CN112300668A - High-performance environment-friendly flame-retardant epoxy resin for electrician and electricity - Google Patents

Abstract

The invention discloses a high-performance environment-friendly flame-retardant epoxy resin for electricians and electricians, which comprises resin, a curing agent and a silicon micropowder filler, wherein the resin comprises the following raw materials in parts by weight: the modified bisphenol A epoxy resin, the phosphorus flame retardant, the reactive diluent, the reactive toughening agent, the defoaming agent, the silane coupling agent and the nano titanium dioxide, wherein the curing agent comprises the following raw materials in parts by weight: the invention discloses a modified curing agent, an accelerant, an active toughening agent, a dispersing agent, an anti-settling agent, a leveling agent and an antioxidant, and relates to the technical field of epoxy resin. The high-performance environment-friendly flame-retardant epoxy resin for electricians and electricians has higher glass transition temperature, excellent electrical property, mechanical property and flame retardant property after being cured, is suitable for APG pressure gel process, vacuum casting process and normal-temperature encapsulation process, can be widely applied to electricians and electrical products with flame retardant and environment-friendly requirements, and has wide application range, high practicability and longer service life of cured products.

Description

High-performance environment-friendly flame-retardant epoxy resin for electrician and electricity

Technical Field

The invention relates to the technical field of epoxy resin, in particular to high-performance environment-friendly flame-retardant epoxy resin for electricians and electricians.

Background

The electrical and electrical industry mainly covers products such as dry-type transformers, mutual inductors, wall-penetrating sleeves, contact boxes, insulators, solid-sealed polar columns and the like, and complete systems and control systems formed by the devices; with the rapid development of intelligent power grids in China, in order to ensure the safety and reliability of power supply, national power grids and power grids in the south all put forward higher requirements on the flame resistance of electrical and electrical products, while the oxygen index of the conventional bisphenol A epoxy resin condensate is only about 19.5, and the conventional bisphenol A epoxy resin condensate belongs to flammable substances, so that the bisphenol A epoxy resin condensate must be modified to improve the flame resistance.

In order to improve the flame retardance of the material, the common method is to add a filler for flame retardance and a flame retardant for flame retardance. For electric products such as mutual inductors, wall bushing, contact boxes and the like, manufacturers generally add silica powder on site in order to reduce cost, so that the difficulty in improving flame retardance through flame retardant fillers is high, and the most feasible method is to add flame retardants. Because common tetrabromobisphenol A is difficult to generate chemical reaction with epoxy resin, the mechanical property of the cured epoxy resin is deteriorated along with the addition of tetrabromobisphenol A, and the cured epoxy resin can generate halide with strong toxicity due to pyrolysis reaction during combustion, thereby not only causing environmental pollution but also threatening the lives and properties of people, and therefore, an environment-friendly flame-retardant epoxy resin which does not influence the vitrification temperature and can improve the mechanical properties such as bending strength, impact strength and the like is urgently needed.

The phosphorus flame retardant is a new flame-retardant environment-friendly material in recent years, has the advantages of low smoke, no toxicity, no halogen and the like, accords with the development direction of the flame retardant, has good development prospect, has self-extinguishing property, low temperature resistance, plasticity, ultraviolet stability and antistatic property superior to those of products added with other flame retardants, can reach flame-retardant grades with different requirements, and has good compatibility with epoxy resin.

The flame-retardant resin modified by the phosphorus flame retardant has a flame-retardant mechanism that a cross-linked solid substance or a carbonized layer with a more stable structure can be generated when the flame-retardant resin is heated, and the carbonized layer can prevent a polymer from being further pyrolyzed on one hand and prevent a thermal decomposition product in the carbonized layer from entering a gas phase to participate in a combustion process on the other hand. Most importantly, the epoxy resin modified by the epoxy resin has the characteristics of high strength, good toughness, high fluidity, high glass transition temperature and the like, and meets the standard requirements of national power grids and southern power grids.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a high-performance environment-friendly flame-retardant epoxy resin for electricians and electricians, which solves the problems that the mechanical property of the cured epoxy resin is deteriorated along with the addition of tetrabromobisphenol A, and the cured epoxy resin generates halide with strong toxicity due to pyrolysis reaction during combustion, thereby not only causing environmental pollution, but also threatening the lives and properties of people.

(II) technical scheme

In order to achieve the purpose, the invention is realized by the following technical scheme: the high-performance environment-friendly flame-retardant epoxy resin for electricians and electricians comprises resin, a curing agent and a silicon micro powder filler, wherein the ratio of the resin to the curing agent to the silicon micro powder filler is 100: 50-100: 300-400 parts by weight of the silica powder filler, wherein the addition amount of the silica powder filler is 300-400 parts by weight.

The resin comprises the following raw materials in parts by weight: 60-80 parts of modified bisphenol A epoxy resin, 5-22 parts of phosphorus flame retardant, 5-10 parts of reactive diluent, 5-10 parts of reactive toughening agent, 0.5-2 parts of defoaming agent, 0.5-1 part of silane coupling agent and 8-10 parts of nano titanium dioxide.

The curing agent comprises the following raw materials in parts by weight: 80-90 parts of modified curing agent, 0.2-1 part of accelerator, 5-15 parts of active toughening agent, 0.1-0.5 part of dispersing agent, 2-5 parts of anti-settling agent, 0.5-1 part of flatting agent and 0.2-1 part of antioxidant.

Preferably, the modified bisphenol A epoxy resin is obtained by modifying one or two of E51 and E44 bisphenol A epoxy resins through a reaction kettle, and the mechanical property and the processing property of the modified epoxy resin are greatly improved.

Preferably, the phosphorus flame retardant is one of diethyl methylphosphonate, trimethyl phosphate and triethyl phosphate, the amount is 5-22 parts by weight, if the amount is less than 5 parts by weight, the flame retardant effect of the cured product is poor, if the amount is more than 22 parts by weight, the smoke density of the cured product is high, the mechanical property of the cured product is reduced, and the glass transition temperature is also remarkably reduced, the reactive diluent is one or two of propylene oxide butyl ether and propylene oxide phenyl ether, and the reactive diluent is mainly used for reducing the viscosity of epoxy resin and improving the wettability and the permeability.

Preferably, the active toughening agent is one or two of ethylene glycol diglycidyl ether and propenyl glycidyl ether, the active toughening agent mainly plays a role in improving the toughness of the epoxy cured product and improving the cold and hot impact performance, the defoaming agent is a DZ109 type polyether modified organic silicon defoaming agent, and the addition of the defoaming agent can effectively reduce micro bubbles in the material mixing process, so that the formation of microcracks or micro bubbles in the cured product process is avoided, and the unqualified partial discharge test and even the pressure breakdown is avoided.

Preferably, the coupling agent is one of 3-glycidoxypropyltrimethoxysilane, aminopropyltriethoxysilane and methacryloxypropyltrimethoxysilane, and the coupling agent can improve the wettability and the dispersibility of the interface of each mixture of the flame-retardant resin.

Preferably, the modified anhydride curing agent is one or two of tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, aromatic amine, aliphatic amine and polyether amine, and is obtained by special modification of a reaction kettle, the modified anhydride curing agent has good fluidity and moisture absorption resistance, the accelerator is one or two or three of triethylamine, quaternary ammonium salt, dimethyl imidazole, trisphenol and triethanolamine, and can be adjusted according to a pouring process and a pressure gelation process (APG), the adding amount of the general pouring process is 0.1-0.3%, and the pressure gelation process is 0.8-1.2%.

Preferably, the dispersant is one or two of silane ester, polyethylene glycol and sodium polyacrylate which are mixed to obtain the dispersantThe main action mechanism of the anti-settling agent is that the components are promoted to be uniformly dispersed in a medium, a stable and uniform suspension is formed after mixing, and meanwhile, the sedimentation and agglomeration of particles can be prevented, the anti-settling agent is one or two of fumed silica and precipitated silica, and the specific surface area of the anti-settling agent is 100-500 m²The leveling agent is bentonite, the main action mechanism of the leveling agent is to increase the fluidity of the mixture and obviously help to improve the partial discharge of an electrical product, the antioxidant is antioxidant BHT, and the antioxidant can improve the antioxidant capacity of a cured material, so that the service life is prolonged.

The invention also discloses a preparation method of the high-performance environment-friendly flame-retardant epoxy resin condensate for electricians and electricians, which specifically comprises the following steps:

s1, resin preparation: adding a proper amount of modified bisphenol A epoxy resin, a phosphorus flame retardant, a reactive diluent, a reactive toughening agent, a defoaming agent, a silane coupling agent and nano titanium dioxide into a reaction kettle together, heating to 130 ℃, stirring at a high speed, vacuumizing to 500Pa, maintaining the pressure, continuously stirring for 1-2 h, uniformly mixing, and fully defoaming to obtain resin;

s2, preparing a curing agent: adding a proper amount of modified curing agent, an accelerator, an active toughening agent, a dispersing agent, an anti-settling agent, a leveling agent and an antioxidant into a reaction kettle, heating to 80-130 ℃, stirring at a high speed, vacuumizing to 500-2000 Pa, maintaining the pressure, continuously stirring for 1-2 h, uniformly mixing, and fully defoaming to obtain a curing agent;

s3, mixing and curing: mixing the resin obtained in the step S1, the curing agent obtained in the step S2 and the 400-mesh common silicon micropowder according to the weight ratio of 100: 50-100: uniformly mixing the components in a ratio of 300-400, and keeping the temperature at 25-130 ℃ for 1-4 h for curing to obtain the cured epoxy resin.

(III) advantageous effects

The invention provides a high-performance environment-friendly flame-retardant epoxy resin for electricians and electricians. Compared with the prior art, the method has the following beneficial effects:

(1) the high-performance environment-friendly flame-retardant epoxy resin for electricians and electricians is prepared from the following components in parts by weight: 50-100: 300-400 parts by weight of silicon micro powder filler, wherein the addition amount of the silicon micro powder filler is 300-400 parts by weight; the resin comprises the following raw materials in parts by weight: 60-80 parts of modified bisphenol A epoxy resin, 5-22 parts of phosphorus flame retardant, 5-10 parts of reactive diluent, 5-10 parts of reactive toughening agent, 0.5-2 parts of defoaming agent, 0.5-1 part of silane coupling agent and 8-10 parts of nano titanium dioxide; the curing agent comprises the following raw materials in parts by weight: 80-90 parts of modified curing agent, 0.2-1 part of accelerator, 5-15 parts of active toughening agent, 0.1-0.5 part of dispersant, 2-5 parts of anti-settling agent, 0.5-1 part of flatting agent and 0.2-1 part of antioxidant, the cured epoxy resin has high strength, good toughness, high fluidity and high glass transition temperature, is suitable for APG pressure gel process, vacuum pouring process and normal temperature encapsulation process, can be widely applied to electrical and electrical products with flame retardant and environmental protection requirements, and has wide application range and high practicability.

(2) The high-performance environment-friendly flame-retardant epoxy resin for electricians and electricians has stronger ultraviolet resistance, weather resistance and scrub resistance by adding the nano titanium dioxide into the epoxy resin, and prolongs the service life of a cured product of the epoxy resin.

Drawings

FIG. 1 is a process flow diagram of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.

Referring to fig. 1, the embodiment of the present invention provides three technical solutions: the high-performance environment-friendly flame-retardant epoxy resin for electricians and electricians specifically comprises the following embodiments:

example one

S1, resin preparation: adding 72 parts of modified bisphenol A type E51 epoxy resin, 20 parts of diethyl methylphosphonate phosphorus flame retardant, 2 parts of epoxypropane butyl ether reactive diluent, 4 parts of propenyl glycidyl ether reactive flexibilizer, 1.2 parts of DZ109 type polyether modified organic silicon defoamer, 0.8 part of aminopropyltriethoxysilane coupling agent and 8 parts of nano titanium dioxide into a reaction kettle, heating to 130 ℃, stirring at high speed, vacuumizing to 500Pa, maintaining the pressure, continuously stirring for 1-2 h, uniformly mixing and fully defoaming to obtain resin;

s2, preparing a curing agent: adding 85 parts of modified curing agent, 1 part of trisphenol accelerator, 12 parts of propenyl glycidyl ether active flexibilizer, 0.3 part of silane ester dispersing agent, 1.2 parts of 200m2/g fumed silica anti-settling agent, 0.5 part of bentonite leveling agent and 0.5 part of antioxidant BHT into a reaction kettle, heating to 130 ℃, stirring at high speed, vacuumizing to 500Pa, maintaining the pressure, continuously stirring for 1-2 h, uniformly mixing, and fully defoaming to obtain the curing agent;

s3, mixing and curing: mixing the resin obtained in the step S1, the curing agent obtained in the step S2 and the 400-mesh common silicon micropowder according to the weight ratio of 100: 75: 350, the mixture has good fluidity, the mixture is cured at the temperature of 130 ℃ for 1 hour to prepare the cured epoxy resin, the flame retardant property of the cured epoxy resin reaches UL-94 standard V0 level flame retardant, the compound has good electrical and mechanical properties, the bending strength is 116Mpa, the impact strength is 12.2Mpa, the dielectric strength is 27KV/mm, the glass transition temperature reaches 80 ℃, an APG pressure gel process is adopted, and the epoxy resin is suitable for the fields of contact boxes, wall-penetrating sleeves, mutual inductors and the like with V0 flame retardant requirements.

Example two

S1, resin preparation: adding 75 parts of modified bisphenol A type E51 epoxy resin, 16 parts of trimethyl phosphate phosphorus flame retardant, 3.2 parts of epoxypropane phenyl ether reactive diluent, 5.5 parts of ethylene glycol diglycidyl ether reactive toughening agent, 1 part of DZ109 type polyether modified organic silicon defoaming agent, 0.3 part of 3-glycidyl ether oxypropyl trimethoxy silane coupling agent and 9 parts of nano titanium dioxide into a reaction kettle, heating to 130 ℃, stirring at high speed, vacuumizing to 500Pa, maintaining the pressure, continuously stirring for 1-2 hours, uniformly mixing and fully defoaming to obtain resin;

s2, preparing a curing agent: adding 85 parts of Jiangte special modified curing agent, 0.2 part of dimethyl imidazole accelerator, 13 parts of ethylene glycol diglycidyl ether active flexibilizer, 0.3 part of polyethylene glycol dispersant, 1 part of 200m2/g fumed silica anti-settling agent, 0.5 part of bentonite leveling agent and 1 part of antioxidant BHT into a reaction kettle, heating to 130 ℃, stirring at high speed, vacuumizing to 500Pa, maintaining the pressure, continuously stirring for 1-2 h, uniformly mixing, and fully defoaming to obtain the curing agent;

s3, mixing and curing: taking the resin prepared in the step S1, the curing agent prepared in the step S2 and the 400-mesh common silicon powder according to the weight ratio of 100: 80: 360, the mixture has good fluidity, the mixture is cured at the temperature of 130 ℃ for 4 hours to prepare the cured epoxy resin, the flame retardant property of the cured epoxy resin reaches UL-94 standard V0 level flame retardant, the compound has good electrical and mechanical properties, the bending strength is 125Mpa, the impact strength is 13.4Mpa, the dielectric strength is 27KV/mm, the glass transition temperature reaches 80 ℃, a vacuum pouring process is adopted, and the epoxy resin is suitable for the fields of mutual inductors, dry transformers and the like with V1 flame retardant requirements.

EXAMPLE III

S1, resin preparation: adding 79 parts of modified bisphenol A epoxy resin, 16 parts of triethyl phosphate phosphorus flame retardant, 3.2 parts of propenyl glycidyl ether active toughening agent, 1.6 parts of DZ109 polyether modified organic silicon defoaming agent, 0.2 part of 3-glycidyl ether oxypropyl trimethoxy silane coupling agent and 10 parts of nano titanium dioxide into a reaction kettle, heating to 130 ℃, stirring at high speed, vacuumizing to 500Pa, maintaining the pressure, continuously stirring for 1-2 hours, uniformly mixing and fully defoaming to obtain resin;

s2, preparing a curing agent: adding 88 parts of modified polyether amine curing agent, 11 parts of allyl glycidyl ether active toughening agent, 0.5 part of polyethylene glycol dispersant, 0.5 part of bentonite leveling agent and 1 part of antioxidant BHT into a reaction kettle, heating to 80 ℃, stirring at high speed, vacuumizing to 2000Pa, maintaining pressure, continuing stirring for 1-2 h, uniformly mixing, and fully defoaming to obtain the curing agent;

s3, mixing and curing: mixing the resin obtained in the step S1, the curing agent obtained in the step S2 and the 400-mesh common silicon micropowder according to the weight ratio of 100: 50: 350, the mixture has good fluidity, and the epoxy resin cured product is prepared after curing at the normal temperature of 25 ℃ for 4 hours, the flame retardant property of the cured product reaches UL-94 standard V0 level flame retardant, the compound has good electrical and mechanical properties, bending strength of 110Mpa, impact strength of 8Mpa, dielectric strength of 18KV/mm and vitrification temperature of 60 ℃, and the epoxy resin cured product is applied to the fields of low-voltage transformers, zero-sequence transformers, electronic transformers and the like with V0 flame retardant requirements by adopting a normal-temperature encapsulation process.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (8)

1. The high-performance environment-friendly flame-retardant epoxy resin for electricians and electricians comprises resin, a curing agent and a silicon micropowder filler, and is characterized in that: the proportion of the resin, the curing agent and the silicon micro powder filler is 100: 50-100: 300-400;

the resin comprises the following raw materials in parts by weight: 60-80 parts of modified bisphenol A epoxy resin, 5-22 parts of phosphorus flame retardant, 5-10 parts of reactive diluent, 5-10 parts of reactive toughening agent, 0.5-2 parts of defoaming agent, 0.5-1 part of silane coupling agent and 8-10 parts of nano titanium dioxide;

the curing agent comprises the following raw materials in parts by weight: 80-90 parts of modified curing agent, 0.2-1 part of accelerator, 5-15 parts of active toughening agent, 0.1-0.5 part of dispersing agent, 2-5 parts of anti-settling agent, 0.5-1 part of flatting agent and 0.2-1 part of antioxidant.

2. The high-performance environment-friendly flame-retardant epoxy resin for electrical engineering and electric use according to claim 1, wherein: the modified bisphenol A epoxy resin is obtained by modifying one or two of E51 and E44 bisphenol A epoxy resins through a reaction kettle.

3. The high-performance environment-friendly flame-retardant epoxy resin for electrical engineering and electric use according to claim 1, wherein: the phosphorus flame retardant is one of diethyl methylphosphonate, trimethyl phosphate and triethyl phosphate, and the reactive diluent is one or a mixture of propylene oxide butyl ether and propylene oxide phenyl ether.

4. The high-performance environment-friendly flame-retardant epoxy resin for electrical engineering and electric use according to claim 1, wherein: the active toughening agent is obtained by mixing one or two of ethylene glycol diglycidyl ether and propenyl glycidyl ether, and the defoaming agent is a DZ109 type polyether modified organic silicon defoaming agent.

5. The high-performance environment-friendly flame-retardant epoxy resin for electrical engineering and electric use according to claim 1, wherein: the coupling agent is one of 3-glycidoxypropyltrimethoxysilane, aminopropyltriethoxysilane and methacryloxypropyltrimethoxysilane.

6. The high-performance environment-friendly flame-retardant epoxy resin for electrical engineering and electric use according to claim 1, wherein: the modified anhydride curing agent is one or two of tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, aromatic amine, aliphatic amine and polyether amine, and is obtained by special modification of a reaction kettle, and the accelerator is one or two or three of triethylamine, quaternary ammonium salt, dimethyl imidazole, trisphenol and triethanolamine.

7. The high-performance environment-friendly flame-retardant epoxy resin for electrical engineering and electric use according to claim 1, wherein: the dispersant is obtained by mixing one or two of silane ester, polyethylene glycol and sodium polyacrylate, the anti-settling agent is obtained by mixing one or two of fumed silica and precipitated silica, the leveling agent is bentonite, and the antioxidant is antioxidant BHT.

8. An environment-friendly flame-retardant epoxy resin with high performance for electrical and electrician according to claims 1 to 7, wherein: the preparation method of the cured product comprises the following steps:

s1, resin preparation: adding a proper amount of modified bisphenol A epoxy resin, a phosphorus flame retardant, a reactive diluent, a reactive toughening agent, a defoaming agent, a silane coupling agent and nano titanium dioxide into a reaction kettle together, heating to 130 ℃, stirring at a high speed, vacuumizing to 500Pa, maintaining the pressure, continuously stirring for 1-2 h, uniformly mixing, and fully defoaming to obtain resin;

s2, preparing a curing agent: adding a proper amount of modified curing agent, an accelerator, an active toughening agent, a dispersing agent, an anti-settling agent, a leveling agent and an antioxidant into a reaction kettle, heating to 80-130 ℃, stirring at a high speed, vacuumizing to 500-2000 Pa, maintaining the pressure, continuously stirring for 1-2 h, uniformly mixing, and fully defoaming to obtain a curing agent;

s3, mixing and curing: mixing the resin obtained in the step S1, the curing agent obtained in the step S2 and the 400-mesh common silicon micropowder according to the weight ratio of 100: 50-100: uniformly mixing the components in a ratio of 300-400, and keeping the temperature at 25-130 ℃ for 1-4 h for curing to obtain the cured epoxy resin.

Images