Preparation method of prepreg tape resin

Abstract

The invention provides a preparation method of prepreg tape resin. The preparation method of the prepreg tape resin comprises the following steps: dividing liquid resin in preparation raw materials of the prepreg tape resin into two parts, namely liquid resin a and liquid resin b; mixing the solid resin with the liquid resin a, and dispersing to obtain a paste mixture A; mixing the liquid resin b with a curing agent, an optional accelerant and an optional auxiliary agent, and dispersing to obtain a liquid mixture B; and mixing the paste mixture A and the liquid mixture B, and sequentially dispersing, grinding and shearing to obtain the prepreg tape resin. The prepreg tape resin prepared by the preparation method of the prepreg tape resin has the advantages of long pot life, no curing reaction after high and low temperature circulation for multiple times, uniform system, no particle and the like.

Description

Technical Field

[0001] The invention relates to the field of thermosetting polymer materials, in particular to a method for preparing a prepreg tape resin. Background Art

[0002] Prepreg tape is a unidirectional fiber reinforced material that is pre-impregnated with resin before use. It is increasingly used in the field of composite materials due to its ease of use, high consistency and surface finish. Prepreg tape resins are mainly divided into thermosetting resins and thermoplastic resins. Thermoplastic resins generally have a high softening point and poor processability, making it difficult to impregnate unidirectional fibers; while thermosetting resins are usually liquid or have a lower softening temperature before curing, and their processability is significantly better than that of thermoplastic resins. Therefore, common prepreg tapes are mainly thermosetting resins.

[0003] Considering the overall performance, epoxy resin is the most preferred material for preparing prepreg resin due to its good processability, mechanical properties and dimensional stability. A single epoxy resin does not have mechanical properties, and must be combined with a curing agent and various additives to obtain a product with good performance. Common epoxy resins are all two-component, namely a resin component and a curing agent component, but prepreg resin is a single-component resin. The system contains both resin and curing agent components. Therefore, the resin is required to have good storage stability, no curing reaction at room temperature or low temperature, and can be quickly cured at high temperature. At the same time, in the prepreg, the performance of carbon fiber is uniform and stable, so the performance of the prepreg depends on the formula design of the prepreg resin and the resin preparation process.

[0004] CN201710912748.2 discloses an epoxy resin for prepreg and a preparation method thereof, the method comprising the following steps: pouring bisphenol A epoxy resin and a toughening agent into a mixing kettle for mixing to obtain a uniform liquid mixture, and vacuum degassing; after cooling, discharging the resin into a clean and dry resin barrel through a press for standby use; pouring the mixture obtained in the previous step, a multifunctional epoxy resin, and a phenolic epoxy resin into a mixing kettle for mixing to obtain a uniform liquid mixture, and vacuum degassing; adding a curing agent and an accelerator into the mixing kettle for mixing, stirring, and vacuum degassing to obtain a uniform liquid mixture; and pouring the prepared epoxy resin composition into trays for packaging through a press, cooling naturally at room temperature, and packaging into finished products.

[0005] CN108264727A discloses an epoxy resin composition and epoxy resin mixture and preparation methods thereof as well as epoxy resin prepreg and composite materials. The preparation method comprises the following steps: (1) grinding bisphenol A type liquid epoxy resin, curing agent and accelerator to obtain a ground material; (2) melting bisphenol A type semi-solid and / or solid epoxy resin and phenolic epoxy resin, and then optionally adding auxiliary materials to obtain a molten material; (3) stirring and mixing the molten material obtained in step (2) and the ground material obtained in step (1) at 55-80°C.

[0006] Although heating in the above method can reduce the viscosity of the resin and improve the mixing effect, the stability of the resin and the curing agent decreases as the temperature rises. The temperature rise causes the epoxy resin to open its ring and cross-link with the curing agent, and heat accumulates during the stirring process. This will cause two defects: (1) As the system temperature rises, the resin and the curing agent aggregate, producing some gel particles, which affects the overall uniformity of the resin; these solid impurities penetrate into the unidirectional fiber reinforced material, causing the surface finish of the prepreg to decrease and the uniformity to decrease; (2) Since the resin has begun to cure, the system is no longer stable, the room temperature storage period of the resin will also decrease, and the performance will decrease.

[0007] In view of this, the present invention is proposed. Summary of the invention

[0008] One of the purposes of the present invention is to provide a method for preparing a prepreg tape resin. The method for preparing a prepreg tape resin of the present invention has better processability, a relatively lower mixing temperature, and can avoid the generation of gel particles.

[0009] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0010] In a first aspect, the present invention provides a method for preparing a prepreg tape resin, the method for preparing the prepreg tape resin comprising the following steps:

[0011] The liquid resin in the raw material for preparing the prepreg tape resin is divided into two parts, namely, liquid resin a and liquid resin b;

[0012] The solid resin is mixed with the liquid resin a, and dispersed to obtain a paste mixture A;

[0013] Mixing and dispersing the liquid resin b with a curing agent, an optional accelerator, and an optional auxiliary agent to obtain a liquid mixture B;

[0014] The paste mixture A and the liquid mixture B are mixed, dispersed, ground and sheared in sequence to obtain the prepreg resin.

[0015] In the present invention, a single mixing system is divided into two parts. The first part is high-temperature melting and mixing of solid resin. Since it does not contain a curing agent component, it can be heated to a sufficiently high temperature for mixing, completely melting the solid resin, and the system is more uniform; the second part is room temperature mixing of liquid resin and curing agent component. Since it does not need to be heated for mixing, the system is more stable and will not reduce the storage period of the prepreg resin. Then the two parts are mixed. Since the two parts have been fully mixed in the early stage, the mixing process has better processability and the mixing temperature is relatively lower, which can avoid the generation of gel particles.

[0016] Preferably, the liquid resin is liquid epoxy resin.

[0017] Preferably, the liquid resin is selected from any one or a combination of at least two of liquid bisphenol A epoxy resin, liquid bisphenol S epoxy resin, liquid bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, liquid novolac epoxy resin, multifunctional liquid epoxy resin or liquid halogenated epoxy resin, preferably any one or a combination of at least two of E-51, F-51, TDE-85, AG-80 or BDGE.

[0018] Preferably, the mass ratio of the liquid resin a to the liquid resin b is (0.8-1.2):1, for example, it can be 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, etc.

[0019] Preferably, the solid resin is a solid epoxy resin.

[0020] Preferably, the solid epoxy resin is selected from any one or a combination of at least two of solid bisphenol A epoxy resin, solid bisphenol S epoxy resin, solid bisphenol F epoxy resin or multifunctional solid epoxy resin, preferably any one or a combination of at least two of E-20, CYDF-2004, J-80, JF-46 or F-44.

[0021] Preferably, the solid resin and the liquid resin a need to be heated to 80-120°C (for example, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, etc.) before dispersion.

[0022] Preferably, the solid resin and liquid resin a are dispersed after mixing by high-speed shear disk dispersion, with a stirring speed of 200-1000rpm, for example, 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm, etc., and a stirring time of 1-5h, for example, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, etc.

[0023] Preferably, after the dispersion, the mixture needs to be cooled to 40-100°C, for example, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, etc., to obtain a paste mixture A.

[0024] Preferably, the curing agent is a latent curing agent.

[0025] Preferably, the latent curing agent is selected from any one or a combination of at least two of micronized dicyandiamide, imidazole derivatives or boron trifluoride complexes, preferably any one or a combination of at least two of 2MZ-AZINE, 2E4MZ-AZINE, diallyl melamine or BF3·MEA.

[0026] Preferably, the accelerator is selected from any one or a combination of at least two of modified imidazole accelerators, modified urea accelerators or epoxy resin amine adduct accelerators, preferably any one or a combination of at least two of 2,4-EMI, DBU, DBN or TAP.

[0027] Preferably, the auxiliary agent includes any one of a defoamer, a wetting agent or a coupling agent or a combination of at least two thereof, preferably any one of BYK-525, BYK-9920, BYK-333 or A-187 or a combination of at least two thereof.

[0028] Preferably, the raw materials for preparing the prepreg resin include, by weight: 80-120 parts of liquid resin, 40-60 parts of solid resin, 4-10 parts of curing agent, 0-5 parts of accelerator and 0-1.5 parts of auxiliary agent.

[0029] The content of the liquid resin is 80-120 parts, for example, it can be 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts, 120 parts, etc.

[0030] Among them, the content of solid resin is 40-60 parts, for example, it can be 40 parts, 42 parts, 44 parts, 46 parts, 48 ​​parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, etc.

[0031] The content of the curing agent is 4-10 parts, for example, it can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.

[0032] Among them, the content of the accelerator is 0-5 parts, for example, it can be 0 part, 0.005 part, 0.01 part, 0.05 part, 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.6 parts, 4.8 parts, 5 parts, etc.

[0033] Among them, the content of the auxiliary agent is 0-1.5 parts, for example, it can be 0 parts, 0.005 parts, 0.01 parts, 0.05 parts, 0.1 parts, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, etc.

[0034] Preferably, the temperature at which the liquid resin b is mixed with the curing agent, the optional accelerator and the optional auxiliary agent is 20-30°C, for example, 20°C, 22°C, 24°C, 26°C, 28°C, 30°C, etc.

[0035] Preferably, the liquid resin b is mixed with a curing agent, an optional accelerator and an optional auxiliary agent and then dispersed using a high-speed shear disk dispersion, with a stirring speed of 200-1000 rpm, for example, 200 rpm, 300 rpm, 400 rpm, 500 rpm, 600 rpm, 700 rpm, 800 rpm, 900 rpm, 1000 rpm, etc., and a stirring time of 1-5 h, for example, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, etc.

[0036] Preferably, the paste mixture A and the liquid mixture B are mixed by adding the liquid mixture B into the paste mixture A.

[0037] Preferably, the liquid mixture A and the liquid mixture B are dispersed after mixing by a high-speed shear disk, with a stirring speed of 100-500 rpm, for example, 100 rpm, 200 rpm, 300 rpm, 400 rpm, 500 rpm, etc., a stirring time of 1-5 h, for example, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, etc., and a stirring temperature of 30-60 ° C, for example, 30 ° C, 35 ° C, 40 ° C, 45 ° C, 50 ° C, 55 ° C, 60 ° C, etc.

[0038] Preferably, the grinding method is to add the dispersed paste mixture C into a three-roll mill for grinding.

[0039] Preferably, the roller speed ratio of the grinding slow roller, medium speed roller and fast roller is 1:(2-8):(5-15), for example, it can be 1:2:5, 1:2:6, 1:2:8, 1:2:10, 1:2:12, 1:2:15, 1:4:5, 1:4:6, 1:4:8, 1:4:10, 1:4:12, 1:4:15, 1:6:5, 1:6:6, 1:6:5 :6:8, 1:6:10, 1:6:12, 1:6:15, 1:8:5, 1:8:6, 1:8:8, 1:8:10, 1:8:12, 1:8:15, etc. The grinding times are 1-5 times, for example, 1 time, 2 times, 3 times, 4 times, 5 times, and the grinding temperature is 30-60°C, for example, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, etc.

[0040] Preferably, the speed of the slow roller in the three-roll mill is 60-200 rpm, for example, it can be 60 rpm, 80 rpm, 100 rpm, 120 rpm, 140 rpm, 160 rpm, 180 rpm, 200 rpm, etc.

[0041] Preferably, the shearing is carried out using a high-speed shear disk, with a stirring speed of 100-500rpm, for example, 100rpm, 200rpm, 300rpm, 400rpm, 500rpm, etc., the stirring time is 1-5h, for example, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, etc., and the stirring temperature is 30-50°C, for example, 30°C, 35°C, 40°C, 45°C, 50°C, etc.

[0042] As a preferred technical solution of the present invention, the method for preparing the prepreg resin comprises the following steps:

[0043] (1) dividing the liquid resin in the raw material for preparing the prepreg tape resin into two parts, liquid resin a and liquid resin b, according to a mass ratio of (0.8-1.2):1;

[0044] (2) mixing the solid resin and the liquid resin a, heating them to 80-120° C., dispersing them using a high-speed shearing disk, stirring at a speed of 200-1000 rpm for 1-5 h, and cooling them to 40-100° C. to obtain a paste mixture A;

[0045] Mixing liquid resin B with curing agent, optional accelerator and optional auxiliary agent at 20-30° C., dispersing with a high-speed shearing disk, stirring at a speed of 200-1000 rpm for 1-5 hours, to obtain a liquid mixture B;

[0046] (3) adding the liquid mixture B to the paste mixture A, dispersing with a high-speed shearing disk, stirring at a speed of 100-500 rpm, stirring for 1-5 h, and stirring at a temperature of 30-60° C., to obtain a paste mixture C;

[0047] (4) slowly adding the paste mixture C to a three-roll mill for grinding and mixing, wherein the roller speed ratio of the slow roller, the medium speed roller and the fast roller is 1:(2-8):(5-15), the grinding number is 1-5 times, and the grinding temperature is 30-60° C., to obtain a paste mixture D;

[0048] (5) The paste mixture D is fully mixed using a high-speed shearing disk at a stirring speed of 100-500 rpm, a stirring time of 1-5 h, and a stirring temperature of 30-50° C. to obtain the prepreg tape resin.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] When the solid resin components of the present invention are mixed, no curing agent is present, and the temperature can be raised to a sufficiently high temperature for mixing, so that the solid resin is completely melted, and the system is more uniform; the curing agent and other components are pre-blended with the liquid resin, and there is no need to heat the mixture, so the system is more stable and the storage period of the prepreg resin is not reduced; and the final mixing process has better processability and avoids the generation of gel particles. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0052] Figure 1 The present invention is a schematic flow chart of the method for preparing the prepreg tape resin. DETAILED DESCRIPTION

[0053] Unless otherwise defined herein, scientific and technical terms used in conjunction with the present invention shall have the meanings commonly understood by those of ordinary skill in the art. The meaning and scope of the terms should be clear, however, in the case of any potential ambiguity, the definitions provided herein take precedence over any dictionary or external definitions. In this application, unless otherwise stated, the use of "or" means "and / or". In addition, the use of the term "including" and other forms is non-limiting.

[0054] Generally, the nomenclature and its technology used in conjunction with cell and tissue culture, molecular biology, immunology, microbiology, genetics, and protein and nucleic acid chemistry and hybridization described herein are those well-known and commonly used in the art. Unless otherwise indicated, the methods and techniques of the present invention are generally carried out according to conventional methods as well-known in the art, and as described in various general and more specific references, which are cited and discussed throughout this specification. Enzymatic reactions and purification techniques are carried out according to the manufacturer's specifications, as generally achieved in the art, or as described herein. The nomenclature and its laboratory procedures and technology used in conjunction with analytical chemistry, synthetic organic chemistry, and medical and pharmaceutical chemistry described herein are those well-known and commonly used in the art.

[0055] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0056] The present invention is further described below by way of examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or directly purchased from the market.

[0057] Figure 1 FIG. 1 is a schematic flow chart of the method for preparing the prepreg resin of the present invention, as shown in FIG. Figure 1 As shown, the preparation method of the prepreg tape resin comprises the following steps:

[0058] The liquid resin in the raw materials for preparing the prepreg tape resin is divided into two parts, namely liquid resin a and liquid resin b; the solid resin is mixed with the liquid resin a, and dispersed to obtain a paste mixture A; the liquid resin b is mixed with a curing agent, an optional accelerator, and an optional auxiliary agent, and dispersed to obtain a liquid mixture B; the paste mixture A and the liquid mixture B are mixed, dispersed in turn to obtain a paste mixture C, ground to obtain a paste mixture D, and sheared to obtain the prepreg tape resin E.

[0059] Example 1

[0060] The present embodiment provides a method for preparing a prepreg tape resin, and the method for preparing the prepreg tape resin comprises the following steps:

[0061] (1) 100 parts of E-51 are selected as the liquid epoxy resin component. First, the liquid resin component is divided into two parts, namely liquid resin a and liquid resin b, each accounting for 50%;

[0062] (2) 50 parts of E-20 solid epoxy resin and 50 parts of E-51 liquid epoxy resin were heated to 110° C., dispersed using a high-speed shear disk, stirred at a speed of 1000 rpm for 4 h, and cooled to 50° C. to obtain a paste mixture A;

[0063] The remaining 50 parts of E-51 liquid epoxy resin, 5 parts of curing agent micronized dicyandiamide, 3 parts of accelerator 2,4-EMI, 0.5 parts of BYK-525 and 0.5 parts of A-187 were mixed at room temperature, and dispersed using a high-speed shear disk at a stirring speed of 800 rpm for 2 hours to obtain a liquid mixture B;

[0064] (3) Slowly add mixture B into mixture A, disperse using a high-speed shear disk, stir at a speed of 500 rpm, stir for 3 h, and mix at a temperature of 50° C. to obtain a paste mixture C;

[0065] (4) slowly adding the mixture C to a three-roll mill and grinding and mixing, with a roller speed ratio of 1:5:10, wherein the speed of the slow roller is 60 rpm, the grinding number is 3 times, and the grinding temperature is 40° C., to obtain a paste-like mixture D;

[0066] (5) using a high-speed shearing disk to thoroughly mix the mixture D at a stirring speed of 500 rpm, a stirring time of 4 h, and a mixing temperature of 40° C. to obtain a final product E;

[0067] (6) Add prepreg resin E to a stainless steel tray, seal it with a sealed bag, and store it in a cold storage.

[0068] Example 2

[0069] The present embodiment provides a method for preparing a prepreg tape resin, and the method for preparing the prepreg tape resin comprises the following steps:

[0070] (1) 100 parts of F-51 are selected as the liquid epoxy resin component, and the liquid resin part is first divided into two parts, namely liquid resin a and liquid resin b, each accounting for 50%;

[0071] (2) 50 parts of CYDF-2004 solid epoxy resin and 50 parts of F-51 liquid epoxy resin were heated to 100° C., dispersed using a high-speed shear disk, stirred at 800 rpm for 3 h, and cooled to 60° C. to obtain a paste mixture A;

[0072] The remaining 50 parts of F-51 liquid epoxy resin, 10 parts of curing agent 2MZ-AZINE, 4 parts of accelerator DBU, 0.5 parts of BYK-333 and 1 part of A-187 were mixed at room temperature and dispersed using a high-speed shear disk at a stirring speed of 600 rpm for 3 hours to obtain a liquid mixture B;

[0073] (3) Slowly add mixture B into mixture A, disperse using a high-speed shear disk, stir at a speed of 400 rpm, stir for 4 h, and mix at a temperature of 40° C. to obtain a paste mixture C;

[0074] (4) slowly adding the mixture C to a three-roll mill and grinding and mixing, with a roller speed ratio of 1:3:12, wherein the speed of the slow roller is 100 rpm, the grinding number is 2 times, and the grinding temperature is 50° C., to obtain a paste-like mixture D;

[0075] (5) Mix the mixture D thoroughly using a high-speed shearing disk at a stirring speed of 300 rpm, a stirring time of 5 h, and a mixing temperature of 30° C. to obtain a final product E;

[0076] (6) Add prepreg resin E to a stainless steel tray, seal it with a sealed bag, and store it in a cold storage.

[0077] Example 3

[0078] The present embodiment provides a method for preparing a prepreg tape resin, and the method for preparing the prepreg tape resin comprises the following steps:

[0079] (1) 100 parts of TDE-85 are selected as the liquid epoxy resin component. First, the liquid resin part is divided into two parts, namely liquid resin a and liquid resin b, each accounting for 50%;

[0080] (2) 50 parts of J-80 solid epoxy resin and 50 parts of TDE-85 liquid epoxy resin were heated to 100° C., dispersed using a high-speed shearing disk, stirred at 800 rpm for 3 h, and cooled to 60° C. to obtain a paste mixture A;

[0081] The remaining 50 parts of TDE-85 liquid epoxy resin, 6 parts of curing agent BF3·MEA, 4 parts of accelerator DBN, 1 part of BYK-9920 and 0.5 parts of A-187 were mixed at room temperature and dispersed using a high-speed shear disk at a stirring speed of 400 rpm for 5 hours to obtain a liquid mixture B;

[0082] (3) Slowly add mixture B into mixture A, disperse using a high-speed shear disk, with a stirring speed of 500 rpm, a stirring time of 2 h, and a mixing temperature of 60° C. to obtain a paste mixture C;

[0083] (4) slowly adding the mixture C to a three-roll mill and grinding and mixing, with a roller speed ratio of 1:6:8, wherein the speed of the slow roller is 150 rpm, the grinding number is 5 times, and the grinding temperature is 30° C., to obtain a paste-like mixture D;

[0084] (5) Mix the mixture D thoroughly using a high-speed shearing disk at a stirring speed of 500 rpm, a stirring time of 2 h, and a mixing temperature of 45° C. to obtain a final product E;

[0085] (6) Add prepreg resin E to a stainless steel tray, seal it with a sealed bag, and store it in a cold storage.

[0086] Example 4

[0087] The present embodiment provides a method for preparing a prepreg tape resin, and the method for preparing the prepreg tape resin comprises the following steps:

[0088] (1) 100 parts of E-51 were selected as the liquid epoxy resin component, and the liquid resin part was first divided into two parts, namely liquid resin a (accounting for 30%) and liquid resin b (accounting for 70%);

[0089] (2) 50 parts of E-20 solid epoxy resin and 30 parts of E-51 liquid epoxy resin were heated to 75° C., dispersed using a high-speed shear disk, stirred at a speed of 1500 rpm for 6 h, and cooled to 30° C. to obtain a paste mixture A;

[0090] The remaining 70 parts of E-51 liquid epoxy resin, 10 parts of curing agent micronized dicyandiamide, 4 parts of accelerator 2,4-EMI, 0.5 parts of BYK-525 and 0.5 parts of A-187 were mixed at room temperature, and dispersed using a high-speed shear disk at a stirring speed of 100 rpm for 6 hours to obtain a liquid mixture B;

[0091] (3) Slowly add mixture B into mixture A, disperse using a high-speed shear disk, with a stirring speed of 1000 rpm, a stirring time of 0.5 h, and a mixing temperature of 70° C. to obtain a paste mixture C;

[0092] (4) slowly adding the mixture C to a three-roll mill and grinding and mixing, with a roller speed ratio of 1:1.5:4, wherein the speed of the slow roller is 30 rpm, the grinding number is 6 times, and the grinding temperature is 25° C., to obtain a paste mixture D;

[0093] (5) Mix the mixture D thoroughly using a high-speed shearing disk at a stirring speed of 1000 rpm, a stirring time of 6 h, and a mixing temperature of 30° C. to obtain a final product E;

[0094] (6) Add prepreg resin E to a stainless steel tray, seal it with a sealed bag, and store it in a cold storage.

[0095] Example 5

[0096] The present embodiment provides a method for preparing a prepreg tape resin, and the method for preparing the prepreg tape resin comprises the following steps:

[0097] (1) 100 parts of E-51 were selected as the liquid epoxy resin component, and the liquid resin part was first divided into two parts, namely liquid resin a (accounting for 70%) and liquid resin b (accounting for 30%);

[0098] (2) 50 parts of E-20 solid epoxy resin and 70 parts of E-51 liquid epoxy resin were heated to 160° C., dispersed using a high-speed shear disk, stirred at a speed of 100 rpm for 6 h, and cooled to 50° C. to obtain a paste mixture A;

[0099] The remaining 30 parts of E-51 liquid epoxy resin, 11 parts of curing agent micronized dicyandiamide, 2.5 parts of accelerator 2,4-EMI, 1 part of BYK-525 and 0.5 parts of A-187 were mixed at room temperature, and dispersed using a high-speed shear disk at a stirring speed of 600 rpm for 6 hours to obtain a liquid mixture B;

[0100] (3) Slowly add mixture B into mixture A, disperse using a high-speed shear disk, stir at a speed of 600 rpm, stir for 8 h, and mix at a temperature of 20° C. to obtain a paste mixture C;

[0101] (4) slowly adding the mixture C to a three-roll mill for grinding and mixing, with a roller speed ratio of 1:9:16, wherein the speed of the slow roller is 100 rpm, the grinding number is 5 times, and the grinding temperature is 60° C., to obtain a paste-like mixture D;

[0102] (5) Mix the mixture D thoroughly using a high-speed shearing disk at a stirring speed of 600 rpm, a stirring time of 6 h, and a mixing temperature of 50° C. to obtain a final product E;

[0103] (6) Add prepreg resin E to a stainless steel tray, seal it with a sealed bag, and store it in a cold storage.

[0104] Comparative Example 1

[0105] This comparative example provides a method for preparing a prepreg tape resin, and the method for preparing the prepreg tape resin comprises the following steps:

[0106] (1) 100 parts of E-51 liquid epoxy resin, 50 parts of E-20 solid epoxy resin, 5 parts of curing agent micronized dicyandiamide, 3 parts of accelerator 2,4-EMI, 0.5 parts of BYK-525 and 0.5 parts of A-187 were mixed at room temperature, dispersed using a high-speed shear disk, with a stirring speed of 1200 rpm and a stirring time of 5 hours to obtain a mixture A;

[0107] (2) Mixture A was dispersed using a high-speed shearing disk at a stirring speed of 1000 rpm, a stirring time of 3 h, and a mixing temperature of 50° C. to obtain a paste-like mixture B;

[0108] (3) slowly adding the mixture C to a three-roll mill and grinding and mixing, with a roller speed ratio of 1:5:10, wherein the speed of the slow roller is 60 rpm, the grinding number is 5 times, and the grinding temperature is 50° C., to obtain a paste-like mixture D;

[0109] (4) using a high-speed shearing disk to thoroughly mix the mixture D at a stirring speed of 500 rpm, a stirring time of 5 h, and a mixing temperature of 50° C. to obtain a final product E;

[0110] (5) Add prepreg resin E to a stainless steel tray, seal it with a sealed bag, and store it in a cold storage.

[0111] Comparative Example 2

[0112] This comparative example provides a method for preparing a prepreg tape resin, and the method for preparing the prepreg tape resin comprises the following steps:

[0113] (1) 50 parts of E-20 solid epoxy resin were heated to 110° C. and dispersed using a high-speed shearing disk at a stirring speed of 1000 rpm for 4 h, and then cooled to 50° C. to obtain a paste mixture A;

[0114] 100 parts of E-51 liquid epoxy resin, 5 parts of curing agent micronized dicyandiamide, 3 parts of accelerator 2,4-EMI, 0.5 parts of BYK-525 and 0.5 parts of A-187 were mixed at room temperature, dispersed using a high-speed shear disk, with a stirring speed of 800 rpm and a stirring time of 2 hours to obtain a liquid mixture B;

[0115] (2) slowly adding mixture B into mixture A, dispersing using a high-speed shearing disk, stirring at a speed of 500 rpm, stirring for 3 h, and mixing at a temperature of 50° C., to obtain a paste mixture C;

[0116] (3) slowly adding the mixture C to a three-roll mill and grinding and mixing, with a roller speed ratio of 1:5:10, wherein the speed of the slow roller is 60 rpm, the grinding number is 3 times, and the grinding temperature is 40° C., to obtain a paste-like mixture D;

[0117] (4) using a high-speed shearing disk to thoroughly mix the mixture D at a stirring speed of 500 rpm, a stirring time of 4 h, and a mixing temperature of 40° C. to obtain a final product E;

[0118] (5) Add prepreg resin E to a stainless steel tray, seal it with a sealed bag, and store it in a cold storage.

[0119] Comparative Example 3

[0120] This comparative example provides a method for preparing a prepreg tape resin, and the method for preparing the prepreg tape resin comprises the following steps:

[0121] (1) 100 parts of E-51 as liquid epoxy resin, 5 parts of curing agent micro powder grade dicyandiamide, 3 parts of accelerator 2,4-EMI, 0.5 parts of BYK-525 and 0.5 parts of A-187 were weighed and mixed at room temperature, dispersed using a high-speed shear disk, stirring at a speed of 800 rpm, and stirring for 2 hours to obtain a liquid mixture B, which was then added to a three-roll mill for grinding and mixing, with a roller speed ratio of 1:5:10, wherein the speed of the slow roller was 60 rpm, the grinding number was 3 times, and the grinding temperature was 40° C., to obtain a grinding material A;

[0122] (2) Weigh E-20 solid epoxy resin and melt it at 90° C., stir it evenly with a stirrer, and disperse it using a high-speed shear disk at a stirring speed of 1000 rpm for 4 hours to obtain a paste mixture B;

[0123] (3) After placing the paste mixture B in a 75° C. water bath for 25 min, add the abrasive A obtained in step (1) and disperse using a high-speed shearing disk at a stirring speed of 800 rpm for 2 h to obtain a resin mixture.

[0124] Comparative Example 4

[0125] This comparative example provides a method for preparing a prepreg tape resin, and the method for preparing the prepreg tape resin comprises the following steps:

[0126] (1) 100 parts of E-51 are selected as the liquid epoxy resin component. First, the liquid resin part is divided into two parts, namely liquid resin a and liquid resin b, each accounting for 50%;

[0127] (2) 50 parts of E-20 solid epoxy resin and 50 parts of E-51 liquid epoxy resin were heated to 110° C., dispersed using a high-speed shear disk, stirred at a speed of 1000 rpm for 4 h, and cooled to 50° C. to obtain a paste mixture A;

[0128] The remaining 50 parts of E-51 liquid epoxy resin, 5 parts of curing agent micronized dicyandiamide, 3 parts of accelerator 2,4-EMI, 0.5 parts of BYK-525 and 0.5 parts of A-187 were mixed at room temperature, and dispersed using a high-speed shear disk at a stirring speed of 800 rpm for 2 hours to obtain a liquid mixture B;

[0129] (3) Slowly add mixture B into mixture A, disperse using a high-speed shear disk, stir at a speed of 500 rpm, stir for 3 h, and mix at a temperature of 50° C. to obtain a paste mixture C;

[0130] (4) slowly adding the mixture C to a three-roll mill and grinding and mixing, with a roller speed ratio of 1:5:10, wherein the speed of the slow roller is 60 rpm, the grinding number is 5 times, and the grinding temperature is 40° C., to obtain a prepreg resin E;

[0131] (5) Add prepreg resin E to a stainless steel tray, seal it with a sealed bag, and store it in a cold storage.

[0132] Comparative Example 5

[0133] This comparative example provides a method for preparing a prepreg tape resin, and the method for preparing the prepreg tape resin comprises the following steps:

[0134] (1) 100 parts of E-51 are selected as the liquid epoxy resin component. First, the liquid resin part is divided into two parts, namely liquid resin a and liquid resin b, each accounting for 50%;

[0135] (2) 50 parts of E-20 solid epoxy resin and 50 parts of E-51 liquid epoxy resin were heated to 110° C., dispersed using a high-speed shear disk, stirred at a speed of 1000 rpm for 4 h, and cooled to 50° C. to obtain a paste mixture A;

[0136] The remaining 50 parts of E-51 liquid epoxy resin, 5 parts of curing agent micronized dicyandiamide, 3 parts of accelerator 2,4-EMI, 0.5 parts of BYK-525 and 0.5 parts of A-187 were mixed at room temperature, and dispersed using a high-speed shear disk at a stirring speed of 800 rpm for 2 hours to obtain a liquid mixture B;

[0137] (3) Slowly add mixture B into mixture A, disperse using a high-speed shear disk, stir at a speed of 500 rpm, stir for 3 h, and mix at a temperature of 50° C. to obtain a paste mixture C;

[0138] (4) The paste mixture C was thoroughly mixed at a stirring speed of 1200 rpm, a stirring time of 8 h, and a mixing temperature of 40° C. to obtain a final product E;

[0139] (5) Add prepreg resin E to a stainless steel tray, seal it with a sealed bag, and store it in a cold storage.

[0140] Comparative Example 6

[0141] The present embodiment provides a method for preparing a prepreg tape resin, and the method for preparing the prepreg tape resin comprises the following steps:

[0142] (1) 100 parts of E-51 are selected as the liquid epoxy resin component. First, the liquid resin part is divided into two parts, namely liquid resin a and liquid resin b, each accounting for 50%;

[0143] (2) 50 parts of E-20 solid epoxy resin and 50 parts of E-51 liquid epoxy resin were heated to 110° C., dispersed using a high-speed shear disk, stirred at a speed of 1000 rpm for 4 h, and cooled to 50° C. to obtain a paste mixture A;

[0144] The remaining 50 parts of E-51 liquid epoxy resin, 5 parts of curing agent micronized dicyandiamide, 3 parts of accelerator 2,4-EMI, 0.5 parts of BYK-525 and 0.5 parts of A-187 were mixed at room temperature, and dispersed using a high-speed shear disk at a stirring speed of 800 rpm for 2 hours to obtain a liquid mixture B;

[0145] (3) slowly adding mixture A and mixture B into a three-roll mill and grinding and mixing, with a roller speed ratio of 1:5:10, wherein the speed of the slow roller is 60 rpm, the grinding number is 5 times, and the grinding temperature is 50° C., to obtain a paste mixture D;

[0146] (4) using a high-speed shearing disk to fully mix the mixture D at a stirring speed of 1000 rpm, a stirring time of 5 h, and a mixing temperature of 50° C. to obtain a final product E;

[0147] (5) Add prepreg resin E to a stainless steel tray, seal it with a sealed bag, and store it in a cold storage.

[0148] Test Example 1

[0149] Stability test

[0150] Test samples: prepreg tape resins provided in Examples 1-5 and prepreg tape resins provided in Comparative Examples 1-6;

[0151] Test method: High and low temperature cycle stability test, complete the applicable period cycle test under the cycle from room temperature to 60℃, and observe the state of the prepreg resin;

[0152] The specific test results are shown in Table 1 below:

[0153] Table 1

[0154]

[0155] It can be seen from the test data in Table 1 that the prepreg resin prepared by the preparation method of the prepreg resin of the present invention has a long application period of more than 12 hours, can be subjected to multiple high and low temperature cycles (more than 5 times) without undergoing a curing reaction, and has the advantages of a uniform system and no particles.

[0156] From the comparison between Example 1 and Comparative Example 1, it can be seen that, instead of adopting the method of dividing a single mixed system into two parts for mixing as in the present application, directly mixing the liquid epoxy resin, solid epoxy resin, curing agent and accelerator as in Comparative Example 1, it is difficult to form a uniform mixture, and since the mixing temperature is too high, gel particles are very easily generated.

[0157] From the comparison between Example 1 and Comparative Example 2, it can be seen that although Comparative Example 2 melts the solid epoxy resin separately on the basis of Comparative Example 1, the liquid epoxy resin is not divided into two parts separately, and one part is not mixed with the solid epoxy resin. Even if the melting time of the solid epoxy resin is prolonged, gel particles are easily generated during the high and low temperature cycle times.

[0158] From the comparison between Example 1 and Comparative Example 3, it can be seen that when the solid epoxy resin melting method such as CN108264727A is adopted, since the solid resin part and the liquid resin part are not fully mixed in the early stage, the temperature of the mixing process is relatively high, and a uniform phase can only be obtained at 75°C, but the system is unstable. Gel particles are generated after one cycle during the high and low temperature cycle process, and the storage period of the prepreg resin is very short.

[0159] From the comparison between Example 1 and Comparative Examples 4-6, it can be seen that even if the solid resin and the liquid resin have been fully mixed in the early stage, if the dispersion, grinding and shearing are not carried out in sequence in the later mixing (such as Comparative Example 4 does not use a high-speed shearing disk to fully mix the mixture D, or as in Comparative Example 5, the mixture C is not slowly added to the three-roll grinder for grinding, but the mixing time is extended, or as in Comparative Example 6, high-speed shearing disk is not used for dispersion, but grinding is directly carried out), the stability of the mixed system is difficult to improve, the room temperature storage period of the resin will also decrease accordingly, and the performance will decrease.

[0160] This fully illustrates that the present invention divides a single mixing system into two parts. The first part is high-temperature melting and mixing of solid resin. Since it does not contain a curing agent component, it can be heated to a sufficiently high temperature for mixing, completely melting the solid resin, and the system is more uniform; the second part is room temperature mixing of liquid resin and curing agent component. Since it does not need to be heated for mixing, the system is more stable and will not reduce the storage period of the prepreg resin. Then the two parts are mixed. Since the two parts have been fully mixed in the early stage, the mixing process has better processability and the mixing temperature is relatively lower, which can avoid the generation of gel particles.

[0161] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a prepreg resin, characterized in that: The preparation method of the prepreg resin comprises the following steps: The liquid resin in the raw material for preparing the prepreg tape resin is divided into two parts, namely, liquid resin a and liquid resin b; The solid resin is mixed with the liquid resin a, and dispersed to obtain a paste mixture A; Mixing and dispersing the liquid resin b with a curing agent, an optional accelerator, and an optional auxiliary agent to obtain a liquid mixture B; The paste mixture A and the liquid mixture B are mixed, dispersed, ground and sheared in sequence to obtain the prepreg resin.

2. The method for preparing the prepreg resin according to claim 1, characterized in that: The liquid resin is a liquid epoxy resin; Preferably, the liquid resin is selected from any one or a combination of at least two of liquid bisphenol A epoxy resin, liquid bisphenol S epoxy resin, liquid bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, liquid novolac epoxy resin, multifunctional liquid epoxy resin or liquid halogenated epoxy resin, preferably any one or a combination of at least two of E-51, F-51, TDE-85, AG-80 or BDGE; Preferably, the mass ratio of the liquid resin a to the liquid resin b is (0.8-1.2):

1.

3. The method for preparing the prepreg resin according to claim 1 or 2, characterized in that: The solid resin is a solid epoxy resin; Preferably, the solid epoxy resin is selected from any one or a combination of at least two of solid bisphenol A epoxy resin, solid bisphenol S epoxy resin, solid bisphenol F epoxy resin or multifunctional solid epoxy resin, preferably any one or a combination of at least two of E-20, CYDF-2004, J-80, JF-46 or F-44.

4. The method for preparing the prepreg resin according to any one of claims 1 to 3, characterized in that: The solid resin and liquid resin a need to be heated to 80-120°C before dispersion; Preferably, the solid resin and the liquid resin a are dispersed by high-speed shearing disk dispersion after mixing, with a stirring speed of 200-1000 rpm and a stirring time of 1-5 h; Preferably, the mixture is cooled to 40-100° C. after dispersion to obtain a paste mixture A.

5. The method for preparing the prepreg resin according to any one of claims 1 to 4, characterized in that: The curing agent is a latent curing agent; Preferably, the latent curing agent is selected from any one or a combination of at least two of micronized dicyandiamide, imidazole derivatives or boron trifluoride complexes, preferably any one or a combination of at least two of 2MZ-AZINE, 2E4MZ-AZINE, diallyl melamine or BF3·MEA; Preferably, the accelerator is selected from any one or a combination of at least two of modified imidazole accelerators, modified urea accelerators or epoxy resin amine adduct accelerators, preferably any one or a combination of at least two of 2,4-EMI, DBU, DBN or TAP; Preferably, the auxiliary agent includes any one or a combination of at least two of a defoamer, a wetting agent or a coupling agent, preferably any one or a combination of at least two of BYK-525, BYK-9920, BYK-333 or A-187; Preferably, the raw materials for preparing the prepreg resin include, by weight: 80-120 parts of liquid resin, 40-60 parts of solid resin, 4-10 parts of curing agent, 0-5 parts of accelerator and 0-1.5 parts of auxiliary agent.

6. The method for preparing the prepreg resin according to any one of claims 1 to 5, characterized in that: The temperature at which the liquid resin b is mixed with the curing agent, the optional accelerator, and the optional auxiliary agent is 20-30° C.; Preferably, the liquid resin b is mixed with the curing agent, the optional accelerator and the optional auxiliary agent and then dispersed by a high-speed shearing disk at a stirring speed of 200-1000 rpm for a stirring time of 1-5 h.

7. The method for preparing the prepreg resin according to any one of claims 1 to 6, characterized in that: The paste mixture A and the liquid mixture B are mixed in a manner of adding the liquid mixture B into the paste mixture A; Preferably, the liquid mixture A and the liquid mixture B are dispersed after mixing using a high-speed shearing disk, with a stirring speed of 100-500 rpm, a stirring time of 1-5 h, and a stirring temperature of 30-60°C.

8. The method for preparing the prepreg resin according to any one of claims 1 to 7, characterized in that: The grinding method is to add the dispersed paste mixture C into a three-roll grinder for grinding; Preferably, the roller speed ratio of the slow roller, the medium speed roller and the fast roller in the grinding is 1:(2-8):(5-15), the grinding times are 1-5 times, and the grinding temperature is 30-60°C; Preferably, the speed of the slow roller in the three-roll mill is 60-200 rpm.

9. The method for preparing the prepreg resin according to any one of claims 1 to 8, characterized in that: The shearing is performed using a high-speed shearing disk, with a stirring speed of 100-500 rpm, a stirring time of 1-5 hours, and a stirring temperature of 30-50°C.

10. The method for preparing the prepreg resin according to any one of claims 1 to 9, characterized in that: The preparation method of the prepreg resin comprises the following steps: (1) dividing the liquid resin in the raw material for preparing the prepreg tape resin into two parts, namely liquid resin a and liquid resin b, wherein the mass ratio of the liquid resin a to the liquid resin b is (0.8-1.2):1; (2) mixing the solid resin and the liquid resin a, heating them to 80-120° C., dispersing them using a high-speed shearing disk, stirring at a speed of 200-1000 rpm for 1-5 h, and cooling them to 40-100° C. to obtain a paste mixture A; Mixing liquid resin B with curing agent, optional accelerator and optional auxiliary agent at 20-30° C., dispersing with a high-speed shearing disk, stirring at a speed of 200-1000 rpm for 1-5 hours, to obtain a liquid mixture B; (3) adding the liquid mixture B to the paste mixture A, dispersing with a high-speed shearing disk, stirring at a speed of 100-500 rpm, stirring for 1-5 h, and stirring at a temperature of 30-60° C., to obtain a paste mixture C; (4) slowly adding the paste mixture C to a three-roll mill for grinding and mixing, wherein the roller speed ratio of the slow roller, the medium speed roller and the fast roller is 1:(2-8):(5-15), the grinding number is 1-5 times, and the grinding temperature is 30-60° C., to obtain a paste mixture D; (5) The paste mixture D is fully mixed using a high-speed shearing disk at a stirring speed of 100-500 rpm, a stirring time of 1-5 h, and a stirring temperature of 30-50° C. to obtain the prepreg tape resin.

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