Hydrocarbon resin as well as preparation method and application thereof

Abstract

The invention provides hydrocarbon resin and a preparation method and application thereof, the hydrocarbon resin is a blend of a composition, and the composition comprises the following components in parts by weight: 10-110 parts of poly-conjugated diene; 10 to 110 parts of a cross-linking agent; 1-10 parts of a curing agent; 1-50 parts of a toughening agent; and 10 to 110 parts of an inorganic filler. In the hydrocarbon resin disclosed by the invention, the poly-conjugated diene is mutually soluble with the cross-linking agent and the toughening agent, so that a uniform system can be obtained.

Description

Technical Field

[0001] The present invention belongs to the technical field of thermosetting resins and their preparation, and particularly relates to a hydrocarbon resin, a preparation method thereof, and an application thereof. Background Art

[0002] With the rapid development of industries such as 5G communication and the Internet of Things, the signal transmission of electronic devices tends to be high-frequency and high-speed, posing higher requirements for performance parameters such as the polarity, heat resistance, dielectric constant, and loss factor of the matrix resin materials used in high-frequency copper clad laminates. Currently, the matrix resins used in the field of high-frequency copper clad laminates include modified epoxy resins, polytetrafluoroethylene resins, polyimide resins, bismaleimide resins, polyhydrocarbon resins, polyphenylene ethers, etc. Among them, polyhydrocarbons are saturated or unsaturated polymers composed of only carbon and hydrogen elements, with molecular weights ranging from several hundred to tens of thousands. Structurally, due to the small polarity of C-H in the polymer molecular chain, the resin exhibits excellent low dielectric (2.0 - 2.8), low loss (<0.005) performance, and extremely low water absorption. Hydrocarbon resin has rich raw material sources, has an obvious cost advantage compared with other copper clad laminate resins, and has excellent processing performance, showing broad application prospects in the field of high-end copper clad laminates.

[0003] Due to its low molecular polarity, hydrocarbon resin is difficult to be miscible with modifiers, crosslinking agents, and curing agents. The cured product obtained by high-temperature curing of the system is in a phase-separated state, which limits its wide application. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a hydrocarbon resin, which is a blend of a composition; the composition, by weight, includes:

[0005]

[0006]

[0007] According to an embodiment of the present invention, the polyconjugated diene is, for example, selected from at least one of polybutadiene, polyisoprene, polystyrene-butadiene block copolymer, polystyrene-isoprene block copolymer, polycyclopentadiene, etc.

[0008] According to an embodiment of the present invention, the weight parts of the crosslinking agent, curing agent, toughening agent, and inorganic filler are based on the weight parts of the polyconjugated diene.

[0009] According to an embodiment of the present invention, the number average molecular weight of the polyconjugated diene is 900 - 7000.

[0010] According to an embodiment of the present invention, the composition, by weight, includes 70 - 100 parts of polyconjugated diene; for example, 70 parts, 80 parts, 90 parts, or 100 parts.

[0011] According to an embodiment of the present invention, the composition comprises, by weight parts, 20 - 50 parts of a crosslinking agent; for example, 20 parts, 30 parts, 40 parts or 50 parts.

[0012] According to an embodiment of the present invention, the composition comprises, by weight parts, 2 - 6 parts of a curing agent; for example, 2 parts, 3 parts, 4 parts, 5 parts or 6 parts.

[0013] According to an embodiment of the present invention, the composition comprises, by weight parts, 8 - 25 parts of a toughening agent; for example, 8 parts, 10 parts, 15 parts, 20 parts or 25 parts.

[0014] According to an embodiment of the present invention, the composition comprises, by weight parts, 10 - 50 parts of an inorganic filler; for example, 10 parts, 20 parts, 30 parts, 40 parts or 50 parts.

[0015] According to an embodiment of the present invention, the crosslinking agent is one or more of triallyl isocyanurate (TAIC), benzocyclobutene (BCB), 3 - aminophenylacetylene (APA), p - vinyltoluene, vinyl resin, epoxy butadiene hydroxy.

[0016] According to an embodiment of the present invention, the curing agent is one or more of benzoyl peroxide (BPO), methyl ethyl ketone peroxide (MEKP), azobisisobutyronitrile (AIBN), dicumyl peroxide (DCP), ammonium persulfate, potassium persulfate, tert - butyl peroxybenzoate.

[0017] According to an embodiment of the present invention, the toughening agent is one or more of vinyl - terminated polyphenylene ether, polyethersulfone containing unsaturated groups, polyetherimide containing unsaturated groups, polyimide containing unsaturated groups.

[0018] According to an embodiment of the present invention, the inorganic filler is one or more of silica, hollow silica, boron nitride, aluminum oxide, microsilica, zirconium carbide ceramic microspheres, zinc borate, magnesium hydroxide.

[0019] The present invention also provides a method for preparing the above - mentioned hydrocarbon resin, and the method is as follows:

[0020] Mix polyconjugated diene, crosslinking agent, curing agent and toughening agent to obtain a transparent solution; add inorganic filler and continue to mix to obtain the hydrocarbon resin.

[0021] According to an embodiment of the present invention, the temperature for mixing polyconjugated diene, crosslinking agent, curing agent and toughening agent is 110 - 160 °C.

[0022] According to an embodiment of the present invention, the mixing time of polyconjugated diene, crosslinking agent, curing agent and toughening agent is 30 - 110 min.

[0023] According to an embodiment of the present invention, the temperature during mixing after adding the inorganic filler is 110 - 160 °C.

[0024] According to an embodiment of the present invention, the mixing time after adding the inorganic filler is 20 - 50 min.

[0025] According to an embodiment of the present invention, the method further includes a post-treatment step, that is, after the inorganic filler is mixed, the system is cooled down, and the cooling is to 50 - 100 °C.

[0026] The present invention also provides a cured resin, which is a cured product of the above-mentioned hydrocarbon resin.

[0027] According to an embodiment of the present invention, the glass transition temperature of the cured resin is 285 - 294 °C.

[0028] According to an embodiment of the present invention, the thermal decomposition temperature of the cured resin > 400 °C.

[0029] According to an embodiment of the present invention, the dielectric constant of the cured resin is 2.57 - 2.64.

[0030] According to an embodiment of the present invention, the dielectric loss of the cured resin is 0.0027 - 0.0031.

[0031] According to an embodiment of the present invention, the water absorption rate of the cured resin in 24 h < 0.06%.

[0032] The present invention also provides a preparation method of the above-mentioned cured resin, which includes:

[0033] Curing the hydrocarbon resin to obtain the cured resin.

[0034] According to an embodiment of the present invention, the curing temperature is 160 - 250 °C.

[0035] According to an embodiment of the present invention, the curing time is 2 - 20 h.

[0036] According to an embodiment of the present invention, the curing process is divided into 5 stages, which are in turn: curing at 160 - 180 °C for 2 - 4 h, curing at 180 - 200 °C for 2 - 4 h, curing at 200 - 220 °C for 2 - 4 h, curing at 220 - 240 °C for 2 - 4 h, curing at 240 - 250 °C for 2 - 8 h; for example, the curing process is specifically: 160 °C / 2 h, 180 °C / 2 h, 200 °C / 2 h, 220 °C / 2 h, 250 °C / 5 h.

[0037] The present invention also provides a composite material, which is a cured product after the above-mentioned hydrocarbon resin and quartz fiber are compounded.

[0038] According to an embodiment of the present invention, the flexural strength of the composite material > 300 MPa.

[0039] The present invention also provides the applications of the above-mentioned hydrocarbon resin, cured resin or composite material in the fields of copper clad laminates, aerospace, etc. Specifically, it is applied in electronic components or radomes.

[0040] Advantages of the present invention:

[0041] The hydrocarbon resin of the present invention is obtained by blending polyconjugated diene, crosslinking agent, curing agent, toughening agent and inorganic filler. Among them, polyconjugated diene is miscible with the crosslinking agent and toughening agent, and a homogeneous system can be obtained.

[0042] The cured resin of the present invention is the cured product of the hydrocarbon resin. The cured resin is uniform and dense. Without affecting its dielectric property and hygroscopicity, its heat resistance and mechanical properties are both improved; significantly improving the heat resistance and mechanical properties of the hydrocarbon resin.

[0043] The glass transition temperature of the cured resin of the present invention is 285 - 294 °C, the thermal decomposition temperature > 400 °C, the dielectric constant is 2.57 - 2.64, the dielectric loss is 0.0027 - 0.0031, and the water absorption rate in 24 h < 0.06%. The flexural strength of the composite material obtained by compounding and curing the cured resin with quartz fiber > 300 MPa.

[0044] The present invention also discloses a method for safely, simply and efficiently preparing the hydrocarbon resin and the cured resin. The prepared hydrocarbon resin and cured resin have excellent heat resistance, dielectric property, mechanical property and hygroscopic property, and are suitable as the resin matrix of high-performance composite materials, and have application value in the fields of copper clad laminates, aerospace, etc., such as electronic components, radomes, etc. Specific embodiments

[0045] The technical solutions of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are only used to illustrate and explain the present invention exemplarily, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0046] Unless otherwise specified, the raw materials and reagents used in the following embodiments are all commercially available products, or can be prepared by known methods.

[0047] Example 1

[0048] Add 100 g of polybutadiene (number-average molecular weight of 3,000) into a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser. Slowly heat up to 120 °C. After the temperature stabilizes, sequentially add 20 g of triallyl isocyanurate (TAIC), 10 g of benzocyclobutene, 10 g of vinyl-terminated polyphenylene ether, and 2 g of benzoyl peroxide (BPO). Stir at a constant temperature of 120 °C for 35 min. Add 10 g of silica powder, stir at 120 °C for 30 min, cool down to 60 °C and discharge to obtain a hydrocarbon resin.

[0049] Example 2

[0050] Add 100 g of polybutadiene (number-average molecular weight of 2,000) into a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser. Slowly heat up to 120 °C. After the temperature stabilizes, sequentially add 20 g of triallyl isocyanurate (TAIC), 10 g of benzocyclobutene (BCB), 10 g of vinyl-terminated polyphenylene ether, and 2 g of dicumyl peroxide (DCP). Stir at a constant temperature of 120 °C for 35 min. Add 15 g of silica powder, stir at 120 °C for 30 min, cool down to 60 °C and discharge to obtain a hydrocarbon resin.

[0051] Example 3

[0052] Add 100 g of polybutadiene (number-average molecular weight of 2,000) into a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser. Slowly heat up to 120 °C. After the temperature stabilizes, sequentially add 15 g of triallyl isocyanurate (TAIC), 10 g of benzocyclobutene (BCB), 10 g of vinyl-terminated polyphenylene ether, and 2 g of dicumyl peroxide (DCP). Stir at a constant temperature of 120 °C for 35 min. Add 10 g of boron nitride, stir at 120 °C for 50 min, cool down to 50 °C and discharge to obtain a hydrocarbon resin.

[0053] Example 4

[0054] Add 100 g of polybutadiene (number-average molecular weight of 2,000) into a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser. Slowly heat up to 120 °C. After the temperature stabilizes, sequentially add 10 g of triallyl isocyanurate (TAIC), 10 g of benzocyclobutene (BCB), 10 g of vinyl-terminated polyphenylene ether, and 2 g of dicumyl peroxide (DCP). Stir at a constant temperature of 120 °C for 40 min. Add 15 g of boron nitride, stir at 120 °C for 50 min, cool down to 50 °C and discharge to obtain a hydrocarbon resin.

[0055] Comparative Example 1

[0056] Add 100 g of polybutadiene (number-average molecular weight of 2,000) into a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser. Slowly heat up to 120 °C. After the temperature stabilizes, add 10 g of hydroxyl-terminated polyphenylene ether and 2 g of dicumyl peroxide (DCP) in sequence. Stir at a constant temperature of 120 °C for 40 min. Add 15 g of boron nitride and stir at 120 °C for 50 min. Cool down to 50 °C and discharge to obtain a hydrocarbon resin.

[0057] Comparative Example 2

[0058] Add 100 g of polybutadiene (number-average molecular weight of 3,000) into a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser. Slowly heat up to 120 °C. After the temperature stabilizes, add 20 g of diphenylmethane bismaleimide and 2 g of benzoyl peroxide (BPO) in sequence. Stir at a constant temperature of 120 °C for 35 min. Add 10 g of silica powder and stir at 120 °C for 30 min. Cool down to 60 °C and discharge to obtain a hydrocarbon resin.

[0059] Comparative Example 3

[0060] Add 100 g of polybutadiene (number-average molecular weight of 3,000) into a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser. Slowly heat up to 120 °C. After the temperature stabilizes, add 20 g of bisphenol A epoxy and 2 g of benzoyl peroxide (BPO) in sequence. Stir at a constant temperature of 120 °C for 35 min. Add 10 g of silica powder and stir at 120 °C for 30 min. Cool down to 60 °C and discharge to obtain a hydrocarbon resin.

[0061] Comparative Example 4

[0062] Add 100 g of polybutadiene (number-average molecular weight of 2,000) into a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser. Slowly heat up to 120 °C. After the temperature stabilizes, add 20 g of triallyl isocyanurate (TAIC) and 2 g of dicumyl peroxide (DCP) in sequence. Stir at a constant temperature of 120 °C for 35 min. Add 15 g of silica powder and stir at 120 °C for 30 min. Cool down to 60 °C and discharge to obtain a hydrocarbon resin.

[0063] Application Examples 1-5

[0064] The hydrocarbon resins obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were placed in a vacuum drying oven at 130 °C and evacuated for 5 to 30 minutes until there were no bubbles in the system. Among them, the hydrocarbon resins in Comparative Examples 1 to 3 showed delamination, the resin was uneven, and no subsequent curing experiments were carried out. The resins in Examples 1 to 4 and Comparative Example 4 were poured into a customized steel mold and cured in stages in an electrothermal constant temperature drying oven to obtain cured resins, which were respectively designated as Application Examples 1 to 5. The curing temperature increase process was as follows: 160 °C / 2 h, 180 °C / 2 h, 200 °C / 2 h, 220 °C / 2 h, 250 °C / 5 h.

[0065] Application Example 7

[0066] The hydrocarbon resins obtained in Examples 1 to 4 and Comparative Example 4 were placed in an oven at 100 °C. After being placed for 2 h, they melted to form a resin glue solution, and then the glue solution was evenly coated on a quartz fiber cloth to make a prepreg. The iron mold was preheated on a flat vulcanizing machine at 140 °C for 1 h.

[0067] The forming steps of the quartz fiber composite material were as follows: (1) Place 8 layers of prepregs cut into 16×11 mm in the iron mold; (2) Set the pressure of the flat vulcanizing machine to 2 MPa, and the curing system to 160 °C / 2 h, 180 °C / 2 h, 200 °C / 2 h, 220 °C / 2 h, 250 °C / 5 h; (3) After the press cooled down, remove the mold to obtain the quartz fiber composite material.

[0068] The cured resins obtained in Application Examples 1 to 5 were subjected to glass transition temperature testing, thermal decomposition temperature testing, dielectric property testing, and water absorption testing. The quartz fiber composite material in Application Example 6 (i.e., the composite material in Table 1) was subjected to flexural strength testing. The test results are shown in Table 1 below.

[0069] In Table 1, the test methods for each parameter are as follows:

[0070] Glass transition temperature testing: Dynamic mechanical thermal analyzer (DMA test, frequency 1 Hz, heating rate 3 °C / min);

[0071] Thermal decomposition temperature testing method: Thermal analyzer (TGA, heating rate 10 °C / min, N2 atmosphere, N2 flow rate 50 mL / min);

[0072] Dielectric property testing method: Resonant cavity method;

[0073] Water absorption testing method: After soaking at room temperature for 24 h, test the weight gain of the composite material;

[0074] Flexural strength testing standard: GB / T 1449 - 2005.

[0075] Table 1

[0076]

[0077]

[0078] As can be seen from Table 1, the glass transition temperature of the cured resin of the present invention is between 285 - 294 °C, the thermal decomposition temperature > 400 °C, the dielectric constant is between 2.57 - 2.64, the dielectric loss is between 0.0027 - 0.0031, and the water absorption rate in 24 hours < 0.06%. The flexural strength of the composite material obtained by compounding and curing the hydrocarbon resin and quartz fiber > 300 MPa.

[0079] It can be seen that the crosslinking agent and toughening agent used in the present invention can be well compatible with polybutadiene, and the cured resin is excellent in heat resistance, dielectric properties, moisture absorption properties, and mechanical properties.

[0080] Above, the embodiments of the present invention have been described by way of example. However, the protection scope of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A hydrocarbon resin, characterized in that, It is a blend of compositions, and the compositions, by parts by weight, include:

2. The hydrocarbon resin according to claim 1, characterized in that, The number average molecular weight of the polyconjugated diene is 900 to 7000.

3. The hydrocarbon resin according to claim 1 or 2, characterized in that, The crosslinking agent is one or more of triallyl isocyanurate, benzocyclobutene, 3-aminophenylacetylene, p-vinyltoluene, vinyl resin, and epoxy butanetriol. Preferably, the curing agent is one or more of benzoyl peroxide, methyl ethyl ketone peroxide, azobisisobutyronitrile, dicumyl peroxide, ammonium persulfate, potassium persulfate, and tert-butyl peroxybenzoate. Preferably, the toughening agent is one or more of vinyl-terminated polyphenylene ether, polyethersulfone containing unsaturated groups, polyetherimide containing unsaturated groups, or polyimide containing unsaturated groups. Preferably, the inorganic filler is one or more of silica, hollow silica, boron nitride, aluminum oxide, microsilica, zirconium carbide ceramic microspheres, zinc borate, or magnesium hydroxide.

4. The preparation method of the hydrocarbon resin according to any one of claims 1 to 3, characterized in that, The method is as follows: Mix the polyconjugated diene, crosslinking agent, curing agent, and toughening agent to obtain a transparent solution; add the inorganic filler and continue mixing to obtain the hydrocarbon resin.

5. A cured resin, characterized in that, It is a cured product of the hydrocarbon resin according to any one of claims 1-3.

6. The cured resin according to claim 5, characterized in that, The glass transition temperature of the cured resin is 285-294 °C; Preferably, the thermal decomposition temperature of the cured resin > 400 °C; Preferably, the dielectric constant of the cured resin is 2.57-2.64; Preferably, the dielectric loss of the cured resin is 0.0027 to 0.0031; Preferably, the water absorption rate of the cured resin in 24 h < 0.06%.

7. The method for preparing the cured resin according to claim 5 or 6, characterized in that, The method is as follows: Cure the hydrocarbon resin to obtain the cured resin.

8. The method according to claim 7, wherein The curing temperature is 160-250 °C; the curing time is 2-20 h.

9. A composite material, characterized in that, The composite material is a cured product after the hydrocarbon resin according to any one of claims 1-3 is compounded with quartz fiber.

10. Application of the hydrocarbon resin according to any one of claims 1-3, or the cured resin according to claim 5 or 6, or the composite material according to claim 9 in the field of copper clad laminates or aerospace, specifically, applied in electronic components or radomes.

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