Phosphorus-containing vinylbenzene polyphenylene ether and resin composition and application thereof

Abstract

The present invention discloses a phosphorus-containing vinylbenzene polyphenylene ether and a resin composition and application thereof. The phosphorus-containing vinylbenzene polyphenylene ether is obtained by reacting a phosphorus-containing vinylbenzene compound and a vinyl polyphenylene ether. Another object of the present invention is to provide a resin composition comprising the phosphorus-containing vinylbenzene polyphenylene ether and at least one cross-linking agent. The resin film, prepreg, laminate or printed circuit board made of the resin composition has the characteristics of low thermal expansion coefficient, high heat resistance, excellent flame retardancy, low dielectric constant, low dielectric loss and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of new materials and relates to polyphenylene ether resin, in particular to phosphorus-containing vinylbenzene polyphenylene ether and resin and application thereof. Background Art

[0002] With the rapid development of electronic technology, especially the popularization of 5G technology around the world, the information processing of electronic products in the fields of mobile communications, autonomous driving, etc. requires high frequency and high-speed digitization. The current main research and development direction of high-frequency and high-speed substrates is to develop low-dielectric resin materials. Considering the requirements of resin material products such as copper foil substrates, it is necessary to simultaneously meet low dielectric constant, low dielectric loss, high reliability, high moisture and heat resistance, high dimensional stability, etc. Based on the above considerations, the current commercialization routes include polytetrafluoroethylene-based substrates, modified epoxy-based substrates, polyphenylene ether material substrates, hydrocarbon resin substrates, etc. The cost of polytetrafluoroethylene-based substrates is too high, the dielectric constant of modified epoxy-based substrates is difficult to further reduce, and the flame retardant properties of hydrocarbon resin systems are poor. In contrast, polyphenylene ether resin has gradually become a more ideal material for today's high-frequency and low-dielectric printed circuit boards due to its good mechanical properties, low dielectric constant and dielectric loss, and certain flame retardant properties.

[0003] Commercial polyphenylene ethers, such as bishydroxy polyphenylene ether SA90 developed by Sabic, bisvinyl modified polyphenylene ether resin SA9000, and bis(vinylbenzyl) polyphenylene ether Ope-2st developed by Mitsubishi Gas, cannot meet the requirements of the printed circuit board industry in some properties, especially flame retardancy. To solve this problem, the usual solution is:

[0004] (1) Adding various flame retardants to the polyphenylene ether resin composition, such as condensed phosphate esters, DOPO compounds (such as Di-DOPO and other products), organic hypophosphites (such as OP-930, OP-935 and other products) and other flame retardants. This type of added flame retardant has strong polarity and hygroscopicity, which will deteriorate the dielectric properties and reduce the heat resistance of the polyphenylene ether resin composition products;

[0005] (2) Introducing polymerizable phosphorus-containing monomers, such as introducing compounds with polymerizable double bonds such as allyl diethyl phosphate, allyl phosphazene flame retardant, and acrylate DOPO flame retardant, in order to take into account the required flame retardancy, heat resistance, and dielectric properties. The system with allyl diethyl phosphate is far inferior to the allyl phosphazene flame retardant and acrylate DOPO flame retardant system in terms of heat resistance and deformation, but the latter two are difficult to commercialize due to their difficulty in manufacturing and high price.

[0006] (3) At present, people have also noticed that in high-frequency and high-speed systems, the introduction of PC-containing flame retardant systems can achieve flame retardant properties without affecting the dielectric properties of the material. For example, people have developed compounds such as PQ-60 and BPE-3. This type of compound has a melting point of more than 300°C, but is almost insoluble in common solvents, resulting in problems of uneven dispersion and poor compatibility.

[0007] Therefore, it is urgent to develop a new generation of phosphorus-containing flame retardants and corresponding polyphenylene ether compounds that take into account dielectric properties, compatibility, heat resistance and low cost. Summary of the invention

[0008] In order to solve the above problems existing in the prior art, the present invention provides a phosphorus-containing vinylbenzene polyphenylene ether obtained by reacting a phosphorus-containing vinylbenzene compound and a vinyl polyphenylene ether.

[0009] Wherein, the phosphorus-containing vinylbenzene compound is a compound having the following structure:

[0010]

[0011] The phosphorus-containing vinylbenzene compound is synthesized according to the following route:

[0012]

[0013] The vinyl polyphenylene ether is any polyphenylene ether compound having an unsaturated double bond at at least one terminal, such as one or more of methacrylate polyphenylene ether and vinyl benzyl polyphenylene ether.

[0014] Another object of the present invention is to provide a resin composition comprising the phosphorus-containing vinylbenzene polyphenylene ether and at least one cross-linking agent.

[0015] The crosslinking agent includes one or more of divinylbenzene, triallyl isocyanurate, divinylphenyl ether, isocyanate, polyphenylene ether resin, maleimide, polyamide, polyimide, styrene maleic anhydride copolymer, styrene-butadiene copolymer, styrene-butadiene-divinylbenzene trimer, polyester, olefin polymer, tricyclodecane dimethanol diacrylate, polybutadiene, trivinylcyclohexane, and anhydride hardener.

[0016] Furthermore, the resin composition further includes one or more of a phosphorus-containing flame retardant, a hardening accelerator, an inorganic filler, and a solvent.

[0017] Preferably, the phosphorus flame retardant is one or more of 2-(diphenylphosphonyl)-1,4-benzenediol, diethyl allyl phosphate flame retardant, phosphazene flame retardant and the like.

[0018] Preferably, the inorganic filler includes one or more combinations of silicon dioxide, aluminum oxide, titanium dioxide, zinc oxide, zirconium oxide, mica, calcined kaolin and the like.

[0019] Preferably, the inorganic filler is spherical or fibrous.

[0020] Preferably, the hardening accelerator includes one or more of dicumyl peroxide, tert-butyl perbenzoate, di-tert-butyl dicumyl peroxide, and 2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexyne.

[0021] Preferably, the solvent is a combination of one or more of ethylene glycol monomethyl ether, acetone, butanone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, dimethylformamide, and propylene glycol methyl ether.

[0022] The hardening accelerator includes one or more of dicumyl peroxide, tert-butyl perbenzoate, di-tert-butyl dicumyl peroxide, and 2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexyne.

[0023] The phosphorus-containing vinylbenzene polyphenylene ether of the present invention is used in the preparation of resin films, prepregs, adhesive-backed copper foils, laminates or printed circuit boards.

[0024] Another object of the present invention is to provide a product made from the above resin composition, which includes a resin film, a prepreg, a self-adhesive copper foil, a laminate or a printed circuit board.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. The present invention develops a new generation of phosphorus-containing flame retardants that take into account dielectric properties, compatibility, heat resistance and low cost, and uses a synthetic vinylbenzyl diphenyl oxyphosphine compound (EPO) and vinyl polyphenylene ether to obtain the corresponding phosphorus-containing vinylbenzene polyphenylene ether prepolymer under the action of peroxide.

[0027] 2. The EPO synthetic raw materials of the present invention are all commercially available industrial products, and the product can be obtained by a one-step synthesis reaction; during the polymerization process, due to the presence of multiple benzene rings, the rigidity is strong, which has a good effect on improving the glass transition temperature of the system. In addition, the PC bond compound has a small polarity, does not hydrolyze, does not increase the dielectric constant of the product, improves the weather resistance of the product, and does not absorb moisture.

[0028] 3. The resin film, prepreg, laminate or printed circuit board prepared from the resin composition containing phosphorus-containing vinylbenzene polyphenylene ether of the present invention has the characteristics of low thermal expansion coefficient, low thermal expansion rate, high heat resistance, excellent flame retardancy, low dielectric constant and low dielectric loss.

[0029] 4. The flame retardancy of the resin composition product containing phosphorus-containing vinylbenzene polyphenylene ether of the present invention can reach V0 or V1 level of UL94 standard. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 . EPO of the present invention 31 P NMR spectrum;

[0031] Figure 2 . is the mass spectrum of EPO of the present invention. DETAILED DESCRIPTION

[0032] The present invention is further described below in conjunction with embodiments, but the present invention is not limited to these embodiments. Any improvements made without departing from the spirit of the present invention shall fall within the protection scope of the present invention.

[0033] A phosphorus-containing vinylbenzene polyphenyl ether is obtained by reacting a phosphorus-containing vinylbenzene compound, vinyl polyphenyl ether and a peroxide under a heating condition, specifically, the phosphorus-containing vinylbenzene compound, vinyl polyphenyl ether and a solvent are added into a stirring tank, and then the peroxide is added, and the mixture is evenly mixed and then heated to 80-110°C, and the mixture is continuously stirred for 3-6 hours, and the solvent is removed by reduced pressure distillation to obtain a prepolymer of the phosphorus-containing vinylbenzene compound and the vinyl polyphenyl ether, namely the phosphorus-containing vinylbenzene polyphenyl ether of the present invention.

[0034] The phosphorus-containing vinylbenzene compound is a p-vinylbenzyldiphenylphosphine oxide compound (EPO) having the following unit structure:

[0035]

[0036] The compound was synthesized according to the following route:

[0037]

[0038] The vinyl polyphenylene ether may be any polyphenylene ether compound having an unsaturated double bond at at least one end, and commercially available methacrylate polyphenylene ether (such as SA-9000 produced by Sabic) or vinyl benzyl polyphenylene ether (vinyl benzyl polyphenylene ether resin OPE-2st produced by Mitsubishi Gas Chemical) may be selected.

[0039] On the other hand, the present invention provides a resin composition, which includes the phosphorus-containing vinylbenzene polyphenylene ether and at least one cross-linking agent, wherein the weight ratio of the cross-linking agent to the phosphorus-containing vinylbenzene polyphenylene ether is 5%-30%.

[0040] The crosslinking agent is a combination of one or more of divinylbenzene, triallyl isocyanurate, divinylphenyl ether isocyanate, polyphenylene ether resin, maleimide, polyamide, polyimide, styrene maleic anhydride copolymer, styrene-butadiene copolymer, styrene-butadiene-divinylbenzene trimer, polyester, olefin polymer, anhydride hardener, tricyclodecane dimethanol diacrylate, polybutadiene, and trivinylcyclohexane.

[0041] In addition, the resin composition of the present invention further comprises a combination of one or more of a phosphorus-containing flame retardant, a hardening accelerator, an inorganic filler, and a solvent.

[0042] The phosphorus-containing flame retardant may be one or more of 2-(diphenylphosphinoyl)-1,4-benzenediol, diethyl allyl phosphate flame retardant, phosphazene flame retardant, etc., but is not limited thereto.

[0043] The hardening accelerator includes a peroxide hardening accelerator that can generate free radicals, including but not limited to one or more of diisopropylbenzene peroxide, tert-butyl perbenzoate, di-tert-butyl diisopropylbenzene peroxide, 2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexyne, etc.

[0044] The inorganic filler includes, but is not limited to, one or more combinations of silicon dioxide, aluminum oxide, titanium dioxide, zinc oxide, zirconium oxide, mica, calcined kaolin, etc. Preferably, the inorganic filler is spherical or fibrous.

[0045] The solvent is a combination of one or more of ethylene glycol monomethyl ether, acetone, butanone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, dimethylformamide, and propylene glycol methyl ether.

[0046] Examples 1-5

[0047] Various raw materials from the following sources were used to prepare various embodiments and comparative examples according to the amounts in Table 1, and were further made into various test samples or products.

[0048] raw material:

[0049] Polyphenylene methacrylate: product name SA-9000, purchased from Sabic.

[0050] Vinyl benzyl polyphenylene ether: product name 0PE-2st, purchased from Mitsubishi Gas Chemical.

[0051] Vinylbenzene diphenoxyphosphine flame retardant: product name EPO, synthesized according to this patented method.

[0052] Dicumyl peroxide (DCP): purchased from Sigma Aldrich.

[0053] Spherical silica: product name SC-2050, purchased from Admatechs.

[0054] DPO-HQ: product name 2-(diphenylphosphonyl)-1,4-benzenediol, purchased from Qingdao Fusilin Huagong Technology Co., Ltd.

[0055] Tricyclodecane dimethanol diacrylate: Sartomer SR833s, purchased from Shanghai Kaiyin Chemical.

[0056] Polybutadiene: product name Ricon142, purchased from Shanghai Kaiyin Chemical.

[0057] 1,2,4-Trivinylcyclohexane (TVCH) was purchased from Evonik.

[0058] Styrene-butadiene copolymer: product name G1657, purchased from Kraton.

[0059] 2,5-Di(tert-butylperoxy)-2,5-dimethyl-3-hexyne: product name 25B, purchased from Aldrich.

[0060] Dibenzoyl peroxide (BPO): purchased from Sigma Aldrich.

[0061] 1. Preparation of phosphorus-containing vinylbenzene compound EPO:

[0062] 230 g of diphenylethoxyphosphine (719-80-2) was dissolved in 500 mL of chlorobenzene, and 155 g of p-chloromethylstyrene (1592-20-7) was added in batches. The temperature was raised to 135°C, and the reaction was continued for 3-5 hours to obtain a light yellow solution. The solvent was evaporated to obtain a light yellow viscous liquid, which was the phosphorus-containing vinylbenzene compound EPO.

[0063] 2. Preparation of prepolymer:

[0064] The polyphenylene ether prepolymer used in the resin compositions of the examples and comparative examples of the present invention is prepared with reference to the following description.

[0065] Prepolymer YJT: 70g of vinylbenzyl polyphenylene ether OPE-2st, 30g of phosphorus-containing vinylbenzene compound EPO, 0.05g of BPO and 150g of toluene are added into a stirring tank. After the uniformly mixed solution is heated to 95°C, stirring is continued for 4h. Then water is added and stirred, and the waste liquid is removed. The solvent is removed by distillation under reduced pressure. The obtained product is called prepolymer YJT.

[0066] 3. Preparation of prepreg resin composition:

[0067] As shown in Table 1 below, each component of each embodiment or comparative example is added into a stirring tank according to the dosage in the table, stirred, and uniformly mixed to form a prepreg resin composition.

[0068] Table 1 Composition of the resin composition of the embodiment and the comparative example (unit: weight part)

[0069]

[0070] 4. Preparation of prepreg, including the following steps:

[0071] A prepreg resin composition was prepared according to the components and proportions of the embodiment;

[0072] The glass fiber cloth is impregnated in the prepreg resin composition and baked to obtain a semi-cured sheet.

[0073] According to one aspect of the present invention, the baking temperature is 150-180° C., and the baking time is 3-8 min.

[0074] 5. Preparation of laminated board, including the following steps:

[0075] The method for preparing a prepreg is used to prepare a prepreg; two metal foils are stacked on the upper and lower surfaces of the prepreg; and the metal foil and the prepreg are laminated to obtain a laminate. The lamination is performed in a vacuum environment. The heating rate of the lamination is 1.1-2.5°C / min. When the temperature of the prepreg reaches 90-120°C, a maximum pressure is applied to the metal foil and the prepreg; preferably, the maximum pressure is 350-450psi. During curing, the temperature of the prepreg is controlled at 195-210°C and kept warm for 90-140min.

[0076] 6. Copper foil substrate made of resin composition:

[0077] Prepreg: Immerse Nan Ya 2116 glass fiber cloth into the resin tank to make the resin composition adhere to the glass fiber cloth, and then heat and bake it in an oven at 150-180℃ to a semi-cured state to obtain a prepreg. Then, use two copper foils and six prepregs made from each sample to be tested to overlap in sequence, and press them for 2 hours under vacuum conditions at 200℃ to form each copper foil substrate.

[0078] Table 2. Performance test table of embodiments and control examples

[0079]

[0080] It can be seen from the embodiments and comparative examples that the use of phosphorus-containing vinyl compounds and vinyl polyphenylene ether for prepolymerization can achieve a higher Tg, a lower thermal expansion coefficient, a lower thermal expansion rate, better T288 heat resistance, lower dielectric properties and better flame retardancy compared to the use of other phosphorus-containing compounds for prepolymerization.

Claims

1. A resin composition, characterized in that: The invention comprises phosphorus-containing vinylbenzene polyphenylene ether and at least one cross-linking agent; and further comprises a phosphorus flame retardant, an inorganic filler and a solvent; The phosphorus-containing vinylbenzene polyphenylene ether is obtained by reacting a phosphorus-containing vinylbenzene compound and vinyl polyphenylene ether, wherein the phosphorus-containing vinylbenzene compound is a compound having the following structure: The phosphorus-containing vinylbenzene compound is synthesized according to the following route: The vinyl polyphenylene ether is vinyl benzyl polyphenylene ether; The phosphorus flame retardant is 2-(diphenylphosphino)-1,4-benzenediol; The inorganic filler is a combination of one or more of silicon dioxide, aluminum oxide, titanium dioxide, zinc oxide, zirconium oxide, mica, and calcined kaolin; The solvent is a combination of toluene and methyl ethyl ketone in a weight ratio of 100:30; The weight ratio of the crosslinking agent to phosphorus-containing vinylbenzene polyphenylene ether is 5%-30%.

2. The resin composition according to claim 1, wherein: The crosslinking agent is one or more of divinylbenzene, triallyl isocyanurate, styrene-butadiene copolymer, styrene-butadiene-divinylbenzene trimer, tricyclodecane dimethanol diacrylate, polybutadiene, and trivinylcyclohexane.

3. The resin composition according to claim 2, characterized in that: Also included are hardening accelerators.

4. The resin composition according to claim 3, wherein: The hardening accelerator is one or more of dicumyl peroxide, tert-butyl perbenzoate, di-tert-butyl dicumyl peroxide, and 2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexyne.

5. Use of the resin composition according to claim 1 in the preparation of resin films, prepregs, adhesive-backed copper foils, laminates or printed circuit boards.

6. A product made from the resin composition according to claim 1, which is a resin film, a prepreg, a self-adhesive copper foil, a laminate or a printed circuit board.

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