Anti-puncture epoxy resin composition as well as preparation method and application thereof

Abstract

The invention relates to the technical field of materials, and provides an anti-puncture epoxy resin composition and a preparation method and application thereof.The anti-puncture epoxy resin composition is prepared from, by weight, 30-60 parts of matrix resin, 5-25 parts of polyether polymer with active hydroxyl, 2-10 parts of core-shell particles, 10-20 parts of low-molecular-weight polyamide and 3-5 parts of curing agent, 1-3 parts of a coupling agent, 0.05-0.2 part of an accelerant and 20-40 parts of filler. The method has the advantages that the epoxy resin is modified through the polyether polymer with active hydroxyl, the bonding force of the base material and the epoxy resin is improved, the toughening effect is achieved through the low-molecular-weight polyamide, the problem of low brittleness caused by the low-molecular-weight polyamide is solved through the curing agent, the base material absorbs impact energy through the core-shell effect, and the bonding force between the base material and the epoxy resin is improved. Therefore, the anti-puncture capability of the base body is greatly improved in multiple aspects. In addition, the composition in the scheme does not sacrifice good performance of the epoxy resin.

Description

Technical Field

[0001] The present invention relates to the field of materials, and more specifically, to a puncture-resistant epoxy resin composition and a preparation method and application thereof. Background Art

[0002] Epoxy resin is a thermosetting polymer material widely used in the industrial field. Due to its excellent mechanical properties and chemical corrosion resistance, epoxy resin is widely used in coatings, adhesives, composite materials and other fields. However, traditional epoxy resin has the disadvantage of poor puncture resistance and is prone to perforation damage in some applications that need to withstand impact loads, which limits its scope of application. Puncture-resistant epoxy resin can not only meet general mechanical property requirements, but also effectively absorb energy when hit by sharp objects to avoid perforation damage, thereby greatly improving the safety and reliability of the material when used. This material has broad application prospects in military industry, aerospace, transportation, electrical equipment, high-performance sports equipment (such as racing helmets) and other fields.

[0003] At present, the main methods to improve the puncture resistance of epoxy resins are: introducing flexible macromolecular modifiers, infiltrating nano-reinforced phases, designing multiphase structures, etc. However, the existing technical routes still face some challenges in practical applications. Modification toughening and nano-reinforcement technologies often sacrifice other properties of epoxy resins, such as modulus and thermal stability, while improving toughness. The cross-linking density regulation also has the problems of complex process and poor controllability. Therefore, it is necessary to develop a puncture-resistant epoxy resin that does not sacrifice other properties of epoxy resin while improving the puncture resistance. Summary of the invention

[0004] The present invention aims to overcome at least one defect (shortcoming) of the above-mentioned prior art, and provide a puncture-resistant epoxy resin composition and a preparation method and application thereof, so as to improve the puncture resistance of the epoxy resin without sacrificing the performance of the epoxy resin itself.

[0005] An object of the present invention is to provide a puncture-resistant epoxy resin composition comprising the following components in parts by weight:

[0006] 30-60 parts of base resin,

[0007] 5-25 parts of polyether polymer with active hydroxyl groups,

[0008] 2-10 parts of core-shell particles,

[0009] 10-20 parts of low molecular weight polyamide,

[0010] 3-5 parts of curing agent,

[0011] 1-3 parts of coupling agent,

[0012] Accelerator 0.05-0.2 parts,

[0013] 20-40 parts of filler.

[0014] Regarding the role of the polyether polymer with active hydroxyl groups. The polyether polymer modified epoxy resin in this scheme, the active hydroxyl groups on the polyether polymer can improve the bonding force between the substrate and the puncture-resistant epoxy resin composition, so that the interlayer bonding force of the composite sheet laminated with multi-layer prepreg or prepreg is significantly improved, thereby improving its puncture-resistant ability. In addition, the hydroxyl group has a wetting effect, and has a certain wetting effect on the core-shell material, which can improve the dispersibility of the core-shell material in the polyether, thereby increasing the filling ratio.

[0015] About the role of core-shell. From a microscopic point of view, the uniformly distributed core-shell particles undergo plastic deformation during the destruction of the matrix, and through the transformation of strain stress, the matrix yields to achieve the purpose of preventing puncture and absorbing impact energy.

[0016] About the role of low molecular weight polyamide. Low molecular weight polyamide molecules have long aliphatic carbon chains, which can play an internal toughening role, making the cured epoxy resin have a certain toughness.

[0017] Regarding the role of curing agents. Low molecular weight polyamides with too high free amine content, high viscosity, and slow reaction make crosslinking of the curing system difficult; high free amine content causes the reaction to proceed too quickly, and the resulting cured product is prone to undesirable results such as high brittleness and low strength. Additional addition of curing agents can make the composition highly crosslinked and avoid undesirable results such as high brittleness and low strength.

[0018] It can be understood that the present invention modifies epoxy resin by polyether polymer with active hydroxyl groups, improves the bonding force between substrate and epoxy resin, toughens by low molecular weight polyamide, prevents the low brittleness problem caused by low molecular weight polyamide by curing agent, and combines the core-shell effect to make the matrix absorb impact energy, thereby greatly improving the anti-puncture ability of the matrix in many aspects, and the matrix here refers to the matrix formed by the substrate combined with the epoxy resin composition. In addition, compared with traditional methods such as introducing flexible macromolecular modifiers, infiltrating nano-reinforced phases, and designing multiphase structures, the composition of this scheme will not sacrifice the good performance of the epoxy resin itself.

[0019] In some embodiments, the base resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, aliphatic glycidyl ether epoxy resin and glycidyl ester epoxy resin.

[0020] In some embodiments, the polyether polymer with active hydroxyl groups is selected from one or more of hydroxyl-terminated polypropylene glycol, trimethylolpropane polyether, and hydroxyl-terminated polytetrahydrofuran.

[0021] In some embodiments, the core-shell particles are selected from one or more of a polymer whose core is polybutyl acrylate and whose shell is polymethyl methacrylate, a polymer whose core is cross-linked polybutadiene and whose shell is cross-linked polybutadiene, a polymer whose core is silicone rubber and whose shell is polymethyl methacrylate, or a polymer whose core is polybutyl acrylate and whose shell is polymethyl methacrylate.

[0022] In some embodiments, the low molecular weight polyamide is selected from one or more of 200 low molecular weight polyamide, 650 low molecular weight polyamide, and 651 low molecular weight polyamide.

[0023] In some embodiments, the curing agent is selected from one or more of cyanate curing agents, aliphatic polyamine curing agents, alicyclic polyamine curing agents, aromatic amine curing agents, polyamide type curing agents, latent curing agents, Lewis acid-amine complex curing agents, and organic acid anhydride curing agents.

[0024] In some embodiments, the coupling agent is selected from one or more of silane coupling agents, titanate coupling agents, aluminate coupling agents, bimetallic coupling agents, phosphate coupling agents, borate coupling agents, chromium complexes, and other coupling agents of higher fatty acids, alcohols, and esters.

[0025] In some embodiments, the accelerator is selected from one or more of imidazole accelerators, peroxide accelerators, azo accelerators, tertiary amine accelerators, phenol accelerators, organic metal salt accelerators and inorganic metal salt accelerators.

[0026] In some embodiments, the filler is selected from one or more of titanium dioxide, silicon dioxide, magnesium oxide, magnesium hydroxide, talc, mica powder, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide and barium sulfate.

[0027] Another object of the present invention is to provide a method for preparing any one of the above-mentioned puncture-resistant epoxy resin compositions, comprising the following steps:

[0028] S1. Core-shell modified polyether polymer with active hydroxyl groups. Add the polyether polymer with active hydroxyl groups into a reaction container, add the core-shell particles under stirring, and stir to obtain the core-shell modified polyether polymer with active hydroxyl groups;

[0029] S2. Core-shell modified polyether polymer modified base resin with active hydroxyl groups: Heat the base resin, add low molecular weight polyamide, and stir to obtain core-shell modified polyether polymer modified base resin with active hydroxyl groups.

[0030] In some embodiments, in step S1, the stirring is specifically: high-speed stirring for 4-8 hours; in step S2, the heating is specifically: heating the base resin to 70-90°C; the adding of low molecular weight polyamide is specifically: adding an appropriate amount of low molecular weight polyamide while stirring; in step S2, the stirring time is 5-15 minutes.

[0031] In some embodiments of this solution, the reaction formula of step S2 is as follows:

[0032]

[0033] Another object of the present invention is to provide a prepreg prepared by using any one of the above-mentioned puncture-resistant epoxy resin compositions.

[0034] Another object of the present invention is to provide a laminated board prepared using the prepreg.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention modifies the epoxy resin by a polyether polymer with active hydroxyl groups, improves the bonding force between the substrate and the epoxy resin, toughens the epoxy resin by low molecular weight polyamide, prevents the brittleness problem caused by low molecular weight polyamide by a curing agent, and combines the core-shell effect to make the matrix absorb impact energy, thereby greatly improving the anti-puncture ability of the matrix in many aspects. In addition, compared with traditional methods such as introducing flexible macromolecular modifiers, infiltrating nano-reinforced phases, and designing multiphase structures, the composition of this scheme will not sacrifice the good performance of the epoxy resin itself. In this way, the present invention greatly improves its anti-puncture ability without sacrificing the performance of the epoxy resin itself. DETAILED DESCRIPTION

[0036] In order to enable those skilled in the art to better understand the technical solution of the present application, the present application is further described in detail below in conjunction with specific embodiments.

[0037] An object of the present invention is to provide a puncture-resistant epoxy resin composition comprising the following components in parts by weight:

[0038] 30-60 parts of base resin,

[0039] 5-25 parts of polyether polymer with active hydroxyl groups,

[0040] 2-10 parts of core-shell particles,

[0041] 10-20 parts of low molecular weight polyamide,

[0042] 3-5 parts of curing agent,

[0043] 1-3 parts of coupling agent,

[0044] Accelerator 0.05-0.2 parts,

[0045] 20-40 parts of filler.

[0046] Furthermore, the matrix resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, aliphatic glycidyl ether epoxy resin and glycidyl ester epoxy resin.

[0047] Furthermore, the polyether polymer with active hydroxyl groups is selected from one or more of hydroxyl-terminated polypropylene glycol, trimethylolpropane polyether and hydroxyl-terminated polytetrahydrofuran.

[0048] Furthermore, the core-shell particles are selected from one or more of a polymer whose core is polybutyl acrylate and whose shell is polymethyl methacrylate, a polymer whose core is cross-linked polybutadiene and whose shell is cross-linked polybutadiene, a polymer whose core is silicone rubber and whose shell is polymethyl methacrylate, or a polymer whose core is polybutyl acrylate and whose shell is polymethyl methacrylate.

[0049] Furthermore, the low molecular weight polyamide is selected from one or more of 200 low molecular weight polyamide, 650 low molecular weight polyamide, and 651 low molecular weight polyamide.

[0050] Furthermore, the curing agent is selected from one or more of cyanate curing agents, fatty polyamine curing agents, alicyclic polyamine curing agents, aromatic amine curing agents, polyamide type curing agents, latent curing agents, Lewis acid-amine complex curing agents, and organic acid anhydride curing agents.

[0051] Another object of the present invention is to provide a method for preparing any one of the above-mentioned puncture-resistant epoxy resin compositions, characterized in that it comprises the following steps:

[0052] S1, adding a polyether polymer with active hydroxyl groups into a reaction container, adding core-shell particles under stirring, and stirring to obtain a core-shell modified polyether polymer with active hydroxyl groups;

[0053] S2, heating the base resin, adding low molecular weight polyamide, stirring, and obtaining a core-shell modified polyether polymer modified base resin with active hydroxyl groups.

[0054] Furthermore, in step S1, the stirring is specifically: high-speed stirring for 4-8 hours; in step S2, the heating is specifically: heating the base resin to 70-90°C.

[0055] Another object of the present invention is to provide a prepreg prepared by using any one of the above-mentioned puncture-resistant epoxy resin compositions.

[0056] Another object of the present invention is to provide a laminated board prepared using the above-mentioned prepreg.

[0057] Example 1

[0058] The present embodiment provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 30 parts of bisphenol A epoxy resin, 15 parts of terminal hydroxyl polypropylene glycol, 5 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 15 parts of 200 low molecular weight polyamide, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0059] The puncture-resistant epoxy resin composition of this embodiment is prepared by the following method: 15 parts of terminal hydroxyl polypropylene glycol are added to a mixing bottle, and 5 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate are added under stirring. After complete addition, high-speed stirring is performed for 4 hours, and 30 parts of bisphenol A epoxy resin are added. The mixing bottle is heated to 80° C., and 15 parts of 200 low-molecular-weight polyamide are added while stirring. After stirring for 10 minutes, the temperature is lowered to 25° C., and then 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide are added to the mixing bottle. After high-speed dispersion for 1 hour, a glue solution is prepared, i.e., the puncture-resistant epoxy resin composition.

[0060] Example 2

[0061] The present embodiment provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 40 parts of bisphenol A epoxy resin, 15 parts of terminal hydroxyl polypropylene glycol, 5 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 15 parts of 200 low molecular weight polyamide, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0062] The puncture-resistant epoxy resin composition of this embodiment is prepared by the following method: 15 parts of terminal hydroxyl polypropylene glycol are added to a mixing bottle, 5 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate are added under stirring, after complete addition, high-speed stirring is performed for 5 hours, 40 parts of bisphenol A epoxy resin are added, the mixing bottle is heated to 80° C., 15 parts of 200 low molecular weight polyamide are added while stirring, after stirring for 5 minutes, the temperature is lowered to 25-40° C., and then 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide are added to the mixing bottle, and a glue solution is prepared after high-speed dispersion for 1 hour, i.e., the puncture-resistant epoxy resin composition.

[0063] Example 3

[0064] The present embodiment provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 50 parts of bisphenol A epoxy resin, 15 parts of terminal hydroxyl polypropylene glycol, 5 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 15 parts of 200 low molecular weight polyamide, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0065] The puncture-resistant epoxy resin composition of this embodiment is prepared by the following method: 15 parts of terminal hydroxyl polypropylene glycol are added to a mixing bottle, and 5 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate are added under stirring. After complete addition, high-speed stirring is performed for 8 hours, and 50 parts of bisphenol A epoxy resin are added. The mixing bottle is heated to 80° C., and 15 parts of 200 low molecular weight polyamide are added while stirring. After stirring for 10 minutes, the temperature is lowered to 40° C., and then 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide are added to the mixing bottle. After high-speed dispersion for 0.5 hours, a glue solution is prepared, i.e., the puncture-resistant epoxy resin composition.

[0066] Example 4

[0067] The present embodiment provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 60 parts of bisphenol A epoxy resin, 15 parts of terminal hydroxyl polypropylene glycol, 5 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 15 parts of 200 low molecular weight polyamide, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0068] The puncture-resistant epoxy resin composition of this embodiment is prepared by the following method: 15 parts of terminal hydroxyl polypropylene glycol are added to a mixing bottle, 5 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate are added under stirring, and after complete addition, high-speed stirring is performed for 8 hours, 60 parts of bisphenol A epoxy resin are added, the mixing bottle is heated to 80° C., 15 parts of 200 low molecular weight polyamide are added while stirring, and after stirring for 15 minutes, the temperature is lowered to 30° C., and then 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide are added to the mixing bottle, and a glue solution is prepared after high-speed dispersion for 1 hour, i.e., the puncture-resistant epoxy resin composition.

[0069] Example 5

[0070] The present embodiment provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 30 parts of bisphenol A epoxy resin, 25 parts of terminal hydroxyl polypropylene glycol, 10 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 20 parts of 200 low molecular weight polyamide, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0071] The puncture-resistant epoxy resin composition of this embodiment is prepared by the following method: 25 parts of terminal hydroxyl polypropylene glycol are added to a mixing bottle, and 10 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate are added under stirring. After complete addition, high-speed stirring is performed for 8 hours, and 30 parts of bisphenol A epoxy resin are added. The mixing bottle is heated to 80° C., and 20 parts of 200 low-molecular-weight polyamide are added while stirring. After stirring for 5 minutes, the temperature is lowered to 40° C., and then 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide are added to the mixing bottle. After high-speed dispersion for 0.6 hours, a glue solution is prepared, i.e., the puncture-resistant epoxy resin composition.

[0072] Example 6

[0073] The present embodiment provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 60 parts of bisphenol A epoxy resin, 25 parts of terminal hydroxyl polypropylene glycol, 10 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 20 parts of 200 low molecular weight polyamide, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0074] The puncture-resistant epoxy resin composition of this embodiment is prepared by the following method: 25 parts of terminal hydroxyl polypropylene glycol are added to a mixing bottle, and 10 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate are added under stirring. After complete addition, high-speed stirring is performed for 8 hours, 60 parts of bisphenol A epoxy resin are added, and the mixing bottle is heated to 80° C., and 20 parts of 200 low-molecular-weight polyamide are added while stirring. After stirring for 15 minutes, the temperature is lowered to 40° C., and then 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide are added to the mixing bottle. After high-speed dispersion for 1 hour, a glue solution is prepared, i.e., the puncture-resistant epoxy resin composition.

[0075] Example 7

[0076] The present embodiment provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 30 parts of bisphenol A epoxy resin, 5 parts of terminal hydroxyl polypropylene glycol, 2 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 10 parts of 200 low molecular weight polyamide, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0077] The puncture-resistant epoxy resin composition of this embodiment is prepared by the following method: 5 parts of terminal hydroxyl polypropylene glycol are added to a mixing bottle, and 2 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate are added under stirring. After complete addition, high-speed stirring is performed for 4 hours, and 30 parts of bisphenol A epoxy resin are added. The mixing bottle is heated to 80° C., and 10 parts of 200 low molecular weight polyamide are added while stirring. After stirring for 15 minutes, the temperature is lowered to 40° C., and then 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide are added to the mixing bottle. After high-speed dispersion for 0.5 hours, a glue solution is prepared, i.e., the puncture-resistant epoxy resin composition.

[0078] Example 8

[0079] The present embodiment provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 60 parts of bisphenol A epoxy resin, 5 parts of terminal hydroxyl polypropylene glycol, 2 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 10 parts of 200 low molecular weight polyamide, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0080] The puncture-resistant epoxy resin composition of this embodiment is prepared by the following method: 5 parts of terminal hydroxyl polypropylene glycol are added to a mixing bottle, and 2 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate are added under stirring. After complete addition, high-speed stirring is performed for 8 hours, 60 parts of bisphenol A epoxy resin are added, and the mixing bottle is heated to 80° C., and 10 parts of 200 low molecular weight polyamide are added while stirring. After stirring for 15 minutes, the temperature is lowered to 40° C., and then 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide are added to the mixing bottle. After high-speed dispersion for 1 hour, a glue solution is prepared, i.e., the puncture-resistant epoxy resin composition.

[0081] Example 9

[0082] The present embodiment provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 30 parts of bisphenol A epoxy resin, 5 parts of terminal hydroxyl polypropylene glycol, 2 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 10 parts of 200 low molecular weight polyamide, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0083] The puncture-resistant epoxy resin composition of this embodiment is prepared by the following method: 5 parts of terminal hydroxyl polypropylene glycol are added to a mixing bottle, and 2 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate are added under stirring. After complete addition, high-speed stirring is performed for 8 hours, and 30 parts of bisphenol A epoxy resin are added. The mixing bottle is heated to 80° C., and 20 parts of 200 low-molecular-weight polyamide are added while stirring. After stirring for 15 minutes, the temperature is lowered to 40° C., and then 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 20 parts of silicon dioxide are added to the mixing bottle. After high-speed dispersion for 1 hour, a glue solution is prepared, i.e., the puncture-resistant epoxy resin composition.

[0084] Example 10

[0085] The present embodiment provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 30 parts of bisphenol A epoxy resin, 5 parts of terminal hydroxyl polypropylene glycol, 2 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 10 parts of 200 low molecular weight polyamide, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 40 parts of silicon dioxide.

[0086] The puncture-resistant epoxy resin composition of this embodiment is prepared by the following method: 5 parts of terminal hydroxyl polypropylene glycol are added to a mixing bottle, and 2 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate are added under stirring. After complete addition, high-speed stirring is performed for 4 hours, and 30 parts of bisphenol A epoxy resin are added. The mixing bottle is heated to 80° C., and 10 parts of 200 low molecular weight polyamide are added while stirring. After stirring for 5 minutes, the temperature is lowered to 25° C., and then 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 40 parts of silicon dioxide are added to the mixing bottle. After high-speed dispersion for 1 hour, a glue solution is prepared, i.e., the puncture-resistant epoxy resin composition.

[0087] Embodiment 11

[0088] The present embodiment provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 60 parts of bisphenol A epoxy resin, 5 parts of terminal hydroxyl polypropylene glycol, 2 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 10 parts of 200 low molecular weight polyamide, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 20 parts of silicon dioxide.

[0089] The puncture-resistant epoxy resin composition of this embodiment is prepared by the following method: 5 parts of terminal hydroxyl polypropylene glycol are added to a mixing bottle, and 2 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate are added under stirring. After complete addition, high-speed stirring is performed for 8 hours, 60 parts of bisphenol A epoxy resin are added, and the mixing bottle is heated to 80° C., and 10 parts of 200 low-molecular-weight polyamide are added while stirring. After stirring for 15 minutes, the temperature is lowered to 40° C., and then 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 20 parts of silicon dioxide are added to the mixing bottle. After high-speed dispersion for 1 hour, a glue solution is prepared, i.e., the puncture-resistant epoxy resin composition.

[0090] Example 12

[0091] The present embodiment provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 60 parts of bisphenol A epoxy resin, 5 parts of terminal hydroxyl polypropylene glycol, 2 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 10 parts of 200 low molecular weight polyamide, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 40 parts of silicon dioxide.

[0092] The puncture-resistant epoxy resin composition of this embodiment is prepared by the following method: 5 parts of terminal hydroxyl polypropylene glycol are added to a mixing bottle, 2 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate are added under stirring, and after complete addition, high-speed stirring is performed for 8 hours, 60 parts of bisphenol A epoxy resin are added, the mixing bottle is heated to 80° C., 10 parts of 200 low molecular weight polyamide are added while stirring, and after stirring for 10 minutes, the temperature is lowered to 40° C., and then 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 40 parts of silicon dioxide are added to the mixing bottle, and a glue solution is prepared after high-speed dispersion for 1 hour, i.e., the puncture-resistant epoxy resin composition.

[0093] Embodiment 13

[0094] This embodiment provides a laminated board, and the laminated board of this embodiment is prepared by using the puncture-resistant epoxy resin composition provided by Embodiments 1 to 12.

[0095] Embodiment 14

[0096] This embodiment provides a method for preparing a laminate, which is used to prepare the laminate provided in embodiment 13. The preparation method comprises:

[0097] Nylon fiber cloth (basic weight 205g / m 2 ), and baked in a hot air circulation oven at 170° C. for 3 min to obtain a semi-cured sheet with a resin content of 42%.

[0098] Two prepregs were stacked, and a matte release film was covered on each of the upper and lower sides of the stack. The stack was placed in a programmable temperature and pressure controlled vacuum press. 2 The product was cured at 170°C for 60 minutes to produce a laminate with a thickness of 0.6 mm.

[0099] Comparative Example 1

[0100] The present comparative example provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 40 parts of bisphenol A epoxy resin, 15 parts of hydroxy-terminated polypropylene glycol, 15 parts of 200 low molecular weight polyamide, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0101] The puncture-resistant epoxy resin composition of this comparative example was prepared by the following method:

[0102] Add 15 parts of terminal hydroxyl polypropylene glycol and 40 parts of bisphenol A epoxy resin into a mixing bottle, stir at high speed for 0.5 hours, heat the mixing bottle to 80°C, add 15 parts of 200 low molecular weight polyamide while stirring, stir for 15 minutes, cool to 40°C, then add 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole and 30 parts of silicon dioxide into the mixing bottle, disperse at high speed for 1 hour to prepare a glue solution, i.e., the puncture-resistant epoxy resin composition.

[0103] Comparative Example 2

[0104] The present comparative example provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 55 parts of bisphenol A epoxy resin, 15 parts of 200 low molecular weight polyamide, 5 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0105] The puncture-resistant epoxy resin composition of this comparative example was prepared by the following method:

[0106] Add 55 parts of bisphenol A epoxy resin into a mixing bottle, add 5 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate under stirring, after complete addition, stir at high speed for 8 hours, heat the mixing bottle to 80°C, add 15 parts of 200 low molecular weight polyamide while stirring, stir for 15 minutes, cool to 40°C, then add 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide into the mixing bottle, and disperse at high speed for 1 hour to prepare a glue solution, i.e., a puncture-resistant epoxy resin composition.

[0107] Comparative Example 3

[0108] The present comparative example provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 40 parts of bisphenol A epoxy resin, 15 parts of terminal hydroxyl polypropylene glycol, 5 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0109] The puncture-resistant epoxy resin composition of this comparative example was prepared by the following method:

[0110] Add 15 parts of terminal hydroxyl polypropylene glycol to a mixing bottle, add 5 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate under stirring, after complete addition, stir at high speed for 8 hours, add 40 parts of bisphenol A epoxy resin, stir for 15 minutes, then add 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide to the mixing bottle, and disperse at high speed for 1 hour to prepare a glue solution, i.e., a puncture-resistant epoxy resin composition.

[0111] Comparative Example 4

[0112] The present comparative example provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 40 parts of bisphenol A epoxy resin, 15 parts of glycidyl ester epoxy resin, 15 parts of 200 low molecular weight polyamide, 5 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0113] The puncture-resistant epoxy resin composition of this comparative example was prepared by the following method:

[0114] Add 15 parts of glycidyl ester epoxy resin into a mixing bottle, add 5 parts of resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate under stirring, after complete addition, stir at high speed for 8 hours, add 40 parts of bisphenol A epoxy resin, heat the mixing bottle to 80°C, add 15 parts of 200 low molecular weight polyamide while stirring, stir for 15 minutes, cool to 40°C, then add 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole and 30 parts of silicon dioxide into the mixing bottle, and disperse at high speed for 1 hour to prepare a glue solution, i.e., a puncture-resistant epoxy resin composition.

[0115] Comparative Example 5

[0116] The present comparative example provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 40 parts of bisphenol A epoxy resin, 30 parts of terminal hydroxyl polypropylene glycol, 15 parts of 200 low molecular weight polyamide, 5 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0117] The puncture-resistant epoxy resin composition of this comparative example was prepared by the following method:

[0118] Add 30 parts of terminal hydroxyl polypropylene glycol to a mixing bottle, add 5 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate under stirring, after complete addition, stir at high speed for 8 hours, add 40 parts of bisphenol A epoxy resin, heat the mixing bottle to 80°C, add 15 parts of 200 low molecular weight polyamide while stirring, stir for 15 minutes, cool to 40°C, then add 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silica to the mixing bottle, and disperse at high speed for 1 hour to prepare a glue solution, i.e., a puncture-resistant epoxy resin composition.

[0119] Comparative Example 6

[0120] The present comparative example provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 40 parts of bisphenol A epoxy resin, 15 parts of terminal hydroxyl polypropylene glycol, 15 parts of 200 low molecular weight polyamide, 15 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0121] The puncture-resistant epoxy resin composition of this comparative example was prepared by the following method:

[0122] Add 15 parts of terminal hydroxyl polypropylene glycol to a mixing bottle, add 15 parts of a resin with a core of styrene-butadiene rubber and a shell of polymethyl methacrylate under stirring, after complete addition, stir at high speed for 4 hours, add 40 parts of bisphenol A epoxy resin, heat the mixing bottle to 80°C, add 15 parts of 200 low molecular weight polyamide while stirring, stir for 5-15 minutes, cool to 40°C, then add 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide to the mixing bottle, and disperse at high speed for 1 hour to prepare a glue solution, i.e., a puncture-resistant epoxy resin composition.

[0123] Comparative Example 7

[0124] The present comparative example provides a puncture-resistant epoxy resin composition, comprising the following components in parts by weight: 40 parts of bisphenol A epoxy resin, 15 parts of terminal hydroxyl hyperbranched polymer, 15 parts of 200 low molecular weight polyamide, 15 parts of a resin having a core of styrene-butadiene rubber and a shell of polymethyl methacrylate, 4 parts of dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole, and 30 parts of silicon dioxide.

[0125] The puncture-resistant epoxy resin composition of this comparative example was prepared by the following method:

[0126] Add 15 parts of terminal hydroxyl hyperbranched polymer into a mixing bottle, add 15 parts of resin with styrene-butadiene rubber as core and polymethyl methacrylate as shell under stirring, after complete addition, stir at high speed for 8 hours, add 40 parts of bisphenol A epoxy resin, heat the mixing bottle to 80°C, add 15 parts of 200 low molecular weight polyamide while stirring, stir for 15 minutes, cool to 40°C, then add 4 parts of dissolved dicyandiamide, 2 parts of coupling agent KH550, 0.1 parts of 2-methylimidazole and 30 parts of silicon dioxide into the mixing bottle, and prepare a glue solution after high-speed dispersion for 1 hour, i.e., the puncture-resistant epoxy resin composition.

[0127] The material model information selected in the embodiments of the present invention and the comparative examples is as follows:

[0128] Bisphenol A epoxy resin: brand name is Nan Ya 128;

[0129] Hydroxyl-terminated polypropylene glycol: Nanjing Chemical Reagent Co., Ltd.;

[0130] The core is styrene-butadiene rubber and the shell is polymethyl methacrylate resin: the brand is Kane Ace MX-125 from Japan;

[0131] 200 low molecular weight polyamide: Jinjinle Chemical;

[0132] Dicyandiamide: Shandong Hui'an Chemical Co., Ltd.;

[0133] Coupling agent: KH550;

[0134] 2-Methylimidazole: Guangzhou Deshui Chemical Co., Ltd.;

[0135] Silica: Evonik Degussa R202.

[0136] The puncture-resistant epoxy resin compositions provided in Comparative Examples 1 to 7 are used to prepare laminates, and the preparation method of the laminates is the preparation method provided in Example 14.

[0137] The laminates prepared corresponding to the puncture-resistant epoxy resin compositions of Examples 1 to 12 and Comparative Examples 1 to 7 were subjected to the following tests:

[0138] (1) Refer to IPC-TM-650 2.4.8.1 for interlayer adhesion test;

[0139] (2) Refer to QC / T 744-2006 6.2.12.7 for puncture resistance test;

[0140] (3) Refer to GB / T 1040.1-2018 for tensile strength test.

[0141] The dosage of each component in Examples 1 to 9 and the test results of the corresponding prepared laminates are shown in Table 1.

[0142] Table 1

[0143]

[0144]

[0145] The dosage of each component of Examples 10 to 12 and Comparative Examples 1 to 7 and the test results of the corresponding prepared laminates are shown in Table 2.

[0146] Table 2

[0147]

[0148] According to the test results of Examples 1 to 12, the laminates prepared using the puncture-resistant epoxy resin composition of the present invention have excellent interlayer adhesion and puncture resistance while maintaining good tensile properties.

[0149] According to the test results of Comparative Examples 1 to 4, the lack of any one of the components of the polyether polymer with active hydroxyl groups, core-shell particles or low molecular weight polyamide in the puncture-resistant epoxy resin composition of the present invention will lead to a significant decrease in the puncture resistance of the laminate, and because it will affect the toughness of the composition and the bonding strength with the substrate, the tensile properties will also be greatly affected.

[0150] According to the test results of Comparative Examples 5 to 7, the effect of the composition of the present invention cannot be achieved when the components of the present invention are added in an amount exceeding the range specified by the present invention, or other substances containing terminal hydroxyl groups are used to replace the polyether polymer with active hydroxyl groups.

[0151] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the technical solution of the present invention, and are not intended to limit the specific implementation methods of the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the claims of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A puncture-resistant epoxy resin composition, characterized in that: The composition comprises the following components in parts by weight: 30-60 parts of base resin, 5-25 parts of polyether polymer with active hydroxyl groups, 2-10 parts of core-shell particles, 10-20 parts of low molecular weight polyamide, 3-5 parts of curing agent, 1-3 parts of coupling agent, Accelerator 0.05-0.2 parts, 20-40 parts of filler.

2. The puncture-resistant epoxy resin composition according to claim 1, characterized in that: The matrix resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, aliphatic glycidyl ether epoxy resin and glycidyl ester epoxy resin.

3. The puncture-resistant epoxy resin composition according to claim 1, characterized in that: The polyether polymer with active hydroxyl groups is selected from one or more of hydroxyl-terminated polypropylene glycol, trimethylolpropane polyether and hydroxyl-terminated polytetrahydrofuran.

4. The puncture-resistant epoxy resin composition according to claim 1, characterized in that: The core-shell particles are one or more of a polymer having a core of polybutyl acrylate and a shell of polymethyl methacrylate, a polymer having a core of cross-linked polybutadiene and a shell of cross-linked polybutadiene, a polymer having a core of silicone rubber and a shell of polymethyl methacrylate, or a polymer having a core of polybutyl acrylate and a shell of polymethyl methacrylate.

5. The puncture-resistant epoxy resin composition according to claim 1, characterized in that: The low molecular weight polyamide is selected from one or more of 200 low molecular weight polyamide, 650 low molecular weight polyamide and 651 low molecular weight polyamide.

6. The puncture-resistant epoxy resin composition according to any one of claims 1 to 5, characterized in that: The curing agent is selected from one or more of cyanate curing agents, fatty polyamine curing agents, alicyclic polyamine curing agents, aromatic amine curing agents, polyamide type curing agents, latent curing agents, Lewis acid-amine complex curing agents, and organic acid anhydride curing agents.

7. A method for preparing the puncture-resistant epoxy resin composition according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1, adding a polyether polymer with active hydroxyl groups into a reaction container, adding core-shell particles under stirring, and stirring to obtain a core-shell modified polyether polymer with active hydroxyl groups; S2, heating the base resin, adding low molecular weight polyamide, stirring, and obtaining a core-shell modified polyether polymer modified base resin with active hydroxyl groups.

8. The preparation method according to claim 7, characterized in that: In step S1, the stirring is specifically: high-speed stirring for 4-8 hours; in step S2, the heating is specifically: heating the base resin to 70-90°C.

9. A prepreg prepared using the puncture-resistant epoxy resin composition according to claims 1 to 6.

10. A laminated board prepared using the prepreg according to claim 9.

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