Polymerization of polyisoprene in the presence of a catalyst comprising a transition metal compound

Abstract

The application discloses a polyacetylene curing agent, a resin composition and a laminated insulating film. The resin composition with excellent dielectric properties is prepared by selecting a polyacetylene curing agent with a specific structure and a thermosetting resin, and adding a curing accelerator and an inorganic filler in the resin system, so that a better thermal expansion coefficient is obtained, and the processing performance of the resin composition is improved. By selecting the polyacetylene curing agent with the specific structure, and R being a hydrocarbon chain segment, in the curing reaction with the thermosetting resin, R is substituted, and the resin composition with excellent dielectric properties can be obtained. In the resin composition, the acetylene group is introduced, so that the mechanical properties of the resin composition are enhanced, the thermal expansion coefficient is reduced, and the processing performance of the resin composition is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of technology, in particular to a poly-cymene curing agent, a resin composition and a laminated insulating film. BACKGROUND

[0002] In the field of high-speed signal transmission, signal integrity is a key factor that cannot be ignored in package design. Signal loss is mainly divided into two parts: conduction loss and radiation loss. The dielectric constant and loss tangent are two core parameters that affect loss. High dielectric constant will slow down the transmission speed of the signal, and high loss tangent will increase the loss of signal energy, thereby affecting the transmission quality of the signal and the overall performance of the electronic device.

[0003] In order to cope with these challenges, selecting low-loss materials becomes the primary task for preparing Low Loss laminated insulating adhesive film. The ideal low-loss material should have low dielectric constant and low loss tangent, and at the same time, it also needs to ensure excellent mechanical properties and processability. At present, PTFE, LCP, PI and their modified materials are widely used in the preparation of such adhesive films due to their low-loss characteristics. The difficulty of preparing Low Loss laminated insulating adhesive film lies in how to further improve the mechanical strength and processing performance of the material while maintaining its low-loss characteristics. Therefore, it is necessary to propose a new scheme to solve the above problems. SUMMARY

[0004] Therefore, the present application aims to provide a poly-cymene curing agent, a resin composition and a laminated insulating film, which has low-loss characteristics, as well as excellent mechanical properties and processing performance.

[0005] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0006] A poly-cymene curing agent, the structural formula of the poly-cymene curing agent is as follows:

[0007] ;

[0008] R is a hydrocarbon chain segment, and n and m are both integers greater than 1.

[0009] As a preferred scheme, n and m are both integers from 1 to 15, wherein n is preferably an integer from 3 to 12, more preferably an integer from 5 to 12, and m is preferably an integer from 3 to 10.

[0010] As a preferred scheme, the number average molecular weight of the poly-cymene curing agent is 300-5000, and the number average molecular weight thereof is preferably 1000-2800.

[0011] As a preferred scheme, the structural formula of the poly-cymene curing agent is

[0012] 、

[0013] 、

[0014]

[0015] Any one of claims 1-5.

[0016] A resin composition comprising the following components by weight:

[0017] thermosetting resin 80-120 parts, curing accelerator 0.01-10 parts, inorganic filler 300-500 parts, and the aforementioned poly-cinnamene curing agent 80-180 parts.

[0018] As a preferred solution, the thermosetting resin is at least one of polyimide resin, phenoxy resin, polyamide resin, polyamide-imide resin, polyvinyl acetal resin, preferably one or a mixture of both of polyimide resin and phenoxy resin.

[0019] As a preferred solution, the number average molecular weight of the thermosetting resin is 2000-100000, preferably 5000-50000.

[0020] As a preferred solution, the curing accelerator is one of imidazole-based curing accelerator, tertiary amine-based curing accelerator, phosphine-based curing accelerator, photobase generator, sulfonium salt-based curing accelerator; the inorganic filler is at least one of silicon dioxide, aluminum oxide, barium sulfate, talc, clay, mica, magnesium oxide, aluminum hydroxide, aluminum nitride, boron nitride, silicon nitride, glass powder, glass frit, glass fiber, carbon fiber, preferably silicon dioxide, more preferably fused silicon dioxide.

[0021] As a preferred solution, the equivalent ratio of the thermosetting resin to the poly-cinnamene curing agent is 1: (0.3-2), preferably 1: (0.6-1.5).

[0022] A laminated insulation film is prepared by the following steps: the aforementioned resin composition is coated on a base film made of PET or BOPP material using a coating machine; after coating, drying is performed, the drying temperature is 100°C, and the drying time is 10 min; after drying, the base film is removed to obtain the laminated insulation film.

[0023] Compared with the prior art, the present application has obvious advantages and beneficial effects, specifically, from the above technical solution, it can be known that:

[0024] By selecting a specific structure of poly-cymene curing agent, and R is a hydrocarbon segment, in the curing reaction with thermosetting resin, R is replaced, a resin composition with excellent dielectric properties can be obtained, and the introduction of cymene group in the resin composition, so that the mechanical properties of the resin composition is enhanced, the thermal expansion coefficient is reduced, thereby improving the processing performance of the resin composition.

[0025] To make the structural features and effects of the present application clearer, the present application will be described in detail below with specific examples: DETAILED DESCRIPTION

[0026] The present application discloses a poly-cymene curing agent, the structural formula of the poly-cymene curing agent is as follows:

[0027] ;

[0028] R is a hydrocarbon segment, n and m are both integers greater than 1; Specifically, as a preferred solution, the n and m are both integers of 1-15, wherein n is preferably an integer of 3-12, more preferably an integer of 5-12, m is preferably an integer of 3-10; And the number average molecular weight of the poly-cymene curing agent is 300-5000, preferably 1000-2800; The structural formula of the poly-cymene curing agent is

[0029] 、

[0030] 、

[0031]

[0032] Any one of the above.

[0033] The present application also discloses a resin composition, comprising the following components by weight:

[0034] A thermosetting resin 80-120 parts, a curing accelerator 0.01-10 parts, an inorganic filler 300-500 parts, and the aforementioned poly-cinnamene curing agent 80-180 parts; within the specific component ranges of the thermosetting resin, the flow characteristics of the resulting resin composition, the bending resistance after curing become more excellent, the heat resistance becomes more excellent, the thermosetting resin is at least one of a polyimide resin, a phenoxy resin, a polyamide resin, a polyamide-imide resin, a polyvinyl acetal resin, preferably one or a mixture of both of a polyimide resin and a phenoxy resin; the number average molecular weight of the thermosetting resin is 2000-100000, preferably 5000-50000; the curing accelerator is one of an imidazole-based curing accelerator, a tertiary amine-based curing accelerator, a phosphine-based curing accelerator, a photobase generator, a sulfonium salt-based curing accelerator; the inorganic filler is at least one of silica, alumina, barium sulfate, talc, clay, mica, magnesium oxide, aluminum hydroxide, aluminum nitride, boron nitride, silicon nitride, glass powder, glass frit, glass fiber, carbon fiber, the inorganic filler is preferably silica, more preferably fused silica; the equivalent ratio of the thermosetting resin to the poly-cinnamene curing agent is 1:(0.3-2), preferably 1:(0.6-1.5).

[0035] The present application also discloses a laminated insulation film, which is prepared by the following steps: coating the aforementioned resin composition on a base film made of PET or BOPP material using a coating machine; after coating, drying is performed, the drying temperature is 100°C, and the drying time is 10 min; after drying, the base film is removed to obtain the laminated insulation film.

[0036] The following is illustrated by a plurality of examples and comparative examples, the raw materials used and the proportions are shown in Table 1 and Table 2, respectively.

[0037]

[0038] Table 1

[0039] The preparation method of the poly-cinnamene curing agent A is as follows:

[0040] Take 400 g of cymene, 400 mL of xylene and appropriate amount of divinylbenzene, put the three substances into a 1000 mL reactor equipped with a stirrer, condenser, thermometer and nitrogen protection device, stir, heat, slowly raise the temperature of the reaction system to 90℃, continue to stir for a period of time, until the above three substances are completely dissolved, at this time the solution reaches a uniform state; then accurately weigh 3.2 g of benzoyl peroxide BPO, add it to the reaction system, stir for 4 hours, during the 4 hours of reaction, the stirrer continues to stir, the nitrogen protection device continues to provide nitrogen protection, and the condenser continues to condense and reflux, to ensure the stability of the reaction system. After 4 hours of reaction, the polymerization reaction is completed, and finally the polymerization liquid A is obtained. Through 1H-NMR, GPC and FT-IR analysis, it is confirmed that the polymerization liquid A contains the compound represented by the following structural formula,

[0041] ;

[0042] It is a poly-cymene type curing agent A, and the number average molecular weight of the poly-cymene type curing agent A is 1400.

[0043] The preparation method of the poly-cymene type curing agent B is as follows:

[0044] Take 400 g of cymene, 400 mL of xylene and appropriate amount of 1,2-bis(p-vinylphenyl) methane, put the three substances into a 1000 mL reactor equipped with a stirrer, condenser, thermometer and nitrogen protection device, stir, heat, slowly raise the temperature of the reaction system to 90℃. Continue to stir for a period of time, until the above three substances are completely dissolved, at this time the solution reaches a uniform state; then accurately weigh 3.2 g of benzoyl peroxide BPO, add it to the reaction system, stir for 4 hours, during the 4 hours of reaction, the stirrer continues to stir, the nitrogen protection device continues to provide nitrogen protection, and the condenser continues to condense and reflux, to ensure the stability of the reaction system. After 4 hours of reaction, the polymerization reaction is completed, and finally the polymerization liquid B is obtained. Through 1H-NMR, GPC and FT-IR analysis, it is confirmed that the polymerization liquid B contains the compound represented by the following structural formula,

[0045] ;

[0046] It is a poly-cymene type curing agent B, and the number average molecular weight of the poly-cymene type curing agent B is 1700.

[0047] The preparation method of the poly-cymene type curing agent C is as follows:

[0048] Take 400 g cumin, 400 mL dimethylbenzene, and appropriate amount of 1,2-bis (p-vinyl) ethane, and put them into a 1000 mL reactor equipped with a stirrer, condenser, thermometer, and nitrogen protection device, stir, heat, slowly raise the temperature of the reaction system to 90°C, continue to stir for a period of time until the above three substances are completely dissolved, at this time the solution reaches a uniform state; then, accurately weigh 3.2 g of benzoyl peroxide BPO, add it to the reaction system, stir for 4 hours, and during the 4 hours of reaction, the stirrer continues to stir, the nitrogen protection device continues to provide nitrogen protection, and the condenser continues to condense and reflux to ensure the stability of the reaction system. After 4 hours of reaction, the polymerization reaction is completed, and the final polymeric liquid C is obtained. Through 1H-NMR, GPC and FT-IR analysis, it is confirmed that the polymeric liquid C contains compounds represented by the following structural formula,

[0049] ;

[0050] It is a poly-cumin curing agent C, and the number average molecular weight of the poly-cumin curing agent C is 1100.

[0051] Table 2

[0052] The above examples and comparative examples are tested for performance, the test method is as follows, and the test results are shown in Table 3.

[0053] Physical property test: according to IPC TM-650 2.5.5.132007 standard "relative dielectric constant and loss tangent using split-cylinder resonator", take a square-shaped cured lamination film sample with a size of 50mm x 70mm x 0.5mm, and use Keysight Technologies 8722ES to test the dielectric constant Dk and loss factor Df of the sample at a frequency of 10GHz;

[0054] X / Y-CTE test: after heating and curing the prepared lamination film at 180°C for 2h, sample preparation is performed, and TA's TMA-450 is used to test X / Y-CTE. a1 is the CTE before TG.

[0055] Table 3

[0056] From the analysis of the experimental data, it can be seen from Examples 1-6 that the resin composition obtained by using the poly-caryophyllene curing agent of the present application and the thermosetting resin for curing can achieve good dielectric properties and low thermal expansion coefficient, thereby obtaining better processing performance; compared with Comparative Example 1, Examples 2 and 6 use different curing agents, and under the condition that other conditions are the same and the amount of the curing agent is close, the dielectric constant of the resin composition prepared by the three is close and there is no obvious difference, but the dielectric loss of Comparative Example 1 is more than twice that of Example 2 and more than three times that of Example 6, and the thermal expansion coefficient of Comparative Example 1 is nearly twice that of Examples 2 and 6, so it can be seen that the commonly used curing agent, such as cyanate ester, can also obtain a resin composition with excellent dielectric constant after curing with the thermosetting resin, but it cannot obtain better dielectric loss and thermal expansion coefficient, and the use of the poly-caryophyllene of the present application and the thermosetting resin for curing can simultaneously obtain a resin composition with excellent dielectric constant, dielectric loss and thermal expansion coefficient; in addition, Examples 1-3 are only different in the amount of poly-caryophyllene curing agent, but there is no obvious difference in performance; and compared with Example 1 and Example 4, the inorganic filler used in Example 4 is less, but Example 4 achieves a lower dielectric constant, but the dielectric loss and thermal expansion coefficient are obviously increased, so a lower filler ratio can bring better dielectric constant, but it will have a negative impact on the dielectric loss and thermal expansion coefficient.

[0057] The above is only a preferred embodiment of the present application, and does not limit the technical scope of the present application, so any slight modification, equivalent change and modification made according to the technical essence of the present application to the above embodiment are still within the scope of the technical solution of the present application.

Claims

1. A polycarbyne curing agent, characterized by: The poly-cinnamene curing agent has the following structural formula: 。 2. A resin composition characterized by: The poly-cinnamene curing agent has the following structural formula: The poly-cinnamene curing agent has the following structural formula:

3. The resin composition according to claim 2, characterized by: The thermosetting resin is at least one of polyimide resin, phenoxy resin, polyamide resin, polyamide-imide resin, polyvinyl acetal resin.

4. The resin composition according to claim 2, characterized by: The thermosetting resin has a number average molecular weight of 2000-100000.

5. The resin composition according to claim 2, characterized by: The curing accelerator is one of imidazole-based curing accelerator, tertiary amine-based curing accelerator, phosphine-based curing accelerator, photobase generator, sulfonium salt-based curing accelerator; the inorganic filler is at least one of silica, alumina, barium sulfate, talc, clay, mica, magnesium oxide, aluminum hydroxide, aluminum nitride, boron nitride, silicon nitride, glass frit, carbon fiber.

6. The resin composition according to claim 2, characterized by: The equivalent ratio of the thermosetting resin to the poly-cinnamene curing agent is 1:(0.3-2).

7. A build-up insulating film characterized by comprising: The resin composition of any one of claims 2-6 is coated on a base film made of PET or BOPP material by a coating machine; after coating, drying is performed at a temperature of 100°C for 10 minutes; after drying, the base film is removed to obtain a laminated insulation film.

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