Bisphenol E cyanate ester and preparation method thereof
By adding modified Elosite nanotubes to the bisphenol E cyanate resin and adopting a specific preparation method, the problem of poor toughness of cyanate resin is solved, significantly improving its mechanical properties and safety properties, and expanding its application range.
Patent Information
- Application Number
- CN202411619202.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-13
- Publication Date
- 2025-03-07
AI Technical Summary
The toughness of cyanate resins is poor, which affects its promotion and application in certain application fields.
The mechanical properties of the cyanate resin are improved by adding the modified Elosite nanotubes to the bisphenol E cyanate resin and adopting a specific preparation method, including heating and stirring, adding a catalyst and performing vacuum polymerization.
It effectively improves the toughness of bisphenol E cyanate material, improves its mechanical properties, and enhances its safety performance and service life during use, expanding its application field.
Smart Images
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Figure BDA0005133020930000081
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of cyanate resins, and particularly relates to bisphenol E cyanate and a preparation method thereof. Background Art
[0002] Cyanate Ester (CE) resin is one of the key and hot spots in the current research field of resin-based composite materials. Cyanate ester resin monomers contain two or more cyanate functional groups (-OCN), and form highly cross-linked triazine cyclized polymers after curing reaction. The unique relationship between the chemical properties of the monomers and the structure / performance of the cured resin gives CE resins excellent comprehensive properties, showing the advantages of excellent mechanical properties, high heat resistance, and low water absorption. It has broad application prospects in many fields such as aerospace, automobiles, electronics, and military industry.
[0003] However, due to the high crosslinking density of cyanate resin monomer after polymerization, the highly symmetrical triazine ring structure in the molecule, and the high crystallinity, cyanate is relatively brittle, and in many applications, its fracture toughness is still insufficient, which seriously affects the promotion and application of cyanate resin. In order to improve the mechanical properties of cyanate resin materials, the method of adding inorganic fillers in the material is often adopted to enhance the mechanical properties of cyanate resin, which can improve its mechanical properties such as elastic modulus, strength, toughness, wear resistance, creep resistance and fatigue resistance. However, the compatibility and dispersibility of inorganic fillers with cyanate are poor, and the dispersing effect in cyanate resin is not ideal, and agglomeration phenomenon or even precipitation may occur easily during the curing process; simultaneously, when the amount of inorganic fillers added is too large, the heat resistance of the system will be greatly reduced, which greatly limits the application of cyanate resin nanocomposite materials. Summary of the invention
[0004] The object of the present invention is to provide a bisphenol E cyanate ester and a preparation method thereof, so as to solve the problem that the toughness of the cyanate ester resin is poor.
[0005] The purpose of the present invention can be achieved through the following technical solutions:
[0006] The first aspect of the present invention provides a method for preparing bisphenol E cyanate, comprising the following preparation steps:
[0007] Step 1, weighing by weight, heating and stirring bisphenol E cyanate resin monomer and thermoplastic polymer until they become liquid, adding modified halloysite nanotubes, stirring at 100-120° C. for 35-50 minutes, and obtaining a mixed solution;
[0008] Step 2, adding the catalyst to the mixed solution obtained above, stirring at 100-120° C. to obtain a mixture;
[0009] Step 3: The mixture is evacuated at 120-125° C. for 20-30 min, and then heated for polymerization reaction to obtain bisphenol E cyanate.
[0010] As a further solution of the present invention, the modified halloysite nanotubes are prepared by the following steps:
[0011] The epoxy resin and halloysite nanotubes are added to an acetone solution, stirred to obtain a mixed solution, vacuumed at room temperature for 10-12 minutes, then added to an aqueous sodium dodecyl sulfate solution and stirred for 2-2.5 hours to obtain a suspension, which is filtered, washed and freeze-dried to obtain modified halloysite nanotubes.
[0012] As a further embodiment of the present invention, the usage ratio of epoxy resin, halloysite nanotubes, acetone solution and sodium dodecyl sulfate aqueous solution is 1-1.25 g: 0.2-0.25 g: 200 mL: 500 mL.
[0013] As a further solution of the present invention, the diameter of the halloysite nanotube is 50-100 nm and the length is 500-1000 nm.
[0014] As a further embodiment of the present invention, the temperature of the heating polymerization reaction in step 3 is 140-150°C.
[0015] As a further embodiment of the present invention, in the preparation method, the weight ratio of bisphenol E cyanate resin monomer, thermoplastic polymer, modified halloysite nanotubes and catalyst is 80-90 parts: 0.5-2 parts: 3-8 parts: 0.05-0.2 parts.
[0016] As a further embodiment of the present invention, the thermoplastic polymer is one of polypropylene, polymethyl methacrylate and polystyrene.
[0017] As a further embodiment of the present invention, the catalyst is one of zinc acetylacetonate, copper acetylacetonate and stannous octoate.
[0018] The second aspect of the present invention provides bisphenol E cyanate obtained by the preparation method described in the first aspect.
[0019] Beneficial effects of the present invention:
[0020] The bisphenol E cyanate resin prepared in the present invention is prepared from a bisphenol E cyanate resin monomer, a thermoplastic polymer, a modified halloysite nanotube and a catalyst. The halloysite nanotube with a multi-layer structure is added to the bisphenol E cyanate resin, which can effectively improve the toughness of the bisphenol E cyanate material, enhance its mechanical properties, and further enhance the safety performance of the bisphenol E cyanate resin material during use, extend its service life, and further expand the application field of the bisphenol E cyanate resin material. At the same time, the preparation method of the bisphenol E cyanate provided in the present invention has a simple process flow, economical cost, and is suitable for large-scale production.
[0021] The modified halloysite nanotubes in the present invention are prepared by filling the halloysite nanotubes with epoxy resin. On the one hand, the epoxy resin is infiltrated into the halloysite nanotubes with a multi-layer structure, which effectively increases the strength and compatibility of the halloysite nanotubes and the dispersibility in the bisphenol E cyanate resin composite material without destroying the structure of the halloysite nanotubes. At the same time, the fracture absorption energy of the halloysite nanotubes filled with epoxy resin is high, and after being mixed with materials such as bisphenol E cyanate resin, the mechanical properties and thermal stability of the bisphenol E cyanate resin system can be effectively improved. DETAILED DESCRIPTION
[0022] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0023] Example 1
[0024] This embodiment provides a method for preparing bisphenol E cyanate, comprising the following preparation steps:
[0025] Step 1, weighing by weight, 80 parts of bisphenol E cyanate resin monomer and 0.5 parts of polypropylene are heated and stirred until they become liquid, and 3.5 parts of modified halloysite nanotubes are added, and stirred at 100° C. for 35 minutes to obtain a mixed solution;
[0026] Step 2, adding zinc acetylacetonate to the mixed solution obtained above, stirring at 100° C. to obtain a mixture;
[0027] Step 3: The mixture obtained above is evacuated at 120° C. for 20 minutes, and then heated to 140° C. for polymerization to obtain bisphenol E cyanate.
[0028] The modified halloysite nanotubes are prepared by the following steps:
[0029] 1 g of epoxy resin and 0.2 g of halloysite nanotubes (diameter 60 nm, length 800 nm) were added to 200 mL of acetone solution, stirred to obtain a mixed solution, and evacuated at room temperature for 10 min. The solution was then added to 500 mL of sodium dodecyl sulfate aqueous solution (0.5 wt%) and stirred for 2 h. During the stirring process, acetone gradually precipitated, the epoxy resin hardened, and a suspension was obtained. After filtration, washing and freeze-drying, modified halloysite nanotubes were obtained.
[0030] The bisphenol E cyanate is prepared through the above steps.
[0031] Example 2
[0032] Compared with Example 1, the only difference is:
[0033] The modified halloysite nanotubes are prepared by the following steps:
[0034] 1.25 g of epoxy resin and 0.25 g of halloysite nanotubes (diameter 60 nm, length 800 nm) were added to 200 mL of acetone solution and stirred to obtain a mixed solution. The solution was evacuated at room temperature for 12 min and then added to 500 mL of sodium dodecyl sulfate aqueous solution (0.5 wt%) and stirred for 2.5 h. During the stirring process, acetone gradually precipitated and the epoxy resin hardened to obtain a suspension. After filtration, washing and freeze-drying, modified halloysite nanotubes were obtained.
[0035] Example 3
[0036] Compared with Example 1, the only difference is:
[0037] 3.5 parts of modified halloysite nanotubes were replaced with 5 parts of modified halloysite nanotubes.
[0038] Example 4
[0039] Compared with Example 1, the only difference is:
[0040] 3.5 parts of modified halloysite nanotubes were replaced with 7.5 parts of modified halloysite nanotubes.
[0041] Example 5
[0042] Compared with Example 1, the only difference is:
[0043] Step 1: Weigh by weight, heat and stir 88 parts of bisphenol E cyanate resin monomer and 1.5 parts of polypropylene until they become liquid, add 4.5 parts of modified halloysite nanotubes, stir at 100° C. for 35 minutes, and obtain a mixed solution.
[0044] Example 6
[0045] Compared with Example 1, the only difference is:
[0046] Step 2: Add zinc acetylacetonate to the mixed solution obtained above, and stir at 115° C. to obtain a mixture.
[0047] Example 7
[0048] Compared with Example 1, the only difference is:
[0049] Step 3: The mixture obtained above is evacuated at 125° C. for 25 minutes, and then heated to 145° C. for polymerization to obtain bisphenol E cyanate.
[0050] Comparative Example 1
[0051] This comparative example provides a method for preparing bisphenol E cyanate, comprising the following preparation steps:
[0052] Step 1, weighing by weight, 80 parts of bisphenol E cyanate resin monomer and 0.5 parts of polypropylene, heating and stirring until they become liquid, stirring at 100° C. for 35 minutes to obtain a mixed solution;
[0053] Step 2, adding zinc acetylacetonate to the mixed solution obtained above, stirring at 100° C. to obtain a mixture;
[0054] Step 3: The mixture obtained above is evacuated at 120° C. for 20 minutes, and then heated to 140° C. for polymerization to obtain bisphenol E cyanate.
[0055] Comparative Example 2
[0056] This comparative example provides a method for preparing bisphenol E cyanate, comprising the following preparation steps:
[0057] Step 1, weighing by weight, 80 parts of bisphenol E cyanate resin monomer and 0.5 parts of polypropylene are heated and stirred until they become liquid, and 3.5 parts of halloysite nanotubes are added, and stirred at 100° C. for 35 minutes to obtain a mixed solution;
[0058] Step 2, adding zinc acetylacetonate to the mixed solution obtained above, stirring at 100° C. to obtain a mixture;
[0059] Step 3: The mixture obtained above is evacuated at 120° C. for 20 minutes, and then heated to 140° C. for polymerization to obtain bisphenol E cyanate.
[0060] Comparative Example 3
[0061] Compared with Example 1, the only difference is:
[0062] 3.5 parts of modified halloysite nanotubes were replaced with 2.5 parts of modified halloysite nanotubes.
[0063] Comparative Example 4
[0064] Compared with Example 1, the only difference is:
[0065] 3.5 parts of modified halloysite nanotubes were replaced with 9.5 parts of modified halloysite nanotubes.
[0066] Comparative Example 5
[0067] Compared with Example 1, the only difference is:
[0068] Step 1: Weigh by weight, heat and stir 65 parts of bisphenol E cyanate resin monomer and 1.5 parts of polypropylene until they become liquid, add 4.5 parts of modified halloysite nanotubes, stir at 100° C. for 35 minutes, and obtain a mixed solution.
[0069] Comparative Example 6
[0070] Compared with Example 1, the only difference is:
[0071] Step 1: Weigh by weight, heat and stir 85 parts of bisphenol E cyanate resin monomer and 2.5 parts of polypropylene until they become liquid, add 1.5 parts of modified halloysite nanotubes, stir at 100° C. for 35 minutes, and obtain a mixed solution.
[0072] Comparative Example 7
[0073] Compared with Example 1, the only difference is:
[0074] Step 2: Add zinc acetylacetonate to the mixed solution obtained above, and stir at 85° C. to obtain a mixture.
[0075] Comparative Example 8
[0076] Compared with Example 1, the only difference is:
[0077] Step 3: The mixture obtained above is evacuated at 115° C. for 15 minutes, and then heated to 145° C. for polymerization to obtain bisphenol E cyanate.
[0078] Performance tests were conducted on Examples 1 to 7 and Comparative Examples 1 to 8: (1) Mechanical properties test: The test was conducted using a 5982 electronic universal material testing machine from Instron, USA, in accordance with GB / T 2567-2008. The tensile specimen gauge length was 50 mm, the thickness was 4 mm, the clamp span was 120 mm, and the loading speed was 2 mm / min; the bending specimen size was 80 mm×15 mm×4 mm, and the loading speed was 2 mm / min; the test results are shown in Table 1:
[0079] Table 1
[0080]
[0081]
[0082] It can be seen from the data in Table 1 that, compared with the bisphenol E cyanate resin obtained in Comparative Examples 1-8, the tensile strength, tensile modulus and elongation at break of the bisphenol E cyanate resin prepared in Example 1-7 are all higher than those of Comparative Examples 1-8, which shows that the prepared bisphenol E cyanate resin has excellent mechanical properties. In summary, the raw material composition, ratio and process parameter settings in the process of preparing the bisphenol E cyanate resin in the present invention will affect the performance of the bisphenol E cyanate.
[0083] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.
[0084] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.
Claims
1. A method for preparing bisphenol E cyanate, characterized in that: The method comprises the following preparation steps: Step 1, weighing by weight, heating and stirring bisphenol E cyanate resin monomer and thermoplastic polymer until they become liquid, adding modified halloysite nanotubes, stirring at 100-120° C. for 35-50 minutes, and obtaining a mixed solution; Step 2, adding the catalyst to the mixed solution obtained above, stirring at 100-120° C. to obtain a mixture; Step 3: The mixture is evacuated at 120-125° C. for 20-30 min, and then heated for polymerization reaction to obtain bisphenol E cyanate.
2. The method for preparing bisphenol E cyanate according to claim 1, characterized in that: The modified halloysite nanotubes are prepared by the following steps: The epoxy resin and halloysite nanotubes are added to an acetone solution, stirred to obtain a mixed solution, vacuumed at room temperature for 10-12 minutes, then added to an aqueous sodium dodecyl sulfate solution and stirred for 2-2.5 hours to obtain a suspension, which is filtered, washed and freeze-dried to obtain modified halloysite nanotubes.
3. The method for preparing bisphenol E cyanate according to claim 2, characterized in that: The usage ratio of epoxy resin, halloysite nanotubes, acetone solution and sodium dodecyl sulfate aqueous solution is 1-1.25 g: 0.2-0.25 g: 200 mL: 500 mL.
4. The method for preparing bisphenol E cyanate according to claim 2, characterized in that: The diameter of the halloysite nanotube is 50-100 nm and the length is 500-1000 nm.
5. The method for preparing bisphenol E cyanate according to claim 1, characterized in that: The temperature of the heating polymerization reaction in step 3 is 140-150°C.
6. The method for preparing bisphenol E cyanate according to claim 1, characterized in that: In the preparation method, the weight ratio of the bisphenol E cyanate resin monomer, the thermoplastic polymer, the modified halloysite nanotube and the catalyst is 80-90 parts: 0.5-2 parts: 3-8 parts: 0.05-0.2 parts.
7. The method for preparing bisphenol E cyanate according to claim 1, characterized in that: The thermoplastic polymer is one of polypropylene, polymethyl methacrylate and polystyrene.
8. The method for preparing bisphenol E cyanate according to claim 1, characterized in that: The catalyst is one of zinc acetylacetonate, copper acetylacetonate and stannous octoate.
9. A bisphenol E cyanate, characterized in that: Prepared by the preparation method according to any one of claims 1 to 8.