A method for preparing and using a polydicyclopentadiene material

Abstract

This invention discloses a polydicyclopentadiene material, prepared from dicyclopentadiene monomers and phenolic or amine compounds containing norbornene or norbornene structures under the catalysis of a main catalyst and a co-catalyst. The phenolic or amine compounds containing norbornene or norbornene structures not only possess antioxidant capabilities but can also undergo cross-linking reactions with dicyclopentadiene under the action of the dicyclopentadiene ring-opening metathesis polymerization system and the catalyst, forming a fully interpenetrating polymer network with dicyclopentadiene. This simultaneously achieves the purposes of reinforcement, toughening, and anti-aging, resulting in a polydicyclopentadiene material with high strength, toughness, and anti-aging properties, as well as good dielectric properties.

Description

Technical Field

[0001] This invention belongs to the technical field of polydicyclopentadiene materials, specifically relating to a polydicyclopentadiene material modified with phenol or amine compounds. Background Technology

[0002] PDCPD, or polydicyclopentadiene, is included in Item 130 of the National Key New Materials First Application Demonstration Guidance List (2021 Edition) due to its lightweight, high physical and mechanical properties, resistance to high and low temperatures, corrosion resistance, and environmental friendliness. PDCPD's main properties include low density, corrosion resistance, suitability for large and complex structural products, excellent coatability, good wave transmission, environmental friendliness, impact resistance, and short molding cycle. Therefore, as an excellent thermosetting material, it is widely used, especially in engineering machinery, heavy trucks, military, chemical, medical, and outdoor fields.

[0003] In some applications, in addition to requiring high strength and toughness, polydicyclopentadiene also needs to have good aging resistance. However, existing polydicyclopentadiene materials cannot meet these requirements and further improvements are needed. Summary of the Invention

[0004] To address the aforementioned problems in the existing technology, the present invention aims to provide a polydicyclopentadiene material with high strength, toughness, and excellent anti-aging and dielectric properties. The present invention introduces phenolic or amine compounds containing norbornene or norbornene structures, which not only possess antioxidant capabilities but also undergo cross-linking reactions with dicyclopentadiene under the action of a ring-opening metathesis polymerization system and catalyst, forming a fully interpenetrating polymer network. This simultaneously achieves the purposes of reinforcement, toughening, and anti-aging, resulting in a modified polydicyclopentadiene material with high strength, toughness, and excellent anti-aging and dielectric properties.

[0005] To achieve the above-mentioned objectives, the present invention adopts the following solution:

[0006] In a first aspect, the present invention provides a phenolic or amine compound containing a norbornene or norbornene structure, with the following structure:

[0007]

[0008] For example, 1,2-R-3,6-dihydroxybenzonorbornene, 1,2-R-3,6-dihydroxybenzonorbornane, 1,2-R-3,6-dihydroxycyclohexanorbornane, 1,2-R-3,6-bis(4-aminophenoxy)benzonorbornene, 1,2-R-3,6-bis(4-aminophenoxy)benzonorbornane, 1,2-R-3,6-bis(4-aminophenoxy)cyclohexanorbornane, 1,2-R-3,6-bis(4-amino-5-methylphenoxy)benzonorbornene, 1,2-R-3,6-bis(4-amino-5-methylphenoxy)benzonorbornane, 1,2-R-3,6-bis(4-amino-5-methylphenoxy)benzonorbornane, 1,2-R-3,6-bis(4-amino-5-methylphenoxy)benzonorbornane, 1,2-R-3,6-bis(4-amino-5-methylphenoxy)benzonorbornane, 1,2-R-3,6-bis(4-amino-5-methylphenoxy)benzonorbornane, The following are compounds: phenoxycyclohexanobornene, 1,2-R-3,6-bis(4-amino-3,5-methylphenoxy)benzobornene, 1,2-R-3,6-bis(4-amino-3,5-methylphenoxy)benzobornene, 1,2-R-3,6-bis(4-amino-3,5-methylphenoxy)cyclohexanobornene, 1,2-R-3,6-bis(4-amino-2-trifluoromethylphenoxy)benzobornene, 1,2-R-3,6-bis(4-amino-2-trifluoromethylphenoxy)benzobornene, 1,2-R-3,6-bis(4-amino-2-trifluoromethylphenoxy)cyclohexanobornene, wherein R is hydrogen or methyl, preferably hydrogen.

[0009] Secondly, the present invention provides a method for preparing a phenolic or amine compound containing a norbornene or norbornene structure, the steps of which include:

[0010] The product is prepared by mixing norbornene monomers containing phenol or ammonia with anhydrous ethanol and a hydrogenation catalyst under nitrogen conditions, introducing hydrogen gas, and heating to carry out a hydrogenation reaction.

[0011] In this invention, the monomers include, for example, 1,2-R-3,6-dihydroxybenzonorbornene, 1,2-R-3,6-bis(4-aminophenoxy)benzonorbornene, 1,2-R-3,6-bis(4-amino-5-methylphenoxy)benzonorbornene, 1,2-R-3,6-bis(4-amino-3,5-methylphenoxy)benzonorbornene, and 1,2-R-3,6-bis(4-amino-2-trifluoromethylphenoxy)benzonorbornene, wherein R is hydrogen or methyl, preferably hydrogen, and the monomers most preferably are 3,6-dihydroxybenzonorbornene and 3,6-bis(4-aminophenoxy)benzonorbornene;

[0012] In this invention, the mass ratio of the norbornene monomer containing phenol or ammonia to the volume ratio of anhydrous ethanol is 50-150 g / L, for example, 50, 70, 90, 110, 130, or 150 g / L.

[0013] In this invention, the hydrogenation catalyst is a conventional choice in the field, such as at least one of homogeneous catalysts containing metals such as nickel and / or palladium, and supported catalysts containing metals such as palladium and / or nickel. Preferably, at least one of supported catalysts containing palladium and / or nickel is preferred, and more preferably, at least one of supported catalysts such as palladium / carbon, palladium / silica, and Raney nickel is preferred. Preferably, the active metal content in the hydrogenation catalyst is 5-10 wt%, for example, 5, 6, 7, 8, 9, or 10 wt%.

[0014] The amount of hydrogenation catalyst used is 2-15% of the mass of norbornene monomers containing phenol or ammonia, for example 2, 3, 4, 5, 6, 8, 10, 12, 14, 15%.

[0015] In this invention, the pressure of hydrogen gas introduced is 4-10 MPa, for example 4, 5, 6, 7, 8, 9, 10 MPa, preferably 5-10 MPa.

[0016] In this invention, the hydrogenation reaction is carried out at a temperature of 60-220°C, for example, 60, 80, 100, 150, 170, 190, 210, or 220°C, preferably 80-220°C; and the reaction time is 8-12 hours, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12 hours.

[0017] In this invention, after the hydrogenation reaction is completed, post-processing processes such as cooling, filtration, crystallization, washing, and drying are also included. These are all conventional operations in the field, and this invention does not have any special requirements.

[0018] Thirdly, the present invention provides the use of the above-mentioned phenolic or amine compounds containing norbornene or norbornene structures in the preparation of polydicyclopentadiene.

[0019] A method for preparing polydicyclopentadiene, comprising the following steps:

[0020] Under nitrogen protection, dicyclopentadiene monomer, phenol or amine compound containing norbornene or norbornene structure, and main catalyst are added to the reactor. Co-catalyst is added under mechanical stirring, and the mixture is rapidly mixed and reacted.

[0021] In this invention, the molar ratio of the main catalyst, the co-catalyst, and the dicyclopentadiene monomer is from 1:10:2500 to 1:80:5000.

[0022] The amount of the phenol or amine compound containing norbornene or norbornene structure added is 5-25% of the mass of the dicyclopentadiene monomer.

[0023] The selected main catalyst is a tungsten-based catalyst and / or a molybdenum-based catalyst, preferably a tungsten-based catalyst containing phenols, such as the one described in CN116063662A. The R substituent can be H or an alkyl group below C10, preferably methyl, ethyl, propyl, or butyl; the tungsten-based catalyst is preferably WOCl2(OC6H2-2,6-Cl2-4-CH3)2.

[0024] The cocatalyst is an organotin compound and / or an alkylaluminum compound, preferably an alkylaluminum compound R. n AlH 4-n R can be methyl, ethyl, propyl, butyl, or octyl, and alkyl aluminum compounds are preferably triethylaluminum or triisobutylaluminum;

[0025] The reaction temperature is 70-180℃, and the reaction time is 1-4h.

[0026] The beneficial effects of this invention are as follows:

[0027] The modified polydicyclopentadiene material of the present invention has high strength, toughness, and excellent anti-aging and dielectric properties. Detailed Implementation

[0028] To better understand the technical solution of the present invention, the content of the present invention will be further described below with reference to the following specific embodiments, but the content of the present invention is not limited to the following embodiments.

[0029] The main raw material sources in the embodiments and comparative examples of this invention are as follows; unless otherwise specified, all other raw materials were obtained through ordinary commercial channels:

[0030] Palladium on carbon (5%): Beijing Innocare Technology Co., Ltd.;

[0031] 3,6-Bis(4-aminophenoxy)benzonorbornene: synthesized according to patent CN113511980B;

[0032] Tungsten-based catalysts containing phenols: synthesized according to CN116063662A;

[0033] Dicyclopentadiene: Beijing Innocare Technology Co., Ltd.;

[0034] Triisobutylaluminum: Beijing Innocare Technology Co., Ltd.;

[0035] Triethylaluminum: Beijing Innocare Technology Co., Ltd.;

[0036] 3,6-Dihydroxy-benzonorbornene: Beijing Innocare Technology Co., Ltd.

[0037] Example 1

[0038] Preparation of cyclohexane and norbornene compounds containing phenolic groups:

[0039] 16.5 g of palladium on carbon (5%) catalyst was added to a reactor. Under nitrogen conditions, 110 g of 3,6-dihydroxy-benzonorbornene and 1 L of anhydrous ethanol were added to a 2 L reactor. The reactor was purged with nitrogen three times and hydrogen three times to maintain a hydrogen environment. The system was then heated to 200 °C and the hydrogen pressure was set to 5 MPa. The reaction was carried out for 8 h. After the reaction was completed, the palladium on carbon catalyst was removed by filtration. The filtrate was then poured into a large amount of water for low-temperature crystallization. The precipitate was collected, filtered, washed, and vacuum dried to obtain 106 g of white powder, namely 3,6-dihydroxy-cyclohexanenorbornene.

[0040] The structure is as follows:

[0041] Characterization: H 1 NMR(CDCl3)δ1.00-3.00(14,m),3.50-5.00(2,m),3.50-5.00(2,s).

[0042] Example 2

[0043] Preparation of compounds containing aminobenzonorbornene:

[0044] 2.25 g of palladium on carbon (5%) catalyst was added to a reactor. Under nitrogen conditions, 112.5 g of 3,6-bis(4-aminophenoxy)benzonorbornene and 1 L of anhydrous ethanol were added to a 2 L reactor. The reactor was purged with nitrogen three times and hydrogen three times to maintain a hydrogen environment. The system was then heated to 60 °C and the hydrogen pressure was set to 5 MPa. The reaction was carried out for 12 h. After the reaction was completed, the palladium on carbon catalyst was removed by filtration. The filtrate was then poured into a large amount of water for low-temperature crystallization. The precipitate was collected, filtered, washed, and vacuum dried to obtain 108.4 g of white powder, namely 3,6-bis(4-aminophenoxy)benzonorbornene.

[0045] The structure is as follows:

[0046] Evidence: H 1 NMR(CDCl3)δ1.00-2.00(6H,m),2.00-4.00(2H,m),5.00-6.00(4H,s),6.00-7.00(10H,m).

[0047] Example 3

[0048] Preparation of compounds containing aminocyclohexane and norbornene:

[0049] 3,6-bis(4-aminocyclohexyloxy)cyclohexane and norbornene were prepared according to Example 1 of CN117776939A.

[0050] The structure is as follows:

[0051] Preparation of polydicyclopentadiene

[0052] Example 4

[0053] 3,6-Dihydroxy-benzoborneol

[0054] Under nitrogen atmosphere, 100g (0.76mol) of dicyclopentadiene, 294.5mg (0.152mmol) of WOCl2(OC6H2-2,6-Cl2-4-CH3) and 15g of 3,6-dihydroxy-benzonorbornene were added to a reaction vessel, followed by 12.2ml (1mol / L) of triisobutylaluminum / toluene solution. The mixture was stirred rapidly for 3 minutes, then pressurized and the reaction mixture was forced into a mold under pressure. The reaction was carried out at 180℃ for 4 hours.

[0055] The molar ratio of the main catalyst, co-catalyst, and dicyclopentadiene monomer is 1:80:5000, and the amount of 3,6-dihydroxy-benzonorbornene added is 15% of the mass of the dicyclopentadiene monomer.

[0056] Example 5

[0057] Under nitrogen atmosphere, 100g (0.76mol) of dicyclopentadiene, 1189mg (0.304mmol) of WOCl2(OC6H2-2,6-Cl2-4-CH3)2 and 5g of 3,6-dihydroxy-benzonorbornene were added to a reaction vessel, followed by 3ml (1mol / L) of triisobutylaluminum / toluene solution. The mixture was stirred rapidly for 3min, then pressurized and the reaction mixture was forced into a mold under pressure. The reaction was carried out at 70℃ for 1h.

[0058] The molar ratio of the main catalyst, co-catalyst, and dicyclopentadiene monomer is 1:10:2500, and the amount of 3,6-dihydroxy-benzonorbornene added is 5% of the mass of the dicyclopentadiene monomer.

[0059] Example 6

[0060] Under nitrogen atmosphere, 100g (0.76mol) of dicyclopentadiene, 1158mg (0.2533mmol) of WOCl2(OC6H2-2,6-Cl2-4-CH3)2, and 10g of 3,6-dihydroxy-cyclohexane and norbornene were added to a reaction vessel, followed by 12.5ml (1mol / L) of triethylaluminum toluene solution. The mixture was stirred rapidly for 3 minutes, then pressurized and the reaction mixture was forced into a mold under pressure. The reaction was carried out at 90℃ for 2 hours.

[0061] The molar ratio of the main catalyst, co-catalyst, and dicyclopentadiene monomer is 1:50:3000, wherein the added 3,6-dihydroxy-cyclohexane and norbornene accounts for 10% of the mass of the dicyclopentadiene monomer.

[0062] Example 7

[0063] The amounts of main catalyst, co-catalyst, and dicyclopentadiene monomer added were the same as in Example 4, except that 3,6-dihydroxybenzonorbornene was replaced with 3,6-bis(4-aminophenoxy)benzonorbornene, with an addition amount of 25g. The reaction temperature was set to 150℃ and the reaction time was 2h.

[0064] Example 8

[0065] The amounts of main catalyst, co-catalyst, and dicyclopentadiene monomer added were the same as in Example 5, except that 3,6-dihydroxybenzonorbornene was replaced with 3,6-bis(4-aminophenoxy)benzonorbornene, and the amount added was 20g. The reaction temperature and reaction time were the same as in Example 5.

[0066] Example 9

[0067] The amounts of main catalyst, co-catalyst, and dicyclopentadiene monomer added were the same as in Example 6, except that 3,6-dihydroxy-cyclohexanenorbornene was replaced with 3,6-bis(4-aminocyclohexyloxy)cyclohexanenorbornene, with an addition amount of 16g. The reaction temperature and reaction time were the same as in Example 6.

[0068] Comparative Example 1

[0069] The amounts of main catalyst, co-catalyst, and dicyclopentadiene monomer added were the same as in Example 4, while the amount of 3,6-dihydroxy-benzonorbornene added was 0, and the reaction temperature and reaction time were the same as in Example 4.

[0070] The performance test parameters and corresponding test methods in the various embodiments and comparative examples of this invention are as follows:

[0071] Tensile strength: GB / T 1040.1-2018;

[0072] Elongation at break: GB / T 1040.1-2018;

[0073] Contact angle: GB / T 30693-2014;

[0074] Aging test: GB / T 3512-2014;

[0075] Impact strength: GB / T 1043.1-2008;

[0076] Dielectric properties: GB / T1409-2006;

[0077] The test results of tensile strength, elongation at break, and contact angle in the various embodiments and comparative examples of this invention are shown in Table 1:

[0078] Table 1. Performance test results of the examples and comparative examples.

[0079] sample Tensile strength (MPa) Elongation at break / % Contact angle / ° Example 4 58.6 8.1 20.5 Example 5 56.5 7.2 26.4 Example 6 57.4 7.5 20.4 Example 7 59.2 7.2 21.3 Example 8 56.2 7.5 20.5 Example 9 57.4 7.8 23.5 Comparative Example 1 45.2 4.2 83.5

[0080] The aging performance test results of the various embodiments and comparative examples of this invention are shown in Table 2:

[0081] Table 2 Performance test results of the examples and comparative examples

[0082]

[0083]

[0084] The dielectric performance test results of the various embodiments and comparative examples of this invention are shown in Table 3:

[0085] Table 3. Dielectric property test results of the examples and comparative examples.

[0086]

Claims

1. A polydicyclopentadiene, characterized in that, The raw material contains a phenolic or amine compound with a norbornene or norbornene structure, selected from the following structures: 3,6-dihydroxy-benzonorbornene, 3,6-dihydroxy-benzonorbornene, 3,6-dihydroxy-cyclohexanorbornene, 3,6-bis(4-aminophenoxy)benzonorbornene, 3,6-bis(4-aminophenoxy)benzonorbornene, 3,6-bis(4-aminocyclohexyloxy)cyclohexanorbornene; The amount of the phenol or amine compound containing norbornene or norbornene structure added is 5-15% of the mass of the dicyclopentadiene monomer.

2. A method for preparing polydicyclopentadiene, comprising: Under nitrogen protection, dicyclopentadiene monomer, phenol or amine compound containing norbornene or norbornene structure, main catalyst, and co-catalyst are added to the reaction vessel, and reaction is carried out. The phenolic or amine compounds containing the norbornene or norbornene structure are selected from the following structures: 3,6-dihydroxy-benzonorbornene, 3,6-dihydroxy-benzonorbornene, 3,6-dihydroxy-cyclohexanorbornene, 3,6-bis(4-aminophenoxy)benzonorbornene, 3,6-bis(4-aminophenoxy)benzonorbornene, and 3,6-bis(4-aminocyclohexyloxy)cyclohexanorbornene; The amount of the phenol or amine compound containing norbornene or norbornene structure added is 5-15% of the mass of the dicyclopentadiene monomer.

3. The method according to claim 2, wherein, The molar ratio of the main catalyst, co-catalyst, and dicyclopentadiene monomer is from 1:10:2500 to 1:80:5000.

4. The method according to any one of claims 2-3, wherein, The main catalyst is a tungsten-based catalyst and / or a molybdenum-based catalyst.

5. The method according to claim 4, wherein, The main catalyst is a tungsten-based catalyst containing phenols.

6. The method according to claim 5, wherein, The main catalyst is WOCl2(OC6H2-2,6-Cl2-4-CH3)2.

7. The method according to any one of claims 2-3, wherein, The cocatalyst is an organotin compound and / or an alkylaluminum compound.

8. The method according to claim 7, wherein, The cocatalyst is an alkylaluminum compound R. n AlH 4-n R represents methyl, ethyl, propyl, butyl, or octyl.

9. The method according to claim 8, wherein, The alkylaluminum compounds are selected from triethylaluminum and triisobutylaluminum.

10. The method according to any one of claims 2-3, wherein, The reaction temperature is 70-180℃, and the reaction time is 1-4h.

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