Flame-retardant epoxy resin system, application thereof and pultrusion composite material

Abstract

The invention belongs to the technical field of epoxy resin, and particularly relates to a flame-retardant epoxy resin system, application thereof and a pultrusion composite material. The flame-retardant epoxy resin system provided by the invention comprises a material A and a material B which are independently subpackaged, the material A comprises the following components in parts by mass: 70 parts of flame-retardant epoxy resin; 22 to 26 parts of epoxy diluent; 5-7 parts of a toughening agent; the material B comprises the following components in parts by mass: 95-97 parts of an anhydride curing agent; 0.3 to 2 parts of accelerant; 0.5 to 1.5 parts of an antioxidant; and 0.1 to 0.6 part of a release agent. The material A and the material B in the flame-retardant epoxy resin system provided by the invention select proper components and mass ratios of the components, so that the pultrusion material product has a flame-retardant effect while the modulus advantage, the lightweight characteristic, the high fiber volume content and the excellent mechanical property requirements of the pultrusion material product are maintained, and the flame-retardant epoxy resin system can be suitable for places with relatively high fireproof grades.

Description

Technical Field

[0001] The invention belongs to the technical field of epoxy resins, and in particular relates to a flame retardant epoxy resin system and application thereof, and a pultruded composite material. Background Art

[0002] Pultruded composite profiles are widely used in electrical equipment, wind power equipment, corrosion-resistant components, construction engineering, transportation industry, military and other fields, and are currently in a stage of rapid development. Pultrusion is to impregnate continuous fiber bundles or ribbons with thermosetting or thermoplastic resins under a certain traction force, and then heat and solidify them through a molding die of a specific shape, and finally form a continuous length of pultruded composite profiles with a specific interface shape.

[0003] The matrix resins suitable for fiber composite pultrusion include saturated polyester resin, vinyl resin, epoxy resin, etc. Among them, epoxy resin is widely used in the production of pultruded composite profile products due to its excellent reactivity, good mechanical properties, excellent chemical resistance, low curing shrinkage and excellent electrical insulation.

[0004] However, epoxy resin has poor flame retardant properties, and when commercially available epoxy resin with flame retardant properties is used as a resin for pultruded composite materials, it is impossible to make the pultruded composite materials have a flame retardant effect while maintaining good mechanical properties of the pultruded composite materials. Summary of the invention

[0005] The purpose of the present invention is to provide a flame retardant epoxy resin system and its application, and a pultruded composite material. The flame retardant epoxy resin system provided by the present invention can not only meet the mechanical and chemical property requirements of the pultruded composite material, but also enable the pultruded composite material to have excellent flame retardant properties.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a flame retardant epoxy resin system, comprising independently packaged material A and material B;

[0008] The A material includes the following components in parts by weight:

[0009] Flame retardant epoxy resin 70 parts;

[0010] Epoxy diluent 22-26 parts;

[0011] 5-7 parts of toughening agent;

[0012] The epoxy diluent comprises at least two of low molecular weight polyethylene glycol, low molecular weight polypropylene glycol, low molecular weight polyol and low molecular weight ester compound; the molecular weights of the low molecular weight polyethylene glycol, the low molecular weight polypropylene glycol, the low molecular weight polyol and the low molecular weight ester compound are less than 1000;

[0013] The B material includes the following components in parts by weight:

[0014] 95-97 parts of anhydride curing agent;

[0015] 0.3-2 parts of accelerator;

[0016] 0.5-1.5 parts of antioxidant;

[0017] 0.1 to 0.6 parts of release agent;

[0018] The accelerator includes at least two of quaternary phosphonium salts, quaternary ammonium salts, tertiary amine compounds, heterocyclic amine compounds, imidazole compounds, Lewis acid compounds and organic metal complexes.

[0019] Preferably, the mass ratio of the A material to the B material is 100:(80-120).

[0020] Preferably, the flame retardant epoxy resin includes one or more of a phosphorus-containing flame retardant epoxy resin, a bromine-containing flame retardant epoxy resin and a nitrogen-containing flame retardant epoxy resin.

[0021] Preferably, the phosphorus-containing flame-retardant epoxy resin is prepared by chemical reaction of epoxy resin and reactive phosphorus-containing flame retardant.

[0022] Preferably, the reactive phosphorus-containing flame retardant includes DOPO.

[0023] Preferably, the toughening agent includes one or more of a polyamide toughening agent, a polyether toughening agent, a polyester toughening agent, a polyimide toughening agent and a polyurethane toughening agent.

[0024] Preferably, the anhydride curing agent includes one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, tung oil anhydride, succinic anhydride, dodecenylsuccinic anhydride, glutaric anhydride, polyazetaedioic anhydride, maleic anhydride and dimaleic anhydride-based methylethylbenzene.

[0025] Preferably, the release agent includes one or more of fatty acid esters, fatty alcohols, fatty alcohol phosphates and fatty alcohol polyoxyethylene ether phosphates.

[0026] The present invention provides the use of the flame retardant epoxy resin system described in the above technical solution as an epoxy resin pultrusion material.

[0027] The present invention provides a pultruded composite material, comprising an epoxy resin matrix and fibers, wherein the epoxy resin matrix is ​​the flame retardant epoxy resin system described in the above technical solution.

[0028] The invention provides a flame retardant epoxy resin system, comprising independently packaged A material and B material; the A material comprises the following components in parts by mass: 70 parts of flame retardant epoxy resin; 22-26 parts of epoxy diluent; 5-7 parts of toughening agent; the epoxy diluent comprises at least two of low molecular weight polyethylene glycol, low molecular weight polypropylene glycol, low molecular weight polyol and low molecular weight ester compound; the molecular weights of the low molecular weight polyethylene glycol, the low molecular weight polypropylene glycol, the low molecular weight polyol and the low molecular weight ester compound are less than 1000; the B material comprises the following components in parts by mass: 95-97 parts of anhydride curing agent; 0.3-2 parts of accelerator; 0.5-1.5 parts of antioxidant; 0.1-0.6 parts of release agent; the accelerator comprises at least two of quaternary phosphonium salt, quaternary ammonium salt, tertiary amine compound, heterocyclic amine compound, imidazole compound, Lewis acid compound and organic metal complex. The material A in the flame-retardant epoxy resin system provided by the present invention is a combination of a flame-retardant epoxy resin and a specific type of epoxy diluent, and at least two types of epoxy diluents are used. By controlling the type of epoxy diluent and the mass ratio of the flame-retardant epoxy resin and the epoxy diluent, the appropriate viscosity requirement can be achieved. At the same time, the acid anhydride curing agent of the material B and a specific type of accelerator are matched, especially using at least two types of accelerators, a flame-retardant epoxy resin system suitable for pultrusion materials with low viscosity, high mechanical properties and flame-retardant effect can be obtained. The flame-retardant epoxy resin system provided by the present invention has high storage stability, can be stored for a long time, has good wetting performance on fibers, has a fast reaction time and excellent curing effect, and can be suitable for special pultrusion materials with flame-retardant effect.

[0029] The flame retardant epoxy resin system provided by the present invention has the following beneficial effects:

[0030] The main raw materials of the invention are flame retardant epoxy resin and acid anhydride curing agent, the raw materials are easy to react, the cost is low, and the flame retardant effect is excellent.

[0031] The material A and the material B in the flame retardant epoxy resin system provided by the present invention are selected from suitable components and mass ratios of the components, so that the viscosity of the material A and the material B are both low, and the moderate viscosity has good wettability to the fiber.

[0032] The cured product obtained after curing the A material and the B material in the flame-retardant epoxy resin system provided by the present invention has excellent mechanical properties such as tensile strength, bending strength, shear strength and impact strength and can be fireproof and flame-retardant.

[0033] In summary, the flame retardant epoxy resin system provided by the present invention maintains the modulus advantage, lightweight characteristics, high fiber volume content (the volume content of fiber in the pultrusion material is 75-85%) and excellent mechanical performance requirements of the pultrusion product, while making the pultrusion product have a flame retardant effect, and can be suitable for materials used in places with a higher fire protection level.

[0034] Furthermore, in the present invention, the flame retardant epoxy resin is a phosphorus-containing flame retardant epoxy resin. The flame retardant epoxy resin system provided by the present invention is halogen-free and flame retardant, and is safer and more environmentally friendly. DETAILED DESCRIPTION

[0035] The present invention provides a flame retardant epoxy resin system, comprising independently packaged material A and material B;

[0036] The A material includes the following components in parts by weight:

[0037] Flame retardant epoxy resin 70 parts;

[0038] Epoxy diluent 22-26 parts;

[0039] 5-7 parts of toughening agent;

[0040] The epoxy diluent comprises at least two of low molecular weight polyethylene glycol, low molecular weight polypropylene glycol, low molecular weight polyol and low molecular weight ester compound; the molecular weights of the low molecular weight polyethylene glycol, the low molecular weight polypropylene glycol, the low molecular weight polyol and the low molecular weight ester compound are less than 1000;

[0041] The B material includes the following components in parts by weight:

[0042] 95-97 parts of anhydride curing agent;

[0043] 0.3-2 parts of accelerator;

[0044] 0.5-1.5 parts of antioxidant;

[0045] 0.1 to 0.6 parts of release agent;

[0046] The accelerator includes at least two of quaternary phosphonium salts, quaternary ammonium salts, tertiary amine compounds, heterocyclic amine compounds, imidazole compounds, Lewis acid compounds and organic metal complexes.

[0047] In the present invention, unless otherwise specified, all preparation raw materials / components are commercially available products well known to those skilled in the art.

[0048] The flame retardant epoxy resin system provided by the present invention comprises independently packaged material A. In the present invention, the material A comprises the following components in parts by weight: 70 parts of flame retardant epoxy resin; 22-26 parts of epoxy diluent; and 5-7 parts of toughening agent.

[0049] In terms of mass percentage, the material A includes 70 parts of flame-retardant epoxy resin. The flame-retardant epoxy resin includes one or more of phosphorus-containing flame-retardant epoxy resin, bromine-containing flame-retardant epoxy resin and nitrogen-containing flame-retardant epoxy resin, and in the embodiment, it can be a phosphorus-containing flame-retardant epoxy resin. In the present invention, the phosphorus-containing flame-retardant epoxy resin is preferably prepared by chemical reaction of epoxy resin and reactive phosphorus-containing flame retardant, and the epoxy resin is preferably bisphenol A epoxy resin. The reactive phosphorus-containing flame retardant preferably includes DOPO. The preparation method of the phosphorus-containing flame-retardant epoxy resin preferably includes the following steps: in a protective gas atmosphere, mixing the epoxy resin, the first DOPO and the catalyst for a first-stage reaction to obtain a first-stage reaction liquid; mixing the first-stage reaction liquid and the second DOPO for a second-stage reaction to obtain the phosphorus-containing flame-retardant epoxy resin. The ratio of the mass of the epoxy resin to the total mass of the first DOPO and the second DOPO is preferably 6:1. The mass ratio of the first DOPO to the second DOPO is 3:2. The catalyst is preferably triphenylphosphine, and the mass of the catalyst preferably accounts for 1‰ of the total mass of the first DOPO and the second DOPO. The temperature of the first stage reaction is preferably 160-165°C, and the insulation time of the first stage reaction is preferably 1-1.5h. The temperature of the second stage reaction is preferably 160-165°C, and the insulation time of the second stage reaction is preferably 2.5-3h. The protective gas is preferably nitrogen. The mixing of the epoxy resin, the first DOPO and the catalyst preferably includes the following steps: raising the temperature of the epoxy resin and the first DOPO to 110-120°C to obtain a mixed solution; and raising the temperature of the mixed solution and the catalyst to the temperature of the first stage reaction.

[0050] Based on the mass fraction of the flame retardant epoxy resin, the A material includes 22 to 26 parts of epoxy diluent. In the present invention, the epoxy diluent preferably includes one or more of a monofunctional epoxy diluent, a difunctional epoxy diluent and a multifunctional epoxy diluent. The epoxy diluent includes one or more of low molecular weight polyethylene glycol, low molecular weight polypropylene glycol, low molecular weight polyol and low molecular weight ester compounds, more preferably includes at least two of low molecular weight polyethylene glycol, low molecular weight polypropylene glycol, low molecular weight polyol and low molecular weight ester compounds, and in the embodiment, it can be two of the above substances. In the present invention, the molecular weight of the low molecular weight polyethylene glycol is preferably <1000. The molecular weight of the low molecular weight polypropylene glycol is preferably <1000. The molecular weight of the low molecular weight polyol is preferably <1000. The molecular weight of the low molecular weight ester compound is preferably <1000. The low molecular weight polyethylene glycol preferably includes polyethylene glycol glycidyl ether and / or tetrabutylene glycol glycidyl ether, and in the embodiment, it can be tetrabutylene glycol glycidyl ether. The low molecular weight polypropylene glycol preferably includes polypropylene glycol glycidyl ether. The low molecular weight polyol preferably includes castor oil derivative polyol and / or benzyl glycidyl ether. The low molecular weight ester compound preferably includes butyl acetate.

[0051] The epoxy diluent preferably includes a first epoxy diluent and a second epoxy diluent. Based on the mass fraction of the flame retardant epoxy resin, the A material includes 11 to 13 parts of the first epoxy diluent and 11 to 13 parts of the second epoxy diluent. The first epoxy diluent preferably includes low molecular weight polyethylene glycol, low molecular weight polypropylene glycol, low molecular weight polyol or low molecular weight ester compound. The second epoxy diluent preferably includes low molecular weight polyethylene glycol, low molecular weight polypropylene glycol, low molecular weight polyol or low molecular weight ester compound. The present invention can effectively reduce the viscosity of the A material at room temperature (25°C) by compounding the first epoxy diluent and the second epoxy diluent.

[0052] Based on the mass fraction of the flame retardant epoxy resin, the material A includes 5 to 7 parts of a toughening agent, and in the embodiment, it can be 5 parts, 6 parts or 7 parts. In the present invention, the toughening agent preferably includes one or more of a polyamide toughening agent, a polyether toughening agent, a polyester toughening agent, a polyimide toughening agent and a polyurethane toughening agent, and in the embodiment, it is specifically a polyether polyol.

[0053] In the present invention, the material A is compounded with at least two epoxy diluents to obtain material A with suitable room temperature viscosity, thereby improving the wettability to the fiber. In the present invention, the viscosity of the material A at room temperature (25° C.) is preferably 3500 to 5800 cp·s.

[0054] The preparation method of the material A provided by the present invention comprises the following steps:

[0055] The flame retardant epoxy resin, epoxy diluent and toughening agent are mixed to obtain material A. The mixing is performed under stirring, and the mixing temperature is preferably room temperature.

[0056] The flame retardant epoxy resin system provided by the present invention includes independently packaged B material. In the present invention, the B material includes the following components in parts by weight: 95-97 parts of anhydride curing agent; 0.3-2 parts of accelerator; 0.5-1.5 parts of antioxidant; 0.1-0.6 parts of release agent; the accelerator includes at least two of quaternary phosphonium salts, quaternary ammonium salts, tertiary amine compounds, heterocyclic amine compounds, imidazole compounds, Lewis acid compounds and organic metal complexes.

[0057] In parts by mass, the B material includes 95 to 97 parts of anhydride curing agent, and in the embodiment, it can be 96.8 parts. In the present invention, the anhydride curing agent preferably includes one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, tung oil anhydride, succinic anhydride, dodecenylsuccinic anhydride, glutaric anhydride, polyazelaic anhydride, maleic anhydride and dimaleic anhydride-based methylethylbenzene.

[0058] In terms of the mass fraction of the anhydride curing agent, the B material includes 0.3 to 2 parts of an accelerator, and in the embodiment, it can be 1.3 parts. In the present invention, the accelerator includes at least two of a quaternary phosphonium salt, a quaternary ammonium salt, a tertiary amine compound, a heterocyclic amine compound, an imidazole compound, a Lewis acid compound, and an organic metal complex. The quaternary phosphonium salt preferably includes triphenylphosphine, the quaternary ammonium salt preferably includes tetramethylammonium chloride, the tertiary amine compound preferably includes DMP-30, the heterocyclic amine compound preferably includes a special accelerator for polyetheramine 4082, the imidazole compound preferably includes 1-methylimidazole, the Lewis acid compound preferably includes boron trifluoride, and the organic metal complex preferably includes zinc naphthenate.

[0059] In the present invention, the accelerator preferably includes a first accelerator and a second accelerator. The B material includes 0.15-1 part of the first accelerator and 0.15-1 part of the second accelerator in terms of the mass fraction of the acid anhydride curing agent; in the embodiment, the B material may be 0.5 part of the first accelerator and 0.8 part of the second accelerator. In the present invention, the first accelerator includes one or more of quaternary phosphonium salts, quaternary ammonium salts, tertiary amine compounds, heterocyclic amine compounds, imidazole compounds, Lewis acid compounds and organic metal complexes. The second accelerator includes one or more of quaternary phosphonium salts, quaternary ammonium salts, tertiary amine compounds, heterocyclic amine compounds, imidazole compounds, Lewis acid compounds and organic metal complexes. The present invention can effectively promote the gelation of the flame retardant epoxy resin system and shorten the gelation time of the flame retardant epoxy resin system by compounding the first accelerator and the second accelerator.

[0060] Calculated by the mass fraction of the anhydride curing agent, the material B includes 0.5 to 1.5 parts of antioxidant, and in the embodiment, it can be 1.3 parts. In the present invention, the antioxidant preferably includes a diphenol antioxidant, specifically DTPD (3100).

[0061] In terms of the mass fraction of the anhydride curing agent, the B material includes 0.1 to 0.6 parts of a release agent, and in the embodiment, it can be 0.6 parts. In the present invention, the release agent preferably includes one or more of fatty acid esters, fatty alcohols, fatty alcohol phosphates, and fatty alcohol polyoxyethylene ether phosphates. The fatty acid ester preferably includes pentaerythritol stearate and / or alkyl silicone oil, the fatty alcohol preferably includes n-heptyl alcohol, the fatty alcohol phosphate preferably includes cetostearyl alcohol phosphate C16-18P, and the fatty alcohol polyoxyethylene ether phosphate preferably includes fatty alcohol polyoxyethylene ether.

[0062] In the present invention, the B material can obtain a flame retardant epoxy resin system with a suitable gel time by using at least two accelerators to obtain the best gel effect. In the present invention, the gel time of the flame retardant epoxy resin system (the mass ratio of A material to B material is 100:80) at 120°C is preferably 380 to 385s, the gel time at 140°C is preferably 120 to 130s, and the gel time at 160°C is preferably 15 to 50s.

[0063] The preparation method of the material B provided by the present invention comprises the following steps:

[0064] The anhydride curing agent, accelerator, antioxidant and release agent are mixed to obtain material B. The mixing is performed under stirring, and the mixing temperature is preferably room temperature.

[0065] In the present invention, the mass ratio of the material A to the material B is preferably 100:(80-120), and in the embodiment it can be 100:80.

[0066] The present invention provides the use of the flame retardant epoxy resin system described in the above technical solution as an epoxy resin pultrusion material.

[0067] The present invention provides a pultruded composite material, comprising an epoxy resin matrix and fibers, wherein the epoxy resin matrix is ​​the flame retardant epoxy resin system described in the above technical solution.

[0068] In the present invention, the fibers preferably include carbon fibers and / or glass fibers. In the present invention, the volume percentage of the fibers in the pultruded composite material is preferably 75-85%.

[0069] The flame retardant epoxy resin system described in the above technical solution provided by the present invention makes the viscosity of the entire resin system low by reasonably modifying the formula of the epoxy resin system, and the fiber wettability will be better. It can not only meet the mechanical and chemical property requirements of pultrusion molding, but also have flame retardant properties. The tensile strength, tensile modulus, bending strength, and bending modulus of the pultruded composite material prepared by the flame retardant epoxy resin system provided by the present invention are more excellent; and the flame retardancy of the pultruded composite material is increased. The pultruded composite material obtained by the flame retardant epoxy resin body described in the above technical solution is more competitive and adaptable.

[0070] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0071] "Parts" in the following examples all represent parts by mass.

[0072] Example 1

[0073] The epoxy resin system provided in this embodiment includes material A and material B, wherein material A and material B respectively include the following components in parts by weight:

[0074] Material A:

[0075]

[0076] The preparation method of phosphorus-containing flame-retardant bisphenol A epoxy resin specifically includes:

[0077] Add bisphenol A epoxy resin and the first DOPO (Wansheng DOPO) into the reactor, pass nitrogen, heat, and raise the temperature to 120°C. After the first DOPO is completely dissolved, add the catalyst (triphenylphosphine), slowly raise the temperature to about 160°C to observe its temperature surge, and finally keep it between 160 and 165°C for 1 hour, and add the second DOPO, wherein the mass ratio of bisphenol A epoxy resin to the total mass of the first DOPO and the second DOPO is 6:1, the mass ratio of the first DOPO and the second DOPO is 2:3, and the mass ratio of the catalyst to the total mass of the first DOPO and the second DOPO is 1‰. Continue to keep the temperature at 160-165°C for 3 hours. After the end of the heat preservation, cool down to 120°C, and then add diluent 1, diluent 2 and toughening agent to prepare material A.

[0078] The diluent 1 in material A is specifically mono-tetrabutylene glycol glycidyl ether, the diluent 2 is specifically benzyl glycidyl ether, and the toughening agent is specifically polyether polyol.

[0079] Material B:

[0080]

[0081] Among them, the accelerator 1 in material B is specifically 1-methylimidazole, the accelerator 2 is specifically DMP-30, the antioxidant is specifically DTPD (3100), and the release agent is specifically alkyl silicone oil.

[0082] The steps of preparing the sample strips using the above epoxy resin system in this embodiment include:

[0083] The preparation method of material A comprises: cooling phosphorus flame retardant bisphenol A epoxy resin to 120° C., adding diluent 1 and diluent 2; then adding toughening agent at room temperature (25° C.), and fully mixing and stirring in a stirring kettle to obtain material A.

[0084] The preparation method of material B comprises: adding methyltetrahydrophthalic anhydride, accelerator 1, accelerator 2, antioxidant and release agent into a stirring kettle at room temperature, stirring and mixing them fully to obtain material B.

[0085] Material A and material B were mixed at a mass ratio of 100:80, stirred thoroughly and placed in a 40°C vacuum oven for degassing for 30 minutes, and then poured into a mold for curing to obtain a cured specimen 1.

[0086] Comparative Example 1

[0087] The epoxy resin system provided in this comparative example includes material A and material B, wherein material A and material B respectively include the following components in parts by weight:

[0088] Material A: 70 parts of phosphorus-containing flame-retardant bisphenol A epoxy resin;

[0089] Diluent 1 25 parts;

[0090] 5 parts of toughening agent;

[0091] The preparation method of the phosphorus-containing flame-retardant bisphenol A epoxy resin in material A is the same as that in Example 1, the diluent 1 is specifically mono-tetrabutylene glycol glycidyl ether, and the toughening agent is specifically polyether polyol.

[0092] Material B:

[0093]

[0094] Among them, the accelerator 1 in material B is specifically 1-methylimidazole, the accelerator 2 is specifically DMP-30, the antioxidant is specifically DTPD (3100), and the release agent is specifically alkyl silicone oil.

[0095] The steps of preparing the sample strips using the above epoxy resin system in this comparative example include:

[0096] The preparation method of material A comprises: cooling phosphorus flame retardant bisphenol A epoxy resin to 120° C., adding diluent 1; then adding toughening agent at room temperature (25° C.), and fully mixing and stirring in a stirring kettle to obtain material A.

[0097] The preparation method of material B comprises: adding methyltetrahydrophthalic anhydride, accelerator 1, accelerator 2, antioxidant and release agent into a stirring kettle at room temperature, stirring and mixing them fully to obtain material B.

[0098] Material A and material B were mixed at a mass ratio of 100:80, stirred thoroughly and evenly, placed in a 40°C vacuum oven for degassing for 30 minutes, and then poured into a mold for curing to obtain a cured specimen 2.

[0099] Comparative Example 2

[0100] The epoxy resin system provided in this comparative example includes material A and material B, wherein material A and material B respectively include the following components in parts by weight:

[0101] Material A: 70 parts of phosphorus-containing flame-retardant bisphenol A epoxy resin;

[0102] Diluent 2 25 parts;

[0103] 5 parts of toughening agent;

[0104] The preparation method of the phosphorus-containing flame-retardant bisphenol A epoxy resin in material A is the same as that in Example 1, the diluent 2 is specifically benzyl glycidyl ether, and the toughening agent is specifically polyether polyol.

[0105] Material B:

[0106]

[0107] Among them, the accelerator 1 in material B is specifically 1-methylimidazole, the accelerator 2 is specifically DMP-30, the antioxidant is specifically DTPD (3100), and the release agent is specifically alkyl silicone oil.

[0108] The steps of preparing the sample strips using the above epoxy resin system in this comparative example include:

[0109] The preparation method of material A comprises: cooling phosphorus flame retardant bisphenol A epoxy resin to 120° C., adding diluent 2; then adding toughening agent at room temperature (25° C.), and fully mixing and stirring in a stirring kettle to obtain material A.

[0110] The preparation method of material B comprises: adding methyltetrahydrophthalic anhydride, accelerator 1, accelerator 2, antioxidant and release agent into a stirring kettle at room temperature, stirring and mixing them fully to obtain material B.

[0111] Material A and material B were mixed at a mass ratio of 100:80, stirred thoroughly and evenly, placed in a 40°C vacuum oven for degassing for 30 minutes, and then poured into a mold for curing to obtain a cured specimen 3.

[0112] Example 2

[0113] The epoxy resin system provided in this embodiment includes material A and material B, wherein material A and material B respectively include the following components in parts by weight:

[0114] Material A:

[0115]

[0116] The preparation method of the phosphorus-containing flame-retardant bisphenol A epoxy resin in material A is the same as that in Example 1. The diluent 1 in material A is specifically monobutylene glycol glycidyl ether, the diluent 2 is specifically benzyl glycidyl ether, and the toughening agent is specifically polyether polyol.

[0117] Material B:

[0118]

[0119] Among them, the accelerator 1 in material B is specifically 1-methylimidazole, the accelerator 2 is specifically DMP-30, the antioxidant is specifically DTPD (3100), and the release agent is specifically alkyl silicone oil.

[0120] The steps of preparing the sample strips using the above epoxy resin system in this embodiment include:

[0121] The preparation method of material A comprises: cooling phosphorus flame retardant bisphenol A epoxy resin to 120° C., adding diluent 1 and diluent 2; then adding toughening agent at room temperature (25° C.), and fully mixing and stirring in a stirring kettle to obtain material A.

[0122] The preparation method of material B comprises: adding methyltetrahydrophthalic anhydride, accelerator 1, accelerator 2, antioxidant and release agent into a stirring kettle at room temperature, stirring and mixing them fully to obtain material B.

[0123] Material A and material B were mixed at a mass ratio of 100:70, stirred thoroughly and placed in a 40°C vacuum oven for degassing for 30 minutes, and then poured into a mold for curing to obtain a cured specimen 4.

[0124] Example 3

[0125] The epoxy resin system provided in this embodiment includes material A and material B, wherein material A and material B respectively include the following components in parts by weight:

[0126] Material A:

[0127]

[0128] Among them, the preparation method of the phosphorus-containing flame-retardant bisphenol A epoxy resin in material A is the same as that in Example 1, the diluent 1 in material A is specifically tetrabutylene glycol glycidyl ether, the diluent 2 is specifically benzyl glycidyl ether, and the toughening agent is specifically polyether polyol.

[0129] Material B:

[0130]

[0131] Among them, the accelerator 1 in material B is specifically 1-methylimidazole, the accelerator 2 is specifically DMP-30, the antioxidant is specifically DTPD (3100), and the release agent is specifically alkyl silicone oil.

[0132] The steps of preparing the sample strips using the above epoxy resin system in this embodiment include:

[0133] The preparation method of material A comprises: cooling phosphorus flame retardant bisphenol A epoxy resin to 120° C., adding diluent 1 and diluent 2; then adding toughening agent at room temperature (25° C.), and fully mixing and stirring in a stirring kettle to obtain material A.

[0134] The preparation method of material B comprises: adding methyltetrahydrophthalic anhydride, accelerator 1, accelerator 2, antioxidant and release agent into a stirring kettle at room temperature, stirring and mixing them fully to obtain material B.

[0135] Material A and material B were mixed at a mass ratio of 100:90, stirred thoroughly and placed in a 40° C. vacuum oven for degassing for 30 minutes, and then poured into a mold for curing to obtain a cured specimen 5.

[0136] Comparative Example 3

[0137] The epoxy resin system provided in this comparative example includes material A and material B, wherein material A and material B respectively include the following components in parts by weight:

[0138] Material A:

[0139]

[0140] Among them, the diluent 1 in material A is specifically monobutylene glycol glycidyl ether, the diluent 2 is specifically benzyl glycidyl ether, and the toughening agent is specifically polyether polyol.

[0141] Material B:

[0142]

[0143] Among them, the accelerator 1 in material B is specifically 1-methylimidazole, the accelerator 2 is specifically DMP-30, the antioxidant is specifically DTPD (3100), and the release agent is specifically alkyl silicone oil.

[0144] The steps of preparing the sample strips using the above epoxy resin system in this comparative example include:

[0145] The preparation method of material A comprises: cooling bisphenol A epoxy resin to 120° C., adding diluent 1 and diluent 2; then adding toughening agent at room temperature (25° C.), and fully mixing and stirring in a stirring kettle to obtain material A.

[0146] The preparation method of material B comprises: adding methyltetrahydrophthalic anhydride, accelerator 1, accelerator 2, antioxidant and release agent into a stirring kettle at room temperature and stirring and mixing them thoroughly to obtain material B.

[0147] Material A and material B were mixed at a mass ratio of 100:80, stirred thoroughly and placed in a 40°C vacuum oven for degassing for 30 minutes, and then poured into a mold for curing to obtain a cured specimen 6.

[0148] Test Example 1

[0149] Related test data:

[0150] 1. The viscosity data of material A and material B prepared in Example 1, Comparative Example 1, Example 2 and Comparative Example 3 at 25° C. are tested. The results are shown in Table 1.

[0151] Table 1 25°C viscosity data of material A and material B in Example 1, Comparative Example 1, Example 2 and Comparative Example 3

[0152]

[0153] From the test results in Table 1, it can be seen that the use of two diluents in Example 1 and Example 2 can synergistically reduce the viscosity of material A of the resin system, and the use of a curing agent with a lower viscosity makes the viscosity of the entire system low, which will have better fiber wettability.

[0154] 2. Gel time

[0155] The gel time of Examples 1 to 3 and Comparative Examples 1 to 3 at 120°C, 140°C and 160°C was tested, that is, the material A and material B prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were mixed at a mass ratio of 100:80, and the materials were fully stirred for gel time under different temperature conditions. The test method is GB12007.7-1989, and the test is performed 3 times in parallel under each temperature condition, and the test results of the 3 measurement data are shown in Table 2.

[0156] Table 2 Gel time at 120°C, 140°C and 160°C for Examples 1 to 3 and Comparative Examples 1 to 3

[0157]

[0158] It can be seen from the data in Table 2 that the B material in the epoxy resin system in Examples 1 to 3 uses two accelerators in coordination, which can effectively control the gelation time of the resin system. The optimal curing mass ratio of A material to B material is 100:80, which is significantly helpful for the curing of the pultruded material in the production and construction.

[0159] 3. Spline performance indicators

[0160] The mechanical property data of the specimens prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were tested, and the test results are shown in Table 3.

[0161] Table 3 Mechanical properties test results of the samples prepared in Examples 1 to 3 and Comparative Examples 1 to 3

[0162]

[0163]

[0164] It can be seen from Table 3 that in Examples 1 to 3, material A uses phosphorus-containing flame-retardant bisphenol A epoxy resin with two diluents, and material B uses a low-viscosity medium-temperature curing agent with two accelerators, which not only makes the viscosity of the system low and the reaction temperature controllable, but also makes the tensile strength, tensile modulus, flexural strength, and flexural modulus of the cured strips more excellent; and the use of phosphorus-containing flame-retardant epoxy resin increases the flame retardancy of the pultruded material. The pultruded materials of the epoxy resin system formula provided in Examples 1 to 3 are more competitive and adaptable.

[0165] Comparative Example 4

[0166] The epoxy resin system provided in this comparative example includes material A and material B, wherein material A and material B respectively include the following components in parts by weight:

[0167] Material A:

[0168]

[0169] The preparation method of the phosphorus-containing flame-retardant bisphenol A epoxy resin in material A is the same as that in Example 1, the diluent 1 is specifically monobutylene glycol glycidyl ether, the diluent 2 is specifically benzyl glycidyl ether, and the toughening agent is specifically polyether polyol.

[0170] Material B:

[0171]

[0172] Among them, the accelerator 1 in material B is specifically 1-methylimidazole, the accelerator 2 is specifically DMP-30, the antioxidant is specifically DTPD (3100), and the release agent is specifically alkyl silicone oil.

[0173] The steps of preparing the sample strips using the above epoxy resin system in this comparative example include:

[0174] The preparation method of material A comprises: cooling phosphorus flame retardant bisphenol A epoxy resin to 120° C., adding diluent 1 and diluent 2; then adding toughening agent at room temperature (25° C.), and fully mixing and stirring in a stirring kettle to obtain material A.

[0175] The preparation method of material B comprises: adding methyltetrahydrophthalic anhydride, accelerator 1, accelerator 2, antioxidant and release agent into a stirring kettle at room temperature, stirring and mixing them fully to obtain material B.

[0176] Material A and material B were mixed at a mass ratio of 100:80, stirred thoroughly and placed in a 40°C vacuum oven for degassing for 30 minutes, and then poured into a mold for curing to obtain a cured specimen 7.

[0177] Comparative Example 5

[0178] The epoxy resin system provided in this comparative example includes material A and material B, wherein material A and material B respectively include the following components in parts by weight:

[0179] Material A:

[0180]

[0181] The preparation method of the phosphorus-containing flame-retardant bisphenol A epoxy resin in material A is the same as that in Example 1, the diluent 1 is specifically monobutylene glycol glycidyl ether, the diluent 2 is specifically benzyl glycidyl ether, and the toughening agent is specifically polyether polyol.

[0182] Material B:

[0183]

[0184] Among them, the accelerator 1 in material B is specifically 1-methylimidazole, the accelerator 2 is specifically DMP-30, the antioxidant is specifically DTPD (3100), and the release agent is specifically alkyl silicone oil.

[0185] The steps of preparing the sample strips using the above epoxy resin system in this comparative example include:

[0186] The preparation method of material A includes: cooling the phosphorus flame retardant bisphenol A epoxy resin to 120°C, adding diluent 1 and diluent 2; then adding a toughening agent at room temperature (25°C), and fully mixing and stirring in a stirring kettle to obtain material A.

[0187] The preparation method of material B comprises: adding methyltetrahydrophthalic anhydride, accelerator 1, accelerator 2, antioxidant and release agent into a stirring kettle at room temperature, stirring and mixing them fully to obtain material B.

[0188] Material A and material B were mixed at a mass ratio of 100:80, stirred thoroughly and placed in a 40°C vacuum oven for degassing for 30 minutes, and then poured into a mold for curing to obtain a cured specimen 8.

[0189] Test Example 2

[0190] The viscosity data of material A and material B prepared in Example 1, Comparative Example 4 and Comparative Example 5 at 25° C., and the flame retardant effect of the specimens prepared in Example 1, Comparative Example 4 and Comparative Example 5 were tested, and the results are shown in Table 4.

[0191] Table 4 Test results of viscosity and flame retardant effect in Example 1 and Comparative Examples 4 to 5

[0192]

[0193] It can be seen from Table 4 that in the preparation process of material A in the epoxy resin system, the dosage ratio of the phosphorus-containing flame-retardant epoxy resin and the diluent is crucial to the viscosity requirement, but the flame retardant effect must also be maintained. Therefore, in Example 1, the amount of the phosphorus-containing flame-retardant bisphenol A type epoxy resin is 70 parts, which can maintain low viscosity and have a flame retardant effect.

[0194] Comparative Example 6

[0195] The epoxy resin system provided in this comparative example includes material A and material B, wherein material A and material B respectively include the following components in parts by weight:

[0196] Material A:

[0197]

[0198] The preparation method of the phosphorus-containing flame-retardant bisphenol A epoxy resin in material A is the same as that in Example 1, the diluent 1 is specifically monobutylene glycol glycidyl ether, the diluent 2 is specifically benzyl glycidyl ether, and the toughening agent is specifically polyether polyol.

[0199] Material B:

[0200]

[0201] Among them, the accelerator 1 in material B is specifically 1-methylimidazole, the antioxidant is specifically DTPD (3100), and the release agent is specifically alkyl silicone oil.

[0202] The steps of preparing the sample strips using the above epoxy resin system in this comparative example include:

[0203] The preparation method of material A comprises: cooling phosphorus flame retardant bisphenol A epoxy resin to 120° C., adding diluent 1 and diluent 2; then adding toughening agent at room temperature (25° C.), and fully mixing and stirring in a stirring kettle to obtain material A.

[0204] The preparation method of material B comprises: adding methyltetrahydrophthalic anhydride, accelerator 1, antioxidant and release agent into a stirring kettle at room temperature and stirring and mixing them thoroughly to obtain material B.

[0205] Comparative Example 7

[0206] The epoxy resin system provided in this comparative example includes material A and material B, wherein material A and material B respectively include the following components in parts by weight:

[0207] Material A:

[0208]

[0209] Among them, the preparation method of the phosphorus-containing flame-retardant bisphenol A epoxy resin in material A is the same as that in Example 1, the diluent 1 is specifically 1-methylimidazole, the accelerator 2 is specifically DMP-30, the antioxidant is specifically DTPD (3100), and the release agent is specifically alkyl silicone oil.

[0210] Material B:

[0211]

[0212] Among them, the accelerator 2 in material B is specifically DMP-30, the antioxidant is specifically DTPD (3100), and the release agent is specifically alkyl silicone oil.

[0213] The steps of preparing the sample strips using the above epoxy resin system in this comparative example include:

[0214] The preparation method of material A comprises: cooling phosphorus flame retardant bisphenol A epoxy resin to 120° C., adding diluent 1 and diluent 2; then adding toughening agent at room temperature (25° C.), and fully mixing and stirring in a stirring kettle to obtain material A.

[0215] The preparation method of material B comprises: adding methyltetrahydrophthalic anhydride, accelerator 2, antioxidant and release agent into a stirring kettle at room temperature and stirring and mixing them thoroughly to obtain material B.

[0216] Test Example 3

[0217] The gel time of Example 1, Comparative Example 4 and Comparative Example 5 at 140° C. was tested. The test results are shown in Table 5.

[0218] Table 5 Gel time of Example 1, Comparative Example 4 and Comparative Example 5 at 140°C

[0219]

[0220] It can be seen from Table 5 that in Comparative Examples 4 and 1, a single type of accelerator is used, and the gel time does not reach the expected effect, and the first item of gel time is unqualified, so the gel effect of material B in Example 1 using a mixed accelerator is the best.

[0221] It can be seen from the above embodiments that the flame retardant epoxy resin system provided by the present invention makes the viscosity of the entire resin system low by reasonably modifying the formula of the epoxy resin system, and the fiber wettability will be better. It can not only meet the mechanical and chemical property requirements of pultrusion molding, but also have flame retardant properties. The tensile strength, tensile modulus, bending strength, and bending modulus of the pultruded composite material prepared by the flame retardant epoxy resin system provided by the present invention are more excellent; and the flame retardancy of the pultruded composite material is increased. The pultruded composite material obtained by the flame retardant epoxy resin body described in the above technical solution is more competitive and adaptable.

[0222] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A flame retardant epoxy resin system, characterized in that: Including independently packaged material A and material B; The A material includes the following components in parts by weight: Flame retardant epoxy resin 70 parts; Epoxy diluent 22-26 parts; 5-7 parts of toughening agent; The epoxy diluent comprises at least two of low molecular weight polyethylene glycol, low molecular weight polypropylene glycol, low molecular weight polyol and low molecular weight ester compound; the molecular weights of the low molecular weight polyethylene glycol, the low molecular weight polypropylene glycol, the low molecular weight polyol and the low molecular weight ester compound are less than 1000; The B material includes the following components in parts by weight: 95-97 parts of anhydride curing agent; 0.3-2 parts of accelerator; 0.5-1.5 parts of antioxidant; 0.1 to 0.6 parts of release agent; The accelerator includes at least two of quaternary phosphonium salts, quaternary ammonium salts, tertiary amine compounds, heterocyclic amine compounds, imidazole compounds, Lewis acid compounds and organic metal complexes.

2. The flame retardant epoxy resin system according to claim 1, characterized in that: The mass ratio of the A material to the B material is 100:(80-120).

3. The flame retardant epoxy resin system according to claim 1, characterized in that: The flame retardant epoxy resin includes one or more of a phosphorus-containing flame retardant epoxy resin, a bromine-containing flame retardant epoxy resin and a nitrogen-containing flame retardant epoxy resin.

4. The flame retardant epoxy resin system according to claim 3, characterized in that: The phosphorus-containing flame-retardant epoxy resin is prepared by chemical reaction between epoxy resin and reactive phosphorus-containing flame retardant.

5. The flame retardant epoxy resin system according to claim 4, characterized in that: The reactive phosphorus-containing flame retardant includes DOPO.

6. The flame retardant epoxy resin system according to claim 1, characterized in that: The toughening agent includes one or more of a polyamide toughening agent, a polyether toughening agent, a polyester toughening agent, a polyimide toughening agent and a polyurethane toughening agent.

7. The flame retardant epoxy resin system according to claim 1, characterized in that: The anhydride curing agent includes one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, tung oil anhydride, succinic anhydride, dodecenylsuccinic anhydride, glutaric anhydride, polyazetaedioic anhydride, maleic anhydride and dimaleic anhydride-based methylethylbenzene.

8. The flame retardant epoxy resin system according to claim 1, characterized in that: The release agent includes one or more of fatty acid esters, fatty alcohols, fatty alcohol phosphates and fatty alcohol polyoxyethylene ether phosphates.

9. Use of the flame retardant epoxy resin system according to any one of claims 1 to 8 as epoxy resin pultrusion material.

10. A pultruded composite material, characterized in that: The invention comprises an epoxy resin matrix and fibers, wherein the epoxy resin matrix is ​​the flame retardant epoxy resin system according to any one of claims 1 to 8.

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