CN118459935A - A kind of organosilicon modified epoxy resin reinforced material and its preparation method and application - Google Patents

Abstract

The present invention relates to an organosilicon-modified epoxy resin reinforced material and a preparation method and application thereof, comprising the following components: an aromatic epoxy resin, an organosilicon-modified epoxy resin, a curing agent A, a curing agent B, an accelerator, a thixotropic agent, and an anti-aging agent. The present invention generates an oxazolidinone structure with higher heat resistance during the reaction process by adding an organosilicon-modified epoxy resin, thereby 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 is also greatly improved, and has good market application prospects.

Description

A kind of organosilicon modified epoxy resin reinforced material and its preparation method and application

Technical Field

The invention belongs to the technical field of polymer materials, and particularly relates to an organosilicon-modified epoxy resin reinforced material and a preparation method and application thereof.

Background Art

Lightweight modules 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, the current requirement for high module efficiency places higher requirements on module size.

Usually, the power of a single lightweight flexible component is between 200 and 420 W, while the latest single lightweight flexible component exceeds 450 W, or even higher than 500 W. The number of bypass diodes in larger components remains unchanged, and the higher the power of the component, the higher the temperature under the hot spot, reaching a maximum temperature of over 165°C under extreme test conditions. Larger-sized lightweight components put forward new requirements for the heat resistance and thermal oxidation aging of packaging materials.

CN 107100008 A discloses a resin-based composite film material and a preparation method thereof, and a solar cell module. Resin powder is applied to glass fiber cloth, heated for semi-prepreg, and the resin is solidified synchronously by utilizing the temperature during encapsulation. The composite material has low cost and is easy to produce. However, due to the limited prepreg time and temperature, the heat resistance of the material after molding is poor, and the fiber and interface are also poor, which easily leads to de-felting during high temperature and high humidity testing.

CN 110832138 A discloses a composite packaging material for photovoltaic modules and a resin matrix using acrylate and polyester powder resin as a reinforcing layer in the composite packaging material. The glass transition temperature of these two types of resins is below 100°C and they soften at high temperatures, so the heat resistance of the material is poor.

Summary of the invention

The technical problem to be solved by the present invention is to provide an organosilicon-modified epoxy resin reinforced material, a preparation method and an application thereof. The reinforced material generates an oxazolidinone structure with higher heat resistance during the reaction process by adding an organosilicon-modified epoxy resin, thereby 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 is also greatly improved, which has good market application prospects.

The present invention provides an organosilicon-modified epoxy resin reinforced material, which comprises the following components in parts by weight:

Aromatic epoxy resin 40-80 parts;

5-15 parts of silicone modified epoxy resin;

Curing agent A 20-30 parts;

Curing agent B 2-5 parts;

Accelerator 0.5-1 part;

Thixotropic agent 0.5-1.5 parts;

Anti-aging agent 0.5-2 parts;

The organosilicon-modified epoxy resin is obtained by reacting the following components in parts by weight:

Acrylate monomer 40-50 parts;

Containing double bonds and epoxy resin monomers 30-40 parts;

1-5 parts of double bond-containing organosilane;

Hydroxy acrylic acid 20-30 parts.

Preferably, the aromatic epoxy resin is one or both of bisphenol A polyether epoxy resin and bisphenol F epoxy resin.

Preferably, the acrylic acid ester monomer is one or more of methyl methacrylate, ethyl methacrylate, and butyl methacrylate.

Preferably, the double bond-containing epoxy resin monomer is one or more of allyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 1,2-epoxy-4-vinylcyclohexane, and 4-vinylepoxycyclohexane ester. More preferably, the double bond-containing epoxy resin monomer is allyl glycidyl ether.

Preferably, the double bond-containing organosilane is one or both of 3-methacryloxypropyltrimethoxysilane and vinyltriethoxysilane.

Preferably, the hydroxy acrylic acid is one or more of ethoxylated trimethylolpropane triacrylate, hydroxyethyl acrylate, and tripropylene glycol triacrylate.

Preferably, 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. More preferably, the curing agent A is diaminodiphenyl sulfone.

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. More preferably, the curing agent B is a phenol-type blocked isocyanate curing agent.

Preferably, the accelerator is one or more of an organic urea accelerator and a boron amine complex accelerator. More preferably, the accelerator is a boron trifluoride monoethylamine salt accelerator.

Preferably, the thixotropic agent is fumed silica.

Preferably, 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.

The present invention also provides a method for preparing an organosilicon-modified epoxy resin reinforced material, 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.

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

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

The present invention also provides an application of an organosilicon-modified epoxy resin reinforced material in a lightweight flexible photovoltaic module.

In the present invention, curing agent A mainly reacts with curing agent B to generate primary amines at a temperature below 140°C. By controlling the equivalent ratio of the polyamine to be less than 1 and the molecular weight between crosslinking points to be less than 500, after the primary amine groups react, as the temperature continues to rise, the terminal hydroxyl groups after the curing agent reacts with the epoxy resin react to reduce the hydroxyl ratio and increase the degree of crosslinking. During the reaction, the silicone-modified epoxy resin generates an oxazolidinone epoxy resin with higher heat resistance, and its heat resistance meets the RTI 130°C, which is much higher than the 110°C 1500V system voltage requirement of IEC62788, and can be used for flexible photovoltaic modules with a higher power of more than 450W.

Beneficial Effects

(1) The present invention adds silicone-modified epoxy resin to generate a more heat-resistant oxazolidinone structure during the reaction process, thereby 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 is also greatly improved, which has good market application prospects.

(2) The present invention increases the activity of the hydroxyl group after the first step of the cross-linking reaction between the amine curing agent and the epoxy resin by adding an aromatic epoxy resin.

DETAILED DESCRIPTION

The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended 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 fall within the scope limited by the appended claims of the application equally.

Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

Table 1 Formula of silicone-modified epoxy resin (parts by weight)

raw material Brand 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 Cathay Chemical 30 30 30 30 30 Vinyltriethoxysilane GeniosilGF56 WACKER 1 3 5 1 3-Methacryloyloxypropyltrimethoxysilane TCI 1 Hydroxyethyl acrylate Commercially available 20 20 20 20 20

The preparation method of organosilicon-modified epoxy resin comprises the following steps:

1. A 10L reactor was equipped with a reflux condenser, a constant pressure funnel, and a nitrogen inlet.

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

3. Add 0.3 g of azobisisobutyronitrile to the above system and titrate a 5wt% azobisisobutyronitrile solution (solvent is xylene) and stir at a constant temperature of 60°C for 10 min to 20 min.

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

5. The epoxy equivalent in the resin was determined using the hydrochloric acid acetone method and was between 600 and 700 g/eq.

Table 2 Reinforcement material formula (parts by weight)

Reinforcement materials include the following steps:

Aromatic epoxy resin, silicone modified epoxy resin, curing agent A, curing agent B, accelerator, thixotropic agent and anti-aging agent are mixed according to a proportion, the epoxy mole number: _NH2 mole number is controlled between 1.1 and 1.2, and the mixture is reacted at 70°C for 20 minutes to obtain a silicone modified epoxy resin reinforced material.

Table 3 Performance test results (I)

Table 4 Performance test results (II)

From the test results of Table 3 and Table 4, it can be seen that the Tg point of the materials prepared in Examples 1-8 reaches above 130°C, the RTI value reaches 130°C, and at the same time ΔTR <4.2%, ΔYI <1.5, the heat resistance and moisture and heat resistance are both good, and have good comprehensive performance. From Comparative Example 1, it can be seen that when ordinary epoxy resin is used instead of silicone-modified epoxy resin, the light transmittance, heat resistance and moisture and heat resistance of the obtained material are all reduced, 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 curing agent A uses other types of curing agents, the heat resistance and moisture and heat resistance of the obtained material are all reduced, the Tg point is only 108°C, the RTI value is only 115°C, ΔTR=5.8%, ΔYI=5.5. It can be seen from Comparative Example 3 that when curing agent B is not added, the heat resistance and moisture-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 transmittance is only 81.6%, which cannot meet the use requirements.

Claims (10)

1. An organosilicon modified epoxy resin reinforcing material is characterized in that: the coating comprises the following components in parts by weight:

40-80 parts of aromatic epoxy resin;

5-15 parts of organic silicon modified epoxy resin;

20-30 parts of curing agent A;

2-5 parts of curing agent B;

0.5-1 part of promoter;

0.5-1.5 parts of thixotropic agent;

0.5-2 parts of anti-aging agent;

the organic silicon modified epoxy resin is prepared by reacting the following components in parts by weight:

40-50 parts of acrylate monomer;

30-40 parts of double bond-containing and epoxy resin monomers;

1-5 parts of organosilane containing double bonds;

20-30 parts of hydroxy acrylic acid.

2. The silicone-modified epoxy resin reinforcing material according to claim 1, wherein: the aromatic epoxy resin is one or two of bisphenol A polyether type epoxy resin and bisphenol F type epoxy resin.

3. The silicone-modified epoxy resin reinforcing material according to claim 1, wherein: the acrylic ester monomer is one or more of methyl methacrylate, ethyl methacrylate and butyl methacrylate; the double bond-containing epoxy resin monomer is one or more of allyl glycidyl ether, 3, 4-epoxy cyclohexyl methyl acrylate, 1, 2-epoxy-4-vinyl cyclohexane and 4-vinyl epoxy cyclohexane ester; the double bond-containing organosilane is one or two of 3-methacryloxypropyl trimethoxy silane and vinyl triethoxy silane; the hydroxy acrylic acid is one or more of ethoxylated trimethylolpropane triacrylate, hydroxyethyl acrylate and tripropylene glycol triacrylate.

4. The silicone-modified epoxy resin reinforcing material according to claim 1, wherein: the curing agent A is one of m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, a mixture of 60-70 wt% of m-phenylenediamine and 30-40 wt% of 4, 4-dimethyldiphenyldisulfone; the curing agent B is a closed isocyanate curing agent, and the adopted sealing agent is one or more of diethyl malonate, methyl ethyl ketoxime, acetone oxime, epsilon-caprolactam and phenol.

5. The silicone-modified epoxy resin reinforcing material according to claim 1, wherein: the accelerator is one or more of organic urea accelerators and boron amine complex accelerators.

6. The silicone-modified epoxy resin reinforcing material according to claim 1, wherein: the thixotropic agent is fumed silica.

7. The silicone-modified epoxy resin reinforcing material according to claim 1, wherein: the anti-aging agent is one or more of hindered phenol antioxidant, hindered amine antioxidant, benzotriazole ultraviolet absorbent and benzophenone ultraviolet absorbent.

8. A method of preparing the silicone modified epoxy resin reinforcing material of any one of claims 1-7, comprising the steps of:

(1) Mixing acrylate monomer, double bond-containing epoxy resin monomer, double bond-containing organosilane and hydroxy acrylic acid according to a proportion, adding a solvent, stirring and dissolving; then adding an initiator, stirring at the constant temperature of 60-80 ℃ for 10-20 min, and reacting at the temperature of 80-100 ℃ for 30-40min to obtain the organosilicon modified epoxy resin; wherein the addition amount of the initiator is 0.1-1 wt% of the total mass of the reaction system;

(2) Mixing the aromatic epoxy resin, the organosilicon modified epoxy resin, the curing agent A, the curing agent B, the accelerator, the thixotropic agent and the anti-aging agent according to the proportion, and controlling the mole number of epoxy: NH ₂ mol number=1.1-1.2, and reacting for 20-30min at 60-70 ℃ to obtain the organosilicon modified epoxy resin reinforcing material.

9. The method of manufacturing according to claim 8, wherein: the solvent in the step (1) is dimethylbenzene, and the addition amount is 1-2L/100g of the total mass of the reaction system; the initiator is one or more of azodiisobutyronitrile, benzoyl peroxide and dicumyl peroxide.

10. Use of the silicone modified epoxy resin reinforced material according to any one of claims 1-7 in lightweight flexible photovoltaic modules.