those elements or components expressly listed, but may include other elements or steps not expressly listed or inherent to such process, method, article, or apparatus.
In the following examples, the preparation method of the silicon-containing epoxy resin is as follows: adding 1g of silane coupling agent KH550 into 4g of deionized water, carrying out mixed ultrasonic treatment for 1h, adding 25g of methanol solution, carrying out ultrasonic treatment for 0.5h, then adding 5g of dihydroxy polydimethylsiloxane, carrying out condensation reaction to obtain polysiloxane particles with amine end groups on the surfaces, dispersing the particles into acetone solution, adding 80g of bisphenol A epoxy resin, carrying out reaction for 3h at 140 ℃, washing, carrying out vacuum filtration, and drying to obtain the silicon-containing epoxy resin with the number average molecular weight of 3500.
In the following examples, the conditions used may be further adjusted according to specific requirements, and the conditions not specified are generally those in routine experiments. The raw materials used in the examples are all industrial products unless otherwise specified. The% mentioned means mass% unless otherwise specified.
Example 1
This example provides a phosphorus-containing unsaturated polyester resin prepared as follows:
adding 1.5mol of resorcinol into 200ml of xylene, heating to 125 ℃ to melt the resorcinol, starting stirring, dropwise adding 0.6mol of phenyl phosphoryl dichloride under the stirring condition, and reacting for 9 hours at 125 ℃. And after the reaction is finished, adding 1.5mol of maleic anhydride and 1mol of neopentyl glycol, heating to 160 ℃, then gradually heating to 190 ℃ at a speed of 10 ℃/h, keeping the temperature until the acid value is less than or equal to 30mg KOH/g, carrying out reduced pressure distillation to obtain the phosphorus-containing unsaturated polyester resin, and measuring to obtain a light yellow solid with the number average molecular weight of 850.
Example 2
This example provides a phosphorus-containing unsaturated polyester resin prepared as follows:
adding 1.8mol of resorcinol into 200ml of xylene, heating to 125 ℃ to melt the resorcinol, starting stirring, dropwise adding 0.8mol of phenyl phosphoryl dichloride under the stirring condition, and reacting for 12 hours at 125 ℃. After the reaction is finished, 2mol of maleic anhydride and 1.5mol of neopentyl glycol are added, the temperature is raised to 160 ℃, then the temperature is gradually raised to 190 ℃ at the speed of 10 ℃/h, the temperature is maintained until the acid value is less than or equal to 30mg KOH/g, reduced pressure distillation is carried out, the phosphorus-containing unsaturated polyester resin is obtained, and the measured number average molecular weight of the yellow solid is 1000.
Example 3
This example provides a phosphorus-containing unsaturated polyester resin prepared as follows:
adding 1.7mol of resorcinol into 200ml of xylene, heating to 125 ℃ to melt the resorcinol, starting stirring, dropwise adding 0.8mol of phenyl phosphoryl dichloride under the stirring condition, and reacting for 11 hours at 125 ℃. After the reaction is finished, 1.6mol of maleic anhydride and 1.3mol of neopentyl glycol are added, the temperature is raised to 160 ℃, then the temperature is gradually raised to 190 ℃ at the speed of 10 ℃/h, the temperature is kept until the acid value is less than or equal to 30mg KOH/g, the pressure is reduced and the distillation is carried out, the phosphorus-containing unsaturated polyester resin is obtained, and the measured number average molecular weight is 800 light yellow solid.
Example 4
This example provides a phosphorus-containing unsaturated polyester resin prepared as follows:
adding 1.6mol of resorcinol into 200ml of xylene, heating to 125 ℃ to melt the resorcinol, starting stirring, dropwise adding 0.7mol of phenyl phosphoryl dichloride under the stirring condition, and reacting for 10 hours at 125 ℃. And after the reaction is finished, adding 1.7mol of maleic anhydride and 1.4mol of neopentyl glycol, heating to 160 ℃, then gradually heating to 190 ℃ at a speed of 10 ℃/h, keeping the temperature until the acid value is less than or equal to 30mg KOH/g, and carrying out reduced pressure distillation to obtain the phosphorus-containing unsaturated polyester resin, wherein the measured number average molecular weight of the red brown solid is 1200.
Example 5
This example provides a phosphorus-containing unsaturated polyester resin prepared as follows:
adding 1.5mol of resorcinol into 200ml of xylene, heating to 125 ℃ to melt the resorcinol, starting stirring, dropwise adding 0.6mol of phenyl phosphoryl dichloride under the stirring condition, and reacting for 12 hours at 125 ℃. After the reaction is finished, 1.5mol of maleic anhydride and 1.2mol of neopentyl glycol are added, the temperature is raised to 160 ℃, then the temperature is gradually raised to 190 ℃ at the speed of 10 ℃/h, the temperature is kept until the acid value is less than or equal to 30mg KOH/g, the reduced pressure distillation is carried out, the phosphorus-containing unsaturated polyester resin is obtained, and the reddish brown solid with the number average molecular weight of 1300 is measured.
Example 6
The embodiment provides a halogen-free flame-retardant insulating paint, which is prepared by the following steps:
adding 20g of the phosphorus-containing unsaturated polyester resin prepared in the example 1 and 30g of silicon-containing epoxy resin into a reaction kettle, heating to 120 ℃, vacuumizing and reacting for 30min, cooling to 80 ℃, adding 25g of triethylene glycol dimethacrylate, and keeping the temperature and stirring for 30 min; cooling to 70 ℃, adding 0.5g of accelerant aluminum acetylacetonate, and stirring for 40min under heat preservation; cooling to 60 ℃, adding 15g of flame retardant tricresyl phosphate, and stirring for 30min under heat preservation; cooling to 50 ℃, adding 10g of curing agent methyl tetrahydrophthalic anhydride, and stirring for 30min under heat preservation; and cooling to 40 ℃, adding 0.5g of initiator benzoyl oxide, keeping the temperature and stirring for 30min, filtering and packaging to obtain the insulating paint.
When the insulating paint is used, the insulating paint can be applied to different paint dipping processes such as immersion, rolling immersion, dripping immersion and the like, and can be cured for 2 hours at 100 ℃ and then cured for 2 hours at 140 ℃ to obtain an insulating layer.
Example 7
The embodiment provides a halogen-free flame-retardant insulating paint, which is prepared by the following steps:
adding 25g of the phosphorus-containing unsaturated polyester resin prepared in the example 2 and 25g of silicon-containing epoxy resin into a reaction kettle, heating to 110 ℃, vacuumizing and reacting for 40 min; cooling to 90 ℃, adding 20g of 1, 6-hexanediol dimethacrylate, and stirring for 20min under heat preservation; cooling to 70 ℃, adding 18g of flame retardant triphenyl phosphite, and stirring for 30min under heat preservation; cooling to 60 ℃, adding 16g of curing agent methyl hexahydrophthalic anhydride, and stirring for 30min under heat preservation; and cooling to 40 ℃, adding 0.8g of accelerator zinc isooctanoate and 0.6g of initiator methyl ethyl ketone peroxide, keeping the temperature and stirring for 30min, filtering and packaging to obtain the insulating paint.
When the insulating paint is used, the insulating paint can be applied to different paint dipping processes such as immersion, rolling immersion, dripping immersion and the like, and the insulating paint is cured for 1 hour at 120 ℃ and then cured for 1 hour at 150 ℃ to obtain an insulating layer.
Example 8
The embodiment provides a halogen-free flame-retardant insulating paint, which is prepared by the following steps:
adding 30g of the phosphorus-containing unsaturated polyester resin prepared in the example 3 and 20g of silicon-containing epoxy resin into a reaction kettle, heating to 130 ℃, vacuumizing and reacting for 20 min; cooling to 70 ℃, adding 22g of 1, 4-butanediol dimethacrylate and 0.6g of accelerant chromium acetylacetonate, and stirring for 30min under heat preservation; cooling to 60 ℃, adding 20g of flame retardant tricresyl phosphate, and stirring for 30min under heat preservation; cooling to 50 ℃, adding 14g of curing agent methyl nadic anhydride, and stirring for 40min under the condition of heat preservation; and cooling to 40 ℃, adding 0.8g of initiator dicumyl peroxide, keeping the temperature and stirring for 30min, filtering and packaging to obtain the insulating paint.
When the insulating paint is used, the insulating paint can be applied to different paint dipping processes such as immersion, rolling immersion, dripping immersion and the like, and can be cured for 1 hour at 110 ℃ and then cured for 2 hours at 145 ℃ to obtain an insulating layer.
Example 9
The embodiment provides a halogen-free flame-retardant insulating paint, which is prepared by the following steps:
adding 26g of the phosphorus-containing unsaturated polyester resin prepared in the embodiment 4 and 24g of silicon-containing epoxy resin into a reaction kettle, heating to 120 ℃, vacuumizing and reacting for 40 min; cooling to 80 ℃, adding 22g of trimethylolpropane trimethacrylate, and stirring for 30min under the condition of heat preservation; cooling to 60 ℃, adding 20g of flame retardant cyclic phosphate, and stirring for 30min under heat preservation; cooling to 50 ℃, adding 18g of curing agent dodecenyl succinic anhydride, and stirring for 30min under the condition of heat preservation; cooling to 40 ℃, adding 0.5g of accelerator zinc naphthenate and 0.6g of initiator dicumyl peroxide, keeping the temperature and stirring for 30min, filtering and packaging to obtain the insulating paint.
When the insulating paint is used, the insulating paint can be applied to different paint dipping processes such as immersion, rolling immersion, dripping immersion and the like, and the insulating paint is cured for 1 hour at 120 ℃ and then cured for 2 hours at 145 ℃ to obtain an insulating layer.
Example 10
The embodiment provides a halogen-free flame-retardant insulating paint, which is prepared by the following steps:
adding 28g of the phosphorus-containing unsaturated polyester resin prepared in the example 5 and 20g of silicon-containing epoxy resin into a reaction kettle, heating to 110 ℃, vacuumizing and reacting for 50 min; cooling to 85 ℃, adding 25g of tripropylene glycol dimethacrylate, and stirring for 30min under the condition of heat preservation; cooling to 70 ℃, adding 18g of flame retardant triphenyl phosphite and 1g of accelerant aluminum acetylacetonate, and stirring for 30min under heat preservation; cooling to 55 ℃, adding 18g of curing agent tung oil anhydride, and stirring for 30min under heat preservation; and cooling to 40 ℃, adding 1g of initiator benzoyl peroxide butyl ester, keeping the temperature and stirring for 30min, filtering and packaging to obtain the insulating paint.
When the insulating paint is used, the insulating paint can be applied to different paint dipping processes such as immersion, rolling immersion, dripping immersion and the like, and the insulating paint is cured for 1 hour at 120 ℃ and then cured for 2 hours at 150 ℃ to obtain an insulating layer.
Comparative example 1
The present example provides a halogen-free flame retardant insulating paint, the preparation process is substantially the same as example 6, except that the weight ratio of the phosphorus-containing unsaturated polyester resin, the silicon-containing epoxy resin and the triethylene glycol dimethacrylate is 1: 2: 1.
the performance indexes of the insulating paints prepared in examples 6 to 10 and comparative example 1 are shown in Table 1.
TABLE 1
The above table shows that the halogen-free flame-retardant insulating paint has good flame retardant property, small volatility, no odor and good environmental protection property, the viscosity of the insulating paint can be 88-130 seconds (4 cup coating and 23 ℃), the insulating paint has good application manufacturability, can be suitable for various paint dipping processes such as dipping, dripping dipping and rolling dipping, and simultaneously has excellent electrical property and mechanical property, good heat dissipation property, high temperature resistance index and stable storage.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A halogen-free flame-retardant insulating paint is characterized in that: the insulating paint comprises the following raw materials: phosphorus-containing unsaturated polyester resin, silicon-containing epoxy resin, bifunctional methacrylate, a curing agent, an accelerator and an initiator;
the structural formula of the phosphorus-containing unsaturated polyester resin is as follows:
the number average molecular weight of the phosphorus-containing unsaturated polyester resin is 750-1500;
the mass ratio of the phosphorus-containing unsaturated polyester resin to the silicon-containing epoxy resin to the bifunctional methacrylate is 1: 0.6-1.5: 0.6 to 1.25;
the mass ratio of the phosphorus-containing unsaturated polyester resin to the silicon-containing epoxy resin to the bifunctional methacrylate is 1: 1.2-1.5: 0.8 to 0.9.
2. The halogen-free flame-retardant insulating paint according to claim 1, characterized in that: the bifunctional group methacrylate is one or more of triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate and trimethylolpropane trimethacrylate.
3. The halogen-free flame-retardant insulating paint according to claim 1, characterized in that: the silicon-containing epoxy resin is prepared by reacting a silane coupling agent KH550, dihydroxy polydimethylsiloxane and epoxy resin, and the number average molecular weight is 3500-7500.
4. The halogen-free flame-retardant insulating paint according to claim 3, characterized in that: the epoxy resin is one or more of phenolic epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin and aliphatic epoxy resin.
5. The halogen-free flame-retardant insulating paint according to claim 1, characterized in that: the raw materials of the insulating paint also comprise a flame retardant, wherein the flame retardant is one or a combination of more of tricresyl phosphate, triphenyl phosphite, triisopropylphenyl phosphate, cresyldiphenyl phosphate and cyclic phosphate; and/or the curing agent is one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, tung oil anhydride and dodecenyl succinic anhydride; and/or the accelerant is one or more of aluminum acetylacetonate, chromium acetylacetonate, zinc isooctanoate and zinc naphthenate; and/or the initiator is one or the combination of benzoyl oxide, benzoyl butyl peroxide, methyl ethyl ketone peroxide and dicumyl peroxide.
6. The halogen-free flame-retardant insulating paint according to any one of claims 1 to 5, characterized in that: the insulating paint comprises the following raw materials, by mass, 20-30 parts of phosphorus-containing unsaturated polyester resin, 20-30 parts of silicon-containing epoxy resin, 20-25 parts of bifunctional methacrylate, 10-20 parts of a curing agent, 0.5-1 part of an accelerator, 0.5-1 part of an initiator and 15-20 parts of a flame retardant.
7. The halogen-free flame-retardant insulating paint according to claim 1, characterized in that: the curing conditions of the insulating paint are as follows: firstly, curing for 1-2 hours at 100-120 ℃, and then curing for 1-2 hours at 140-150 ℃.
8. A method for preparing the halogen-free flame retardant insulating paint according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
(1) preparing the phosphorus-containing unsaturated polyester resin: adding resorcinol into xylene, heating to melt resorcinol, adding phenyl phosphoryl dichloride under the condition of stirring, and reacting for 8-12 hours at 120-130 ℃; after the reaction is finished, adding maleic anhydride and neopentyl glycol, heating to 160-190 ℃, reacting, keeping the temperature until the acid value is less than or equal to 30mg KOH/g, and carrying out reduced pressure distillation to obtain the phosphorus-containing unsaturated polyester resin;
(2) preparing insulating paint: adding phosphorus-containing unsaturated polyester resin and silicon-containing epoxy resin into a reaction kettle, heating to 110-130 ℃, vacuumizing and reacting, cooling to 75-85 ℃, adding bifunctional methacrylate, and stirring while keeping the temperature; cooling to 65-75 ℃, adding an accelerant aluminum acetylacetonate, and stirring while keeping the temperature; cooling to 55-65 ℃, adding a flame retardant, and stirring while keeping the temperature; cooling to 45-55 ℃, adding a curing agent, and stirring while keeping the temperature; and cooling to 35-45 ℃, adding an initiator, keeping the temperature, stirring, filtering and packaging to obtain the insulating paint.
9. The method for preparing the halogen-free flame retardant insulating paint according to claim 8, characterized in that: in the step (1), the feeding molar ratio of the maleic anhydride to the neopentyl glycol is 1:0.6-1: 1; the feeding molar ratio of the phenyl phosphoryl dichloride to the resorcinol is 1:2-1: 3.
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| DE102006049519A1 (en) * | 2006-10-20 | 2008-04-24 | Lanxess Deutschland Gmbh | Flame retardant for curable molding materials comprises ethylenediamine phosphate, a halogen-free phosphorus compound and a halogen-free nitrogen compound |
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| WO2004079844A1 (en) * | 2003-03-06 | 2004-09-16 | Toray Industries, Inc. | Polymer electrolyte material, polymer electrolyte part, membrane electrode composite and polymer electrolyte type fuel cell |
| KR101362871B1 (en) * | 2010-12-29 | 2014-02-14 | 제일모직주식회사 | Cross-linked polyphosphonate, method for preparing thereof and flame retardant thermoplastic resin composition comprising the same |
| CN102212174B (en) * | 2011-05-11 | 2012-12-05 | 华南理工大学 | Transparent reaction type phosphorus-boron-silicon flame-retardant unsaturated polyester and preparation method thereof |
| CN104513387A (en) * | 2013-09-29 | 2015-04-15 | 青岛市首胜实业有限公司 | Synthesis method for reactive phosphorus-containing flame retardant unsaturated polyester |
| CN111925629A (en) * | 2020-08-18 | 2020-11-13 | 江苏中航百慕新材料技术有限公司 | Composite resin with hydrophobicity as well as preparation method and application thereof |
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| DE102006049519A1 (en) * | 2006-10-20 | 2008-04-24 | Lanxess Deutschland Gmbh | Flame retardant for curable molding materials comprises ethylenediamine phosphate, a halogen-free phosphorus compound and a halogen-free nitrogen compound |
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