An organosilicon-modified epoxy resin reinforcing material, its preparation method and application

Abstract

The present invention relates to a silicone-modified epoxy resin reinforcing material, its preparation method and application, which include the following components: aromatic epoxy resin, silicone-modified epoxy resin, curing agent A, curing agent B, accelerator, thixotropic agent, anti-aging agent. By adding the silicone-modified epoxy resin, the present invention generates an oxazolidinone structure with higher heat resistance during the reaction process, improving the heat resistance of the material. The Tg point of the material reaches above 130°C, the RTI value reaches 130°C, and the damp heat resistance is also greatly improved, having good market application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a silicone-modified epoxy resin reinforcing material, a preparation method thereof, and an application thereof. Background Art

[0002] Lightweight components are widely used in weight-restricted building roofs because of their low weight and do not require special installation and frame structures. As an important product category in BAPV, currently under the requirement of high component efficiency, higher requirements are put forward for the size of the components.

[0003] Generally, the power of a single lightweight flexible component is between 200 and 420 W. The latest lightweight flexible component has a single-component power exceeding 450 W, and even higher than 500 W. The number of bypass diodes in larger components remains unchanged. The higher the power of the component, the higher the temperature under hot spot. In extreme test cases, the temperature reaches above 165 °C. Larger-sized lightweight components pose new requirements for the heat resistance and thermal-oxidative aging resistance of the encapsulation material.

[0004] CN 107100008 A discloses a resin-based composite film material, a preparation method thereof, and a solar cell module. Resin powder is coated on a glass fiber cloth and heated for semi-preimpregnation. Using the temperature during encapsulation, the resin is cured synchronously. The composite material has a lower cost and is convenient for production. However, due to the limited preimpregnation time and temperature, the heat resistance of the formed material is poor, and its fibers and interfaces are also poor, which easily leads to felt shedding during high-temperature and high-humidity tests.

[0005] CN 110832138 A discloses a composite encapsulation material for photovoltaic modules and uses acrylate and polyester powder resins as the resin matrix of the reinforcing layer. The glass transition temperatures of these two types of resins are below 100 °C and will soften at high temperatures. Therefore, the heat resistance of the material is poor. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a silicone-modified epoxy resin reinforcing material, a preparation method thereof, and an application thereof. By adding silicone-modified epoxy resin, an oxazolidinone structure with higher heat resistance is generated during the reaction process, improving the heat resistance of the material. The Tg point of the material reaches above 130 °C, the RTI value reaches 130 °C, and the moisture and heat resistance performance is also greatly improved, having good market application prospects.

[0007] The present invention provides a silicone-modified epoxy resin reinforcing material, which comprises the following components in parts by weight:

[0008] Aromatic epoxy resin: 40 - 80 parts;

[0009] Silicone-modified epoxy resin: 5 - 15 parts;

[0010] 20 - 30 parts of curing agent A;

[0011] 2 - 5 parts of curing agent B;

[0012] 0.5 - 1 part of accelerator;

[0013] 0.5 - 1.5 parts of thixotropic agent;

[0014] 0.5 - 2 parts of anti - aging agent;

[0015] Among them, the organosilicon - modified epoxy resin is obtained by reacting the following components according to weight parts:

[0016] 40 - 50 parts of acrylate monomer;

[0017] 30 - 40 parts of double - bond - containing and epoxy resin monomer;

[0018] 1 - 5 parts of double - bond - containing organosilane;

[0019] 20 - 30 parts of hydroxy acrylic acid.

[0020] Preferably, the aromatic epoxy resin is one or two of bisphenol A polyether type epoxy resin and bisphenol F epoxy resin.

[0021] Preferably, the acrylate monomer is one or several of methyl methacrylate, ethyl methacrylate, and butyl methacrylate.

[0022] Preferably, the double - bond - containing and epoxy resin monomer is one or several of allyl glycidyl ether, 3,4 - epoxycyclohexylmethyl methacrylate, 3,4 - epoxycyclohexyl acrylate, 1,2 - epoxy - 4 - vinylcyclohexane, and 4 - vinylcyclohexyl epoxy acrylate. More preferably, the double - bond - containing and epoxy resin monomer is allyl glycidyl ether.

[0023] Preferably, the double - bond - containing organosilane is one or two of 3 - methacryloxypropyltrimethoxysilane and vinyltriethoxysilane.

[0024] Preferably, the hydroxy acrylic acid is one or several of ethoxylated trimethylolpropane triacrylate, hydroxyethyl acrylate, and tripropylene glycol triacrylate.

[0025] Preferably, the curing agent A is one of m - phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m - phenylene diamine, and a mixture of 60wt% - 70wt% m - phenylene diamine and 30wt% - 40wt% 4,4 - dimethyldiphenyl disulfone. More preferably, the curing agent A is diaminodiphenylsulfone.

[0026] The curing agent B is a blocked isocyanate curing agent, and the blocking agent used is one or more of diethyl malonate, methyl ethyl ketoxime, acetone oxime, ε-caprolactam, and phenol. More preferably, the curing agent B is a phenol-type blocked isocyanate curing agent.

[0027] Preferably, the accelerator is one or more of organic urea accelerators and boramine complex accelerators. More preferably, the accelerator is boron trifluoride monoethylamine salt accelerator.

[0028] Preferably, the thixotropic agent is fumed silica.

[0029] Preferably, the anti-aging agent is one or more of hindered phenol antioxidants, hindered amine antioxidants, benzotriazole ultraviolet absorbers, and benzophenone ultraviolet absorbers.

[0030] The present invention also provides a preparation method of an organosilicon-modified epoxy resin reinforcing material, comprising the following steps:

[0031] (1) Mix acrylate monomers, double bond-containing epoxy resin monomers, double bond-containing organosilanes, and hydroxyacrylic acid according to the ratio, add a solvent and stir to dissolve; then add an initiator, first stir at a constant temperature of 60 - 80 °C for 10 min - 20 min, and then react at 80 - 100 °C for 30 - 40 min to obtain an organosilicon-modified epoxy resin; wherein, the addition amount of the initiator is 0.1 wt% - 1 wt% of the total mass of the reaction system;

[0032] (2) Mix aromatic epoxy resin, organosilicon-modified epoxy resin, curing agent A, curing agent B, accelerator, thixotropic agent, and anti-aging agent according to the ratio, control the epoxy molar number: NH 2 molar number = between 1.1 and 1.2, and react at 60 - 70 °C for 20 - 30 min to obtain an organosilicon-modified epoxy resin reinforcing material.

[0033] Preferably, the solvent in step (1) is xylene, and the addition amount is 1 - 2 L / 100 g of the total mass of the reaction system.

[0034] Preferably, the initiator in step (1) is one or more of azobisisobutyronitrile, benzoyl peroxide, and diisopropylbenzene peroxide.

[0035] The present invention also provides an application of the organosilicon-modified epoxy resin reinforcing material in lightweight flexible photovoltaic modules.

[0036] In the present invention, below 140°C, curing agent A mainly reacts with curing agent B to form primary amines. By controlling the equivalent ratio of polyamines <1 and the molecular weight Mc between crosslinking points <500, after the reaction of primary amine groups, as the temperature continues to rise, the curing agent reacts with the terminal hydroxyl groups after reacting with epoxy resin, reducing the hydroxyl group ratio and increasing the crosslinking degree. During the reaction process, organosilicon-modified epoxy resin generates oxazolidinone epoxy resin with higher heat resistance, and its heat resistance meets the requirement of RTI 130°C, which is much higher than the 110°C of IEC62788 for a 1500V system voltage, and can be used for flexible photovoltaic modules with a power of more than 450W.

[0037] Beneficial effects

[0038] (1) By adding organosilicon-modified epoxy resin in the present invention, an oxazolidinone structure with higher heat resistance is generated during the reaction process, improving the heat resistance of the material. The Tg point of the material reaches above 130°C, the RTI value reaches 130°C, and the damp heat resistance performance is also greatly improved, having good market application prospects.

[0039] (2) By adding aromatic epoxy resin in the present invention, the activity of hydroxyl groups after the crosslinking reaction of the first-step amine curing agent and epoxy resin is increased. Specific embodiments

[0040] The following further elaborates the present invention in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0041] The reagents, methods, and equipment used in the present invention are all conventional reagents, methods, and equipment in the technical field, unless otherwise specified.

[0042] Table 1 Formulation of organosilicon-modified epoxy resin (parts by weight)

[0043] Raw materials Grade Source Si-EP-2-A1 Si-EP-2-A2 Si-EP-2-A3 Si-EP-2-A4 Si-EP-2-A5 Methyl methacrylate Commercially available 49 47 45 49 Ethyl methacrylate Commercially available 49 Allyl glycidyl ether Kaisai Chemical Industry 30 30 30 30 30 Vinyltriethoxysilane Geniosil GF56 Wacker 1 3 5 1 3-Methacryloxypropyltrimethoxysilane TCI 1 2-Hydroxyethyl acrylate Commercially available 20 20 20 20 20

[0044] The preparation method of organosilicon-modified epoxy resin includes the following steps:

[0045] 1. A 10L reaction kettle is equipped with a reflux condenser, a constant pressure funnel, and a nitrogen inlet.

[0046] 2. Add raw material components according to parts by weight (total amount is 100g), and add 2L of xylene, and stir to dissolve.

[0047] 3. To the above system, add 0.3 g of azobisisobutyronitrile by mass, and titrate with an azobisisobutyronitrile solution with a concentration of 5 wt% (the solvent is xylene), stir at a constant temperature of 60 °C for 10 min to 20 min.

[0048] 4. Raise the reaction temperature to 90 °C, keep it at a constant temperature for 30 min. After the reaction is completed, rotary evaporate the excess solvent and unreacted allyl glycidyl ether to obtain a viscous liquid.

[0049] 5. Use the hydrochloric acid-acetone method to measure the epoxy equivalent in the resin, which is between 600 and 700 g / eq.

[0050] Table 2 Reinforcing Material Formulation (parts by weight)

[0051]

[0052] The reinforcing material includes the following steps:

[0053] Mix aromatic epoxy resin, silicone-modified epoxy resin, curing agent A, curing agent B, accelerator, thixotropic agent, and anti-aging agent according to the ratio, control the epoxy mole number: NH 2 Mole number = between 1.1 and 1.2, react at 70 °C for 20 min to obtain a silicone-modified epoxy resin reinforcing material.

[0054] Table 3 Performance Test Results (I)

[0055]

[0056] Table 4 Performance Test Results (II)

[0057]

[0058] From the test results in Table 3 and Table 4, it can be seen that the Tg points of the materials prepared in Examples 1-8 reach above 130 °C, the RTI values reach 130 °C, while ΔTR < 4.2% and ΔYI < 1.5. They have good heat resistance and damp heat resistance, and possess good comprehensive properties. From Comparative Example 1, it can be seen that when ordinary epoxy resin instead of silicone-modified epoxy resin is used, the light transmittance, heat resistance and damp heat resistance of the obtained material all decrease. The Tg point is only 120 °C, the RTI value is only 125 °C, ΔTR = 5.2%, ΔYI = 5.1, and the light transmittance is only 80.1%. From Comparative Example 2, it can be seen that when other types of curing agents are used for Curing Agent A, the heat resistance and damp heat resistance of the obtained material both decrease. The Tg point is only 108 °C, the RTI value is only 115 °C, ΔTR = 5.8%, ΔYI = 5.5. From Comparative Example 3, it can be seen that when Curing Agent B is not added, the heat resistance and damp heat resistance of the obtained material are relatively worse. The Tg point is only 122 °C, the RTI value is only 122 °C, ΔTR = 10%, ΔYI = 5.8, and the light transmittance is only 81.6%, which cannot meet the usage requirements.

Claims

1. An organosilicon-modified epoxy resin reinforced material, characterized in that: In parts by weight, it comprises the following components: The curing agent A is one of m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, m-phenylenediamine, and a mixture of 60wt% to 70wt% m-phenylenediamine and 30wt% to 40wt% 4.4-dimethyldiphenyl disulfone; the curing agent B is a blocked isocyanate curing agent, and the blocking agent used is one or more of diethyl malonate, methyl ethyl ketone oxime, acetone oxime, ε-caprolactam, and phenol; The organosilicon-modified epoxy resin is obtained by reacting the following components in parts by weight: The acrylate monomer is one or more of methyl methacrylate, ethyl methacrylate, and butyl methacrylate; the double bond-containing and epoxy resin monomers are one or more of allyl glycidyl ether, 3,4-epoxycyclohexyl methyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 1,2-epoxy-4-vinylcyclohexane; the double bond-containing organosilane is one or two of 3-methacryloxypropyltrimethoxysilane and vinyltriethoxysilane; the hydroxy acrylic acid is one or more of ethoxylated trimethylolpropane triacrylate and hydroxyethyl acrylate.

2. The organosilicon-modified epoxy resin reinforced material according to claim 1, characterized in that: The aromatic epoxy resin is one or both of bisphenol A polyether epoxy resin and bisphenol F epoxy resin.

3. The organosilicon-modified epoxy resin reinforced material according to claim 1, characterized in that: The accelerator is one or more of an organic urea accelerator and a boron amine complex accelerator.

4. The organosilicon-modified epoxy resin reinforced material according to claim 1, characterized in that: The thixotropic agent is fumed silica.

5. The organosilicon-modified epoxy resin reinforced material according to claim 1, characterized in that: The anti-aging agent is one or more of a hindered phenol antioxidant, a hindered amine antioxidant, a benzotriazole ultraviolet absorber, and a benzophenone ultraviolet absorber.

6. A method for preparing the organosilicon-modified epoxy resin reinforced material according to any one of claims 1 to 5, comprising the following steps: (1) Mixing acrylate monomer, double bond-containing and epoxy resin monomer, double bond-containing organosilane, and hydroxy acrylic acid according to a ratio, adding a solvent and stirring to dissolve; then adding an initiator, stirring at a constant temperature of 60-80° C. for 10 min to 20 min, and then reacting at 80-100° C. for 30-40 min to obtain an organosilicon-modified epoxy resin; wherein: The amount of the initiator added is 0.1wt%-1wt% of the total mass of the reaction system; (2) Mix aromatic epoxy resin, silicone modified epoxy resin, curing agent A, curing agent B, accelerator, thixotropic agent and anti-aging agent according to a ratio, control the epoxy mole number: NH2 mole number to be between 1.1 and 1.2, react at 60-70° C. for 20-30 minutes, and obtain a silicone modified epoxy resin reinforced material.

7. The preparation method according to claim 6, characterized in that: The solvent in step (1) is xylene, and the added amount is 1-2 L / 100 g of the total mass of the reaction system; the initiator is one or more of azobisisobutyronitrile, benzoyl peroxide, and diisopropylbenzene peroxide.

8. Use of the organosilicon-modified epoxy resin reinforced material according to any one of claims 1 to 5 in a lightweight flexible photovoltaic module.

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