Low-dielectric polyphenyl siloxane resin as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of resin preparation, and particularly discloses low-dielectric polyphenyl siloxane resin and a preparation method and application thereof, and the preparation method comprises the following steps: respectively adding a component A, a component B, a component C and a catalyst into a reaction container; introducing inert gas, and heating to obtain an intermediate product D; adding a component E into the intermediate product D to obtain an intermediate product F; and uniformly stirring and mixing the intermediate product F, a component G and a catalyst, and then carrying out segmented curing to finally obtain the bi-crosslinked polyphenylsiloxane resin. According to the low-dielectric polyphenyl siloxane resin and the preparation method and application thereof, curing is achieved through double-bond crosslinking and peroxidation crosslinking between siloxane silane molecules, and a large number of phenyl, siloxane, phosphorus / phosphine derivatives and other structures which are large in volume steric hindrance, low in polarity and excellent in heat stability are introduced; the excellent functions of excellent thermal stability, low dielectric property and the like are maintained, and an excellent flame-retardant effect is also endowed.

Description

Technical Field

[0001] This invention relates to the field of resin preparation technology, and in particular to low-dielectric polyphenylsiloxane resin, its preparation method and application. Background Technology

[0002] With the advent of the 5G information age, the development of ultra-high frequency, ultra-high speed, and ultra-low latency communication technologies has been promoted. Packaging materials for semiconductor components, copper-clad laminates, and polymer materials for printed circuit boards must simultaneously meet comprehensive performance requirements such as high flame retardancy, high heat resistance, and low dielectric constant over a wide frequency range. Existing 4G epoxy resin systems contain a large number of hydrocarbon structures, which generate a large number of flammable small gas molecules upon thermal decomposition, making them highly flammable. Furthermore, the hydroxyl groups in cured epoxy resin are prone to orientation polarization under an external electric field, exhibiting high rotational freedom and deteriorating dielectric properties (dielectric constant Dk, dielectric loss Df). This falls far short of meeting the high requirements of high flame retardancy, high heat resistance, and low dielectric constant for polymer materials used in 5G electronic components. Therefore, the independent development of organic polymer materials that combine high flame retardancy, high heat resistance, and low dielectric constant is urgently needed.

[0003] Traditional polymer resins are flammable, and the introduction of intrinsic flame-retardant functional groups or flame retardants into the resin, either through blending or by mixing, often deteriorates the resin's heat resistance and dielectric properties. Therefore, research on polysiloxane resins with high heat resistance, high flame retardancy, and low dielectric properties is essential. Summary of the Invention

[0004] The purpose of this invention is to provide a low-dielectric polyphenylsiloxane resin, its preparation method, and its applications. This resin not only possesses excellent heat resistance and flame retardancy but also exhibits low dielectric properties. Another purpose of this invention is to provide a method for preparing the low-dielectric polyphenylsiloxane resin.

[0005] To achieve the above objectives, the present invention provides a method for preparing low-dielectric polyphenylsiloxane resin, comprising the following steps:

[0006] Step 1: At room temperature, add components A, B, C and catalyst to the reaction vessel separately and stir continuously; component A is any one of diphenylsilanediol and dimethylsilanediol; component B is any one of methylvinyldimethoxysilane and vinyltrimethoxysilane; component C is any one of diphenylphosphine oxide and 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide.

[0007] Step 2: Inert gas is introduced, the temperature is raised to 70-90℃, and the reaction is carried out for 4-15 hours to obtain intermediate product D;

[0008] Step 3: Add component E to intermediate product D and stir continuously, introduce inert gas, heat to 60-110℃, and react for 4-8 hours to obtain intermediate product F; component E is any one of triphenylsilanol, trimethylsilanol, and dimethylphenylsilanol.

[0009] Step 4: Mix intermediate product F with component G and catalyst at 60-90℃ until homogeneous, and defoam under vacuum. Pour the mixture evenly into a mold and then cure in stages at 120-200℃ for 2-10 hours to obtain polyphenylsiloxane resin. Component G is any one of phenyltris(trimethylsiloxy)silane or p-vinylphenyltris(trimethylsiloxy)silane.

[0010] Preferably, in step 1, the molar ratio of component A: component B: component C is 1:(1-1.2):(0.01-0.1).

[0011] Preferably, in step 2, the chemical structural formula of intermediate product D is as follows:

[0012]

[0013] In the formula, R1 and R2 are either benzene rings or -CH3, and the values ​​of m, n and z are any integers between 1 and 10.

[0014] Preferably, in step 3, the chemical structural formula of intermediate product F is as follows:

[0015]

[0016] In the formula, R1 and R2 are either benzene rings or -CH3, and the values ​​of m, n, and z are any integers between 1 and 10.

[0017] Preferably, in step 3, the molar ratio of intermediate product D to component E is 1:(0.1-0.3).

[0018] Preferably, in step 4, the molar ratio of intermediate product F to component G is 1:(0.1-0.2).

[0019] Preferably, in step 4, the curing of the polyphenylsiloxane resin is achieved through double bond crosslinking and peroxidative crosslinking between siloxane molecules.

[0020] The present invention also provides a low-dielectric polyphenylsiloxane resin, which is prepared by the above-described preparation method.

[0021] This invention also provides applications of low-dielectric polyphenylsiloxane resin, applied to packaging materials for semiconductor components as well as low-dielectric polymer materials for copper-clad laminates and printed circuit boards.

[0022] The advantages and beneficial effects of the present invention using the above-mentioned low-dielectric polyphenylsiloxane resin, its preparation method, and its application are as follows:

[0023] 1. The curing of the polyphenylsiloxane resin of this invention is achieved through double bond crosslinking and peroxidative crosslinking between siloxane alkyl silane molecules. The polyphenylsiloxane resin incorporates a large number of phenyl, siloxane, and phosphorus / phosphine derivatives with high steric hindrance, low polarity, and excellent thermal stability. This not only maintains excellent thermal stability and low dielectric properties but also endows it with excellent flame retardant effects. Therefore, the prepared polyphenylsiloxane resin possesses high heat resistance, high flame retardancy, and low dielectric properties, adding a new variety to the fields of encapsulation materials and printed circuit board resins.

[0024] 2. The polyphenylsiloxane resin monomer of the present invention contains a large number of vinyl groups, which can undergo double bond crosslinking reaction; at the same time, combined with the peroxidation crosslinking between siloxane alkyl silane molecules, the polyphenylsiloxane resin achieves double curing crosslinking, thereby improving the degree of crosslinking of the material, thereby improving the heat resistance of the material, and further reducing the dielectric properties of the material.

[0025] 3. The preparation method of the present invention is mature, simple and convenient, easy to control and industrialized.

[0026] The technical solution of the present invention will be further described in detail below through embodiments. Detailed Implementation

[0027] The technical solution of the present invention will be further described below through embodiments.

[0028] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0029] Unless otherwise defined, all reagents, equipment and other materials used in this invention are commercially available.

[0030] Example 1

[0031] The preparation method of low-dielectric polyphenylsiloxane resin includes the following steps:

[0032] Step 1: At room temperature, diphenylsilanediol, methylvinyldimethoxysilane, diphenylphosphine oxide and barium hydroxide monohydrate (catalyst) are added to the reaction vessel and stirred continuously; the molar ratio of diphenylsilanediol:methylvinyldimethoxysilane:diphenylphosphine oxide is 1:1:0.01.

[0033] Step 2: Inert gas is introduced, the temperature is raised to 70°C, and the reaction is carried out for 4 hours to obtain intermediate product D;

[0034] Step 3: Add triphenylsilanol to intermediate product D, wherein the molar ratio of intermediate product D to triphenylsilanol is 1:0.1 and stir continuously, introduce inert gas, heat to 60°C, and react for 6 hours to obtain intermediate product F, which is a phosphorus-containing phenylsiloxane monomer with double bond.

[0035] Step 4: Intermediate product F is mixed evenly with phenyltris(trimethylsiloxy)silane and 2,5-dimethyl-2,5-di-(tert-butylperoxy)-3-hexyne (catalyst) at 60℃. The molar ratio of intermediate product F to phenyltris(trimethylsiloxy)silane is 1:0.2. The mixture is then defoamed under vacuum and poured evenly into a mold. It is then cured at 120℃, 150℃, and 170℃ for 2 hours each, finally yielding a double-crosslinked polyphenylsiloxane resin. The obtained resin composite material reaches a temperature of 430℃ when the weight loss is 5wt%; it meets the UL-94 V-0 standard; at a frequency of 1GHz, the dielectric constant of the material is 2.84, and the dielectric loss is 0.003.

[0036] The chemical structural formula of intermediate product D is:

[0037]

[0038] The chemical structural formula of intermediate product F is:

[0039]

[0040] Example 2

[0041] The preparation method of low-dielectric polyphenylsiloxane resin includes the following steps:

[0042] Step 1: At room temperature, dimethylsilanediol, methylvinyldimethoxysilane, diphenylphosphine oxide and barium hydroxide monohydrate are added to the reaction vessel and stirred continuously; the molar ratio of dimethylsilanediol: methylvinyldimethoxysilane: diphenylphosphine oxide is 1:1:0.05.

[0043] Step 2: Inert gas is introduced, the temperature is raised to 70°C, and the reaction is carried out for 4 hours to obtain intermediate product D;

[0044] Step 3: Trimethylsilanol is added to intermediate product D, wherein the molar ratio of intermediate product D to trimethylsilanol is 1:0.2. The mixture is stirred continuously, an inert gas is introduced, the temperature is raised to 90°C, and the reaction is carried out for 4 hours to obtain intermediate product F, which is a phosphorus-containing phenylsiloxane monomer with double bond.

[0045] Step 4: Intermediate product F is mixed with phenyltris(trimethylsiloxy)silane and 2,5-dimethyl-2,5-di-(tert-butylperoxy)-3-hexyne at 90℃ until homogeneous. The molar ratio of intermediate product F to phenyltris(trimethylsiloxy)silane is 1:0.1. The mixture is then defoamed under vacuum and poured evenly into a mold. It is then cured at 140℃, 170℃, and 200℃ for 3 hours each, respectively, to obtain a double-crosslinked polyphenylsiloxane resin. The resulting resin composite material exhibits a temperature of 410℃ at which a 5wt% weight loss occurs; it meets the UL-94 V-0 standard; and at a frequency of 1 GHz, the dielectric constant is 2.74 and the dielectric loss is 0.0020.

[0046] The chemical structural formula of intermediate product D is:

[0047]

[0048] The chemical structural formula of intermediate product F is:

[0049]

[0050] Example 3

[0051] The preparation method of low-dielectric polyphenylsiloxane resin includes the following steps:

[0052] Step 1: At room temperature, diphenylsilanediol, methylvinyldimethoxysilane, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and barium hydroxide monohydrate are added to the reaction vessel and stirred continuously; the molar ratio of diphenylsilanediol:methylvinyldimethoxysilane:9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide is 1:1.1:0.03.

[0053] Step 2: Inert gas is introduced, the temperature is raised to 90°C, and the reaction is carried out for 8 hours to obtain intermediate product D;

[0054] Step 3: Add dimethylphenylsilanol to intermediate product D, wherein the molar ratio of intermediate product D to dimethylphenylsilanol is 1:0.15, and stir continuously, introduce inert gas, heat to 80℃, and react for 8 hours to obtain intermediate product F, which is a phosphorus-containing phenylsiloxane monomer with double bond.

[0055] Step 4: Intermediate product F is mixed evenly with p-vinylphenyltris(trimethylsiloxy)silane and 2,5-dimethyl-2,5-di-(tert-butylperoxy)-3-hexyne at 70°C. The molar ratio of intermediate product F to p-vinylphenyltris(trimethylsiloxy)silane is 1:0.15. The mixture is then defoamed under vacuum. The mixture is poured evenly into a mold and cured at 140°C for 2 hours, 160°C for 2 hours, and 180°C for 6 hours to obtain a double-crosslinked polyphenylsiloxane resin. The obtained resin composite material reaches a temperature of 426°C when the weight loss is 5 wt%; it meets the UL-94 V-0 standard; at a frequency of 1 GHz, the dielectric constant of the material is 2.79, and the dielectric loss is 0.0018.

[0056] The chemical structural formula of intermediate product D is:

[0057]

[0058] The chemical structural formula of intermediate product F is:

[0059]

[0060] Example 4

[0061] The preparation method of low-dielectric polyphenylsiloxane resin includes the following steps:

[0062] Step 1: At room temperature, diphenylsilanediol, vinyltrimethoxysilane, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and barium hydroxide monohydrate are added to the reaction vessel and stirred continuously; the molar ratio of diphenylsilanediol:vinyltrimethoxysilane:9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide is 1:1:0.1.

[0063] Step 2: Inert gas is introduced, the temperature is raised to 80°C, and the reaction is carried out for 15 hours to obtain intermediate product D;

[0064] Step 3: Add dimethylphenylsilanol to intermediate product D, wherein the molar ratio of intermediate product D to dimethylphenylsilanol is 1:0.3, and stir continuously, introduce inert gas, heat to 110℃, and react for 6 hours to obtain intermediate product F, namely, phosphorus-containing phenylsiloxane monomer with double bond.

[0065] Step 4: Intermediate product F is mixed thoroughly with p-vinylphenyltris(trimethylsiloxy)silane and 2,5-dimethyl-2,5-di-(tert-butylperoxy)-3-hexyne at 60°C. The molar ratio of intermediate product F to p-vinylphenyltris(trimethylsiloxy)silane is [insert molar ratio here].

[0066] The mixture was prepared by mixing a 1:0.2 ratio of polyphenylsiloxane resin with vacuum defoaming, and then poured evenly into a mold. The mixture was then cured at 140℃ for 2 hours, 160℃ for 2 hours, and 180℃ for 6 hours to obtain a double-crosslinked polyphenylsiloxane resin. The resulting resin composite material exhibits a weight loss of 5 wt% at a temperature of 428℃; it meets the UL-94 V-0 standard; and at a frequency of 1 GHz, the material has a dielectric constant of 2.75 and a dielectric loss of 0.0017.

[0067] The chemical structural formula of intermediate product D is:

[0068]

[0069] The chemical structural formula of intermediate product F is:

[0070]

[0071] Example 5

[0072] The preparation method of low-dielectric polyphenylsiloxane resin includes the following steps:

[0073] Step 1: At room temperature, dimethylsilanediol, methylvinyldimethoxysilane, diphenylphosphine oxide and barium hydroxide monohydrate are added to the reaction vessel and stirred continuously; the molar ratio of dimethylsilanediol: methylvinyldimethoxysilane: diphenylphosphine oxide is 1:1.2:0.08.

[0074] Step 2: Inert gas is introduced, the temperature is raised to 90°C, and the reaction is carried out for 12 hours to obtain intermediate product D;

[0075] Step 3: Add dimethylphenylsilanol to intermediate product D, wherein the molar ratio of intermediate product D to dimethylphenylsilanol is 1:0.2, and stir continuously, introduce inert gas, heat to 100℃, and react for 8 hours to obtain intermediate product F, which is a phosphorus-containing phenylsiloxane monomer with double bond.

[0076] Step 4: Intermediate product F is mixed evenly with p-vinylphenyltris(trimethylsiloxy)silane and 2,5-dimethyl-2,5-di-(tert-butylperoxy)-3-hexyne at 80°C. The molar ratio of intermediate product F to p-vinylphenyltris(trimethylsiloxy)silane is 1:0.15. The mixture is then defoamed under vacuum. The mixture is poured evenly into a mold and cured at 140°C for 3 hours, 160°C for 3 hours, and 180°C for 4 hours to obtain a double-crosslinked polyphenylsiloxane resin. The obtained resin composite material reaches a temperature of 432°C when the weight loss is 5 wt%; it meets the UL-94 V-0 standard; at a frequency of 1 GHz, the dielectric constant of the material is 2.70, and the dielectric loss is 0.0022.

[0077] The chemical structural formula of intermediate product D is:

[0078]

[0079] The chemical structural formula of intermediate product F is:

[0080]

[0081] Example 6

[0082] The preparation method of low-dielectric polyphenylsiloxane resin includes the following steps:

[0083] Step 1: At room temperature, dimethylsilanediol, vinyltrimethoxysilane, diphenylphosphine oxide and barium hydroxide monohydrate are added to the reaction vessel and stirred continuously; the molar ratio of dimethylsilanediol:vinyltrimethoxysilane:diphenylphosphine oxide is 1:1:0.05.

[0084] Step 2: Inert gas is introduced, the temperature is raised to 90°C, and the reaction is carried out for 10 hours to obtain intermediate product D;

[0085] Step 3: Add dimethylphenylsilanol to intermediate product D, wherein the molar ratio of intermediate product D to dimethylphenylsilanol is 1:0.15, and stir continuously, introduce inert gas, heat to 70℃, and react for 6 hours to obtain intermediate product F, which is a phosphorus-containing phenylsiloxane monomer with double bond.

[0086] Step 4: Intermediate product F is mixed evenly with phenyltris(trimethylsiloxy)silane and 2,5-dimethyl-2,5-di-(tert-butylperoxy)-3-hexyne at 60℃. The molar ratio of intermediate product F to phenyltris(trimethylsiloxy)silane is 1:0.17. The mixture is then defoamed under vacuum and poured evenly into a mold. It is then cured at 140℃ for 2 hours, 160℃ for 2 hours, and 180℃ for 4 hours to obtain a double-crosslinked polyphenylsiloxane resin. The obtained resin composite material reaches a temperature of 435℃ when the weight loss is 5wt%; it meets the UL-94 V-0 standard; at a frequency of 1GHz, the dielectric constant of the material is 2.65, and the dielectric loss is 0.0017.

[0087] The chemical structural formula of intermediate product D is:

[0088]

[0089] The chemical structural formula of intermediate product F is:

[0090]

[0091] Application examples

[0092] After the polyphenylsiloxane resin prepared in Example 4 was processed into a copper-clad laminate, the dielectric constant of the copper-clad laminate was 2.95 and the dielectric loss was 0.0015.

[0093] After the polyphenylsiloxane resin prepared in Example 5 was processed into a copper-clad laminate, the dielectric constant of the copper-clad laminate was 2.93 and the dielectric loss was 0.0018.

[0094] Therefore, this invention utilizes the aforementioned low-dielectric polyphenylsiloxane resin, its preparation method, and its applications. Curing is achieved through double bond crosslinking and peroxidative crosslinking between siloxane alkyl silane molecules. The polyphenylsiloxane resin incorporates numerous phenyl, siloxane, and phosphorus / phosphine derivatives with high steric hindrance, low polarity, and excellent thermal stability, thus maintaining not only excellent thermal stability and low dielectric properties but also superior flame-retardant effects.

[0095] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing low-dielectric polyphenylsiloxane resin, characterized in that, Includes the following steps: Step 1: At room temperature, add components A, B, C and catalyst to the reaction vessel separately and stir continuously; component A is any one of diphenylsilanediol and dimethylsilanediol; component B is any one of methylvinyldimethoxysilane and vinyltrimethoxysilane; component C is any one of diphenylphosphine oxide and 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide. Step 2: Inert gas is introduced, the temperature is raised to 70-90℃, and the reaction is carried out for 4-15 hours to obtain intermediate product D; Step 3: Add component E to intermediate product D and stir continuously, introduce inert gas, heat to 60-110℃, and react for 4-8 hours to obtain intermediate product F; component E is any one of triphenylsilanol, trimethylsilanol, and dimethylphenylsilanol. Step 4: Mix intermediate product F with component G and catalyst at 60-90℃ until homogeneous, and defoam under vacuum. Pour the mixture evenly into a mold and then cure in stages at 120-200℃ for 2-10 hours to obtain double crosslinked polyphenylsiloxane resin. Component G is any one of phenyltris(trimethylsiloxy)silane or p-vinylphenyltris(trimethylsiloxy)silane.

2. The method for preparing low-dielectric polyphenylsiloxane resin according to claim 1, characterized in that: In step 1, the molar ratio of component A: component B: component C is 1:(1-1.2):(0.01-0.1).

3. The method for preparing low-dielectric polyphenylsiloxane resin according to claim 1, characterized in that, In step 2, the chemical structural formula of intermediate product D is as follows: In the formula, R1 and R2 are either benzene rings or -CH3, and the values ​​of m, n and z are any integers between 1 and 10.

4. The method for preparing low-dielectric polyphenylsiloxane resin according to claim 1, characterized in that, In step 3, the chemical structural formula of intermediate product F is as follows: In the formula, R1 and R2 are either benzene rings or -CH3, and the values ​​of m, n, and z are any integers between 1 and 10.

5. The method for preparing low-dielectric polyphenylsiloxane resin according to claim 1, characterized in that, In step 3, the molar ratio of intermediate product D to component E is 1:(0.1-0.3).

6. The method for preparing low-dielectric polyphenylsiloxane resin according to claim 1, characterized in that: In step 4, the molar ratio of intermediate product F to component G is 1:(0.1-0.2).

7. The method for preparing low-dielectric polyphenylsiloxane resin according to claim 1, characterized in that: In step 4, the curing of polyphenylsiloxane resin is achieved through double bond crosslinking and peroxidative crosslinking between siloxane molecules.

8. A low-dielectric polyphenylsiloxane resin, characterized in that: It is prepared by the preparation method described in any one of claims 1-7.

9. The application of the low-dielectric polyphenylsiloxane resin as described in claim 8, characterized in that: It is used in packaging materials for semiconductor components, as well as low-dielectric polymer materials for copper-clad laminates and printed circuit boards.

Images