CN102108185B - Epoxy matrix resin and prepreg and preparation method thereof and device for preparation thereof - Google Patents

Abstract

An epoxy matrix resin, a prepreg, a preparation method thereof, and a device used for preparing the prepreg relate to an epoxy matrix resin, a prepreg, a preparation method thereof, and a device used for preparing the prepreg. Solve the phenomenon that the toughening phase state in the existing epoxy matrix resin cured product is not uniform, or even does not occur phase separation, resulting in poor performance of the epoxy matrix resin cured product, and the preparation method of the existing prepreg is complex and the prepreg The control of the resin content in the medium is relatively inaccurate, and the existing equipment for preparing prepregs has high manufacturing costs. Epoxy matrix resin is made of novolac epoxy resin, bisphenol A epoxy resin, core-shell polymer, curing agent and curing accelerator; epoxy matrix resin and fiber woven cloth are made into prepreg; hot melt method is used An apparatus for producing prepregs produces prepregs. Before and after the resin is cured, the state of the toughening phase does not change, the dispersion is uniform, and the toughening effect is good and stable. The mechanical properties of the composite material obtained by curing the prepreg are good.

Description

Epoxy matrix resin, prepreg, preparation method thereof, and device used for preparing prepreg

technical field

The invention relates to an epoxy matrix resin, a prepreg, a preparation method thereof and a device for preparing the prepreg.

Background technique

Epoxy/glass fiber composite materials have the characteristics of light weight, high strength, large modulus, good corrosion resistance, excellent electrical properties, wide range of raw materials, good craftsmanship, easy processing and molding, high production efficiency, etc., and have strong material designability It has become an irreplaceable important material in the national economy, national defense construction and scientific and technological development, and is one of the most widely used composite materials at present.

Medium-temperature curing epoxy matrix resin has been widely used in glass fiber reinforced composite material prepregs because of its advantages such as low curing temperature, short molding cycle, and meeting storage requirements. However, because the cured product of the untoughened epoxy matrix resin is brittle, the composite material made of it will be destroyed due to the premature failure of the epoxy matrix resin. Therefore, the toughening modification of epoxy matrix resin is particularly important.

Currently, epoxy matrix resins can be toughened by rubber elastomers, thermoplastics, etc. There are also new data showing that the use of hyperbranched polymers to toughen epoxy resins has achieved good results. Regardless of traditional liquid rubber or thermoplastics, their blends with epoxy resins will undergo phase separation during curing. Under normal circumstances, the toughening agent will precipitate out of the blend, and phase separation and curing reactions are competing processes. . Therefore, the aggregated structure and properties of the cured product depend on the curing specification, the nature and amount of the toughener added. Only by strictly controlling these factors can the best toughening effect be achieved.

Prepreg is the intermediate substrate for preparing composite materials, and its quality directly affects the quality of composite components. The production process of prepreg mainly includes solution impregnation method and hot melt method. Compared with the solution method, the advantages of the hot melt method are as follows: ①Prepreg resin content is precisely controlled; ②The volatile matter content is low; ③Environmental protection, no environmental pollution; ④The prepared composite material has good heat and humidity resistance and high production speed. Fast and efficient. Therefore, the hot melt prepreg process is the current development direction of prepreg.

Most of the existing hot-melt prepregs use two production devices: film machine and hot-melt prepreg machine. On the impregnation machine, composite prepreg is performed at a certain temperature, speed and pressure, and the resin content of the prepreg can be controlled by adjusting the thickness of the film; another process is to impregnate the fiber woven cloth with the hot-melt matrix resin under the action of the transmission device, and then Drive to the scraping device to remove excess resin on the fiber woven cloth to control the resin content of the prepreg. The manufacturing cost of the above-mentioned device is high, the production process is complicated, and the control of the resin content of the prepreg is relatively inaccurate.

Contents of the invention

The purpose of the present invention is to solve the phenomenon that the state of the toughening phase in the cured product of the existing epoxy matrix resin is not uniform, or even no phase separation occurs, resulting in poor performance of the cured product of the epoxy matrix resin, which cannot meet the performance requirements of the composite material, and the current The preparation method of the prepreg is complicated, the resin content in the prepreg is controlled inaccurately, and the manufacturing cost of the existing prepreg preparation device is high. The invention provides an epoxy matrix resin, a prepreg and its preparation Method and apparatus used for the preparation of prepregs.

The epoxy matrix resin of the present invention consists of 40 parts by mass of novolac epoxy resin, 60 parts of bisphenol A epoxy resin, 2 to 10 parts of core-shell polymer, 15 to 24 parts of curing agent and 3.0 to 6.0 parts of curing accelerator, the curing agent is a combination of dicyandiamide and 4,4'-diaminodiphenyl sulfone, wherein the mass parts of 4,4'-diaminodiphenyl sulfone and dicyandiamide are respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts; the curing accelerator is organic urea or its derivatives.

The preparation method of the epoxy matrix resin of the present invention is realized through the following steps: 1. Take by weight 40 parts of novolac epoxy resin, 60 parts of bisphenol A epoxy resin, 2 to 10 parts of core-shell polymer, 15-24 parts of curing agent and 3.0-6.0 parts of curing accelerator, the curing agent is a combination of dicyandiamide and 4,4'-diaminodiphenylsulfone, wherein 4,4'-diaminodiphenylsulfone The mass parts of phenyl sulfone and dicyandiamide are respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts, and the curing accelerator is an organic urea or a derivative thereof; 2. Mix 40 parts of novolac epoxy resin, 60 parts of bisphenol A epoxy resin and 2 to 10 parts of core-shell polymer weighed in step 1 into the container, and then heat it to 150 ° C under stirring conditions, and then add The 4,4'-diaminodiphenylsulfone curing agent weighed in step 1, continue to stir and heat to 150°C, keep it warm for 3 to 5 minutes, and then cool to room temperature to obtain B-stage resin; 3. Take 30 parts of B-stage resin obtained in step 2 Put the first-grade resin into the three-roll mill, then add the dicyandiamide curing agent weighed in step one and 3.0 to 6.0 parts of curing accelerator weighed in step one, and then grind in the three-roll mill for 3 to 6 and then add the remaining B-stage resin prepared in step 2, and continue grinding in the three-roll mill for 3 to 6 times to obtain the epoxy matrix resin; the temperature of the three-roll mill in step 3 is maintained at 60-60 70°C.

The number of parts in the 30 parts of the B-stage resin obtained in step two described in the step three of the preparation method of epoxy matrix resin of the present invention is the same as the standard of the number of parts used when weighing in step one.

The prepreg of the present invention is made of epoxy matrix resin and fiber woven cloth, and the mass content of volatile matter is controlled to be less than 1%, wherein the mass content of epoxy matrix resin is 37% to 43%, and the epoxy matrix resin is as follows: Parts by mass are made of 40 parts of novolac epoxy resin, 60 parts of bisphenol A epoxy resin, 2 to 10 parts of core-shell polymer, 15 to 24 parts of curing agent, and 3.0 to 6.0 parts of curing accelerator. Described curing agent is the compound curing agent of dicyandiamide and 4,4'-diaminodiphenylsulfone, wherein the mass parts of 4,4'-diaminodiphenylsulfone and dicyandiamide are 18 parts and 6 parts, 14 parts respectively part and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts, the curing accelerator is organic urea or its derivatives.

The preparation method of prepreg of the present invention is realized through the following steps: one, prepare epoxy base resin: a, take by mass parts 40 parts of novolak type epoxy resins, 60 parts of bisphenol A epoxy resins, 2～ 10 parts of core-shell polymer, 15-24 parts of curing agent, 3.0-6.0 parts of curing accelerator, the curing agent is a combined curing agent of dicyandiamide and 4,4'-diaminodiphenyl sulfone, of which 4 , the mass parts of 4'-diaminodiphenyl sulfone and dicyandiamide are respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts, and the curing accelerator is organic Ureas or derivatives thereof; b, 40 parts of novolac epoxy resins, 60 parts of bisphenol A epoxy resins and 2 to 10 parts of core-shell polymers weighed in step 1 are mixed and added to the container, and then mixed under stirring conditions Heat to 150°C, then add the 4,4'-diaminodiphenylsulfone curing agent weighed in step 1, continue to stir and heat to 150°C, keep warm for 3-5min, then cool to room temperature to obtain B-stage resin; c, take Put 30 parts of the B-stage resin obtained in step 2 into a three-roll mill, then add the dicyandiamide curing agent weighed in step one and 3.0 to 6.0 parts of curing accelerator, then grind in a three-roll mill for 3 ~ 6 times, then add the remaining B-stage resin prepared in step 2, and continue to grind 3 ~ 6 times in the three-roll mill to obtain epoxy matrix resin; the temperature of the three-roll mill described in step 3 is kept at 60～70℃;

2. Preparation of prepreg: a. Hang the single-sided release paper on the single-sided release paper winding roller 1, the middle roller 5 and the single-sided release paper winding roller 4 in turn, so that the single-sided release paper The paper winding roller 1, the intermediate roller 5 and the single-sided release paper take-up and winding roller 4 form a transmission connection, and then the double-sided release paper is hung on the double-sided release paper winding roller 2, the middle roller in turn 5 and the product winding roller 3, make the double-sided release paper winding roller 2, the middle roller 5 and the product winding roller 3 form a transmission connection, and then set the fiber woven cloth to the single-sided release paper Between the single-sided release paper and the double-sided release paper between the paper winding roller 1 and the double-sided release paper winding roller 2, the single-sided release paper is in contact with the middle roller 5, and then the single-sided release paper is in contact with the middle roller Preheat the roll 1 of the paper winding roll and the winding roll 2 of the double-sided release paper to 75-85°C; b. Pour the epoxy matrix resin prepared in step 1 into the winding roll 1 of the single-side release paper and the fiber weaving In the "V-shaped" space formed by the cloth, the device is then activated to make the fiber woven cloth and epoxy matrix resin pass through the gap between the single-sided release paper winding roller 1 and the double-sided release paper winding roller 2 to obtain two The prepregs with single-sided release paper and double-sided release paper are attached to the sides respectively, and the distance between the winding roller shaft 1 of the single-sided release paper and the winding roller shaft 2 of the double-sided release paper is controlled to be 0.1-2mm , the line speed of the double-sided release paper winding roller 2 is 100-300m/h, and the temperature of the epoxy matrix resin is 75-85°C; c, under the action of the single-sided release paper winding winding roller 4, the The single-sided release paper is peeled off, and at the same time, the product winding winding roller 3 winds up the prepreg with double-sided release paper attached to one side, and the preparation of the prepreg is completed.

The device used in the preparation of prepregs of the present invention, the device includes a single-sided release paper winding roller, a double-sided release paper winding roller, a product winding winding roller, and a single-sided release paper winding winding roller , intermediate roller shaft, third chain drive, first shaft, first chain drive, second shaft, second chain drive and first gear drive, second gear drive, third shaft, single-sided Model paper winding feed roller shaft, double-sided release paper winding feed roller shaft, fourth chain transmission mechanism and frame, the first shaft is connected to the second shaft through the first chain transmission mechanism, and the second shaft passes through the second The chain transmission mechanism is connected to the double-sided release paper winding roller shaft, and the double-sided release paper winding roller shaft is connected to the single-sided release paper winding roller shaft through the first gear transmission mechanism, and the single-sided release paper winding roller shaft passes through The single-sided release paper is connected to the single-sided release paper winding feed roller shaft transmission, and the double-sided release paper winding roller shaft is connected to the double-sided release paper winding feed roller shaft through the double-sided release paper. The first shaft The third shaft is connected with the third shaft through the third chain transmission mechanism, the third shaft is connected with the product winding roller shaft through the second gear transmission mechanism, and the third shaft is wound with the single-sided release paper through the fourth chain transmission mechanism Roller transmission connection, characterized in that the device also includes a fiber woven cloth winding roller shaft, a spring and an adjusting screw, and the fiber woven cloth winding roller shaft is set on the single-sided release paper winding roller shaft 1 and the double-sided release paper winding roller shaft. In the gap between the paper winding rollers, the fiber woven cloth winding roller is connected to the double-sided release paper winding roller through the fiber woven cloth, and the double-sided release paper winding roller passes the prepreg molding product and the intermediate roller Shaft transmission connection, the intermediate roller shaft is connected with the winding roller shaft of the product through the prepreg molding product, the intermediate roller shaft is connected by single-sided release paper and single-sided release paper winding roller shaft transmission connection, single-sided release paper A spring is arranged between the shaft end of the paper winding roller shaft and the double-sided release paper winding roller shaft. Double-sided release paper winding roller, product winding winding roller, single-sided release paper winding winding roller, intermediate roller, first shaft, second shaft, third shaft, single-sided release paper winding input The material roll shaft, the double-sided release paper winding feed roll shaft and the fiber woven cloth winding roll shaft are all mounted on the frame.

In the device of the present invention, the product winding winding roller shaft, the single-sided release paper winding winding roller shaft, the fiber woven cloth winding roller shaft, the single-sided release paper winding feeding roller shaft and the double-sided releasing paper winding feeding roller The shafts are equipped with magnetic powder clutches.

In the device of the present invention, the single-sided release paper winding roller shaft and the double-sided release paper winding roller shaft are provided with closed cavities filled with circulating heating medium, and the two closed cavities are connected through pipelines.

The device of the present invention also includes two baffles. The two ends of the single-sided release paper winding roller shaft and the double-sided release paper winding roller shaft are respectively provided with a baffle board for preventing the matrix resin from overflowing.

Bisphenol A epoxy resin described in the present invention is E-51 epoxy resin, E-44 epoxy resin or E-20 epoxy resin; Described novolak type epoxy resin is F-44 novolak type epoxy resin, F-48 phenolic epoxy resin or F-51 phenolic epoxy resin. The core-shell polymer uses polybutadiene rubber, styrene-butadiene rubber or polymethylsiloxane as the soft core, and polymethyl methacrylate as the hard shell.

The epoxy matrix resin of the present invention has a glass transition temperature of 133-138°C, an impact strength of 10-22KJ/m ² , and a tensile strength of 65-85MPa when cured at 120°C for 2-3 hours. The tensile modulus is 3.0-3.6GPa, the elongation at break is 2.6-4.6%, the bending strength is 100-140MPa, and the bending modulus is 2.6-3.6GPa. Before and after curing, the toughening phase state does not change, the dispersion state is uniform, and the toughening effect is good and stable.

The prepreg of the invention has good stability, and the gelation time under the condition of 120 DEG C is 9-20 minutes. The preparation method adopts the hot-melt method to manufacture the prepreg process. The fiber woven cloth is passed through the impregnating roller under the protection of the release paper, and the hot-melt matrix resin is impregnated with the fiber woven cloth under the action of its own weight and the pressure of the impregnating roller to control the resin content. The single-layer prepreg is formed by automatic winding, and the production process is simple.

The at least three-layer prepregs obtained by superimposing the prepregs prepared in the present invention are cured at 120°C for 2 to 3 hours by using an autoclave process to obtain a composite material laminate, wherein the prepregs The number of layers depends on the specific situation. The tensile strength of the obtained composite laminate is 500-600MPa, the tensile modulus is 22-26GPa; the bending strength is 700-800MPa, the bending modulus is 24-28GPa; the layer shear strength is 72-82MPa, and the mechanical properties are good .

The present invention has the following advantages:

1. The present invention adopts core-shell polymer to replace traditional rubber and thermoplastic resin (TP) to toughen epoxy matrix resin. The results prove that after the pre-designed core-shell polymer particles are blended with the modified resin, its composition, shape, size and distribution in the resin are unchanged before and after curing, that is, it has nothing to do with the curing process. Using core-shell polymers to toughen epoxy resins, the toughness, tensile strength, and flexural strength of epoxy matrix resins and composite laminates obtained have been greatly improved, while Tg and modulus have not decreased significantly.

2. The prepreg of the present invention adopts a hot-melt one-step process. Compared with the solvent method, it has low volatile matter content, environmental protection, and no environmental pollution; compared with the hot-melt adhesive film transfer method (the matrix resin is first rolled into a film) shape, and then impregnated with fiber woven cloth), which has higher work efficiency and lower manufacturing cost.

3. The prepreg prepared by the present invention has the characteristics of stability, can be stored for 3 months under normal conditions (25°C), and can be stored for 6 months below -18°C.

4. The device for preparing prepreg of the present invention completes the impregnation process of epoxy matrix resin and fiber all over woven cloth in one step. Compared with the existing hot melt method prepreg production device, the manufacturing cost of equipment and device is lower, and the production process is more advanced. Simplicity, higher production efficiency, and more precise control of prepreg resin content.

Description of drawings

Fig. 1 is the device used in the preparation of prepreg in the present invention. Fig. 2 is a top view at point A in Fig. 1 .

Detailed ways

The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

Specific embodiment one: The epoxy matrix resin of this embodiment consists of 40 parts by mass of novolac epoxy resin, 60 parts of bisphenol A epoxy resin, 2 to 10 parts of core-shell polymer, and 15 to 24 parts of curing agent and 3.0 to 6.0 parts of curing accelerator, wherein the curing agent is a combination of dicyandiamide and 4,4'-diaminodiphenyl sulfone, wherein 4,4'-diaminodiphenyl sulfone and bis The mass parts of cyanamide are respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts; the curing accelerator is organic urea or its derivatives.

The core-shell polymer according to this embodiment has a particle diameter of 100 to 300 nm. The core-shell polymer can be a commercially available product or can be prepared by an existing published preparation method.

Carry out performance test to the cured product of the epoxy matrix resin of the present embodiment cured 2～3 hours under the condition of 120 ℃, test method and parameter are as follows: 1, adopt DMA method (dynamic mechanical analysis method) to measure glass transition temperature, adopt three Point bending loading mode, spline size (18±0.5mm)×(5±0.2mm)×(1.5±0.2mm), frequency 1Hz, heating rate 5°C/min; 2. According to GB/T2568 resin casting body stretching Performance test method to test tensile strength, tensile elastic modulus and elongation; 3. Test bending strength and flexural modulus according to GB/T2570 resin casting body bending performance test method; 4. According to GB/T2571 resin casting body impact test The method is to test the impact strength. The size of the impact strength sample is 80mm±2mm in length, 10mm±0.5mm in width and 4±0.2mm in thickness.

The test results are: the glass transition temperature of the cured product of the epoxy matrix resin in this embodiment (curing conditions: 2-3 hours at 120°C) is 133-138°C, and the impact strength is 10-22KJ/m ² , The tensile strength is 65-85MPa, the tensile modulus is 3.0-3.6GPa, the elongation at break is 2.6-4.6%, the bending strength is 100-140MPa, and the bending modulus is 2.6-3.6GPa. The epoxy matrix resin of this embodiment has good performance.

Specific embodiment two: the difference between this embodiment and specific embodiment one is that the epoxy matrix resin consists of 40 parts by mass of novolac epoxy resin, 60 parts of bisphenol A epoxy resin, 3 to 8 parts of core-shell polymer, 18-22 parts of curing agent and 4.0-5.0 parts of curing accelerator. Other parameters are the same as in the first embodiment.

In this embodiment, it is more preferable that the epoxy matrix resin consists of 40 parts of novolac epoxy resin, 60 parts of bisphenol A epoxy resin, 5 parts of core-shell polymer, 24 parts of curing agent and 5.0 parts of curing agent by mass parts. Accelerators are made.

Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that the core-shell polymer uses polybutadiene rubber, styrene-butadiene rubber or polymethylsiloxane as the soft core, and polymethylsiloxane as the soft core. Methyl acrylate is hard shell. Other parameters are the same as in the first embodiment.

Embodiment 4: The difference between this embodiment and Embodiment 1, 2 or 3 is that the epoxy value of the novolac epoxy resin is 0.42-0.54, and the epoxy value of the bisphenol A epoxy resin is 0.41-0.56 . Other parameters are the same as those in Embodiment 1, 2 or 3.

Embodiment 5: The difference between this embodiment and one of Embodiments 1 to 4 is that the curing accelerator is N, N'-dimethyldiphenylurea, N, N'-diethyldiphenylurea , N-p-chlorophenyl-N, N'-dimethylurea, 3-phenyl 1,1-dimethylurea, 3-p-chlorophenyl 1,1-dimethylurea (chlorourea) or Thiourea. Other parameters are the same as one of the specific embodiments 1 to 4.

Specific embodiment six: this embodiment is the preparation method of epoxy matrix resin described in specific embodiment one, and the preparation method of epoxy matrix resin is realized through the following steps: one, take by mass parts 40 parts of phenolic rings Oxygen resin, 60 parts of bisphenol A epoxy resin, 2 to 10 parts of core-shell polymer, 15 to 24 parts of curing agent and 3.0 to 6.0 parts of curing accelerator, wherein the curing agent is dicyandiamide and 4, A complex curing agent for 4'-diaminodiphenylsulfone, wherein the mass parts of 4,4'-diaminodiphenylsulfone and dicyandiamide are 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts respectively , or 6 parts and 9 parts, the curing accelerator is organic ureas or derivatives thereof; 2, 40 parts of novolac epoxy resins, 60 parts of bisphenol A epoxy resins and 2 to 10 parts of bisphenol A epoxy resins taken by step 1 Parts of core-shell polymers were mixed and added to the container, and then heated to 150°C under stirring conditions, and then the 4,4'-diaminodiphenylsulfone curing agent weighed in step 1 was added, continued to stir and heated to 150°C, and kept warm for 3 ~5min, then cooled to room temperature to obtain B-stage resin; 3. Take 30 parts of B-stage resin obtained in step 2 and put it into a three-roll mill, and then add the dicyandiamide curing agent weighed in step 1 and weighed in step 1. Take 3.0-6.0 parts of the curing accelerator, and then grind it in the three-roll mill for 3-6 times, then add the remaining B-stage resin prepared in step 2, and continue to grind it in the three-roll mill for 3-6 times , to obtain an epoxy matrix resin; the temperature of the three-roll mill described in step 3 is maintained at 60-70°C.

The preparation method of this embodiment is simple and easy to operate. The core-shell polymer described in step 1 can be a commercially available product or be prepared by an existing published preparation method. The number of parts in the 30 parts of the B-stage resin obtained in step 2 described in step 3 of this embodiment is the same as that used when weighing in step 1.

Using the performance test method and parameters of epoxy resin curing as described in the specific embodiment 1, the cured product of the epoxy matrix resin prepared in this embodiment (curing conditions: curing for 2 to 3 hours at 120°C) was tested, and the obtained The glass transition temperature is 133-138°C, the impact strength is 10-22KJ/m ² , the tensile strength is 65-85MPa, the tensile modulus is 3.0-3.6GPa, the elongation at break is 2.6-4.6%, and the bending strength 100~140MPa, flexural modulus 2.6~3.6GPa. The epoxy matrix resin of this embodiment has good performance.

Embodiment 7: The difference between this embodiment and Embodiment 6 is that in step 1, 40 parts by mass of novolac epoxy resin, 60 parts of bisphenol A epoxy resin, 3 to 8 parts of core-shell polymer, 18-22 parts of curing agent and 4.0-5.0 parts of curing accelerator. Other parameters are the same as those in Embodiment 6.

More preferably in this embodiment, in step 1, take by weight 40 parts of novolac epoxy resins, 60 parts of bisphenol A epoxy resins, 5 parts of core-shell polymers, 24 parts of curing agents and 5.0 parts of curing accelerator.

Embodiment 8: The difference between this embodiment and Embodiment 6 or 7 is that the core-shell polymer described in step 1 uses polybutadiene rubber, styrene-butadiene rubber or polymethylsiloxane as the soft core, and Polymethylmethacrylate is the hard shell. Other parameters are the same as those in Embodiment 6 or 7.

Specific embodiment nine: the difference between this embodiment and specific embodiment six, seven or eight is that the epoxy value of the novolac epoxy resin described in step one is 0.42 to 0.54, and the epoxy value of the bisphenol A epoxy resin is 0.41～0.56. Other parameters are the same as in Embodiment 6, 7 or 8.

Embodiment 10: This embodiment differs from Embodiment 6 to Embodiment 9 in that the curing accelerator described in step 1 is N, N'-dimethyldiphenylurea, N, N'-diethyl Diphenylurea, N-p-chlorophenyl-N, N'-dimethylurea, 3-phenyl 1,1-dimethylurea, 3-p-chlorophenyl 1,1-dimethylurea ( chlorourea) or thiourea. Other parameters are the same as one of the sixth to ninth specific embodiments.

Embodiment 11: This embodiment is a prepreg, which is made of epoxy matrix resin and fiber woven cloth, and the mass content of volatile matter is controlled to be less than 1%, wherein the mass content of epoxy matrix resin is 37% %～43%, the epoxy matrix resin consists of 40 parts by mass of novolac epoxy resin, 60 parts of bisphenol A epoxy resin, 2～10 parts of core-shell polymer, 15～24 parts of curing agent and 3.0～6.0 parts Parts of curing accelerator, the curing agent is a combination of dicyandiamide and 4,4'-diaminodiphenyl sulfone curing agent, wherein the mass parts of 4,4'-diaminodiphenyl sulfone and dicyandiamide 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts respectively, and the curing accelerator is an organic urea or a derivative thereof.

The core-shell polymer described in this embodiment can be a commercially available product or be prepared by an existing published preparation method. The core-shell polymer uses polybutadiene rubber, styrene-butadiene rubber or polymethylsiloxane as the soft core, and polymethyl methacrylate as the hard shell.

The performance of the prepreg in this embodiment is stable, and it can be stored for 3 months under normal conditions (25°C), and can be stored for 6 months below -18°C.

In this embodiment, the volatile content of the prepreg is measured according to "HB7736.4 Test method for physical properties of composite material premix - Part 4: Determination of volatile content", and the mass content of the volatile content in the prepreg is less than 1%.

In this embodiment, the resin content of the prepreg is measured according to "HB 7736.5 Test Method for Physical Properties of Composite Prepreg Part 5: Determination of Resin Content", and the mass content of the epoxy matrix resin in the prepreg is obtained to be 37% to 43%. %.

In this embodiment, the gelation time of the prepreg is measured according to "HB 7736.7 Test Method for Physical Properties of Prepregs of Composite Materials Part 7: Determination of Gelation Time", and the gelation time of the prepreg at 120°C is obtained. The time is 9-20 minutes.

The at least three-layer prepreg obtained by stacking the prepregs of this embodiment is cured at 120° C. for 2 to 3 hours by an autoclave process to obtain a composite material laminate. The obtained composite laminate has a tensile strength of 500-600MPa, a tensile modulus of 22-26GPa; a bending strength of 700-800MPa, a bending modulus of 24-28GPa; a layer shear strength of 72-82MPa.

Embodiment 12: This embodiment is different from Embodiment 11 in that the fiber woven cloth is a glass fiber woven fabric or a carbon fiber woven fabric. Other parameters are the same as those in Embodiment 11.

Embodiment 13: This embodiment is different from Embodiment 11 in that the fiber woven fabric is glass fiber woven fabric with the brand name SW110, SW220, SW280, EW110 or EW220 produced by Nanjing Glass Fiber Research and Design Institute. Other parameters are the same as those in Embodiment 11.

The present embodiment is not limited to the glass fiber braids listed above.

Embodiment 14: This embodiment differs from Embodiment 11 in that the fiber woven cloth is a carbon fiber woven cloth with a brand name of G827 or T300 carbon fiber woven cloth produced by Toray Corporation of Japan. Other parameters are the same as those in Embodiment 11.

This embodiment is not limited to the carbon fiber woven fabrics listed above.

Embodiment 15: This embodiment is the preparation method of the prepreg described in Embodiment 11. The preparation method of the prepreg is realized through the following steps: 1. Preparation of epoxy matrix resin: a. by quality Weigh 40 parts of novolac epoxy resin, 60 parts of bisphenol A epoxy resin, 2 to 10 parts of core-shell polymer, 15 to 24 parts of curing agent and 3.0 to 6.0 parts of curing accelerator, the curing agent It is a compound curing agent for dicyandiamide and 4,4'-diaminodiphenyl sulfone, wherein the mass parts of 4,4'-diaminodiphenyl sulfone and dicyandiamide are 18 parts and 6 parts, 14 parts and 7 parts respectively part, 10 parts and 8 parts, or 6 parts and 9 parts, the curing accelerator is organic ureas or derivatives thereof; b, 40 parts of novolac epoxy resins, 60 parts of bisphenol A Epoxy resin and 2 to 10 parts of core-shell polymer are mixed and added into the container, and then heated to 150°C under stirring conditions, and then the 4,4'-diaminodiphenylsulfone curing agent weighed in step 1 is added, and the stirring is continued and Heat to 150°C, keep it warm for 3-5 minutes, then cool to room temperature to obtain B-stage resin; c. Take 30 parts of B-stage resin obtained in step 2 and put it into a three-roll mill, and then add the dicyandiamide weighed in step 1 Amine curing agent and 3.0 to 6.0 parts of curing accelerator weighed in step 1, and then grind 3 to 6 times in a three-roll mill, and then add the remaining B-stage resin prepared in step 2, and continue to grind on the three-roll Grinding in the machine for 3 to 6 times to obtain epoxy matrix resin; the temperature of the three-roll mill described in step 3 is maintained at 60 to 70°C;

2. Preparation of prepreg: a. Hang the single-sided release paper on the single-sided release paper winding roller 1, the middle roller 5 and the single-sided release paper winding roller 4 in turn, so that the single-sided release paper The paper winding roller 1, the intermediate roller 5 and the single-sided release paper take-up and winding roller 4 form a transmission connection, and then the double-sided release paper is hung on the double-sided release paper winding roller 2, the middle roller in turn 5 and the product winding roller 3, make the double-sided release paper winding roller 2, the middle roller 5 and the product winding roller 3 form a transmission connection, and then set the fiber woven cloth to the single-sided release paper Between the single-sided release paper and the double-sided release paper between the paper winding roller 1 and the double-sided release paper winding roller 2, the single-sided release paper is in contact with the middle roller 5, and then the single-sided release paper is in contact with the middle roller Preheat the roll 1 of the paper winding roll and the winding roll 2 of the double-sided release paper to 75-85°C; b. Pour the epoxy matrix resin prepared in step 1 into the winding roll 1 of the single-side release paper and the fiber weaving In the "V-shaped" space formed by the cloth, the device is then activated to make the fiber woven cloth and epoxy matrix resin pass through the gap between the single-sided release paper winding roller 1 and the double-sided release paper winding roller 2 to obtain two The prepregs with single-sided release paper and double-sided release paper are attached to the sides respectively, wherein the distance between the single-sided release paper winding roller shaft 1 and the double-sided release paper winding roller shaft 2 is controlled to be 0.1 ～2mm, the line speed of double-sided release paper winding roller 2 is 100-300m/h, the temperature of epoxy matrix resin is 75-85°C; c, the role of single-sided release paper winding winding roller 4 Next, the single-sided release paper is peeled off, and at the same time, the product winding winding roller 3 winds up the prepreg with double-sided release paper attached to one side, and the preparation of the prepreg is completed.

The number of parts in the 30 parts of the B-stage resin obtained in step 2 in step c in step 1 of this embodiment is the same as the standard of the number of parts used when weighing in step a.

The mass content of volatile matter in the prepreg prepared in this embodiment is less than 1%, the mass content of epoxy matrix resin is 37%-43%, and the gelation time at 120°C is 9-20min.

The prepreg preparation method of the present embodiment adopts a hot-melt one-step process. Compared with the solvent method, it has the problems of low volatile matter content, environmental protection, and no environmental pollution; Formed into a film, and then compounded with fiber woven cloth), its work efficiency is higher and its manufacturing cost is lower.

In this embodiment, the hot-melt matrix resin and fiber woven cloth in the gap between the single-sided release paper winding roller 1 and the double-sided release paper winding roller 2 complete the composite impregnation under certain temperature, rotation speed and pressure. , By adjusting the speed of single-sided release paper winding roller 1 and double-sided release paper winding roller 2, the resin content of prepreg can be precisely controlled.

Embodiment 16: The difference between this embodiment and Embodiment 15 is that 40 parts of novolac epoxy resin, 60 parts of bisphenol A epoxy resin, 3-8 parts of Core-shell polymer, 18-22 parts of curing agent and 4.0-5.0 parts of curing accelerator. Other parameters are the same as in the fifteenth embodiment.

More preferably in the present embodiment, take by mass parts 40 parts of novolac epoxy resins, 60 parts of bisphenol A epoxy resins, 5 parts of core-shell polymers, 24 parts of curing agents and 5.0 parts of curing accelerator.

Embodiment 17: The difference between this embodiment and Embodiment 15 or 16 is that the core-shell polymer in step a of step 1 is polybutadiene rubber, styrene-butadiene rubber or polymethylsiloxane Alkane is the soft core, and polymethyl methacrylate is the hard shell. Other parameters are the same as those in Embodiment 15 or 16.

Embodiment 18: The difference between this embodiment and Embodiment 15, 16 or 17 is that the epoxy value of the novolac epoxy resin in step a of step 1 is 0.42 to 0.54, and the bisphenol A ring The epoxy value of the oxygen resin is 0.41-0.56. Other parameters are the same as those in Embodiment 15, 16 or 17.

Embodiment 19: The difference between this embodiment and Embodiment 15 to Embodiment 18 is that the curing accelerator described in Step a of Step 1 is N, N'-dimethyldiphenylurea, N, N'-diethyldiphenylurea, N-p-chlorophenyl-N, N'-dimethylurea, 3-phenyl 1,1-dimethylurea, 3-p-chlorophenyl 1, 1 Dimethylurea (chlorourea) or thiourea. Other parameters are the same as those in Embodiment 15 to Embodiment 18.

Embodiment 20: In conjunction with Fig. 1 and Fig. 2, this embodiment is used to describe the device used to prepare the prepreg of Embodiment 11 to Embodiment 14. The device includes a single-sided release paper winding roller 1, Double-sided release paper winding roller 2, product winding winding roller 3, single-sided release paper winding winding roller 4, intermediate roller 5, third chain transmission mechanism 6, first shaft 7, first chain Transmission mechanism 8, second shaft 9, second chain transmission mechanism 10, first gear transmission mechanism 11, second gear transmission mechanism 14, third shaft 15, single-sided release paper winding feed roller shaft 16, double-sided release paper The model paper is wound around the feed roller shaft 17, the fourth chain transmission mechanism 18 and the frame 22, the first shaft 7 is connected to the second shaft 9 through the first chain transmission mechanism 8, and the second shaft 9 is connected through the second chain transmission mechanism 10 It is connected to the double-sided release paper winding roller shaft 2, and the double-sided release paper winding roller shaft 2 is connected to the single-sided release paper winding roller shaft 1 through the first gear transmission mechanism 11. The single-sided release paper winding roller shaft 1 through single-sided release paper and single-sided release paper winding feed roller shaft 16 transmission connection, double-sided release paper winding roller shaft 2 through double-sided release paper and double-sided release paper winding feed roller shaft 17 transmission connection, the first shaft 7 is connected to the third shaft 15 through the third chain transmission mechanism 6, the third shaft 15 is connected to the product winding roller shaft 3 through the second gear transmission mechanism 14, and the third shaft 15 is connected through the fourth The chain transmission mechanism 18 is connected with the single-sided release paper winding winding roller shaft 4, and it is characterized in that the device also includes a fiber woven cloth winding roller shaft 12, a spring 13 and an adjusting screw 21, and the fiber woven cloth winding roller shaft 12 The fiber woven cloth is set in the gap between the single-sided release paper winding roller 1 and the double-sided release paper winding roller 2, and the fiber woven cloth winding roller 12 passes through the fiber woven cloth and the double-sided release paper winding roller 2 Transmission connection, double-sided release paper winding roller shaft 2 is connected to the intermediate roller shaft 5 through the prepreg material molding product, and the intermediate roller shaft 5 is transmission connected to the product winding winding roller shaft 3 through the prepreg material molding product, and the intermediate roller shaft Axis 5 is connected by transmission of single-sided release paper and single-sided release paper winding roller shaft 4, and a spring is arranged between the shaft ends of single-sided release paper winding roller shaft 1 and double-sided release paper winding roller shaft 2 13. The adjusting screw 21 passes through the frame 22 and leans against the double-sided release paper winding roller 2, the single-sided release paper winding roller 1, the double-sided release paper winding roller 2, and the product winding winding roller 3. Single-sided release paper winding winding roller shaft 4, middle roller shaft 5, first shaft 7, second shaft 9, third shaft 15, single-sided release paper winding feed roller shaft 16, double-sided release paper The paper winding feed roll 17 and the fiber woven cloth winding roll 12 are all mounted on the frame 22 .

The device used to prepare the prepreg in this embodiment completes the impregnation process of the epoxy matrix resin and the fiber over-woven cloth and the control process of the prepreg resin content in one step. Compared with the existing hot-melt method prepreg production device, the equipment and device The manufacturing cost is lower, the production process is simpler, the production efficiency is higher, and the resin content control of the prepreg is more precise.

In this embodiment, both the single-sided release paper winding roller 1 and the double-sided release paper winding roller 2 are provided with closed cavities filled with circulating heating medium, and the two closed cavities are connected through pipelines.

The device in this embodiment also includes two baffles 20, and each of the two ends of the single-sided release paper winding roller 1 and the double-sided release paper winding roller 2 is provided with a baffle for blocking the matrix resin from overflowing 20.

Embodiment 21: This embodiment differs from Embodiment 20 in that the product winding winding roller 3, the single-sided release paper winding roller 4, the fiber woven cloth winding roller 12, the single-sided release paper Magnetic powder clutch 19 is all housed on model paper winding feed roller shaft 16 and double-sided release paper winding feed roller shaft 17. Other components and connections are the same as those in Embodiment 20.

Specific embodiment twenty-two: This embodiment is an epoxy matrix resin, and the epoxy matrix resin consists of 40 parts by mass of F-44 phenolic epoxy resin, 60 parts of E-51 epoxy resin, and 2 parts of core-shell polymer , 16 parts of 4,4'-diaminodiphenyl sulfone compound curing agent, 8 parts of dicyandiamide curing agent and 5.0 parts of 3-phenyl 1,1-dimethylurea curing accelerator, wherein the The core-shell polymer is polybutadiene rubber as the soft core and polymethyl methacrylate as the hard shell.

The core-shell polymer described in this embodiment is added in the form of a master mixture of Kane Ace MX-125 produced by Kaneka Corporation in Japan, wherein the mass content of Kane Ace MX-125 core-shell polymer is 25%, and the polybutylene Acrylic rubber is the soft core, polymethyl methacrylate is the hard shell, and the particle size is 100nm; the mass content of E-51 epoxy resin is 75%.

A performance test was performed on the cured product of the epoxy matrix resin of this embodiment after being cured at 120° C. for 2 hours, and the test method and parameters used the method and parameters described in the first specific embodiment. The test results are: the glass transition temperature of the cured product of the epoxy matrix resin in this embodiment (curing condition: 2 hours at 120°C) is 138.2°C; the impact strength is 15.7KJ/m ² ; the tensile strength is 69.7 MPa, the tensile modulus is 3.6GPa; the elongation at break is 3.0%; the flexural strength is 118.6MPa, and the flexural modulus is 3.5GPa. The epoxy matrix resin of this embodiment has good performance.

The preparation method of the epoxy matrix resin of the present embodiment is: one, take by mass parts 40 parts of F-44 novolac type epoxy resins, 54 parts of E-51 epoxy resins, 8 parts of Japanese Kaneka company's trade mark that Kaneka produces Ace MX-125 masterbatch, 16 parts of 4,4'-diaminodiphenylsulfone complex curing agent, 8 parts of dicyandiamide curing agent and 5.0 parts of 3-phenyl 1,1-dimethylurea curing accelerator Two, 40 parts of F-44 novolak type epoxy resins, 54 parts of bisphenol A epoxy resins and 8 parts of Japan Kaneka Company's production of 40 parts of F-44 novolac epoxy resins taken by step are mixed and added to the master mixture of Kane Ace MX-125 , then heated to 150°C under stirring conditions, then added 16 parts of 4,4'-diaminodiphenylsulfone curing agent weighed in step 1, continued to stir and heated to 150°C, kept warm for 3 to 5 minutes, and then cooled to Get B-stage resin at room temperature; 3. Take 30 parts of B-stage resin obtained in step 2 and put it into a three-roll mill, then add 8 parts of dicyandiamide curing agent weighed in step 1 and 5 parts of step 1 3-phenyl 1,1-dimethylurea curing accelerator, and then grind 4 times in a three-roll mill, then add the remaining B-stage resin prepared in step 2, and continue to grind in a three-roll mill 4 times to obtain the epoxy matrix resin; the temperature of the three-roll mill in the third step is kept at 60-70°C. Wherein, the number of parts in the 30 parts of the B-stage resin obtained in step two described in step three is the same as the standard of the number of parts used when weighing in step one.

Embodiment 23: This embodiment is a prepreg, which is made of the epoxy matrix resin in Embodiment 22 and glass fiber woven cloth with the grade SW110, and the volatile matter content is less than 1%. , wherein the mass content of the epoxy matrix resin is 37% to 43%.

In this embodiment, the density of the glass fiber woven cloth of SW110 is 110 g/m ² .

The preparation method of the prepreg in this embodiment is as follows: 1. Prepare the epoxy matrix resin: prepare the epoxy matrix resin according to the preparation method recorded in Embodiment 22; 2. Prepare the prepreg: a. The one-sided release paper is hung on the single-sided release paper winding roller 1, the middle roller 5 and the single-sided release paper winding winding roller 4 in turn, so that the single-sided release paper is wound around the roller 1, the middle roller 5 It forms a transmission connection with the single-sided release paper winding roller 4, and then hangs the double-sided release paper on the double-sided release paper winding roller 2, the middle roller 5 and the product winding roller 3 in sequence, Make the double-sided release paper winding roller 2, the intermediate roller 5 and the product winding winding roller 3 form a transmission connection, and then set the fiber woven cloth to the position between the single-sided release paper winding roller 1 and the double-sided release paper Between the single-sided release paper and the double-sided release paper between the winding rollers 2, wherein the single-sided release paper is in contact with the middle roller 5, and then the single-sided release paper is wound around the roller 1 and the double-sided release paper The paper winding roller 2 is preheated to 75-85°C; b. Pour the epoxy matrix resin prepared in step 1 into the "V-shaped" space formed by the single-sided release paper winding roller 1 and the fiber woven cloth, and then Start the device, so that the fiber woven cloth and epoxy matrix resin pass through the gap between the single-sided release paper winding roller 1 and the double-sided release paper winding roller 2, and the single-sided release paper and the double-sided release paper are respectively adhered on both sides. Prepreg material for double-sided release paper, wherein the distance between winding roller 1 of single-sided release paper and winding roller 2 of double-sided release paper is controlled to be 0.15-0.2mm, The linear speed of the axis 2 is 200m/h, and the temperature of the epoxy matrix resin is 75-85°C; c. The single-sided release paper is peeled off under the action of the winding roller 4 of the single-sided release paper, and the product is collected at the same time. The winding roller 3 winds up the prepreg with double-sided release paper adhered on one side, ie the preparation of the prepreg is completed. The number of parts in the 30 parts of the B-stage resin obtained in the c step of step one is the same as the standard of the number of parts when weighing in the step a.

The preparation method of this embodiment adopts the device described in Embodiment 20.

In this embodiment, the gelation time of the prepreg is measured according to "HB 7736.7 Test Method for Physical Properties of Prepregs of Composite Materials Part 7: Determination of Gelation Time", and the gelation time of the prepreg at 120°C is obtained. The time is 9-20 minutes.

At least 3 layers of prepreg obtained by superimposing the prepreg obtained in this embodiment are cured at 120° C. for 3 hours by using an autoclave process to obtain a composite material laminate. The tensile strength of the obtained composite laminate is 540.2MPa, the tensile modulus is 24.8GPa; the flexural strength is 750MPa, the flexural modulus is 25.9GPa; the layer shear strength is 76.5MPa.

Specific Embodiment Twenty-Four: This embodiment is an epoxy matrix resin, and the epoxy matrix resin consists of 40 parts by mass of F-44 phenolic epoxy resin, 60 parts of E-51 epoxy resin, and 3 parts of core-shell polymer , 16 parts of 4,4'-diaminodiphenyl sulfone compound curing agent, 8 parts of dicyandiamide curing agent and 5.0 parts of 3-phenyl 1,1-dimethylurea curing accelerator, wherein the The core-shell polymer is polybutadiene rubber as the soft core and polymethyl methacrylate as the hard shell.

The core-shell polymer described in this embodiment uses the brand name produced by Kaneka Corporation of Japan as kana Ace MX-960. The content of the core-shell polymer is 25%, with polymethylsiloxane as the soft core, and polymethylpropionate as the soft core. The ester is a hard shell, and the particle size is 300nm; the content of the bisphenol A epoxy resin is 75% by mass.

A performance test was performed on the cured product of the epoxy matrix resin of this embodiment after being cured at 120° C. for 2 hours, and the test method and parameters used the method and parameters described in the first specific embodiment. The test results are: the glass transition temperature of the cured product of the epoxy matrix resin in this embodiment (curing condition: 2 hours at 120°C) is 137.3°C; the impact strength is 16.8KJ/m ² ; the tensile strength is 75.6 MPa, the tensile modulus is 3.5GPa; the elongation at break is 3.2%; the bending strength is 126.4MPa, and the bending modulus is 3.4GPa. The epoxy matrix resin of this embodiment has good performance.

The preparation method of the epoxy matrix resin of the present embodiment is: one, take by mass parts 40 parts of F-44 novolac type epoxy resins, 51 parts of E-51 epoxy resins, 12 parts of Japanese Kaneka companies The trade mark produced is Kane Ace MX-960 masterbatch, 16 parts of 4,4'-diaminodiphenylsulfone complex curing agent, 8 parts of dicyandiamide curing agent and 5.0 parts of 3-phenyl 1,1-dimethylurea curing accelerator Two, 40 parts of F-44 novolak type epoxy resins, 51 parts of bisphenol A epoxy resins and 12 parts of Japan Kaneka Company's production of 40 parts of F-44 novolac epoxy resins taken by step 1 are mixed and added to the master mixture of Kane Ace MX-960 , then heated to 150°C under stirring conditions, then added 16 parts of 4,4'-diaminodiphenylsulfone curing agent weighed in step 1, continued to stir and heated to 150°C, kept warm for 3 to 5 minutes, and then cooled to Get B-stage resin at room temperature; 3. Take 30 parts of B-stage resin obtained in step 2 and put it into a three-roll mill, then add 8 parts of dicyandiamide curing agent weighed in step 1 and 5 parts of step 1 3-phenyl 1,1-dimethylurea curing accelerator, and then grind 4 times in a three-roll mill, then add the remaining B-stage resin prepared in step 2, and continue to grind in a three-roll mill 4 times to obtain the epoxy matrix resin; the temperature of the three-roll mill in the third step is kept at 60-70°C. The number of parts in the 30 parts of the B-stage resin obtained in step two described in step three is the same as the standard of the number of parts used when weighing in step one.

The prepreg is prepared by using the preparation method described in Embodiment 23, wherein the preparation method of the epoxy matrix resin is carried out by the method described in this embodiment. The prepared prepreg is made of the epoxy matrix resin of the twenty-fourth embodiment and the glass fiber woven cloth (density 110g/m ² ) of the brand name SW110, and the volatile matter content is less than 1%. The mass content of the matrix resin is 37%-43%. According to "HB 7736.7 Composite Material Prepreg Physical Properties Test Method Part 7: Determination of Gelation Time" to measure the gelation time of the prepreg, the gelation time of the prepreg at 120°C is 9 ~20min.

At least 3 layers of prepregs obtained by superimposing the prepregs obtained in this embodiment are cured at 120° C. for 3 hours by using an autoclave process to obtain a composite material laminate. The tensile strength of the obtained composite laminate is 570.3MPa, the tensile modulus is 24.1GPa; the bending strength is 765MPa, the bending modulus is 25.02GPa; the layer shear strength is 81.2MPa.

Specific Embodiment Twenty-five: This embodiment is an epoxy matrix resin, and the epoxy matrix resin consists of 40 parts by mass of F-44 phenolic epoxy resin, 60 parts of E-51 epoxy resin, and 5 parts of core-shell polymer , 16 parts of 4,4'-diaminodiphenyl sulfone compound curing agent, 8 parts of dicyandiamide curing agent and 5.0 parts of 3-phenyl 1,1-dimethylurea curing accelerator, wherein the The core-shell polymer is polybutadiene rubber as the soft core and polymethyl methacrylate as the hard shell.

The core-shell polymer described in this embodiment is added in the form of a master mixture of Kane Ace MX-125 produced by Kaneka Corporation in Japan, wherein the mass content of Kane Ace MX-125 core-shell polymer is 25%, and the polybutylene Alkene is the soft core, polymethyl methacrylate is the hard shell, and the particle size is 100nm; the mass content of E-51 epoxy resin is 75%.

A performance test was performed on the cured product of the epoxy matrix resin of this embodiment after being cured at 120° C. for 2 hours, and the test method and parameters used the method and parameters described in the first specific embodiment. The test results are: the glass transition temperature of the cured product of the epoxy matrix resin in this embodiment (curing condition: 2 hours at 120°C) is 137.3°C; the impact strength is 16.8KJ/m ² ; the tensile strength is 83.5 MPa, the tensile modulus is 3.4GPa; the elongation at break is 3.5%; the bending strength is 126.4MPa, and the bending modulus is 3.4GPa. The epoxy matrix resin of this embodiment has good performance.

The difference between the preparation method of the epoxy matrix resin of the present embodiment and the preparation method of the epoxy matrix resin recorded in the specific embodiment 22 is that in step 1, 40 parts of F-44 novolac epoxy resin are weighed in parts by mass , 45 parts of E-51 epoxy resin, 20 parts of master mixture of Kane Ace MX-125 produced by Kaneka Corporation in Japan, 16 parts of 4,4'-diaminodiphenyl sulfone with curing agent, 8 parts of dicyandiamide curing agent and 5.0 parts of 3-phenyl 1,1-dimethylurea curing accelerator; in the remaining steps, add the corresponding parts by mass weighed in the first step above.

The prepreg is prepared by using the preparation method described in Specific Embodiment 23, where the difference is that the preparation method of the epoxy matrix resin is carried out by the method described in this embodiment. The prepared prepreg is made of the epoxy matrix resin in Embodiment 25 and the glass fiber woven cloth (density 110g/m ² ) of the grade SW110, and the mass content of the volatile matter is less than 1%. The mass content of the matrix resin is 37%-43%. According to "HB 7736.7 Composite Material Prepreg Physical Properties Test Method Part 7: Determination of Gelation Time" to measure the gelation time of the prepreg, the gelation time of the prepreg at 120°C is 9 ~20min.

The prepregs obtained in this embodiment are superimposed to obtain at least 3 layers of prepregs, which are cured at 120° C. for 3 hours by using an autoclave process to obtain a composite material laminate. The tensile strength of the obtained composite laminate is 598.3MPa, the tensile modulus is 23.5GPa; the flexural strength is 785MPa, the flexural modulus is 24.2GPa; the layer shear strength is 81.2MPa.

Specific Embodiment Twenty-six: This embodiment is a comparative experiment: the epoxy matrix resin is composed of 40 parts by mass of F-44 phenolic epoxy resin, 60 parts of E-51 epoxy resin, and 16 parts of 4,4'-di It is made of compounding curing agent of aminodiphenyl sulfone, 8 parts of dicyandiamide curing agent and 5.0 parts of 3-phenyl 1,1-dimethylurea curing accelerator.

A performance test was performed on the cured product of the epoxy matrix resin of this embodiment after being cured at 120° C. for 2 hours, and the test method and parameters used the method and parameters described in the first specific embodiment. The test results are: the glass transition temperature of the cured product of the epoxy matrix resin in this embodiment (curing condition: 2 hours at 120°C) is 137.8°C; the impact strength is 11.5KJ/m ² ; the tensile strength is 62.5 MPa, the tensile modulus is 3.6GPa; the elongation at break is 2.7%; the bending strength is 108.0MPa, and the bending modulus is 3.5GPa.

The difference between the preparation method of the epoxy matrix resin of the present embodiment and the preparation method of the epoxy matrix resin recorded in the specific embodiment 22 is that in step 1, 40 parts of F-44 novolac epoxy resin are weighed in parts by mass , 60 parts of E-51 epoxy resin, 16 parts of 4,4'-diaminodiphenyl sulfone compound curing agent, 8 parts of dicyandiamide curing agent and 5.0 parts of 3-phenyl 1,1-dimethylurea Curing accelerator; add the corresponding mass parts of the above-mentioned step 1 in the remaining steps.

The prepreg is prepared by using the preparation method described in Embodiment 23, wherein the preparation method of the epoxy matrix resin is carried out by the method described in this embodiment. The prepared prepreg is made of epoxy matrix resin in Embodiment 26 and glass fiber woven cloth (density 110g/m ² ) with brand name SW110, and the mass content of volatile matter is less than 1%. The mass content of the matrix resin is 37%-43%. According to "HB 7736.7 Composite Material Prepreg Physical Properties Test Method Part 7: Determination of Gelation Time" to measure the gelation time of the prepreg, the gelation time of the prepreg at 120°C is 9 ~20min.

The at least 3-layer prepreg obtained by stacking the prepregs obtained in this embodiment is cured at 120°C for 3 hours by using an autoclave process to obtain a composite material laminate. The tensile strength of the obtained composite laminate is 510.5MPa, the tensile modulus is 25.6GPa; the flexural strength is 720MPa, the flexural modulus is 26.3GPa; the layer shear strength is 73.8MPa.

Claims (9)

1. Epoxy matrix resin, it is characterized in that epoxy matrix resin is cured by 40 parts of novolak type epoxy resin, 60 parts of bisphenol A epoxy resins, 2～10 parts of core-shell polymers, 15～24 parts by weight agent and 3.0 to 6.0 parts of curing accelerator, wherein the curing agent is a combination of dicyandiamide and 4,4'-diaminodiphenylsulfone, wherein 4,4'-diaminodiphenylsulfone and The mass parts of dicyandiamide are respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts, and the accelerator is an organic urea; The core-shell polymer uses polybutadiene rubber, styrene-butadiene rubber or polymethylsiloxane as the soft core, and polymethyl methacrylate as the hard shell. 2. epoxy matrix resin according to claim 1 is characterized in that epoxy matrix resin is by weight by 40 parts of novolak type epoxy resins, 60 parts of bisphenol A epoxy resins, 3～8 parts of core-shell polymers , 18-22 parts of curing agent and 4.0-5.0 parts of curing accelerator. 3. The epoxy matrix resin according to claim 1 or 2, characterized in that the epoxy value of the novolac epoxy resin is 0.42-0.54, and the epoxy value of the bisphenol A epoxy resin is 0.41-0.56. 4. the preparation method of epoxy matrix resin as claimed in claim 1 is characterized in that the preparation method of epoxy matrix resin is realized by the following steps: one, take by mass parts 40 parts of novolak type epoxy resins, 60 parts Parts of bisphenol A epoxy resin, 2-10 parts of core-shell polymer, 15-24 parts of curing agent and 3.0-6.0 parts of curing accelerator, the curing agent is dicyandiamide and 4,4'-diamino The compound curing agent of diphenylsulfone, wherein the mass parts of 4,4'-diaminodiphenylsulfone and dicyandiamide are respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts, the curing accelerator is an organic urea; 2. Mix 40 parts of novolac epoxy resin, 60 parts of bisphenol A epoxy resin and 2 to 10 parts of core-shell polymer in the container , then heated to 150°C with stirring, then added the 4,4'-diaminodiphenylsulfone curing agent weighed in step 1, continued to stir and heated to 150°C, kept warm for 3-5min, and then cooled to room temperature to obtain B Three, take 30 parts of the B-stage resin obtained in step two and put it into a three-roll mill, then add the dicyandiamide curing agent weighed in step one and 3.0 to 6.0 parts of curing accelerator weighed in step one agent, and then grind 3 to 6 times in a three-roll grinder, then add the remaining B-stage resin prepared in step 2, and continue to grind 3 to 6 times in a three-roll grinder to obtain an epoxy matrix resin; step 3 The temperature of the three-roll mill described in is maintained at 60-70°C. 5. Prepreg, which is characterized in that the prepreg is made of epoxy matrix resin and fiber woven cloth, and the mass content of volatile matter is controlled to be less than 1%, wherein the mass content of epoxy matrix resin is 37% to 43%, The epoxy matrix resin consists of 40 parts by weight of novolac epoxy resin, 60 parts of bisphenol A epoxy resin, 2 to 10 parts of core-shell polymer, 15 to 24 parts of curing agent, and 3.0 to 6.0 parts of curing accelerator Made, the curing agent is a combination of dicyandiamide and 4,4'-diaminodiphenyl sulfone, wherein the mass parts of 4,4'-diaminodiphenyl sulfone and dicyandiamide are 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts, the curing accelerator is an organic urea; The core-shell polymer uses polybutadiene rubber, styrene-butadiene rubber or polymethylsiloxane as the soft core, and polymethyl methacrylate as the hard shell. 6. The prepreg according to claim 5, characterized in that the fiber woven fabric is a glass fiber woven fabric or a carbon fiber woven fabric. 7. the preparation method of prepreg as claimed in claim 5 is characterized in that the preparation method of prepreg is realized by the following steps: one, prepare epoxy matrix resin: a, take by weight 40 parts of phenolic Type epoxy resin, 60 parts of bisphenol A epoxy resin, 2 to 10 parts of core-shell polymer, 15 to 24 parts of curing agent and 3.0 to 6.0 parts of curing accelerator, wherein the curing agent is dicyandiamide and 4,4'-diaminodiphenyl sulfone compound curing agent, wherein the mass parts of 4,4'-diaminodiphenyl sulfone and dicyandiamide are respectively 18 parts and 6 parts, 14 parts and 7 parts, 10 parts and 8 parts, or 6 parts and 9 parts, the curing accelerator is an organic urea; b, 40 parts of novolak epoxy resin, 60 parts of bisphenol A epoxy resin and 2 to 10 parts of core The shell polymer is mixed and added to the container, and then heated to 150°C under stirring conditions, then add the 4,4'-diaminodiphenylsulfone curing agent weighed in step 1, continue to stir and heat to 150°C, and keep warm for 3 to 5 minutes , and then cooled to room temperature to obtain B-stage resin; c, get 30 parts of B-stage resin obtained in step 2 and put it into a three-roll mill, then add the dicyandiamide curing agent weighed in step 1 and the weighed dicyandiamide curing agent in step 1 3.0 to 6.0 parts of curing accelerator, and then grind 3 to 6 times in a three-roll grinder, then add the remaining B-stage resin prepared in step 2, and continue to grind 3 to 6 times in a three-roll grinder to obtain Epoxy matrix resin; the temperature of the three-roll mill described in step 3 is maintained at 60-70°C; 2. Preparation of prepreg: a. Hang the single-sided release paper to the single-sided release paper winding roller (1), the middle roller (5) and the single-sided release paper winding roller (4) Make the single-sided release paper winding roller shaft (1), the middle roller shaft (5) and the single-sided release paper winding winding roller shaft (4) form a transmission connection, and then hang the double-sided release paper on the double-sided On the side release paper winding roller (2), the intermediate roller (5) and the product winding winding roller (3), the double-sided release paper winding roller (2), the intermediate roller (5) and the product The winding roller shaft (3) forms a transmission connection, and then the fiber woven cloth is set to the single-sided release paper winding roller shaft (1) and the double-sided release paper winding roller shaft (2). Between the paper and the double-sided release paper, wherein the single-sided release paper is in contact with the middle roller (5), and then the single-sided release paper is wound around the roller (1) and the double-sided release paper is wound around the roller (2) Preheat to 75-85°C; b. Pour the epoxy matrix resin prepared in step 1 into the "V-shaped" space formed by the single-sided release paper winding roller (1) and fiber woven cloth, and then start the device. Make the fiber woven cloth and epoxy matrix resin pass through the gap between the single-sided release paper winding roller shaft (1) and the double-sided release paper winding roller shaft (2), so that the two sides are respectively adhered with single-sided release paper and double-sided release paper prepreg, wherein the distance between the single-sided release paper winding roller (1) and the double-sided release paper winding roller (2) is controlled to be 0.1-2mm, The line speed of the paper winding roller (2) is 100-300m/h, and the temperature of the epoxy matrix resin is 75-85°C; c, under the action of the winding roller (4) of the single-sided release paper, the The single-sided release paper is peeled off, and at the same time, the product winding winding roller (3) winds up the prepreg with double-sided release paper attached to one side, and the preparation of the prepreg is completed. 8. The device for preparing the prepreg as claimed in claim 5, said device comprising a single-sided release paper winding roller (1), a double-sided release paper winding roller (2), product winding winding Roller shaft (3), single-sided release paper winding roll shaft (4), middle roller shaft (5), third chain transmission mechanism (6), first shaft (7), first chain transmission mechanism (8 ), the second shaft (9), the second chain transmission mechanism (10) and the first gear transmission mechanism (11), the second gear transmission mechanism (14), the third shaft (15), the single-sided release paper winding into Material roller shaft (16), double-sided release paper winding feed roller shaft (17), fourth chain transmission mechanism (18) and frame (22), the first shaft (7) passes through the first chain transmission mechanism (8 ) is connected with the transmission of the second shaft (9), the second shaft (9) is connected with the transmission of the double-sided release paper winding roller shaft (2) through the second chain transmission mechanism (10), and the double-sided release paper winding roller shaft ( 2) The first gear transmission mechanism (11) is connected to the single-sided release paper winding roller shaft (1), and the single-sided release paper winding roller shaft (1) is wound by the single-sided release paper and the single-sided release paper The feed roller shaft (16) is in transmission connection, the double-sided release paper winding roller shaft (2) is in transmission connection with the double-sided release paper winding feed roller shaft (17), the first shaft (7) The third shaft (15) is connected to the third shaft (15) through the third chain transmission mechanism (6), and the third shaft (15) is connected to the product winding roller shaft (3) through the second gear transmission mechanism (14). (15) through the fourth chain transmission mechanism (18) and single-sided release paper winding winding roller shaft (4) transmission connection, it is characterized in that the device also includes fiber woven cloth winding roller shaft (12), spring (13 ) and adjusting screw (21), the fiber woven cloth of the fiber woven cloth winding roller shaft (12) is arranged in the gap between the single-sided release paper winding roller shaft (1) and the double-sided release paper winding roller shaft (2) Among them, the fiber woven cloth winding roller (12) is connected to the double-sided release paper winding roller (2) through the fiber woven cloth, and the double-sided release paper winding roller (2) is formed by the prepreg material and the intermediate roller The shaft (5) is connected by transmission, the middle roller shaft (5) is connected by the transmission of the prepreg molding product and the product winding winding roller shaft (3), the middle roller shaft (5) is passed through the single-sided release paper and the single-sided release paper The winding winding roller shaft (4) is connected by transmission, a spring (13) is arranged between the shaft ends of the single-sided release paper winding roller shaft (1) and the double-sided release paper winding roller shaft (2), and the adjusting screw rod (21 ) passes through the frame (22) and leans against the double-sided release paper winding roller (2), the single-sided release paper winding roller (1), the double-sided release paper winding roller (2), and the product receiving Roll winding roller (3), single-sided release paper winding winding roller (4), intermediate roller (5), first axis (7), second axis (9), third axis (15), Single-sided release paper winding feed roller shaft (16), double-sided release paper winding feed roller shaft (17) and fiber woven cloth winding roller shaft (12) are all contained on the frame (22). 9. The device according to claim 8, characterized in that the product winding winding roller (3), single-sided release paper winding winding roller (4), fiber woven cloth winding roller (12), single-sided Magnetic powder clutches (19) are all housed on the release paper winding feed roller shaft (16) and the double-sided release paper winding feed roller shaft (17).