Flame-retardant resin composite material, flame-retardant resin composition and preparation method of flame-retardant resin composite material

Abstract

The invention discloses a flame-retardant resin composite material, a flame-retardant resin composition and a preparation method of the flame-retardant resin composite material. The flame-retardant resin composition is prepared from the following raw materials in parts by weight: 200-600 parts of epoxy resin; 100 to 600 parts of cyanate ester; 100 to 300 parts of benzoxazine resin; 50 to 150 parts of a toughening agent; 50 to 200 parts of filler; and 50-300 parts of a curing agent. The flame retardant property, the heat resistance and the dielectric property of the epoxy resin are further improved through the synergistic effect of various fillers.

Description

Technical Field

[0001] This application relates to the technical field of epoxy resins, and particularly relates to a flame-retardant resin composite material, a flame-retardant resin composition, and a preparation method thereof. Background Art

[0002] In order to meet the rigid requirements of ultra-large-capacity information transmission and ultra-fast and ultra-high-density information processing brought about by the rapid development of information technology, higher requirements are put forward for printed circuit boards and copper-clad laminates. The specific requirements for their products are high heat resistance, excellent dielectric properties, low thermal expansion coefficient and water absorption rate, environmental protection and flame retardant properties, etc.

[0003] Epoxy resins and their composite materials have excellent mechanical properties, insulation properties, and corrosion resistance, and are widely used in the automotive industry, aerospace and other fields. However, epoxy resins are easy to burn and release a large amount of heat and toxic gases during the combustion process, posing a serious threat to people's lives and safety, and unable to meet the requirements of flame retardant properties and heat resistance in fields such as aerospace.

[0004] Existing methods for preparing flame-retardant epoxy resins have disadvantages such as low flame retardant grade of the prepared resins, poor heat resistance of the resins, poor dielectric properties, and being too cumbersome to prepare and unable to be industrially produced. Summary of the Invention

[0005] In order to solve the above deficiencies in the art, this application aims to provide a flame-retardant resin composite material, a flame-retardant resin composition, and a preparation method thereof.

[0006] According to one aspect of this application, a flame-retardant resin composition is provided, which is made from raw materials including the following parts by weight:

[0007]

[0008] According to some embodiments of this application, the epoxy resin is selected from one or more of: bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenolic epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin;

[0009] According to some embodiments of this application, the epoxy resin is selected from one or more of: CYD-128, CYD-127, CYD-011, NPEL128, NPEL127, E51, NPEF170, NPEF171, NPEF175, NPPN-631, NPCN-702, AG80H, AG90H, TDE-90;

[0010] According to some embodiments of this application, the cyanate ester is selected from one or more of: phenolic cyanate ester, fluorine-containing cyanate ester, bisphenol A cyanate ester prepolymer;

[0011] According to some embodiments of the present application, the cyanate ester is selected from one or more of: C05C0100, C05CS, C05CS80, C09M0, C09P0, C01M0, CE01M0, CE01P0.

[0012] According to some embodiments of the present application, the toughening agent is selected from one or more of: phenoxy resin, polyvinyl resin, nitrile rubber.

[0013] According to some embodiments of the present application, the filler is selected from one or more of: ammonium polyphosphate, alumina, silica, aluminum hydroxide, zinc borate.

[0014] According to some embodiments of the present application, the curing agent is selected from one or more of: acid anhydrides, amines;

[0015] According to some embodiments of the present application, the curing agent includes: dicyandiamide, 4,4-DDS, 3,3-DDS, methyl nadic anhydride, methyl hexahydrophthalic anhydride.

[0016] According to some embodiments of the present application, the flame retardant resin composition further includes: a filler, a dispersant, and an accelerator.

[0017] According to some embodiments of the present application, the dispersant is selected from one or more of: KH550, KH560, KH570;

[0018] The accelerator is selected from one or more of: organic ureas, imidazoles, cobalt acetylacetonate / dodecylphenol;

[0019] The filler is selected from one or more of: alumina, aluminum hydroxide, magnesium hydroxide, zinc borate, ammonium polyphosphate.

[0020] According to another aspect of the present application, there is also provided a method for preparing the above-mentioned flame retardant resin composition, including:

[0021] Mix the epoxy resin and the toughening agent evenly at 100 - 150 °C, cool down to 100 °C, then add the cyanate ester and the benzoxazine resin, and after stirring evenly, obtain a resin mixture;

[0022] Mix the liquid epoxy resin, the filler, and the dispersant evenly and then grind to obtain a flame retardant slurry;

[0023] Take epoxy resin or surfactant and mix and grind with the curing agent and the accelerator to obtain a curing agent slurry;

[0024] Add the flame retardant slurry to the resin mixture, mix evenly, then add the curing agent slurry, and stir for 20 - 30 min to obtain the flame retardant resin composition.

[0025] According to yet another aspect of the present application, a flame retardant resin composite material is prepared from the following raw materials in parts by weight:

[0026] The above-mentioned flame-retardant resin composition;

[0027] Reinforcing fiber;

[0028] wherein, the areal density of the fiber is 200 g / m 2 , and the resin content is 34-40%;

[0029] wherein, the reinforcing fiber includes: quartz fiber woven fabric, glass fiber woven fabric, glass fiber unidirectional tape, and organic fiber fabric.

[0030] Compared with the prior art, the present application has at least the following beneficial effects:

[0031] The present application provides a flame-retardant resin composition, which modifies epoxy resin by using cyanate ester and benzoxazine resin. The flame-retardant performance, heat resistance and dielectric performance of epoxy resin are further improved through the synergistic effect of using various fillers.

[0032] In the present application, a flame retardant is introduced into epoxy resin, and the synergistic effect of the flame retardant is fully exerted to further improve the flame-retardant performance of epoxy resin. The cured epoxy resin test board has excellent high-temperature resistance (TG>220 °C) and flame-retardant performance (UL94-V0 level).

[0033] The present application also provides a preparation method of the flame-retardant resin composition, the resin preparation process is simple, the technological process is simple, the production efficiency is high, and industrial scale production can be carried out. Specific embodiments

[0034] Next, the technical solutions of the present application will be clearly and completely described in conjunction with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0035] It should be particularly noted that similar substitutions and modifications made to the present application are obvious to those skilled in the art, and they are all considered to be included in the present application. Relevant personnel can obviously make changes or appropriate alterations and combinations to the methods and applications described herein without departing from the content, spirit and scope of the present application to implement and apply the technology of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments.

[0036] If the present application does not specify specific conditions, they are all carried out according to conventional conditions or conditions recommended by the manufacturer. For the raw materials or auxiliary materials used, and for the reagents or instruments used, if the manufacturer is not specified, they are all conventional products that can be obtained through commercial purchase.

[0037] The present application will be described in detail below.

[0038] Example 1

[0039] Weigh 150 parts of liquid phenolic epoxy resin (NPPN-631) and 80 parts of phenoxy resin (PKHH) and add them to a container. Heat up to 145 °C, mechanically stir for 4 h, then cool down to 100 °C. Add 200 parts of benzoxazine resin (CB5211), 200 parts of bisphenol A cyanate ester (CE01M0), and 300 parts of phenolic cyanate ester (C05CS80). After mixing evenly, a resin mixture is obtained.

[0040] Weigh 80 parts of flame retardant (40 parts of aluminum hydroxide and 40 parts of zinc borate) and 150 parts of phosphorus-containing flame retardant (CW2400), and disperse them evenly through a high-speed disperser to obtain a flame retardant slurry.

[0041] Weigh 80 parts of liquid phenolic epoxy resin (NPPN-631), 20 parts of dicyandiamide (DYHARD 100S), and 2 parts of organic urea (DYHARD UR500), and grind them to be evenly mixed through a three-roll mill to obtain a curing agent slurry.

[0042] Weigh 50 parts of dodecylphenol and 0.05 part of cobalt acetylacetonate, and disperse and mix them evenly through a high-speed disperser to obtain an accelerator slurry.

[0043] Under the condition of 70 °C, mix the resin mixture and the flame retardant slurry evenly, then add the curing agent and the accelerator slurry, and stir for 20 - 30 min to obtain a flame retardant resin composition.

[0044] Inject the resin composition into the corresponding mold, perform vacuum treatment to remove bubbles, heat at 150 °C for 120 min and at 180 °C for 120 min to obtain a high heat-resistant flame retardant resin casting.

[0045] Prepare the above-obtained high heat-resistant flame retardant resin into a film through a film coater, and then impregnate and compound the obtained film and carbon fiber cloth HF30F to prepare a high heat-resistant flame retardant epoxy prepreg. Its fiber areal density is 200 g / m 2 , and the resin content is 36 ± 2%.

[0046] Cut, lay, and cure the above prepreg to obtain a composite laminate. The curing process is: 150 °C / 120 min, 180 °C / 120 min, and cure by autoclave molding, with the whole process pressure not less than 5 MPa.

[0047] Example 2

[0048] Weigh 160 parts of trifunctional epoxy resin (AF-80H), 150 parts of tetrafunctional epoxy resin (AFG-90H) and 100 parts of MPS and add them to a container. Heat up to 100 °C, and after mechanical stirring for 1 h, add 350 parts of bisphenol A cyanate prepolymer (C01P0) and 200 parts of phenolic cyanate (C05CS). After mixing evenly, a resin mixture is obtained.

[0049] Weigh 50 parts of zinc borate, 50 parts of phosphorus-containing flame retardant (CW2500), and 20 parts of KH560, and mix them evenly through a three-roll mill to obtain a flame retardant slurry.

[0050] Weigh 150 parts of bisphenol liquid phenolic epoxy resin (NPPN-638), 150 parts of 4,4-DDS, and 10 parts of imidazole (PN-50), and mix them evenly through a high-speed disperser to obtain a curing agent slurry.

[0051] Weigh 20 parts of nonylphenol and 0.007 parts of zinc acetylacetonate, and disperse them evenly at high speed to obtain an accelerator slurry.

[0052] Under the condition of 80 °C, mix the above resin mixture and flame retardant slurry evenly, then add the curing agent and accelerator slurry, and stir for 20 - 30 min to obtain a flame retardant resin composition.

[0053] Inject the flame retardant resin composition into the corresponding mold, perform vacuum treatment to remove bubbles, heat at 150 °C for 120 min and at 180 °C for 120 min to obtain a high heat-resistant flame retardant epoxy resin casting.

[0054] Use a film coater to prepare the high heat-resistant flame retardant epoxy resin obtained above into a film, and then impregnate and compound it with carbon fiber cloth T700S to obtain an epoxy resin prepreg. Its fiber surface density is 200 g / m 2 , and the resin content is 36 ± 2%.

[0055] Cut, lay, and cure the above prepreg to obtain a composite laminate. The curing process is: 150 °C / 120 min, 180 °C / 120 min, and cure by autoclave molding, with the whole process pressure not less than 5 MPa.

[0056] Example 3

[0057] Weigh 150 parts of trifunctional epoxy resin and 60 parts of VINYLE-C and add them to a container. Heat up to 140 °C, and after mechanical stirring for 4 h, cool down to 80 °C and add 200 parts of bisphenol A cyanate (C01M0) and 300 parts of phenolic cyanate (C05CO400). After mixing evenly, a resin mixture is obtained.

[0058] Weigh 40 parts of magnesium hydroxide, 50 parts of phosphorus-containing flame retardant (CW2400), and 80 parts of dodecylphenol, stir evenly, and grind them through a three-roll mill to obtain a flame retardant slurry.

[0059] Weigh 150 parts of bisphenol liquid epoxy resin (E51), 110 parts of 4,4-DDS, and 10 parts of dicyandiamide (DYHARD 100S), and mix them evenly by a high-speed disperser to obtain a curing agent slurry.

[0060] Weigh 30 parts of dodecylphenol and 0.02 part of cobalt acetylacetonate, and disperse them evenly at high speed to obtain an accelerator slurry.

[0061] Under the condition of 80 °C, mix the above resin mixture and the flame retardant slurry evenly, then add the curing agent / accelerator and stir for 20 - 30 min to obtain a flame retardant resin composition.

[0062] Inject the flame retardant resin composition into a mold, perform vacuum treatment to remove bubbles, heat at 150 °C for 120 min and at 180 °C for 120 min to obtain a high heat-resistant flame retardant epoxy resin casting.

[0063] Use a film coater to prepare the high heat-resistant flame retardant epoxy resin obtained above into a film, and then impregnate and compound the obtained film and carbon fiber woven fabric HFW200T to obtain a high heat-resistant flame retardant epoxy resin prepreg. Its fiber surface density is 200 g / m 2 , and the resin content is 38 ± 2%.

[0064] Cut, lay, and cure the above prepreg to obtain a composite laminate. The curing process is: 150 °C / 120 min, 180 °C / 120 min, and cure by autoclave molding, and the whole process pressure is not less than 5 MPa.

[0065] Comparative example

[0066] Weigh 300 parts of liquid phenolic epoxy resin (NPPN-631) and 80 parts of phenoxy resin (PKHH), add them to a container, heat up to 145 °C, mechanically stir for 4 h, then cool down to 70 °C, and then add 40 parts of aluminum hydroxide, 40 parts of zinc borate, and 40 parts of phosphorus-containing flame retardant (CW2400) to obtain a resin mixture.

[0067] Weigh 28 parts of dicyandiamide (DYHARD 100S) and 2 parts of organic urea (DYHARD UR500), add them to the above resin mixture, and stir for 20 - 30 min to obtain a flame retardant resin composition.

[0068] Inject the resin composition into the corresponding mold, perform vacuum treatment to remove bubbles, and heat at 150 °C for 150 min to obtain a high heat-resistant flame retardant resin casting.

[0069] Use a film coater to prepare the high heat-resistant flame retardant resin obtained above into a film, and then impregnate and compound the obtained film and carbon fiber cloth HF30F to obtain a high heat-resistant flame retardant epoxy resin prepreg. Its fiber surface density is 200 g / m2 The resin content is 36 ± 2%.

[0070] The above prepreg is cut, laid, and cured to obtain a composite laminate. The curing process is: 150 °C / 120 min, 180 °C / 120 min, and cured by autoclave molding with the pressure not less than 5 MPa throughout the process.

[0071] Experimental Example

[0072] The materials of the examples and comparative examples were tested for dielectric properties (GB / T 5597 - 1999, test frequency 7 - 18 GHz), glass transition temperature (ASTM D7028 - 2007(2005)), and flame retardant properties according to the UL - 94 standard.

[0073] Table 1 Performance test results of the epoxy resin composition

[0074] DMA Tg (°C) Flexural strength (MPa) Flame retardant rating Example 1 248 127 UL94-V0 Example 2 272 136 UL94-V0 Example 3 230 114 UL94-V0 Comparative example 139 80 UL94-V0

[0075] Table 2 Performance test results of the composite laminate

[0076]

[0077] As can be seen from the above examples and comparative examples, by adding a certain amount of cyanate ester or benzoxazine resin and through special treatments such as grinding and high - speed dispersion of the slurry, the mechanical properties and heat resistance of the epoxy resin can be further improved. In addition, by preparing composites with different fibers, they have excellent flame retardant and heat resistance properties, and also have relatively high mechanical properties, which can meet the requirements of high flame retardancy and heat resistance in fields such as aerospace and automotive.

[0078] The description of the above examples is only used to help understand the method and its core idea of this application. It should be noted that for those of ordinary skill in the art of this technology, without departing from the principle of this application, several improvements and modifications can be made to this application, and these improvements and modifications also fall within the protection scope of the claims of this application.

Claims

1. A flame-retardant resin composition, characterized in that, It is made from the following raw materials in parts by weight:

2. The flame-retardant resin composition according to claim 1, wherein, The epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, trifunctional epoxy resin, and tetrafunctional epoxy resin; Optionally, the epoxy resin is selected from one or more of CYD-128, CYD-127, CYD-011, NPEL128, NPEL127, E51, NPEF170, NPEF171, NPEF175, NPPN-631, NPCN-702, AG80H, AG90H, TDE-90.

3. The flame retardant resin composition according to claim 1, wherein The cyanate ester is selected from one or more of phenolic cyanate ester, fluorine-containing cyanate ester, and bisphenol A cyanate ester prepolymer; Further optionally, the cyanate ester is selected from one or more of C05C0100, C05CS, C05CS80, C09M0, C09P0, C01M0, CE01M0, CE01P0.

4. The flame retardant resin composition according to claim 1, wherein The toughening agent is selected from one or more of phenoxy resin, polyvinyl resin, and nitrile rubber.

5. The flame retardant resin composition according to claim 1, characterized in that, The filler is selected from one or more of ammonium polyphosphate, alumina, silica, aluminum hydroxide, and zinc borate.

6. The flame retardant resin composition according to claim 1, wherein The curing agent is selected from one or more of acid anhydrides and amines; Optionally, the curing agent includes dicyandiamide, 4,4-DDS, 3,3-DDS, methyl nadic anhydride, and methyl hexahydrophthalic anhydride.

7. The flame-retardant resin composition according to any one of claims 1-6, characterized in that, It also includes: Filler, dispersant, and accelerator.

8. The flame retardant resin composition according to claim 7, characterized in that, The dispersant is selected from one or more of KH550, KH560, and KH570; The accelerator is selected from one or more of organic ureas, imidazoles, and cobalt acetylacetonate / dodecylphenol; The filler is selected from one or more of alumina, aluminum hydroxide, magnesium hydroxide, zinc borate, and ammonium polyphosphate.

9. A method for preparing the flame retardant resin composition according to any one of claims 1-8, characterized in that, It includes: Mix the epoxy resin and the toughening agent evenly at 100-150 °C, cool down to 100 °C, then add the cyanate ester and benzoxazine resin, and stir evenly to obtain a resin mixture; Mix the liquid epoxy resin, filler, and dispersant evenly and then grind to obtain a flame retardant slurry; Take epoxy resin or surfactant and mix and grind with the curing agent and accelerator to obtain a curing agent slurry; Add the flame retardant slurry to the resin mixture, mix evenly, then add the curing agent slurry, and stir for 20-30 min to obtain a flame retardant resin composition.

10. A flame-retardant resin composite material, characterized in that, It is prepared from the following raw materials in parts by weight: The flame retardant resin composition according to any one of claims 1-7; Reinforcing fiber; Among them, the fiber surface density is 200 g / m 2 , and the resin content is 34 - 40%; Wherein, the reinforcing fiber includes quartz fiber woven fabric, glass fiber woven fabric, glass fiber unidirectional tape, and organic fiber fabric.

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