Epoxy resin prepreg and preparation method and application thereof

Abstract

The invention discloses an epoxy resin prepreg and a preparation method and application thereof, and belongs to the field of epoxy resin application technology. The epoxy resin prepreg includes an epoxy compound A component, a curing agent B component and a diluent C component, the epoxy compound A component includes 4,4'-isopropylidene diphenol / epichlorohydrin copolymer, the curing agent B component includes polyamide, and the diluent C component includes methyl ethyl ketone; the weight ratio of component A, component B and component C is 30-50:7.5-12.5:37.5-62.5; before use, the epoxy compound A component and the diluent C component are first mixed, and then the curing agent B component is added, mixed evenly, and the epoxy resin prepreg is obtained. The present invention can greatly extend the operating window period of the epoxy resin prepreg, can be used for continuous production of composite materials in the glue tank storage-glue tank dipping process, and at the same time improve the bending toughness and hardness of the prepared product, so that it meets the requirements of bulletproof and stab-proof.

Description

Technical Field

[0001] The invention relates to the technical field of epoxy resin application, and in particular to an epoxy resin prepreg and a preparation method and application thereof. Background Art

[0002] At present, the continuous production of coils through glue tank dipping is the preferred process for the continuous production of composite prepreg industry. It has the advantages of high efficiency, low cost, and stable performance. It is currently the most widely used production process in the field of protective composite materials. However, this process requires that the resin matrix has a long operating window period during the production process in order to realize the glue tank dipping process. In addition, in order to meet the functional requirements of soft bulletproof / stab-proof materials, the resin needs to have excellent bending toughness and hardness requirements after curing.

[0003] Epoxy resin is currently the most widely used high-performance resin matrix in the industrial field. Its mechanical properties are designable according to the choice of curing agent. Among them, epoxy resin cured with amine curing agent has good bending toughness and hardness, and has good application prospects in the fields of soft stab-proof clothing and soft bullet-proof / stab-proof dual-protection clothing. However, due to factors such as the fast heat release of the epoxy resin chain reaction and the short operating window period, it is difficult to realize the glue tank storage-glue tank dipping process in continuous industrial production, that is, it is impossible to realize continuous coil production, which limits the application of epoxy resin in the fields of soft stab-proof clothing and soft bullet-proof / stab-proof dual-protection clothing.

[0004] It can be seen that the above-mentioned existing epoxy resin matrix still has the disadvantage of short operating window period, and further improvement is urgently needed. How to create a new epoxy resin prepreg and its preparation method and application, so that it can extend the operating window period of the epoxy resin matrix by improving the raw materials, formula and preparation method, meet the requirements of the glue tank storage-glue tank dipping process in continuous process production, and meet the requirements of good bending toughness and hardness of the product after resin curing, has become a goal that the industry urgently needs to improve. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide an epoxy resin prepreg, which can extend the operation window period of the epoxy resin matrix by improving the raw materials, formula and preparation method, meet the requirements of the glue tank storage-glue tank dipping process in continuous process production, and meet the requirements that the product has good bending toughness and hardness after the resin is cured, thereby overcoming the shortcomings of the existing epoxy resin matrix.

[0006] In order to solve the above technical problems, the present invention provides an epoxy resin prepreg, comprising an epoxy compound component A, a curing agent component B and a diluent component C, wherein the epoxy compound component A comprises a 4,4'-isopropylidene diphenol / epichlorohydrin copolymer, the curing agent component B comprises a polyamide, the diluent component C comprises methyl ethyl ketone, and the weight ratio of the epoxy compound component A, the curing agent component B and the diluent component C is 30-50:7.5-12.5:37.5-62.5;

[0007] Before using the epoxy resin prepreg, the epoxy compound component A and the diluent component C are first mixed evenly according to a weight ratio, and then the curing agent component B is added according to a weight ratio and mixed evenly to obtain the epoxy resin prepreg suitable for glue tank storage-glue tank dipping process in continuous process production.

[0008] As a further improvement, the epoxy compound component A also includes 3-glycidyloxypropyltrimethoxysilane, and the weight ratio of the 4,4'-isopropylidene diphenol / epichlorohydrin copolymer to 3-glycidyloxypropyltrimethoxysilane is 70-100:0-30.

[0009] As a further improvement, the curing agent component B also includes 4,4'-diaminodicyclohexylmethane, and the weight ratio of the polyamide to 4,4'-diaminodicyclohexylmethane is 80-100:0-20.

[0010] As a further improvement, the diluent component C also includes cyclohexanone, and the weight ratio of the methyl ethyl ketone to the cyclohexanone is 50-100:0-50.

[0011] As a further improvement, the weight ratio of the epoxy compound component A, the curing agent component B and the diluent component C is 40:10:50.

[0012] As a further improvement, the epoxy resin prepreg maintains fluidity and wettability for at least 12 hours at 50°C.

[0013] As another improvement of the present invention, the present invention also provides a method for preparing an epoxy resin prepreg, wherein the epoxy resin prepreg adopts the above-mentioned epoxy resin prepreg, and the preparation method comprises:

[0014] (1) Preparation of epoxy compound component A

[0015] Weighing 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 3-glycidyloxypropyltrimethoxysilane respectively according to weight ratio, and mixing the 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 3-glycidyloxypropyltrimethoxysilane, stirring evenly, to obtain the epoxy compound A component;

[0016] (2) Preparation of curing agent component B

[0017] Weigh polyamide and 4,4'-diaminodicyclohexylmethane respectively according to weight ratio, mix the polyamide and 4,4'-diaminodicyclohexylmethane, and stir evenly to obtain the curing agent B component;

[0018] (3) Preparation of diluent component C

[0019] Weigh methyl ethyl ketone and cyclohexanone respectively according to a weight ratio, mix the methyl ethyl ketone and cyclohexanone, and stir them evenly to obtain the diluent C component;

[0020] (4) Preparation before use

[0021] First, the epoxy compound component A prepared in step (1) and the diluent component C prepared in step (3) are mixed uniformly according to a weight ratio; then the curing agent component B prepared in step (2) is added according to a weight ratio and mixed uniformly to obtain the epoxy resin prepreg.

[0022] Further improvement, the specific steps of mixing and stirring the 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 3-glycidyloxypropyltrimethoxysilane in step (1) are: stirring for not less than 2 hours under heating in a water bath at 40-60°C;

[0023] The specific steps of mixing and stirring the polyamide and 4,4'-diaminodicyclohexylmethane in step (2) are as follows: the stirring time is not less than 30 min;

[0024] The specific steps of mixing and stirring the methyl ethyl ketone and cyclohexanone in step (3) are as follows: the stirring time is not less than 5 min;

[0025] In the step (4), the mixing and stirring time of the epoxy compound component A and the diluent component C is not less than 20 minutes, and after the curing agent component B is added, the stirring time is not less than 20 minutes.

[0026] As a further improvement, the epoxy resin prepreg obtained maintains fluidity and wettability for at least 12 hours at 50°C.

[0027] As another improvement of the present invention, the present invention also provides an application of the above-mentioned epoxy resin prepreg in a production process of a soft stab-proof clothing or a soft bullet-proof / stab-proof dual-protection clothing, so that the soft stab-proof clothing or the soft bullet-proof / stab-proof dual-protection clothing can be produced continuously, and the prepared soft stab-proof clothing or the soft bullet-proof / stab-proof dual-protection clothing has excellent bending toughness and hardness.

[0028] After adopting such a design, the present invention has at least the following advantages:

[0029] The epoxy resin prepreg of the present invention improves the raw material components, proportions and preparation method, so that the operation window of the epoxy resin prepreg is greatly extended, and can be used for the glue tank storage-glue tank dipping process in the continuous production of composite materials, while improving the bending toughness and hardness of the prepared product. The surface density of the prepared bullet-proof and stab-proof composite material is only 5kg / m 2 It can meet the requirements of NI J0101.04ⅢA level ballistic performance and HOSDB SP1 level and NI J0115.00 2 level stab resistance performance. DETAILED DESCRIPTION

[0030] The present invention will be further described below in conjunction with specific examples. The following examples are only used to more clearly illustrate the technical solutions of the present invention, and are not intended to limit the scope of protection of the present invention.

[0031] Embodiment 1

[0032] Preparation of epoxy compound component A in epoxy resin prepreg: Weigh 703.2 g of 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 301.4 g of 3-glycidyloxypropyltrimethoxysilane respectively, add them into a reactor, stir in a 50°C water bath for 3 h, and mix well.

[0033] Preparation of curing agent component B in epoxy resin prepreg: 200.9 g of polyamide and 50.2 g of 4,4'-diaminodicyclohexylmethane were weighed separately, and the two were stirred in another reaction kettle for 1 hour to mix evenly.

[0034] Preparation of diluent component C in epoxy resin prepreg: Weigh 2092.8 g of methyl ethyl ketone and place it in a beaker.

[0035] At room temperature of 25°C, the diluent component C is first added to the epoxy compound component A, stirred for 30 min, and then the prepared curing agent component B is added, stirred for 30 min, and mixed evenly to obtain epoxy resin prepreg 1.

[0036] Embodiment 2

[0037] Preparation of epoxy compound component A in epoxy resin prepreg: Weigh 805.1 g of 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 201.3 g of 3-glycidyloxypropyltrimethoxysilane respectively, add them into a reactor, stir in a 40°C water bath for 3 h, and mix well.

[0038] Preparation of curing agent component B in epoxy resin prepreg: Weigh 213.8 g of polyamide and 37.7 g of 4,4'-diaminodicyclohexylmethane respectively, and stir the two in another reaction kettle for 1 hour to mix them evenly.

[0039] Preparation of diluent component C in epoxy resin prepreg: Weigh 1048.2 g of methyl ethyl ketone and 1048.5 g of cyclohexanone respectively, put them in a beaker, and stir for 5 min.

[0040] At room temperature of 25°C, the prepared diluent component C is first added to the epoxy compound component A, stirred for 20 min, and then the prepared curing agent component B is added, stirred for 20 min, and mixed evenly to obtain epoxy resin prepreg 2.

[0041] Embodiment 3

[0042] Preparation of epoxy compound component A in epoxy resin prepreg: Weigh 901.2 g of 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 100.1 g of 3-glycidyloxypropyltrimethoxysilane respectively, add them into a reactor, stir in a 60°C water bath for 3 h, and mix well.

[0043] Preparation of curing agent component B in epoxy resin prepreg: Weigh 225.3 g of polyamide and 25.1 g of 4,4'-diaminodicyclohexylmethane respectively, and stir the two in another reaction kettle for 1 hour to mix them evenly.

[0044] Preparation of diluent component C in epoxy resin prepreg: Weigh 876.1 g of methyl ethyl ketone and 375.5 g of cyclohexanone respectively, put them in a beaker, and stir for 10 min.

[0045] At room temperature of 25°C, the prepared diluent component C is first added to the epoxy compound component A, stirred for 30 min, and then the prepared curing agent component B is added, stirred for 30 min, and mixed evenly to obtain epoxy resin prepreg 3.

[0046] Embodiment 4

[0047] Preparation of epoxy compound component A in epoxy resin prepreg: Weigh 1002.3 g of 4,4'-isopropylidene diphenol / epichlorohydrin copolymer.

[0048] Preparation of curing agent component B in epoxy resin prepreg: Weigh 250.6 g of polyamide.

[0049] Preparation of diluent component C in epoxy resin prepreg: Weigh 601.4 g of methyl ethyl ketone and 150.3 g of cyclohexanone respectively, put them in a beaker, and stir for 10 min.

[0050] At room temperature of 25°C, the prepared diluent component C is first added to the epoxy compound component A, stirred for 20 min, and then the prepared curing agent component B is added, stirred for 20 min, and mixed evenly to obtain epoxy resin prepreg 4.

[0051] Embodiment 5

[0052] Preparation of epoxy compound component A in epoxy resin prepreg: Weigh 855.6 g of 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 150.9 g of 3-glycidyloxypropyltrimethoxysilane respectively, add them into a reactor, stir in a 50°C water bath for 3 h, and mix well.

[0053] Preparation of curing agent component B in epoxy resin prepreg: Weigh 226.5 g of polyamide and 25.2 g of 4,4'-diaminodicyclohexylmethane respectively, and stir the two in another reaction kettle for 1 hour to mix them evenly.

[0054] Preparation of diluent component C in epoxy resin prepreg: Weigh 754.9 g of methyl ethyl ketone and 503.3 g of cyclohexanone respectively, put them in a beaker, and stir for 10 min.

[0055] At room temperature of 25°C, the prepared diluent component C is first added to the epoxy compound component A, stirred for 30 min, and then the prepared curing agent component B is added, stirred for 30 min, and mixed evenly to obtain epoxy resin prepreg 5.

[0056] Embodiment 6

[0057] Preparation of epoxy compound component A in epoxy resin prepreg: Weigh 5001.3 g of 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 882.6 g of 3-glycidyloxypropyltrimethoxysilane respectively, add them into a reactor, stir in a 50°C water bath for 3 h, and mix well.

[0058] Preparation of curing agent component B in epoxy resin prepreg: 1323.9 g of polyamide and 147.1 g of 4,4'-diaminodicyclohexylmethane were weighed separately, and the two were stirred in another reaction kettle for 1 hour to mix evenly.

[0059] Preparation of diluent component C in epoxy resin prepreg: Weigh 4412.9 g of methyl ethyl ketone and 2941.9 g of cyclohexanone respectively, put them in a beaker, and stir for 10 min.

[0060] At room temperature of 25°C, the prepared diluent component C is first added to the epoxy compound component A, stirred for 30 min, and then the prepared curing agent component B is added, stirred for 30 min, and mixed evenly to obtain epoxy resin prepreg 6.

[0061] Comparative Example 1

[0062] Preparation of epoxy compound component A: Weigh 1006.7 g of 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 177.7 g of 3-glycidyloxypropyltrimethoxysilane respectively, add them into a reaction kettle, stir in a 50°C water bath for 3 h, and mix them evenly.

[0063] Preparation of curing agent component B: Weigh 266.5 g of polyamide and 29.6 g of 4,4'-diaminodicyclohexylmethane respectively, and stir the two in another reaction kettle for 1 hour to mix them evenly.

[0064] At room temperature of 25° C., the epoxy compound component A and the curing agent component B prepared above were mixed and stirred for 30 min until they were evenly mixed to obtain comparative material 1.

[0065] Comparative Example 2

[0066] Preparation of epoxy compound component A: Weigh 999.5 g of 4,4'-isopropylidene diphenol / epichlorohydrin copolymer.

[0067] Preparation of curing agent component B: Weigh 249.9 g of polyamide.

[0068] Preparation of diluent C component: Take 625.6 g of dichloromethane.

[0069] At room temperature of 25°C, the diluent component C was first added to the epoxy compound component A, stirred for 30 min, and then the curing agent component B was added, stirred for 30 min, and mixed evenly to obtain comparative material 2.

[0070] Comparative Example 3

[0071] Preparation of epoxy compound component A: Weigh 1003.1 g of 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 429.9 g of 3-glycidyloxypropyltrimethoxysilane respectively, add them into a reaction kettle, stir in a 50°C water bath for 3 h, and mix them evenly.

[0072] Preparation of curing agent component B: Weigh 286.6 g of polyamide and 71.7 g of 4,4'-diaminodicyclohexylmethane respectively, and stir the two in another reaction kettle for 1 hour to mix them evenly.

[0073] Preparation of diluent component C: Take 1791.3 g of anhydrous ethanol.

[0074] At room temperature of 25°C, the diluent component C was first added to the epoxy compound component A, stirred for 30 min, and then the curing agent component B was added, stirred for 30 min, and mixed evenly to obtain comparative material 3.

[0075] Results Example 1

[0076] The curing time of the epoxy resin prepregs prepared in the above Examples 1-6 and the comparative materials prepared in the above Comparative Examples 1-3 was tested. The specific method is:

[0077] Method 1: Use a glass beaker with a diameter of 145 mm to hold 10 cm high epoxy resin prepreg 1-6 and comparison material 1-3 respectively, simulate the glue storage in the glue tank, and observe its fluidity and wettability at room temperature of 25°C.

[0078] Method 2: Set the oven to 50°C to simulate the ambient temperature in the glue tank during the actual production process. Use a 145mm diameter glass beaker to hold 10cm high epoxy resin prepreg 1-6 to simulate the glue tank storage, and place them in the oven at the same time to observe their fluidity and wettability.

[0079] The results of this example are shown in Table 1 below.

[0080] Table 1 Test results of curing time of epoxy resin prepreg of Examples 1-6 and Comparative Examples 1-3

[0081]

[0082]

[0083] As can be seen from Table 1 above, the epoxy resin prepregs obtained in Examples 1-6 of the present application have a significantly longer curing time than the comparative materials obtained in Comparative Examples 1-3, which greatly improves the operating window of the epoxy resin prepreg, so that it meets the operating requirements of continuous industrial mass production, and provides the possibility of realizing the glue tank storage-glue tank dipping process in continuous industrial production, and provides the necessary conditions for the continuous preparation and production process of epoxy resin in soft stab-proof clothing and soft bullet-proof / stab-proof dual-protection clothing.

[0084] Results Example 2

[0085] The epoxy resin prepregs prepared in the above Examples 1-6 were respectively injected into the glue tanks of the production line, and continuous coils were produced through a glue tank storage-glue tank dipping process, and then prepared into soft bulletproof / stab-proof materials through a curing process.

[0086] The surface density of the prepared bulletproof / stab-proof materials is 5kg / m 2Under the conditions, the bulletproof and stab-proof performance tests were carried out. Among them, the ballistic performance A uses the NIJ 0101.04ⅢA level ballistic test as the reference standard, takes .44Magnum SJHP as the threat type, tests the penetration effect of 6 bullets, requires that none of the 6 bullets penetrate, and the depression depth of the backing glue is ≤44mm. The ballistic performance B uses STANAGE 2920 as the reference standard, takes 1.1g FSP as the threat type, and tests the ballistic limit V50 value. V50 is the ballistic limit speed, which refers to the target speed at which a certain type of bullet forms a 50% penetration probability on the sample. It is one of the universal measurement indicators of the material's ballistic performance. The stab-proof performance A uses the HOSDB SP1 level as the reference standard, takes SP / B cone, E1:24J energy as the threat type, tests the stab-proof effect of 5 cone punctures, and requires the puncture depth to be ≤7mm. Stab resistance performance B uses NI J0115.002 as the reference standard, S1 knife, E1: 33J energy as the threat type, and tests the stab resistance effect of 7 stabs, requiring the puncture depth to be ≤7mm. The test results are shown in Table 2 below.

[0087] Table 2 Test results of bulletproof / stab-proof composite materials prepared using prepregs of Examples 1-6

[0088]

[0089] It can be seen from Table 2 above that the bulletproof / stab-proof materials prepared from the epoxy resin prepregs of Examples 1-6 of the present application meet the existing standard requirements in the bulletproof and stab-proof tests, have good bending toughness and hardness, and can meet the needs of existing bulletproof / stab-proof materials. It provides the necessary conditions for the application of the epoxy resin prepreg of the present application in the production process of soft stab-proof clothing or soft bulletproof / stab-proof dual-protection clothing, and expands the application of epoxy resin in the field of soft stab-proof clothing and soft bulletproof / stab-proof dual-protection clothing.

[0090] The epoxy resin prepreg of the present application has greatly prolonged its curing time by improving the raw material components, proportions and preparation methods, significantly improving the operation window of the prepreg, so that it meets the operation requirements of continuous industrial mass production, provides the possibility of realizing the glue tank storage-glue tank dipping process in continuous industrial production, and provides the necessary conditions for the continuous preparation and production process of epoxy resin in soft stab-proof clothing and soft bullet-proof / stab-proof dual-protection clothing.

[0091] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Those skilled in the art may make some simple modifications, equivalent changes or modifications using the technical contents disclosed above, which all fall within the protection scope of the present invention.

Claims

1. An epoxy resin prepreg, characterized in that: It is composed of epoxy compound component A, curing agent component B and diluent component C. The epoxy compound component A is composed of 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 3-glycidyloxypropyltrimethoxysilane, and the weight ratio of the 4,4'-isopropylidene diphenol / epichlorohydrin copolymer to the 3-glycidyloxypropyltrimethoxysilane is 70-100:0-30; The curing agent B component is composed of polyamide and 4,4'-diaminodicyclohexylmethane, and the weight ratio of the polyamide to the 4,4'-diaminodicyclohexylmethane is 80-100:0-20; The diluent C component consists of methyl ethyl ketone and cyclohexanone, and the weight ratio of methyl ethyl ketone to cyclohexanone is 50:0-50; The weight ratio of the epoxy compound component A, the curing agent component B and the diluent component C is 30:7.5:62.5; Before using the epoxy resin prepreg, the epoxy compound component A and the diluent component C are first mixed evenly according to a weight ratio, and then the curing agent component B is added according to a weight ratio and mixed evenly to obtain the epoxy resin prepreg suitable for the glue tank storage-glue tank dipping process in the continuous process production, and the epoxy resin prepreg maintains fluidity and wettability for at least 12 hours at 50° C.; The epoxy resin prepreg is used to provide necessary conditions for the continuous preparation and production of soft stab-proof clothing or soft bullet-proof / stab-proof dual-protection clothing.

2. A method for preparing an epoxy resin prepreg, characterized in that: The epoxy resin prepreg adopts the epoxy resin prepreg according to claim 1, and the preparation method comprises: (1) Preparation of epoxy compound component A Weigh 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 3-glycidyloxypropyl trimethoxysilane respectively by weight, mix the 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 3-glycidyloxypropyl trimethoxysilane, and stir them evenly to obtain the epoxy compound A component; wherein the mixing and stirring of the 4,4'-isopropylidene diphenol / epichlorohydrin copolymer and 3-glycidyloxypropyl trimethoxysilane comprises the following specific steps: stirring for not less than 2 hours under heating in a water bath at 40-60°C; (2) Preparation of curing agent component B Weigh polyamide and 4,4'-diaminodicyclohexylmethane respectively according to the weight ratio, mix the polyamide and 4,4'-diaminodicyclohexylmethane, and stir them evenly to obtain the curing agent B component; wherein the specific steps of mixing and stirring the polyamide and 4,4'-diaminodicyclohexylmethane are as follows: the stirring time is not less than 30 minutes; (3) Preparation of diluent component C Weigh methyl ethyl ketone and cyclohexanone respectively according to the weight ratio, mix the methyl ethyl ketone and cyclohexanone, and stir them evenly to obtain the diluent C component; wherein the mixing and stirring of the methyl ethyl ketone and cyclohexanone specifically comprises the following steps: stirring time is not less than 5 minutes; (4) Preparation before use First, the epoxy compound component A prepared in step (1) and the diluent component C prepared in step (3) are mixed uniformly according to a weight ratio; then the curing agent component B prepared in step (2) is added according to a weight ratio and mixed uniformly to obtain the epoxy resin prepreg; The mixing time of the epoxy compound component A and the diluent component C is not less than 20 minutes, and the mixing time after adding the curing agent component B is not less than 20 minutes; The epoxy resin prepreg obtained maintains fluidity and wettability for at least 12 hours at 50°C.

3. Use of the epoxy resin prepreg according to claim 1 in the production process of soft stab-proof clothing or soft bullet-proof / stab-proof dual-protection clothing.

Images