A hydrocarbon resin with high bonding strength and low dielectric loss and its preparation method and application

Abstract

The present invention relates to a hydrocarbon resin with high bonding force and low dielectric loss, and a preparation method and application thereof, belonging to the technical field of polymer materials. The present invention uses hydrocarbon resin, double-bond epoxy resin, triallyl isocyanurate and terminal hydroxyl polyphenylene ether as raw materials for reaction, significantly improving the crosslinking density of the resin, thereby improving the mechanical and thermal properties of the resin. The introduction of bisphenol fluorene improves the rigidity and heat resistance of the hydrocarbon resin, while introducing more hydroxyl groups, thereby improving the bonding force between the hydrocarbon resin and the substrate. The introduction of terminal hydroxyl polyphenylene ether improves the mechanical properties and heat resistance of the resin while ensuring the dielectric properties.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a hydrocarbon resin with high bonding strength and low dielectric loss, and a preparation method and application thereof. Background Art

[0002] In recent years, with the development of 5G communication technology and Internet technology, the copper clad laminate industry has been upgraded towards high frequency and high speed, and resins suitable for high frequency applications have become the focus of research by major processing manufacturers. Hydrocarbon resin is a thermoplastic resin. Because of its excellent dielectric properties, it has become a hot spot for development in the field of high frequency and high speed copper clad laminates. However, hydrocarbon resin has the disadvantages of low mechanical properties, poor heat resistance, and low glass temperature, and often requires modification of hydrocarbon resin. Polyphenylene ether has excellent dielectric properties and good heat resistance. Mixing it with hydrocarbon resin can improve the mechanical and thermal properties of hydrocarbon resin, but the compatibility of polyphenylene ether and hydrocarbon resin is poor. At the same time, due to the low polarity of hydrocarbon resin, its adhesion to the substrate is poor. Therefore, it is necessary to provide a hydrocarbon resin with high adhesion and low dielectric loss that can solve the above problems. Summary of the invention

[0003] The object of the present invention is to provide a hydrocarbon resin with high bonding force and low dielectric loss, and a preparation method and application thereof. The hydrocarbon resin, double-bond epoxy resin, triallyl isocyanurate and terminal hydroxyl polyphenylene ether are used as raw materials for reaction, which significantly improves the crosslinking density of the resin, thereby improving the mechanical and thermal properties of the resin. The introduction of bisphenol fluorene improves the rigidity and heat resistance of the hydrocarbon resin, and at the same time introduces more hydroxyl groups, thereby improving the bonding force between the hydrocarbon resin and the substrate. The introduction of terminal hydroxyl polyphenylene ether improves the mechanical properties and heat resistance of the resin while ensuring the dielectric properties.

[0004] The technical problem to be solved by the present invention is that hydrocarbon resin has the disadvantages of low mechanical properties, poor heat resistance, low glass temperature, etc., and hydrocarbon resin often needs to be modified. Polyphenylene ether has excellent dielectric properties and good heat resistance. Mixing it with hydrocarbon resin can improve the mechanical and thermal properties of hydrocarbon resin. However, the compatibility of polyphenylene ether and hydrocarbon resin is poor. At the same time, due to the low polarity of hydrocarbon resin, its adhesion to the substrate is poor.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A method for preparing a hydrocarbon resin with high bonding strength and low dielectric loss comprises the following steps:

[0007] S1. Add hydrocarbon resin, double-bond epoxy resin and triallyl isocyanurate into solvent A, stir and dissolve to obtain a mixed solution; dissolve the initiator in solvent B, add the mixed solution and react at 80-140° C. for 3-6 hours to obtain intermediate 1;

[0008] In the above preparation process, triallyl isocyanurate is used as a cross-linking agent, and the hydrocarbon resin and the double-bond epoxy resin are cross-linked to obtain the intermediate 1.

[0009] Furthermore, in step S1, the hydrocarbon resin includes at least one of styrene-butadiene resin, polybutadiene resin, and polyprene resin.

[0010] Further, in step S1, solvent A or solvent B includes at least one of acetone, toluene, N,N-dimethylformamide and N,N-dimethylacetamide, and solvent A and solvent B may be the same or different.

[0011] Furthermore, in step S1, the initiator includes at least one of dicumyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, dicyclohexyl peroxydicarbonate, and azobisisobutyronitrile.

[0012] Furthermore, in step S1, the mass ratio of hydrocarbon resin, double bond-containing epoxy resin, triallyl isocyanurate, solvent A, initiator and solvent B is (100-120): (10-25): (3-5): (80-130): (0.1-1): (10-30).

[0013] S2, adding intermediate 1, bisphenol fluorene and catalyst 1 into solvent C, reacting at 70-100° C. for 1-3 h to obtain intermediate 2;

[0014] In the above preparation process, the phenolic hydroxyl group of bisphenol fluorene reacts with the epoxy group in the intermediate 1, thereby introducing a rigid structure, further improving the rigidity and heat resistance of the hydrocarbon resin, and introducing more hydroxyl groups to improve the bonding strength between the hydrocarbon resin and the substrate.

[0015] Further, in step S2, the catalyst 1 includes at least one of 2-methylimidazole and 2-ethyl-4-methylimidazole.

[0016] Further, in step S2, the solvent C includes at least one of acetone, toluene, N,N-dimethylformamide and N,N-dimethylacetamide.

[0017] Furthermore, in step S2, the mass ratio of intermediate 1, bisphenol fluorene, catalyst 1 and solvent C is (100-110): (2-5): (0.5-1): (50-100).

[0018] S3. Add intermediate 2, terminal hydroxyl polyphenylene ether and catalyst 2 into solvent D, stir to dissolve, and react at 100-130° C. for 4-9 hours to obtain a hydrocarbon resin with high adhesion and low dielectric loss.

[0019] In the above preparation process, the hydroxyl group of the hydroxyl-terminated polyphenylene ether reacts with the epoxy group, thereby improving the compatibility of the polyphenylene ether and the hydrocarbon resin. The reaction of the hydroxyl group and the epoxy group introduces new hydroxyl groups, thereby further improving the bonding force between the hydrocarbon resin and the substrate. In addition, the reaction of the hydroxyl groups at both ends of the hydroxyl-terminated polyphenylene ether with the epoxy group can further improve the crosslinking density of the resin. Therefore, the introduction of the hydroxyl-terminated polyphenylene ether not only ensures the dielectric properties, but also improves the mechanical properties and heat resistance of the resin.

[0020] Further, in step S3, the catalyst 2 includes at least one of 2-methylimidazole and 2-ethyl-4-methylimidazole.

[0021] Further, in step S3, the solvent D includes at least one of acetone, toluene, N,N-dimethylformamide and N,N-dimethylacetamide.

[0022] Furthermore, in step S3, the mass ratio of intermediate 2, hydroxy-terminated polyphenylene ether, catalyst 2 and solvent D is (90-100):(13-27):(1.5-3):(120-150).

[0023] A hydrocarbon resin with high bonding force and low dielectric loss prepared by the preparation method.

[0024] The present invention also provides the use of the hydrocarbon resin with high bonding force and low dielectric loss in the preparation of high-frequency and high-speed copper-clad laminates.

[0025] Beneficial effects of the present invention:

[0026] (1) In the technical solution of the present invention, hydrocarbon resin, double-bond epoxy resin, triallyl isocyanurate and terminal hydroxyl polyphenylene ether are used as raw materials for reaction, which significantly improves the crosslinking density of the resin, thereby improving the mechanical and thermal properties of the resin.

[0027] (2) In the technical solution of the present invention, the introduction of bisphenol fluorene improves the rigidity and heat resistance of the hydrocarbon resin, and at the same time introduces more hydroxyl groups to improve the bonding strength between the hydrocarbon resin and the substrate.

[0028] (3) In the technical solution of the present invention, the hydroxyl group of the hydroxyl-terminated polyphenylene ether reacts with the epoxy group, thereby improving the compatibility of the polyphenylene ether and the hydrocarbon resin. The reaction of the hydroxyl group and the epoxy group introduces new hydroxyl groups, thereby further improving the bonding force between the hydrocarbon resin and the substrate. In addition, the reaction of the hydroxyl groups at both ends of the hydroxyl-terminated polyphenylene ether with the epoxy group can further increase the crosslinking density of the resin. Therefore, the introduction of the hydroxyl-terminated polyphenylene ether improves the mechanical properties and heat resistance of the resin while ensuring the dielectric properties. DETAILED DESCRIPTION

[0029] 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.

[0030] The sources of the reagents in the following examples and comparative examples are as follows:

[0031] Hydrocarbon resin was purchased from Crayville Ricon 100 from Shanghai Huanyang Chemical Technology Co., Ltd.;

[0032] Double bond-containing epoxy resin: diallyl bisphenol A type epoxy resin purchased from Qingdao Baichen New Material Technology Co., Ltd.;

[0033] Triallyl isocyanurate: purchased from Shandong Poly Chemical Co., Ltd.;

[0034] Hydroxyl-terminated polyphenylene ether: purchased from SABIC, SA120;

[0035] Bisphenol fluorene: purchased from Shanghai MacLean Biochemical Technology Co., Ltd.;

[0036] Diisopropylbenzene peroxide: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0037] Toluene: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0038] N,N-Dimethylformamide: purchased from Shandong Hengshuo Chemical Co., Ltd.;

[0039] 2-Methylimidazole: purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0040] Example 1

[0041] A method for preparing a hydrocarbon resin with high bonding strength and low dielectric loss comprises the following steps:

[0042] S1. Add 100 g of hydrocarbon resin, 10 g of double-bond epoxy resin and 3 g of triallyl isocyanurate into 80 g of toluene, and stir at 40° C. until completely dissolved to obtain a mixed solution; dissolve 0.1 g of diisopropylbenzene peroxide in 10 g of toluene, and add the mixture to the mixed solution, react at 80° C. for 3 h, and remove part of the toluene in vacuo to obtain an intermediate 1 with a solid content of 65%;

[0043] S2, adding 100 g of intermediate 1, 2 g of bisphenol fluorene and 0.5 g of 2-methylimidazole to 50 g of toluene, reacting at 70° C. for 1 h, and removing part of the toluene in vacuo to obtain intermediate 2 with a solid content of 67%;

[0044] S3. Add 90 g of intermediate 2, 13 g of terminal hydroxyl polyphenylene ether and 1.5 g of 2-methylimidazole into 120 g of toluene, stir to dissolve, and react at 100° C. for 4 h to obtain a hydrocarbon resin with high adhesion and low dielectric loss.

[0045] Example 2

[0046] A method for preparing a hydrocarbon resin with high bonding strength and low dielectric loss comprises the following steps:

[0047] S1. Add 100 g of hydrocarbon resin, 15 g of double-bond epoxy resin and 4 g of triallyl isocyanurate into 100 g of toluene, and stir at 40° C. until completely dissolved to obtain a mixed solution; dissolve 0.3 g of diisopropylbenzene peroxide in 16 g of toluene, and add the mixture to the mixed solution, react at 90° C. for 4 h, and remove part of the toluene in vacuo to obtain an intermediate 1 with a solid content of 67%;

[0048] S2, adding 103 g of intermediate 1, 3.5 g of bisphenol fluorene and 0.6 g of 2-methylimidazole to 65 g of toluene, reacting at 80° C. for 1.5 h, and removing part of the toluene in vacuo to obtain intermediate 2 with a solid content of 69%;

[0049] S3. Add 93 g of intermediate 2, 16 g of terminal hydroxyl polyphenylene ether and 2 g of 2-methylimidazole into 130 g of toluene, stir to dissolve, and react at 110° C. for 5 h to obtain a hydrocarbon resin with high adhesion and low dielectric loss.

[0050] Example 3

[0051] A method for preparing a hydrocarbon resin with high bonding strength and low dielectric loss comprises the following steps:

[0052] S1. Add 110 g of hydrocarbon resin, 18 g of double-bond epoxy resin and 4.1 g of triallyl isocyanurate into 100 g of toluene, and stir at 50° C. until completely dissolved to obtain a mixed solution; dissolve 0.6 g of diisopropylbenzene peroxide in 20 g of toluene, and add the mixture to the mixed solution, react at 100° C. for 4.5 h, and remove part of the toluene in vacuo to obtain an intermediate 1 with a solid content of 69%;

[0053] S2, adding 105 g of intermediate 1, 3.8 g of bisphenol fluorene and 0.8 g of 2-methylimidazole to 76 g of toluene, reacting at 90° C. for 2 h, and removing part of the toluene in vacuo to obtain intermediate 2 with a solid content of 65%;

[0054] S3. Add 95 g of intermediate 2, 21 g of terminal hydroxyl polyphenylene ether and 2.4 g of 2-methylimidazole into 140 g of toluene, stir to dissolve, and react at 115° C. for 7 h to obtain a hydrocarbon resin with high adhesion and low dielectric loss.

[0055] Example 4

[0056] A method for preparing a hydrocarbon resin with high bonding strength and low dielectric loss comprises the following steps:

[0057] S1. Add 120 g hydrocarbon resin, 20 g double bond epoxy resin and 4.3 g triallyl isocyanurate to 120 g N, N-dimethylformamide, and stir at 50°C until completely dissolved to obtain a mixed solution; dissolve 0.7 g diisopropylbenzene peroxide in 25 g N, N-dimethylformamide, and add the mixture to the mixed solution, react at 120°C for 4 h, and vacuum extract part of N, N-dimethylformamide to obtain an intermediate 1 with a solid content of 68%;

[0058] S2, adding 110 g of intermediate 1, 4 g of bisphenol fluorene and 0.8 g of 2-methylimidazole to 90 g of N,N-dimethylformamide, reacting at 90° C. for 3 h, and removing part of the toluene in vacuo to obtain intermediate 2 with a solid content of 71%;

[0059] S3. Add 100 g of intermediate 2, 25 g of terminal hydroxyl polyphenylene ether and 2.7 g of 2-methylimidazole into 150 g of N,N-dimethylformamide, stir to dissolve, and react at 130° C. for 6 h to obtain a hydrocarbon resin with high adhesion and low dielectric loss.

[0060] Example 5

[0061] A method for preparing a hydrocarbon resin with high bonding strength and low dielectric loss comprises the following steps:

[0062] S1. Add 120 g hydrocarbon resin, 25 g double bond epoxy resin and 5 g triallyl isocyanurate to 130 g N,N-dimethylformamide, and stir at 50° C. until completely dissolved to obtain a mixed solution; dissolve 1 g diisopropylbenzene peroxide in 30 g N,N-dimethylformamide, and add the mixture to the mixed solution, react at 140° C. for 6 h, and vacuum extract part of N,N-dimethylformamide to obtain an intermediate 1 with a solid content of 70%;

[0063] S2, adding 110 g of intermediate 1, 5 g of bisphenol fluorene and 1 g of 2-methylimidazole to 100 g of N,N-dimethylformamide, reacting at 100° C. for 3 h, and removing part of the toluene under vacuum to obtain intermediate 2 with a solid content of 65%;

[0064] S3. Add 100 g of intermediate 2, 27 g of terminal hydroxyl polyphenylene ether and 3 g of 2-methylimidazole into 150 g of N,N-dimethylformamide, stir to dissolve, and react at 130° C. for 9 h to obtain a hydrocarbon resin with high adhesion and low dielectric loss.

[0065] Comparative Example 1

[0066] Compared with Example 3, no bisphenol fluorene was added in Comparative Example 1, and other steps and raw materials were the same as those in Example 3.

[0067] Comparative Example 2

[0068] Compared with Example 3, no hydroxy-terminated polyphenylene ether was added in Comparative Example 2, and other steps and raw materials were the same as those in Example 3.

[0069] Comparative Example 3

[0070] Compared with Example 3, in Comparative Example 3, step S3 is not performed, that is, the intermediate 2 and the hydroxy-terminated polyphenylene ether are directly blended, and the other steps and raw materials are the same as those in Example 3.

[0071] Performance Testing

[0072] The hydrocarbon resins obtained in Examples 1-5 and Comparative Examples 1-3 were heated at 100°C to remove the solvent, then heated at 180°C for 2h, cooled to room temperature, and then the obtained samples were cut into samples of 50mm×50mm×0.8mm in size for performance testing. Dielectric properties: Use a network analyzer in accordance with 2.5.5.9 in IPC-TM-650 to measure the dielectric constant and dielectric loss factor tangent at 10GHz. Glass transition temperature: According to differential scanning calorimetry, the DSC method specified in 2.4.25 of IPC-TM-650 is used for determination. Thermal decomposition temperature: The temperature at which the thermal weight loss is 5% is determined according to the method specified in 2.4.26 of IPC-TM-650. Peel strength: Test the peel strength of the metal cover layer according to the experimental conditions of "thermal stress" in the method specified in 2.4.8 of IPC-TM-650.

[0073] The hydrocarbon resins prepared in Examples 1-5 and Comparative Examples 1-3 were coated on a copper strip, and pressure (pressure of 0.1 MPa) was applied thereto. The strips were heated at 100°C for 1 h, and then heated at 180°C for 2 h. After cooling to room temperature, a tensile test was performed using a universal tensile testing machine at a speed of 10 mm / min.

[0074]

[0075]

[0076] It can be seen from the data in Tables 1 and 2 that the hydrocarbon resin prepared by the present invention has excellent mechanical properties, heat resistance and dielectric properties, and has high bonding strength with the substrate. It can be seen from the data of Comparative Example 3 and Comparative Example 1 that since bisphenol fluorene was not added in Comparative Example 1, the heat resistance, mechanical properties and peel strength of the hydrocarbon resin decreased. It can be seen from the data of Comparative Example 3 and Comparative Example 2 that since no terminal hydroxyl polyphenylene ether was added in Comparative Example 2, the heat resistance and mechanical properties of the hydrocarbon resin decreased. It can be seen from the data of Comparative Example 3 and Comparative Example 3 that since the intermediate 2 and the terminal hydroxyl polyphenylene ether were directly blended in Comparative Example 3, the terminal hydroxyl polyphenylene ether was not chemically connected to the hydrocarbon resin molecular chain, resulting in a decrease in the heat resistance and mechanical properties of the hydrocarbon resin.

[0077] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0078] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A method for preparing a hydrocarbon resin with high bonding strength and low dielectric loss, characterized in that: The following steps are involved: S1. Add hydrocarbon resin, double-bond epoxy resin and triallyl isocyanurate into solvent A, stir and dissolve to obtain a mixed solution; dissolve the initiator in solvent B, add the mixed solution and react at 80-140° C. for 3-6 hours to obtain intermediate 1; S2, adding intermediate 1, bisphenol fluorene and catalyst 1 into solvent C, reacting at 70-100° C. for 1-3 h to obtain intermediate 2; In step S2, the catalyst 1 includes at least one of 2-methylimidazole and 2-ethyl-4-methylimidazole; S3, adding intermediate 2, terminal hydroxyl polyphenylene ether and catalyst 2 into solvent D, stirring and dissolving, and reacting at 100-130° C. for 4-9 hours to obtain a hydrocarbon resin with high adhesion and low dielectric loss; In step S3, the catalyst 2 includes at least one of 2-methylimidazole and 2-ethyl-4-methylimidazole; In the step S1, the hydrocarbon resin includes at least one of styrene-butadiene resin, polybutadiene resin, and polyprene resin.

2. The method for preparing a hydrocarbon resin with high bonding strength and low dielectric loss according to claim 1, characterized in that: In the step S1, the initiator includes at least one of dicumyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, dicyclohexyl peroxydicarbonate, and azobisisobutyronitrile.

3. The method for preparing a hydrocarbon resin with high bonding strength and low dielectric loss according to claim 1, characterized in that: In the step S1, the mass ratio of hydrocarbon resin, double bond-containing epoxy resin, triallyl isocyanurate, solvent A, initiator and solvent B is (100-120): (10-25): (3-5): (80-130): (0.1-1): (10-30).

4. The method for preparing a hydrocarbon resin with high bonding strength and low dielectric loss according to claim 1, characterized in that: In the step S2, the mass ratio of the intermediate 1, bisphenol fluorene, catalyst 1 and solvent C is (100-110): (2-5): (0.5-1): (50-100).

5. The method for preparing a hydrocarbon resin with high bonding strength and low dielectric loss according to claim 1, characterized in that: In the step S3, the mass ratio of the intermediate 2, the hydroxy-terminated polyphenylene ether, the catalyst 2 and the solvent D is (90-100): (13-27): (1.5-3): (120-150).

6. A hydrocarbon resin with high adhesion and low dielectric loss obtained by the preparation method according to any one of claims 1 to 5.

7. Use of the hydrocarbon resin with high adhesion and low dielectric loss obtained by the preparation method according to any one of claims 1 to 5 in the preparation of high-frequency and high-speed copper-clad laminates.

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