Modified polydicyclopentadiene materials, methods of making and using the same

Abstract

The application belongs to the technical field of forming die materials, and particularly relates to a modified polydicyclopentadiene material and a preparation method and application thereof. Raw materials of the modified polydicyclopentadiene material include A component and B component; the A component includes the following raw material components in parts by weight: 100 parts of dicyclopentadiene, 8-12 parts of a methacryl cage type silsesquioxane, 4-6 parts of a butene-ethylene-styrene copolymer, and 2-3 parts of methylaluminoxane. The modified polydicyclopentadiene material provided by the application has high high-temperature stability, long service life and the like.

Description

Technical Field

[0001] This invention belongs to the field of molding die material technology, specifically relating to a modified polydicyclopentadiene material, its preparation method, and its application. Background Technology

[0002] Polydicyclopentadiene (PDCPD) can not only be used as a material for molding dies, but is also considered an ideal choice for manufacturing large, complex or small-batch dies. Compared with traditional steel or aluminum dies, dies made using PDCPD can be injection molded at low temperature and low pressure, thereby significantly reducing costs and shortening the manufacturing cycle.

[0003] The method for making molds from polydicyclopentadiene (PDCPD) generally involves mixing two low-viscosity liquid raw materials (material A and material B) at room temperature and then injecting them into a master mold. After injection, the raw materials undergo a chemical reaction and rapidly solidify at a low temperature (generally 60℃~80℃) (usually within a few minutes), thereby replicating a high-precision mold cavity.

[0004] However, polydicyclopentadiene (PDCPD) has a heat distortion temperature of approximately 120°C, limiting its application to products requiring lower molding temperatures and making it unsuitable for high-temperature molding processes. Furthermore, in scenarios requiring millions of cycles of mass production, its wear resistance is poor and its service life is short. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a modified polydicyclopentadiene material, its preparation method, and its applications, thereby resolving at least one aspect of the above-mentioned technical issues.

[0006] This invention is achieved through the following technical solution: In a first aspect, the present invention provides a modified polydicyclopentadiene material, the raw materials of which include component A and component B; Component A comprises the following raw materials in parts by weight: 100 parts dicyclopentadiene, 8 to 12 parts methacrylyl cage-type silsesquioxane, 4 to 6 parts butene-ethylene-styrene copolymer, 2 to 3 parts methylaluminoxane; Component B comprises the following raw materials in parts by weight: 100 parts dicyclopentadiene, 0.3 to 0.5 parts tungsten hexachloride, 5 to 10 parts tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester, 3 to 5 parts silane coupling agent modified nano silica, 15 to 20 parts spherical alumina, and 5 to 8 parts graphite powder.

[0007] Secondly, the present invention provides a method for preparing the above-mentioned modified polydicyclopentadiene material, comprising the following steps: After mixing component A and component B, the mixture is poured into a mold and pressed, and then cured.

[0008] Thirdly, the present invention provides an application of the above-mentioned modified polydicyclopentadiene material in a molding die.

[0009] The modified polydicyclopentadiene material provided by this invention has at least the following beneficial technical effects compared with the prior art: The modified polydicyclopentadiene material provided by this invention has advantages such as high high-temperature stability and long service life.

[0010] The method for preparing modified polydicyclopentadiene material provided by this invention has at least the following beneficial technical effects compared with the prior art: The method for preparing modified polydicyclopentadiene material provided by this invention is simple and easy to operate. Detailed Implementation

[0011] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is described and illustrated below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. All other embodiments obtained by those skilled in the art based on the embodiments provided by this invention without inventive effort are within the scope of protection of this invention.

[0012] Obviously, the following description is merely some examples or embodiments of the present invention. Those skilled in the art can apply the present invention to other similar scenarios without any inventive effort. Furthermore, it is understood that although the effort involved in such development may be complex and lengthy, for those skilled in the art related to the content disclosed in this invention, modifications to design, manufacturing, or production based on the technical content disclosed in this invention are merely conventional technical means and should not be construed as insufficient disclosure of the present invention.

[0013] However, there may be instances where unnecessary detailed descriptions are omitted. For example, detailed descriptions of well-known matters or repetitive descriptions of essentially the same structures may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand the invention and is not intended to limit the subject matter of the claims.

[0014] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions, and all technical features and optional technical features of the present invention can be combined with each other to form new technical solutions.

[0015] The first aspect of this invention provides a modified polydicyclopentadiene material, the raw materials of which include component A and component B; Component A comprises the following raw materials in parts by weight: 100 parts dicyclopentadiene, 8 to 12 parts methacrylyl cage-type silsesquioxane, 4 to 6 parts butene-ethylene-styrene copolymer, 2 to 3 parts methylaluminoxane; Component B comprises the following raw materials in parts by weight: 100 parts dicyclopentadiene, 0.3 to 0.5 parts tungsten hexachloride, 5 to 10 parts tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester, 3 to 5 parts silane coupling agent modified nano silica, 15 to 20 parts spherical alumina, and 5 to 8 parts graphite powder.

[0016] The modified polydicyclopentadiene material provided in this embodiment of the invention comprises the following components: In component A: the methacrylate groups in the methacrylic cage-like silsesquioxane have good compatibility with dicyclopentadiene (DCPD); the ethylene-butene segments in the butene-ethylene-styrene copolymer have a similar nonpolar structure to DCPD, which can be dissolved through molecular chain entanglement and does not participate in the polymerization reaction, but exists in the network gaps as physical crosslinking points, absorbing impact energy through the flexibility of the molecular chains. At the same time, the styrene segments increase the Tg (approximately 100°C) of the copolymer, which helps to increase the glass transition temperature of the composite material; the methacrylic cage-like silsesquioxane and the butene-ethylene-styrene copolymer can improve the heat resistance and toughness of the material; methylaluminoxane and tungsten hexachloride in component B act as co-catalysts, reacting with tungsten hexachloride to generate active alkylated tungsten species. In component B: tungsten hexachloride serves as the main catalyst for the polymerization of dicyclopentadiene; tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester can improve the high-temperature stability and toughness of the material; spherical alumina and graphite powder synergistically improve the thermal conductivity of the material.

[0017] In some embodiments, the CAS number for dicyclopentadiene is 77-73-6.

[0018] In some embodiments, the CAS number of the methylpropenyl cage-like silsesquioxane is 1204591-17-2.

[0019] In some embodiments, the CAS number of the butene-ethylene-styrene copolymer is 68648-89-5.

[0020] In some embodiments, the CAS number of methylaluminoxane is 120144-90-3.

[0021] In some embodiments, the CAS number of tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester is 1279820-16-4.

[0022] In some embodiments, the average particle size of the spherical alumina is 5 μm to 10 μm.

[0023] In some embodiments, the average particle size of the graphite powder is 5 μm to 10 μm.

[0024] In some embodiments, the mass ratio of component A to component B is (1~1.02):1.

[0025] A second aspect of this invention provides a method for preparing a modified polydicyclopentadiene material, comprising the following steps: S10. Mix the A component mixture and the B component mixture, inject into the mold, hold under pressure, and then perform a curing process.

[0026] The method for preparing modified polydicyclopentadiene material provided in this invention is simple and easy to operate. The prepared modified polydicyclopentadiene material has advantages such as high high-temperature stability and long service life.

[0027] In some embodiments, in step S10 above, the temperature of the A component mixture is 25°C to 30°C.

[0028] In some embodiments, the preparation of component A mixture in step S10 above includes the following steps: S101. Under an inert atmosphere, dicyclopentadiene, methacryloyl cage-type silsesquioxane and butene-ethylene-styrene copolymer are mixed and then mixed with methylaluminoxane at 25°C to 30°C.

[0029] In the preparation of the above-mentioned component A mixture, it is prepared under an inert atmosphere to avoid the oxidation of methylaluminoxane to aluminum alkoxy. First, dicyclopentadiene, methacryloyl cage-type silsesquioxane and butene-ethylene-styrene copolymer are mixed to form a homogeneous phase. Then, methylaluminoxane is added and mixed at room temperature to avoid side reactions with dicyclopentadiene (DCPD) and to ensure that the components of component A are mixed evenly.

[0030] In some embodiments, in step S101 above, the inert atmosphere is nitrogen, argon or helium.

[0031] In some embodiments, in step S101 above, the temperature at which dicyclopentadiene, methacrylamide cage-like silsesquioxane, and butene-ethylene-styrene copolymer are mixed is 60°C to 65°C. Under these conditions, the viscosity of the system decreases, which promotes the stretching of the methacrylamide cage-like silsesquioxane molecular chains, forming a molecular-level dispersion. After cooling, the methacrylamide cage-like silsesquioxane core is encapsulated by dicyclopentadiene molecules, thereby maintaining a stable dispersion.

[0032] In some embodiments, in step S101 above, the stirring speed for mixing dicyclopentadiene, methacryloyl cage-type silsesquioxane and butene-ethylene-styrene copolymer is 200 rpm to 300 rpm.

[0033] In some embodiments, in step S101 above, the mixing time with methylaluminoxane is 15 min to 30 min.

[0034] In some embodiments, in step S10 above, the temperature of the B component mixture is 25°C to 30°C.

[0035] In some embodiments, the preparation of component B mixture in step S10 above includes the following steps: S102. Under an inert atmosphere, dicyclopentadiene, tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester, silane coupling agent modified nano-silica, spherical alumina and graphite powder are subjected to high-speed shearing, and then tungsten hexachloride is added for further high-speed shearing and mixing.

[0036] In the preparation of the above-mentioned component B mixture, dicyclopentadiene, tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester, silane coupling agent modified nano-silica, spherical alumina and graphite powder are subjected to high-speed shear mixing to uniformly disperse the silane coupling agent modified nano-silica, spherical alumina and graphite powder in the organic phase. Then, tungsten chloride catalyst is added to make the components of component B mixture uniformly mixed.

[0037] In some embodiments, in step S102 above, the rotational speed of the high-speed shear is 3000 rpm to 5000 rpm.

[0038] In some embodiments, in step S102 above, the high-speed shearing time is 30 min to 40 min.

[0039] In some embodiments, in step S102 above, the time for adding tungsten hexachloride and continuing high-speed shear mixing is 10 min to 15 min.

[0040] In some embodiments, the pressure for holding pressure in step S10 is 0.5 MPa to 1 MPa.

[0041] In some embodiments, the pressure holding time in step S10 is 5 min to 8 min.

[0042] In some embodiments, in step S10 above, the heating rate of the curing process is 1°C / min to 2°C / min. In this case, the internal thermal stress of the modified polydicyclopentadiene material can be reduced, thereby preventing cracking of the modified polydicyclopentadiene material caused by thermal shock.

[0043] In some embodiments, in step S10 above, the curing temperature is 120°C to 130°C.

[0044] In some embodiments, the curing time in step S10 is 2h to 3h.

[0045] The following description, in conjunction with specific embodiments, provides further details. For ease of explanation, the following embodiments and comparative examples involve: (1) The CAS number of dicyclopentadiene is 77-73-6.

[0046] (2) The CAS number of methylpropenyl cage-type silsesquioxane is 1204591-17-2.

[0047] (3) The CAS number of the butene-ethylene-styrene copolymer is 68648-89-5.

[0048] (4) The CAS number of methylaluminoxane is 120144-90-3.

[0049] (5) The CAS number of tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester is 1279820-16-4.

[0050] Example 1 Example 1 provides a modified polydicyclopentadiene material, composed of the following raw materials in parts by weight: Component A: 100 parts dicyclopentadiene, 10 parts methacryloyl cage silsesquioxane, 5 parts butene-ethylene-styrene copolymer, 2 parts methylaluminoxane; Component B: 100 parts dicyclopentadiene, 0.4 parts tungsten hexachloride, 8 parts tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester, 4 parts silane coupling agent modified nano-silica, 17 parts spherical alumina, and 7 parts graphite powder.

[0051] The average particle size of the spherical alumina is 8 μm.

[0052] The average particle size of the graphite powder is 9 μm.

[0053] The mass ratio of component A to component B is 1:1.

[0054] This embodiment also provides a method for preparing the above-mentioned modified polydicyclopentadiene material, the steps of which are as follows: Preparation of E10.A component mixture Under a nitrogen atmosphere and a stirring speed of 200 rpm, dicyclopentadiene, methacryloyl cage-type silsesquioxane and butene-ethylene-styrene copolymer were stirred and mixed at 60°C, then cooled to room temperature (25°C~30°C), methylaluminoxane was added, and stirring was continued for 15 min to obtain component A mixture.

[0055] Preparation of E20.B component mixture Under a nitrogen atmosphere and a stirring speed of 3000 rpm, dicyclopentadiene, tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester, silane coupling agent modified nano-silica, spherical alumina and graphite powder were subjected to high-speed shearing for 40 min, followed by the addition of tungsten hexachloride and continued high-speed shearing for 10 min to obtain the B component mixture.

[0056] Preparation of E30 modified polydicyclopentadiene materials After mixing component A and component B, the mixture is poured into a mold and pressed, and then cured. The temperature of component A mixture is 25℃, and the temperature of component B mixture is 25℃. The pressure held is 0.5 MPa for 8 minutes; The curing process was carried out at a heating rate of 2℃ / min, a temperature of 120℃, and a time of 2h.

[0057] Example 2 Example 2 provides a modified polydicyclopentadiene material, composed of the following raw materials in parts by weight: Component A: 100 parts dicyclopentadiene, 8 parts methacryloyl cage silsesquioxane, 4 parts butene-ethylene-styrene copolymer, 3 parts methylaluminoxane; Component B: 100 parts dicyclopentadiene, 0.5 parts tungsten hexachloride, 5 parts tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester, 3 parts silane coupling agent modified nano-silica, 15 parts spherical alumina, and 5 parts graphite powder.

[0058] The average particle size of the spherical alumina is 10 μm.

[0059] The average particle size of the graphite powder is 10 μm.

[0060] The mass ratio of component A to component B is 1:1.

[0061] This embodiment also provides a method for preparing the above-mentioned modified polydicyclopentadiene material, the steps of which are basically the same as those in Example 1.

[0062] Example 3 Example 3 provides a modified polydicyclopentadiene material, composed of the following raw materials in parts by weight: Component A: 100 parts dicyclopentadiene, 12 parts methacrylyl cage-type silsesquioxane, 6 parts butene-ethylene-styrene copolymer, 2 parts methylaluminoxane; Component B: 100 parts dicyclopentadiene, 0.3 parts tungsten hexachloride, 10 parts tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester, 5 parts silane coupling agent modified nano-silica, 20 parts spherical alumina, and 8 parts graphite powder.

[0063] The average particle size of the spherical alumina is 5 μm.

[0064] The average particle size of the graphite powder is 5 μm.

[0065] The mass ratio of component A to component B is 1:1.

[0066] This embodiment also provides a method for preparing the above-mentioned modified polydicyclopentadiene material, the steps of which are basically the same as those in Example 1.

[0067] Comparative Example 1 Comparative Example 1 provides a polydicyclopentadiene material, composed of the following raw materials in parts by weight: Component A: 100 parts dicyclopentadiene, 5 parts butene-ethylene-styrene copolymer, 2 parts methylaluminoxane; Component B: 100 parts dicyclopentadiene, 0.4 parts tungsten hexachloride, 4 parts silane coupling agent modified nano-silica, 17 parts spherical alumina, and 7 parts graphite powder.

[0068] The average particle size of the spherical alumina is 8 μm.

[0069] The average particle size of the graphite powder is 9 μm.

[0070] The mass ratio of component A to component B is 1:1.

[0071] This comparative example also provides a method for preparing the above-mentioned polydicyclopentadiene material, the steps of which are basically the same as those in Example 1.

[0072] Comparative Example 2 Comparative Example 2 provides a polydicyclopentadiene material, composed of the following raw materials in parts by weight: Component A: 100 parts dicyclopentadiene, 5 parts butene-ethylene-styrene copolymer, 2 parts methylaluminoxane; Component B: 100 parts dicyclopentadiene, 0.4 parts tungsten hexachloride, 4 parts silane coupling agent modified nano-silica, 17 parts spherical alumina, and 7 parts graphite powder; The average particle size of the spherical alumina is 8 μm.

[0073] The average particle size of the graphite powder is 9 μm.

[0074] The mass ratio of component A to component B is 1:1.

[0075] This comparative example also provides a method for preparing the above-mentioned polydicyclopentadiene material, the steps of which are basically the same as those in Example 1.

[0076] To verify the advancement of the modified polydicyclopentadiene material and its preparation method provided in this embodiment of the invention, the mechanical properties and heat distortion temperature of the modified polydicyclopentadiene material prepared in this embodiment and the polydicyclopentadiene material prepared in the comparative example were tested, and the results are shown in Table 1 below.

[0077] in: In the mechanical property testing, the bending and tensile properties of the test specimens were tested using an AGS-X10KN Shimadzu universal testing machine. The bending test specimen was 4mm×10mm×60mm, the tensile test specimen was a 4mm×10mm dumbbell-shaped specimen, and the impact test specimen was a 4mm×10mm×60mm notched specimen.

[0078] Table 1

[0079] From Table 1 above, at least the following conclusions can be drawn: (1) The raw materials for Comparative Example 1 did not contain methacrylyl cage-type silsesquioxane (in component A) and tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester (in component B), resulting in a decrease in the flexural strength, tensile strength, elongation at break, and heat distortion temperature of the prepared polydicyclopentadiene material. Therefore, it can be seen that in the modified polydicyclopentadiene material provided by the embodiments of the present invention, the methacrylyl cage-type silsesquioxane and butene-ethylene-styrene copolymer in the raw materials can improve the heat resistance and toughness of the material, while tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester can improve the high-temperature stability and toughness of the material.

[0080] (2) The raw materials for Comparative Example 2 did not contain butene-ethylene-styrene copolymer (component A) and tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester (component B). Although the flexural strength, tensile strength, and elongation at break of the polydicyclopentadiene material prepared in Comparative Example 2 were slightly higher than those in Comparative Example 1, the heat distortion temperature was significantly lower and all were lower than those in the Example. It can be seen that in the modified polydicyclopentadiene material provided in the Examples of the Invention, the ethylene-butene segments in the butene-ethylene-styrene copolymer have a similar nonpolar structure to DCPD. They can be dissolved by molecular chain entanglement and do not participate in the polymerization reaction. Instead, they exist in the network gaps as physical crosslinking points. They absorb impact energy through the flexibility of the molecular chains. At the same time, the styrene segments increase the Tg (about 100°C) of the copolymer, which helps to increase the glass transition temperature of the composite material.

[0081] It should be noted that the present invention is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments that have the same structure and perform the same effects as the technical concept within the scope of the present invention are included within the scope of the present invention. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of the present invention, are also included within the scope of the present invention.

Claims

1. A modified polydicyclopentadiene material, characterized in that, The raw materials include component A and component B; Component A comprises the following raw materials in parts by weight: 100 parts dicyclopentadiene, 8 to 12 parts methacrylyl cage-type silsesquioxane, 4 to 6 parts butene-ethylene-styrene copolymer, 2 to 3 parts methylaluminoxane; Component B comprises the following raw materials in parts by weight: 100 parts dicyclopentadiene, 0.3 to 0.5 parts tungsten hexachloride, 5 to 10 parts tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester, 3 to 5 parts silane coupling agent modified nano silica, 15 to 20 parts spherical alumina, and 5 to 8 parts graphite powder.

2. The modified polydicyclopentadiene material according to claim 1, characterized in that, It satisfies at least one of the following characteristics (1) to (3): (1) The average particle size of the spherical alumina is 5 μm to 10 μm; (2) The average particle size of the graphite powder is 5μm~10μm; (3) The mass ratio of component A to component B is (1~1.02):

1.

3. A method for preparing the modified polydicyclopentadiene material as described in claim 1 or 2, characterized in that, Includes the following steps: After mixing component A and component B, the mixture is poured into a mold and pressed, and then cured.

4. The method for preparing the modified polydicyclopentadiene material according to claim 3, characterized in that, The preparation of the A component mixture includes the following steps: Under an inert atmosphere, dicyclopentadiene, methacryloyl cage-type silsesquioxane and butene-ethylene-styrene copolymer were mixed and then mixed with methylaluminoxane at 25°C to 30°C.

5. The method for preparing the modified polydicyclopentadiene material according to claim 4, characterized in that, It satisfies at least one of the following characteristics (1) to (3): (1) The mixing temperature of dicyclopentadiene, methacrylamide cage-type silsesquioxane and butene-ethylene-styrene copolymer is 60℃~65℃; (2) The stirring speed for mixing dicyclopentadiene, methacrylamide cage-type silsesquioxane and butene-ethylene-styrene copolymer is 200 rpm to 300 rpm; (3) The mixing time with methylaluminoxane is 15 min to 30 min.

6. The method for preparing the modified polydicyclopentadiene material according to claim 5, characterized in that, The preparation of the B component mixture includes the following steps: Under an inert atmosphere, dicyclopentadiene, tert-butyl((2-chloropyrimidin-5-yl)methyl)aminomethyl ester, silane coupling agent modified nano-silica, spherical alumina and graphite powder were subjected to high-speed shearing, followed by the addition of tungsten hexachloride for further high-speed shearing and mixing.

7. The method for preparing the modified polydicyclopentadiene material according to claim 6, characterized in that, It satisfies at least one of the following characteristics (1) to (3): (1) The rotational speed of the high-speed shearing is 3000 rpm to 5000 rpm; (2) The high-speed shearing time is 30 min to 40 min; (3) The time for adding tungsten hexachloride and continuing high-speed shearing and mixing is 10 min to 15 min.

8. The method for preparing the modified polydicyclopentadiene material according to any one of claims 3 to 7, characterized in that, It satisfies at least one of the following characteristics (1) to (2): (1) The pressure for holding the pressure is 0.5 MPa to 1 MPa; (2) The pressure holding time is 5 min to 8 min.

9. The method for preparing the modified polydicyclopentadiene material according to claim 8, characterized in that, It satisfies at least one of the following characteristics (1) to (3): (1) The heating rate of the curing treatment is 1℃ / min to 2℃ / min; (2) The curing temperature is 120℃~130℃; (3) The curing time is 2h~3h.

10. The application of a modified polydicyclopentadiene material as described in claim 1 or 2 in a molding die.

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