A glass fiber-reinforced photocured epoxy acrylate and a method for preparing the same

Abstract

The application discloses a glass fiber reinforced photocuring epoxy acrylate and a preparation method thereof, and relates to the field of photocuring resins. The glass fiber reinforced photocuring epoxy acrylate comprises 60-70 parts by weight of di-functional epoxy acrylate, 20-25 parts by weight of active diluent, 5.8-6.4 parts by weight of modified glass fiber, 3-4 parts by weight of photoinitiator and 0.5-1 part by weight of first polymerization inhibitor. The modified glass fiber is first modified by an amino silane coupling agent to obtain amino silane coupling agent modified glass fiber, and then reacts with the amino silane coupling agent modified glass fiber under the action of carboxyl polyethylene glycol acrylate and a second polymerization inhibitor. The application can obtain a glass fiber reinforced photocuring epoxy acrylate material which has high temperature resistance, high tensile strength and excellent bending resistance.

Description

Technical Field

[0001] This application relates to the field of photocurable resins, and in particular to a glass fiber reinforced photocurable epoxy acrylate and its preparation method. Background Technology

[0002] Photocurable epoxy acrylate materials are widely used in the adhesives industry due to their advantages such as fast curing speed, high production efficiency, and good environmental performance.

[0003] Adding glass fibers to UV-cured epoxy acrylate materials can improve tensile strength, but traditional glass fiber reinforced UV-cured epoxy acrylate materials have many problems. On the one hand, the interfacial bonding force between glass fibers and the resin matrix is ​​weak, causing the glass fibers to easily debond from the resin when the material is subjected to external forces, making it difficult to effectively improve the tensile strength of the material. On the other hand, the addition of glass fibers can easily reduce flexibility, making the material prone to cracking or even breakage during bending, resulting in poor bending resistance and failing to meet the requirements of some application scenarios with high overall material performance.

[0004] Therefore, there is an urgent need to develop a glass fiber reinforced photocurable epoxy acrylate material that can enhance the interfacial bonding and toughness between glass fiber and resin materials, so as to obtain a glass fiber reinforced photocurable epoxy acrylate material that has high temperature resistance, high tensile strength and excellent bending performance. Summary of the Invention

[0005] To improve the weak interfacial bonding between glass fiber and resin matrix and the decrease in flexibility caused by the introduction of glass fiber, this application provides a glass fiber reinforced photocurable epoxy acrylate and its preparation method.

[0006] Firstly, the glass fiber reinforced photocurable epoxy acrylate provided in this application adopts the following technical solution:

[0007] A glass fiber reinforced photocurable epoxy acrylate comprises 60-70 parts by weight of difunctional epoxy acrylate, 20-25 parts by weight of reactive diluent, 5.8-6.4 parts by weight of modified glass fiber, 3-4 parts by weight of photoinitiator, and 0.5-1 parts by weight of a first polymerization inhibitor. The modified glass fiber is first modified with an aminosilane coupling agent to obtain aminosilane coupling agent modified glass fiber, and then reacted with carboxyl polyethylene glycol acrylate under the action of a second polymerization inhibitor to obtain the modified glass fiber.

[0008] In this application, glass fibers are first modified with an aminosilane coupling agent to obtain aminosilane-modified glass fibers. Then, carboxyl polyethylene glycol acrylate is added to further modify the aminosilane-modified glass fibers. This allows unsaturated acrylate groups and polyethylene glycol segments to be grafted onto the glass fibers. The unsaturated acrylate groups can crosslink with difunctional epoxy acrylate or reactive diluents under the action of photoinitiators and light, thereby improving the interfacial bonding between the glass fibers and the resin material. This enhances the material's high-temperature resistance and tensile strength. Furthermore, the polyethylene glycol segments possess excellent flexibility, improving the interfacial toughness between the glass fibers and the resin material, ensuring the material's flexibility, and enhancing its bending resistance.

[0009] In some specific embodiments, the structural formula of the carboxyl polyethylene glycol acrylate is as follows:

[0010]

[0011] Where n takes values ​​between 30 and 40.

[0012] In this application, it is preferable to control the degree of polymerization n of polyethylene glycol in carboxylated polyethylene glycol acrylate within the range of 30-40, which is beneficial to further improve the dispersibility of glass fiber in resin and can further enhance the tensile strength and bending resistance of the material.

[0013] In some specific embodiments, the weight ratio of the aminosilane coupling agent to the glass fiber is (0.04-0.05):10.

[0014] In some specific embodiments, the weight ratio of the carboxylated polyethylene glycol acrylate, the second polymerization inhibitor, and the aminosilane coupling agent modified glass fiber is (10-15):(0.02-0.03):10.

[0015] In this application, controlling the aminosilane coupling agent and carboxylated polyethylene glycol acrylate in the modified glass fiber within a suitable grafting range is beneficial to further improve the dispersibility of the glass fiber in the resin, and can further enhance the tensile strength and bending resistance of the material.

[0016] In some specific embodiments, the glass fiber is alkali-free chopped glass fiber powder with a length of 100-300μm.

[0017] In this application, the glass fiber is preferably alkali-free short-cut glass fiber powder with a length of 100-300μm, which is beneficial to improving the uniform dispersion of the modified glass fiber.

[0018] In some specific embodiments, the difunctional epoxy acrylate is at least one of phenolic epoxy acrylate and bisphenol A epoxy acrylate.

[0019] In some specific embodiments, the reactive diluent is at least one of tripropylene glycol diacrylate, polyethylene glycol diacrylate, and polypropylene glycol diacrylate.

[0020] In this application, the reactive diluent is at least one of tripropylene glycol diacrylate, polyethylene glycol diacrylate, and polypropylene glycol diacrylate, which is beneficial to further improve the flexibility of the material and enhance its bending resistance.

[0021] In some specific embodiments, the photoinitiator is at least one of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 1-hydroxycyclohexylphenyl ketone.

[0022] In some specific embodiments, the first polymerization inhibitor is at least one of p-hydroxyanisole and 2,6-di-tert-butyl-p-cresol.

[0023] Secondly, the preparation method of glass fiber reinforced photocurable epoxy acrylate provided in this application adopts the following technical solution:

[0024] A method for preparing glass fiber reinforced photocurable epoxy acrylate includes the following steps:

[0025] Preparation of modified glass fibers:

[0026] Glass fibers were dispersed in an aqueous ethanol solution, an aminosilane coupling agent was added, the mixture was heated to 50-80℃ and stirred to react, then filtered, and the filter residue was washed and dried to obtain aminosilane coupling agent modified glass fibers.

[0027] Aminosilane coupling agent glass fiber is uniformly dispersed in N,N-dimethylformamide, and then carboxylated polyethylene glycol acrylate and a second polymerization inhibitor are added under nitrogen protection. The mixture is then heated to 140-150℃ to react, and then filtered and washed to obtain modified glass fiber.

[0028] Preparation of UV-cured epoxy acrylate:

[0029] Modified glass fiber, photoinitiator, and first polymerization inhibitor are uniformly dispersed in an active diluent, and then difunctional epoxy acrylate is added and mixed evenly to obtain a photocurable epoxy acrylate composition.

[0030] In summary, this application includes at least the following beneficial technical effects:

[0031] (1) In this application, the glass fiber is first modified with an aminosilane coupling agent to obtain aminosilane coupling agent modified glass fiber, and then carboxylated polyethylene glycol acrylate is added to modify the aminosilane coupling agent modified glass fiber. Unsaturated acrylate groups and polyethylene glycol segments can be grafted onto the glass fiber. The unsaturated acrylate groups can crosslink with difunctional epoxy acrylate or reactive diluent under the action of photoinitiator and light, thereby improving the interfacial bonding force between the glass fiber and the resin material. This can improve the high temperature resistance of the material and further improve the tensile strength of the material. The polyethylene glycol segments have excellent flexibility, which can improve the interfacial toughness between the glass fiber and the resin material, ensuring the flexibility of the material and improving the bending resistance of the material.

[0032] (2) In this application, it is preferable to control the degree of polymerization n of polyethylene glycol in carboxylated polyethylene glycol acrylate to be in the range of 30-40, which is beneficial to further improve the dispersibility of glass fiber in resin and can further improve the tensile strength and bending resistance of the material.

[0033] (3) In this application, controlling the aminosilane coupling agent and carboxylated polyethylene glycol acrylate in the modified glass fiber within a suitable grafting range is beneficial to further improve the dispersibility of the glass fiber in the resin, and can further improve the tensile strength and bending resistance of the material. Detailed Implementation

[0034] The following section provides further explanation of this application in conjunction with specific experiments.

[0035] Example

[0036]

Example 1

[0037] A glass fiber reinforced photocurable epoxy acrylate comprises 60 kg of difunctional epoxy acrylate, 25 kg of reactive diluent, 5.8 kg of modified glass fiber, 3 kg of photoinitiator, and 0.5 kg of primary polymerization inhibitor. The difunctional epoxy acrylate is iLENE 700, a product from Zhaoqing Baojun Chemical Co., Ltd.; the reactive diluent is tripropylene glycol diacrylate; the photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; and the primary polymerization inhibitor is p-hydroxyanisole.

[0038] The raw materials for preparing modified glass fiber include 10 kg of carboxylated polyethylene glycol acrylate, 0.02 kg of a second polymerization inhibitor, 10 kg of aminosilane coupling agent modified glass fiber, and 20 kg of N,N-dimethylformamide. In the carboxylated polyethylene glycol acrylate, the degree of polymerization of polyethylene glycol is 30; the second polymerization inhibitor is p-hydroxyanisole.

[0039] The raw materials for preparing aminosilane coupling agent modified glass fiber include 0.04 kg aminosilane coupling agent, 10 kg glass fiber, and 50 kg of 90% ethanol aqueous solution. Specifically, aminosilane coupling agent KH550 is used, and the glass fiber is alkali-free chopped glass fiber powder with a length of 100-200 μm.

[0040] In this embodiment, the preparation method of glass fiber reinforced photocurable epoxy acrylate includes the following steps:

[0041] Preparation of modified glass fibers:

[0042] Glass fibers were dispersed in an aqueous ethanol solution with a mass concentration of 90%, an aminosilane coupling agent was added, the mixture was heated to 50°C and stirred for 1 hour, then filtered, and the filter residue was washed and dried to obtain aminosilane coupling agent modified glass fibers.

[0043] Aminosilane coupling agent glass fiber was uniformly dispersed in N,N-dimethylformamide, and then carboxylated polyethylene glycol acrylate and a second polymerization inhibitor were added under nitrogen protection. The mixture was then heated to 140℃ and reacted for 2 hours. After filtration and washing, modified glass fiber was obtained.

[0044] Preparation of UV-cured epoxy acrylate:

[0045] Modified glass fiber, photoinitiator, and first polymerization inhibitor are uniformly dispersed in an active diluent, and then difunctional epoxy acrylate is added and mixed evenly to obtain a photocurable epoxy acrylate composition.

[0046]

Example 2

[0047] A glass fiber reinforced photocurable epoxy acrylate comprises 70 kg of difunctional epoxy acrylate, 20 kg of reactive diluent, 6.4 kg of modified glass fiber, 4 kg of photoinitiator, and 1 kg of primary polymerization inhibitor. The difunctional epoxy acrylate is iLENE 700, a product from Zhaoqing Baojun Chemical Co., Ltd.; the reactive diluent is polyethylene glycol diacrylate (in which the number average molecular weight of polyethylene glycol is 200); the photoinitiator is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; and the primary polymerization inhibitor is 2,6-di-tert-butyl-p-cresol.

[0048] The raw materials for preparing modified glass fiber include 15 kg of carboxylated polyethylene glycol acrylate, 0.03 kg of a second polymerization inhibitor, 10 kg of aminosilane coupling agent modified glass fiber, and 20 kg of N,N-dimethylformamide. In the carboxylated polyethylene glycol acrylate, the degree of polymerization of polyethylene glycol is 40; the second polymerization inhibitor is 2,6-di-tert-butyl-p-cresol.

[0049] The raw materials for preparing aminosilane coupling agent modified glass fiber include 0.05 kg aminosilane coupling agent, 10 kg glass fiber, and 50 kg of 90% ethanol aqueous solution. Specifically, aminosilane coupling agent KH550 is used, and the glass fiber is alkali-free chopped glass fiber powder with a length of 200-300 μm.

[0050] In this embodiment, the preparation method of glass fiber reinforced photocurable epoxy acrylate includes the following steps:

[0051] Preparation of modified glass fibers:

[0052] Glass fibers were dispersed in a 90% ethanol aqueous solution, an aminosilane coupling agent was added, the mixture was heated to 80°C and stirred for 0.5 h, then filtered, and the filter residue was washed and dried to obtain aminosilane coupling agent modified glass fibers.

[0053] Aminosilane coupling agent glass fiber was uniformly dispersed in N,N-dimethylformamide, and then carboxylated polyethylene glycol acrylate and a second polymerization inhibitor were added under nitrogen protection. The mixture was then heated to 150°C and reacted for 1 hour. After filtration and washing, modified glass fiber was obtained.

[0054] Preparation of UV-cured epoxy acrylate:

[0055] Modified glass fiber, photoinitiator, and first polymerization inhibitor are uniformly dispersed in an active diluent, and then difunctional epoxy acrylate is added and mixed evenly to obtain a photocurable epoxy acrylate composition.

[0056]

Example 3

[0057] A glass fiber reinforced photocurable epoxy acrylate differs from [Example 1] in that the degree of polymerization of polyethylene glycol in the carboxylated polyethylene glycol acrylate is 20.

[0058]

Example 4

[0059] A glass fiber reinforced photocurable epoxy acrylate differs from [Example 1] in that the degree of polymerization of polyethylene glycol in the carboxylated polyethylene glycol acrylate is 60.

[0060]

Example 5

[0061] A glass fiber reinforced photocurable epoxy acrylate differs from [Example 1] in that: in the modified glass fiber, the amount of carboxylated polyethylene glycol acrylate is 25 kg; in the aminosilane coupling agent modified glass fiber, the amount of aminosilane coupling agent KH550 is 0.1 kg.

[0062] Comparative Example

[0063] Comparative Example 1

[0064] A glass fiber reinforced photocurable epoxy acrylate differs from [Example 1] in that the modified glass fiber is different. In this comparative example, the raw materials for preparing the modified glass fiber include 10 kg of carboxylated polyethylene glycol acrylate, 0.02 kg of a second polymerization inhibitor, 10 kg of glass fiber, and 20 kg of N,N-dimethylformamide. In the carboxylated polyethylene glycol acrylate, the degree of polymerization of polyethylene glycol is 30; the second polymerization inhibitor is p-hydroxyanisole; and the glass fiber is alkali-free chopped glass fiber powder with a length of 100-200 μm.

[0065] The preparation steps of modified glass fiber are as follows:

[0066] Glass fibers were uniformly dispersed in N,N-dimethylformamide, and then carboxylated polyethylene glycol acrylate and a second polymerization inhibitor were added under nitrogen protection. The mixture was then heated to 150°C and reacted for 1 hour. After filtration and washing, modified glass fibers were obtained.

[0067] Comparative Example 2

[0068] A glass fiber reinforced photocurable epoxy acrylate differs from [Example 1] in that: carboxylated polyethylene glycol acrylate is replaced with an equimolar amount of acrylic acid.

[0069] Performance testing

[0070] Sample preparation: Glass fiber reinforced photocurable epoxy acrylate from each example and comparative example was printed onto the surface of transparent glass with a printing thickness of 0.2 mm. The printed transparent glass was then cured with UV light, with a cumulative curing energy of 70 mJ / cm². 2 A light-cured resin is obtained.

[0071] (1) High temperature resistance test: Take the test sample prepared above and conduct a high temperature resistance test. The test conditions are 200℃ baking for 2 hours. Then test the peelability between the light-cured resin and the transparent glass. Use a 100x magnifying glass to observe whether there is any residue. If it can be peeled off without any residue, it is qualified. If either one fails to meet the standard, it is unqualified.

[0072] (2) Tensile strength: The light-cured resin was peeled off the transparent glass and then the tensile strength was tested in a tensile testing machine at a tensile speed of 50 mm / min. The tensile strength data was recorded.

[0073] (3) Bending resistance test: Peel the light-cured resin off the transparent glass, and then fold it repeatedly 10, 50 and 100 times to observe whether it breaks.

[0074] Table 1

[0075] Sample High temperature resistance test Example 1 qualified Example 2 qualified Example 3 qualified Example 4 qualified Example 5 qualified Comparative Example 1 qualified Comparative Example 2 qualified

[0076] Table 2

[0077]

[0078] Table 3

[0079] Sample Fold in half 10 times Fold in half 50 times Fold in half 100 times Example 1 No fracture No fracture No fracture Example 2 No fracture No fracture No fracture Example 3 No fracture No fracture fracture Example 4 No fracture No fracture fracture Example 5 No fracture No fracture fracture Comparative Example 1 No fracture fracture fracture Comparative Example 2 No fracture fracture fracture

[0080] Based on the test data in Example 1, Comparative Examples 1-2, and Tables 1-3, it can be seen that when the step of modifying the glass fiber with an aminosilane coupling agent is omitted or acrylic acid is used instead of carboxylated polyethylene glycol acrylate during the preparation of modified glass fiber, the tensile strength and bending resistance of the photocurable resin are significantly reduced.

[0081] Based on the test data in Examples 1 and 3-4 and Tables 1-3, it can be seen that the degree of polymerization of polyethylene glycol in carboxylated polyethylene glycol acrylate is preferably controlled within the range of 30-40, which is beneficial to further improve the dispersibility of glass fiber in resin and can further improve the tensile strength and bending resistance of the material.

[0082] Based on the test data in Examples 1 and 5 and Tables 1-3, it can be seen that controlling the aminosilane coupling agent and carboxylated polyethylene glycol acrylate in the modified glass fiber within a suitable grafting range is beneficial to further improve the dispersibility of the glass fiber in the resin, and can further enhance the tensile strength and bending resistance of the material.

[0083] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this specific embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A glass fiber reinforced photocurable epoxy acrylate, characterized in that: The product comprises 60-70 parts by weight of difunctional epoxy acrylate, 20-25 parts by weight of reactive diluent, 5.8-6.4 parts by weight of modified glass fiber, 3-4 parts by weight of photoinitiator, and 0.5-1 parts by weight of a first polymerization inhibitor. The modified glass fiber is first modified with an aminosilane coupling agent to obtain aminosilane coupling agent modified glass fiber, and then reacted with carboxyl polyethylene glycol acrylate under the action of a second polymerization inhibitor. The difunctional epoxy acrylate is a bifunctional bisphenol A epoxy acrylate resin.

2. The glass fiber reinforced photocurable epoxy acrylate according to claim 1, characterized in that: The structural formula of the carboxyl-based polyethylene glycol acrylate is as follows: ； Where n takes values ​​between 30 and 40.

3. The glass fiber reinforced photocurable epoxy acrylate according to claim 1, characterized in that: The weight ratio of the aminosilane coupling agent to the glass fiber is (0.04-0.05):

10.

4. The glass fiber reinforced photocurable epoxy acrylate according to claim 1, characterized in that... The weight ratio of the modified glass fiber with carboxylated polyethylene glycol acrylate, the second polymerization inhibitor and the aminosilane coupling agent is (10-15):(0.02-0.03):

10.

5. The glass fiber reinforced photocurable epoxy acrylate according to claim 1, characterized in that: The glass fiber is made of alkali-free chopped glass fiber powder with a length of 100-300μm.

6. A glass fiber reinforced photocurable epoxy acrylate according to any one of claims 1-5, characterized in that: The reactive diluent is at least one of tripropylene glycol diacrylate, polyethylene glycol diacrylate, and polypropylene glycol diacrylate.

7. A glass fiber reinforced photocurable epoxy acrylate according to any one of claims 1-5, characterized in that: The photoinitiator is at least one of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 1-hydroxycyclohexylphenyl ketone.

8. A glass fiber reinforced photocurable epoxy acrylate according to any one of claims 1-5, characterized in that: The first polymerization inhibitor is at least one of p-hydroxyanisole and 2,6-di-tert-butyl-p-cresol.

9. A method for preparing a glass fiber reinforced photocurable epoxy acrylate as described in any one of claims 1-8, characterized in that, Includes the following steps: Preparation of modified glass fibers: Glass fibers were dispersed in an aqueous ethanol solution, an aminosilane coupling agent was added, the mixture was heated to 50-80℃ and stirred to react, then filtered, and the filter residue was washed and dried to obtain aminosilane coupling agent modified glass fibers. Aminosilane coupling agent glass fiber is uniformly dispersed in N,N-dimethylformamide, and then carboxylated polyethylene glycol acrylate and a second polymerization inhibitor are added under nitrogen protection. The mixture is then heated to 140-150℃ to react, and then filtered and washed to obtain modified glass fiber. Preparation of UV-cured epoxy acrylate: Modified glass fiber, photoinitiator, and first polymerization inhibitor are uniformly dispersed in an active diluent, and then difunctional epoxy acrylate is added and mixed evenly to obtain a photocurable epoxy acrylate composition.

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