WO2021097949A1 - 一种无卤阻燃环氧树脂组合物及其应用 - Google Patents

一种无卤阻燃环氧树脂组合物及其应用 Download PDF

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WO2021097949A1
WO2021097949A1 PCT/CN2019/123835 CN2019123835W WO2021097949A1 WO 2021097949 A1 WO2021097949 A1 WO 2021097949A1 CN 2019123835 W CN2019123835 W CN 2019123835W WO 2021097949 A1 WO2021097949 A1 WO 2021097949A1
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epoxy resin
retardant
flame
halogen
parts
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PCT/CN2019/123835
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English (en)
French (fr)
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王忠卫
武军
侯计金
魏振乾
曾冲
段好东
于青
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山东科技大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5397—Phosphine oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to the field of polymer materials, in particular to a halogen-free flame-retardant epoxy resin composition and its application.
  • Epoxy resin is characterized by active epoxy groups in its molecular chain.
  • the cured epoxy resin has excellent electrical properties, good mechanical properties and excellent chemical stability, and is widely used in aviation, Coatings, construction, adhesives, electronic copper clad laminates and many other fields. Since epoxy resin produces a large amount of black smoke during the combustion process, and the oxygen index is about 20, it has a greater flame propagation hazard, so flame retardant modification is generally required.
  • flame-retardant epoxy resins are mostly used to introduce halogen atoms (chlorine, bromine, etc.) into epoxy resins.
  • halogen-based compounds as flame retardants generally has problems such as generation of corrosive gas and high smoke density. It is restricted in more and more fields, so the flame retardant technology of epoxy resin is gradually developing in the direction of high efficiency, high flame retardancy, low smoke and low toxicity.
  • phosphorus-containing flame retardants have the advantages of high flame retardant efficiency and no release of toxic and harmful substances during the combustion process. They have become the research hotspot of flame retardant epoxy resins.
  • the halogen-free flame retardants used for epoxy resins in the industry are mainly DOPO Phosphorus-based flame retardants such as polyphosphazene (HPCTP) and diethyl aluminum hypophosphite (ADP) are mainly used.
  • DOPO reactive flame retardant
  • Epoxy resin reduces the Tg of flame-retardant epoxy resin, and its dielectric properties are relatively poor.
  • Additive phosphorus-based flame retardants are widely used due to their convenient use and high Tg.
  • additive flame retardants usually have various disadvantages in industrial applications: such as low melting point, easy precipitation, poor compatibility, and decreased mechanical properties And other issues.
  • CN102051026A discloses a halogen-free flame-retardant epoxy resin composition and its application. Phosphorus-containing epoxy resin and curing agent and filler system are used. Phosphorus-containing epoxy resin is prepared by reacting linear novolac epoxy resin and DOPO.
  • CN102127289 discloses a halogen-free flame-retardant epoxy resin composition and the adhesive film and copper clad laminate made using it, which are prepared by the reaction of a phosphorous-containing phenolic or epoxy resin prepared by a DOPO derivative as a flame retardant. It has the disadvantages of complicated process, high water absorption, insufficient heat resistance, and poor dielectric properties of the product. At present, DOPO and its derivative flame retardants are prone to generate hydroxyl groups due to the phosphaphenanthrene ring structure, which adversely affects the water absorption and dielectric properties of flame retardant materials. The addition of epoxy resin to DOPO-based flame retardants can no longer be used for high frequency such as 5G.
  • diphenyl phosphine oxide (DPO) groups do not contain phosphinothricin ring and have higher phosphorus content, compared with DOPO group flame retardants in addition, flame retardant efficiency, water resistance, heat resistance It has obvious advantages in terms of performance and dielectric properties.
  • flame retardants with two DPO groups with alkyl groups and alkyl groups with aromatic ring substituents as bridge segments have non-absorbent, low dielectric, high melting point, high decomposition temperature, and have very good properties with epoxy resins. Good compatibility and dispersibility. A variety of excellent characteristics, in the flame-retardant epoxy resin, the transparency of the epoxy itself can be maintained to the maximum.
  • DPO derivative system flame-retardant epoxy resin in the electronics industry compared to commonly used flame-retardant polyphenylene ether, flame-retardant polyimide, polytetrafluorovinyl material, the flame-retardant epoxy resin system has low cost and transparency
  • the advantages of high performance, high bonding strength, convenient processing, etc. have a larger market space in the electronics industry and a wider application field.
  • the development of high-frequency and high-speed technology puts forward higher requirements on the flame retardant properties and dielectric properties of materials.
  • the flame retardant compound with DPO group was selected to have good compatibility with epoxy systems and low polarity.
  • the organic halogen-free phosphorus-nitrogen-based synergistic flame-retardant system finally achieves a flame-retardant epoxy resin system with excellent characteristics such as high flame retardancy, low addition, low dielectric, high thermal stability and high glass transition temperature.
  • the present invention provides a halogen-free flame-retardant epoxy resin composition and its application.
  • the composition material has halogen-free environmental protection, high transparency, good flame retardant effect, high thermal stability, and low water absorption.
  • Advantages of excellent electrical properties, the composition prepared by the invention can be widely used in the fields of prepregs, electronic adhesives, laminates, coating films, copper clad laminates and potting materials that have higher requirements for flame retardancy and dielectric properties.
  • the technical solution adopted by the present invention is: a halogen-free flame-retardant epoxy resin composition and its application, the composition mainly contains epoxy resin and easily available additive type with diphenylphosphine oxide flame-retardant groups
  • Composite halogen-free flame retardant, the polyresin composition is processed by raw materials in the following proportions by weight: 100 parts of epoxy resin, 5-15 parts of main flame retardant, 0-10 parts of synergistic flame retardant, curing 2-30 parts of curing agent, 0-1 part of curing accelerating crosslinking agent.
  • the additive halogen-free flame retardant with diphenyl phosphine oxide flame retardant group is the main flame retardant.
  • the epoxy polyphenylene ether resin contains two or more active epoxy groups in the molecular chain, and is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, and bicyclic epoxy resin. Pentadiene epoxy resin, glycidyl ester/ether epoxy resin, benzoxazine modified epoxy resin, maleimide modified epoxy resin, phosphorous epoxy resin and polyphenylene ether modified ring A resin material made by blending one or more of oxy resins.
  • the main flame retardant is a halogen-free flame retardant containing a diphenyl phosphine oxide structural group, and has the chemical structural formula shown in the following formula (1):
  • R in the chemical formula (1) is optionally selected from a C1-C18 alkyl group, an alkyl group with an aromatic ring or a heterocyclic structure substituent;
  • the R is preferably from Any of them.
  • the structural formula of the main flame retardant is preferably one or a mixture of formula (2), formula (3), and formula (4).
  • the synergistic flame retardant is polyphenyl phosphonate diphenyl sulfone ester, hexaphenoxy cyclotriphosphazene, 1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene- 10-oxide) ethane, 1-benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane, p-xylylene bis (9,10-Dihydro-9-oxo-10-phosphaphenanthrene-10-oxide), a mixture of at least one or more ratios of trihydroxyethyl isocyanurate
  • the halogen-free composite flame retardant is composed of main flame retardant: synergistic flame retardant in a mass ratio of 3-10:3-1.
  • the curing agent is a mixture of one or more of aliphatic amines, aromatic amines, polyamides, modified amines, dicyandiamide, acid anhydrides, and low melting point reactive polyesters.
  • the composition further comprises two or a mixture of two or more of reinforcing fiber, toughening agent, filler, silane coupling agent and solvent.
  • the curing accelerator is preferably one or a mixture of two or more of triphenylphosphine, imidazole, 2-methylimidazole, and 2-phenylimidazole;
  • the reinforcing fiber is preferably electronic fiber cloth, glass One of fibers and basalt fibers;
  • the solvent is preferably one or a mixture of two or more of acetone, methyl ethyl ketone and toluene;
  • the toughening agent is preferably one or a mixture of polymers containing butadiene structure A mixture of two or more;
  • the filler is preferably silica.
  • the invention provides an easily industrialized epoxy resin composition containing diphenyl phosphine oxide (DPO) groups and a composite halogen-free flame-retardant epoxy resin composition and its application.
  • DPO diphenyl phosphine oxide
  • the applicant’s research found that: flame retardants containing diphenyl phosphine oxide (DPO) groups are better than alkyl phosphinates (such as ADP), DOPO derivatives (such as HTP-6123), polyphosphazenes (such as HPTP), etc.
  • Currently commonly used flame retardants have higher flame retardant efficiency in epoxy resins with the same phosphorus content.
  • EDPO can reach V-0 when the phosphorus content of 0.6-0.9% in epoxy resin alone is used, while ADP In the same epoxy curing system, it needs 1.5-1.8% phosphorus content to reach the V-0 level; HTP-6123 needs 1.5% phosphorus content in the same epoxy curing system to reach the V-0 level; HPCTP is in the same ring The oxygen curing system needs 1.2% phosphorus content to reach the V-0 level.
  • the DPO series flame-retardant epoxy resin also has a variety of excellent characteristics such as higher thermal stability, better dielectric properties, and lower water absorption. Moreover, the DOP series composite flame retardant has excellent compatibility with epoxy resin.
  • the new flame retardant has high phosphorus content, high thermal stability, good compatibility with resins, and good chemical stability. It solves the problem that the current DOPO derivative flame retardants are easy to form hydroxyl groups, have poor hygroscopicity, and poor dielectric properties.
  • Aluminum phosphonate (ADP) has poor dispersibility, low efficiency, and poor performance.
  • the DPO series flame retardants are based on the gas phase flame retardant mechanism, when combined with polyphenyl phosphonate diphenyl sulfone ester, 1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene- 10-oxide) ethane, 1-benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane or p-xylylene bis (9,10-Dihydro-9-oxy-10-phosphaphenanthrene-10-oxide) can further enhance the gas phase flame retardant mechanism when one or two or more of them are used in combination, by increasing the inner layer of the surface expanded carbon layer
  • the hole density and the concentration density of free radicals can achieve the excellent flame retardant effect of instant blow-out; when the gas phase flame retardant mechanism is combined with hexaphenoxy cyclotriphosphazene (the main solid phase flame retardant mechanism of HPTP) and trihydroxy E
  • Bisphenol A epoxy resin DCPD phenol novolac epoxy resin, Jinan Shengquan; Polyphenylene ether S202A, Asahi Kasei; Hexaphenoxy cyclotriphosphazene (HPCTP), Dongying Daoyi Biomedical Technology Co., Ltd.; Trihydroxyethyl Isocyanurate (THEIC), Xinxiang Weiye Chemical Co., Ltd.; electronic fiber cloth (7628 glass fiber cloth) purchased from Nanya Plastics; curing agent dicyandiamide, 4,4'diaminodiphenyl sulfone (DDS), 2 -Methylimidazole, Shanxinkui Polymer New Material Co., Ltd.; conventional additives such as solvent acetone are commercially available; silica, Shandong Dongyue Organic Silicon New Material Co., Ltd.; diethyl aluminum hypophosphite (ADP), Qingdao Oppu Ruixin Material Co., Ltd.; DOPO
  • DPO derivative flame retardant EDPO with structural formula (3) The DPO derivative flame retardant PDPO with structural formula (4) and polyphenyl phosphonate diphenyl sulfone ester (PSPPP) are all produced and provided by Qingdao Fuslin Chemical Technology Co., Ltd.
  • the preparation of the flame-retardant epoxy resin solution, the curing of the resin composition and the preparation of the substrate are as follows:
  • the bisphenol A epoxy resin is prepared into an acetone solution with a solid content of 50-70%, and then silicon dioxide, dicyandiamide, and 2-methylimidazole are mixed according to the formula for 5-10 minutes to obtain an epoxy resin composition
  • the acetone solution is a resin varnish with a concentration of 50-60%.
  • the resin composition is attached to the glass fiber cloth by impregnation or coating, and then heated and baked at 155°C for 2 minutes into a semi-cured state to obtain a prepreg.
  • the bisphenol A epoxy resin is formulated into an acetone solution with a solid content of 50-70%, and then silicon dioxide, flame retardant EDPO, curing agent dicyandiamide, and 2-methylimidazole are mixed according to the formula for 5-10 minutes to obtain
  • the acetone solution of the epoxy resin composition is the resin varnish, the concentration is 50-60%, the resin composition is attached to the glass fiber cloth by means of impregnation or coating, and then heated and baked at 155°C for 2 minutes into a semi-cured state.
  • the DCPD phenolic epoxy resin is formulated into a toluene solution with a solid content of 50-70%, and then silicon dioxide, flame retardant PDPO, HTP-6123, curing agent dicyandiamide, and 2-methylimidazole are mixed according to the formula. 5- 10min, obtain the acetone solution of epoxy resin composition, namely resin varnish, with a concentration of 50-60%, make the resin composition adhere to the glass fiber cloth by impregnation or coating, and then heat and bake at 155°C for 2min to become semi-cured State and get a prepreg.
  • the DCPD phenolic epoxy resin is formulated into an acetone solution with a content of 50-70%, and then silicon dioxide, silicon dioxide, flame retardant EDPO, THEIC, HTP-6123, HPTP, curing agent dicyandiamide, 2 are added according to the formula -Methyl imidazole is mixed for 5-10 minutes to obtain a toluene solution of epoxy polyphenylene ether resin composition, ie, resin varnish, with a concentration of 50-60%. Make the resin composition adhere to the glass fiber cloth by impregnation or coating, and then proceed Heat and bake at 155°C for 2 minutes into a semi-cured state to obtain a prepreg.
  • the DCPD phenolic epoxy resin is mixed with polyphenylene ether resin in proportion to a toluene solution with a content of 50-70%, and then silica, flame retardant EDPO, PSPPP, curing agent dicyandiamide, 2-methyl are added according to the formula Mix the imidazole for 5-10 minutes to obtain the toluene solution of the epoxy polyphenylene ether resin composition, that is, the resin varnish, with a concentration of 50-60%.
  • the resin composition is attached to the glass fiber cloth by impregnation or coating, and then the temperature is 155°C. 2min heating and baking into a semi-cured state to obtain a prepreg.
  • the flame-retardant resin composition system When the flame-retardant resin composition system is applied to a substrate, it has good comprehensive performance in an epoxy system or an epoxy composite resin system. It is found that the epoxy resin substrate can reach the V-0 level when 12 parts of flame retardant are added, and there is no adverse effect on the dielectric properties.
  • the flame retardant of diphenyl phosphine oxide derivative is compounded with DOPO derivative or PSPPP, and the flame retardant performance is further improved after compounding with HPTP and THEIC, especially when added to the DCPD phenolic epoxy or epoxy polyphenylene ether composite system When it has better dielectric properties.

Abstract

本发明涉及高分子材料领域，具体为一种无卤阻燃环氧树脂组合物及其应用，该组合物含有环氧树脂和具有二苯基氧膦阻燃基团的无卤复合阻燃剂，包括环氧树脂100份，主阻燃剂5～15份，协效阻燃剂0～10份，固化剂2～30份，固化促进交联剂0～1份。进一步包含增强纤维、增韧剂、填料、硅烷偶联剂、溶剂中至少两种以上的混合物。该含有二苯基氧化膦基团的复合阻燃剂阻燃效率高添加量，与环氧树脂具有优异的相容性分散性，固化过程中可以与环氧树脂达到分子间的分散，保持环氧树脂原有的透明状态。最终固化的阻燃树脂组合物具有低成本、较高透明度、低吸水率、较高玻璃转化温度、较高热稳定性、较低介电常数和介电损耗、高阻燃等特性。

Description

一种无卤阻燃环氧树脂组合物及其应用 技术领域
本发明涉及高分子材料领域，具体涉及到一种无卤阻燃环氧树脂组合物及其应用。
背景技术
环氧树脂是以分子链中含有活泼的环氧基团为其特征，其固化后的环氧树脂由于具有优异的电性能，良好的力学性能以及优秀的化学稳定性，被广泛应用于航空、涂料、建筑、胶粘剂、电子覆铜板等众多领域。由于环氧树脂在燃烧的过程中产生大量的黑烟，同时氧指数在20左右，具有较大的火焰传播危害，因此一般要进行阻燃改性。目前阻燃环氧树脂应用较多是在环氧树脂中引入卤族原子(氯、溴等)，但是用卤系化合物作阻燃剂，普遍存在产生腐蚀性气体，烟密度大等问题，因而在越来越多的领域受到限制，因此环氧树脂的阻燃技术逐渐朝着高效率、高阻燃性、低发烟和低毒性方向发展。
其中含磷阻燃剂具有阻燃效率高，燃烧过程中不释放有毒有害物质等优点，成为阻燃环氧树脂的研究热点，目前工业中用于环氧树脂的无卤阻燃剂主要以DOPO类、聚膦腈(HPCTP)、二乙基次磷酸铝(ADP)等磷系阻燃剂为主，常用的反应型阻燃DOPO其一些衍生物，普遍存在的问题是：其制备的阻燃环氧树脂降低了阻燃环氧树脂的Tg，介电性能比较差。添加型磷系阻燃剂由于使用方便，Tg高等优点广泛使用，但目前添加型阻燃剂在工业应用中通常存在各种缺点：如熔点低，易析出，相容性不好，力学性能下降等问题。
随着电子科技的高速发展，移动通讯、服务器、大型计算机等电子产品的信息处理不断向着“信号传输高频化和高速数字化”的方向发展，目前覆铜板的基体树脂以双酚型环氧树脂为主且对其提出了越来越高的要求。CN102051026A公开了一种无卤阻燃环氧树脂组合物及其应用，采用的是含磷环氧树脂以及固化剂和填料体系，含磷环氧树脂是采用线性酚醛环氧树脂和DOPO反应制备而成；CN102127289公开了无卤阻燃环氧树脂组合物及使用其制作的胶膜与覆铜板，是以DOPO衍生物制备的含磷酚醛或者环氧树脂为阻燃剂反应制备而成。具有工艺复杂，吸水率大，耐热性不足，产品介电性能差的缺点。目前DOPO及其衍生物阻燃剂由于膦杂菲环结构容易产生羟基从而对阻燃材料的吸水性和介电性能的产生不良影响，环氧树脂加入DOPO基阻燃剂已经不能5G等高频高速的电子材料的要求，二苯基氧膦(DPO)基团不含膦杂菲环并且磷含量更高，相比DOPO基团阻燃剂在添加量，阻燃效率，耐水性，耐热性以及介电性能等方面具有明显的优势。并且带有两个DPO基团中间以烷基以及带芳香环取代基的烷基为桥段的阻燃剂具有不吸水、低介电、高熔点、高分解温度、并且与环氧树脂具有很好的相容性分散性多种优良特性，在阻燃环氧树脂可以最大限度的保持环氧自身的 透明度，高Tg，低介电，高热稳定性，拓宽了阻燃环氧树脂的应用领域，尤其是在电子电气行业中具有较大的应用空间。DPO衍生物体系阻燃环氧树脂在电子行业中，相比常用的阻燃聚苯醚，阻燃聚酰亚胺，聚四氟乙烯基材，该阻燃环氧树脂体系具有成本低，透明性高，粘结强度高，加工方便等优势，在电子行业市场空间更大，应用领域更广。高频高速技术的发展对材料的阻燃性能及介电等物性的提出了更高的要求，我们通过遴选带有DPO基团阻燃剂复配与环氧体系相容性好，极性低的有机无卤磷氮系协效阻燃体系，最终达到高阻燃，低添加量，低介电，高热稳定性高玻璃化转变温度等优良特性的阻燃环氧树脂体系。
发明内容
基于上述技术问题，本发明提供一种无卤阻燃环氧树脂组合物及其应用，该组合物材料具有无卤环保、透明度高、阻燃效果好、热稳定性高、吸水率低，介电性能优等优点，本发明制备的组合物可广泛用于对阻燃、介电性能有较高要求的半固化片、电子胶黏剂、层压板、涂覆膜、覆铜板和灌封材料等领域。
本发明所采用的技术解决方案是：一种无卤阻燃环氧树脂组合物及其应用，该组合物主要含有环氧树脂和易得的具有二苯基氧膦阻燃基团的添加型复合无卤阻燃剂，该聚树脂组合物是由以下重量份配比的原料加工组成：环氧树脂100份，主阻燃剂5～15份，协效阻燃剂0～10份，固化剂2～30份，固化促进交联剂0～1份。其中，具有二苯基氧膦阻燃基团的添加型无卤阻燃剂即为主阻燃剂。
所述环氧聚苯醚树脂为分子链中含有两个或者两个以上活泼的环氧基团，选自双酚A型环氧树脂、双酚F型环氧树脂、酚醛环氧树脂、双环戊二烯环氧树脂、缩水甘油酯/醚型环氧树脂、苯并噁嗪改性环氧树脂、马来酰亚胺改性环氧树脂、含磷环氧树脂以及聚苯醚改性环氧基树脂中的一种或多种共混而成的树脂材料。
所述主阻燃剂为含有二苯基氧化膦结构基团的无卤阻燃剂，具有如下式(1)所示的化学结构式：
Figure PCTCN2019123835-appb-000001
其中化学式(1)中R任选自C1-C18的烷基、带有芳香环或者杂环结构取代基的烷基；
进一步的，优选自C1-C6的烷基、带有芳香环或者杂环结构取代基的烷基。
优选的，所述R优选自
Figure PCTCN2019123835-appb-000002
Figure PCTCN2019123835-appb-000003
Figure PCTCN2019123835-appb-000004
中的任一种。
进一步的，所述主阻燃剂其结构式，优选自式(2)、式(3)、式(4)的一种或者多种的混合物。
Figure PCTCN2019123835-appb-000005
所述协效阻燃剂为聚苯基膦酸二苯砜酯、六苯氧基环三磷腈、1,2-双(9,10-二氢-9-氧-10-磷杂菲-10-氧化物)乙烷、1-苯-1,2-双(9,10-二氢-9-氧-10-磷杂菲-10-氧化物)乙烷、对苯二亚甲基双(9,10-二氢-9-氧-10-磷杂菲-10-氧化物)、三羟乙基异氰尿酸酯中的至少一种或多种比例复配的混合物
优选的，所述无卤复合阻燃剂由主阻燃剂：协效阻燃剂按质量比3-10：3-1组成。
优选的，所述固化剂为脂肪胺、芳香胺、聚酰胺、改性胺、双氰胺、酸酐、低熔点活性聚酯中的一种及以上的混合物。
所述组合物进一步包含增强纤维、增韧剂、填料、硅烷偶联剂和溶剂其中两种或其两种以上的混合物。
作为优选，所述固化促进剂优选自三苯基膦、咪唑、2-甲基咪唑、2-苯基咪唑中的一种或两种以上的混合物；所述增强纤维优选自电子纤维布、玻璃纤维、玄武岩纤维中的一种；所述溶剂优选自丙酮、丁酮、甲苯中的一种或两种以上的混合物；所述增韧剂优选自含有丁二烯结构聚合物中的一种或两种以上的混合物；所述填料优选自二氧化硅。
本发明的有益技术效果是：
本发明提供了一种易工业化的含有二苯基氧化膦(DPO)基团复合无卤阻燃的环氧树脂组合物及其应用。申请人研究发现：含有二苯基氧化膦(DPO)基团的阻燃剂比烷基次膦酸盐(如ADP)、DOPO衍生物(如HTP-6123)、聚磷腈(如HPCTP)等目前常用的阻燃剂在相同磷含量时在环氧树脂中具有更高的阻燃效率，如EDPO在环氧树脂中单独使用磷含量0.6-0.9％时就可以达到V-0级，而ADP在相同的环氧固化体系中需要1.5-1.8％磷含量才达到V-0级；HTP-6123在相同的环氧固化体系中需要1.5％磷含量才能达到V-0级；HPCTP在相同的环氧固化体系中需要1.2％磷含量才达到V-0级。该DPO系列阻燃环氧树脂还具有较高的热稳定性，更好的介电性，更低的吸水率等多种优良特性。而且该DOP系列复合阻燃剂与环氧树脂具有优异的相容性，在一定温度混合3-5min可以与环氧树脂达到分子间的分散，呈透明状态，固化完之后可以保持与纯环氧树脂基本一致的透明度。该新型阻燃剂磷含量高，热稳定高，与树脂相容性好，化学稳定性好，解决了目前DOPO衍生物阻燃剂易形成羟基，存在吸湿性介电差问题以及二乙基次膦酸铝(ADP)分散性差效率低性能差的问题。
该DPO系列阻燃剂是以气相阻燃机理为主，当与聚苯基膦酸二苯砜酯、1,2-双(9,10-二氢-9-氧-10-磷杂菲-10-氧化物)乙烷、1-苯-1,2-双(9,10-二氢-9-氧-10-磷杂菲-10-氧化物)乙烷或对苯二亚甲基双(9,10-二氢-9-氧-10-磷杂菲-10-氧化物)的一种或者两种及以上混合使用时可以进一步增强气相阻燃机理，通过增加表面膨胀碳层内层的孔洞密度及自由基的聚集密度，达到瞬间吹熄的优异阻燃效果；当气相阻燃机理阻燃剂再与六苯氧基环三磷腈(HPCTP主要固相阻燃机理)以及三羟乙基异氰尿酸酯THEIC(气源、碳源、交联剂)按最佳比例复配使用可以充分发挥气相阻燃和固相阻燃的优势，提高交联密度，形成致密膨胀碳层提高残炭率降低热氧交换速率，从而提高阻燃效率以及降低产烟量达到最佳的阻燃效果，并且还能保持优异的透明度。最终固化的阻燃树脂组合物具有高透明度、高玻璃转化温度、较低介电常数和介电损耗、高阻燃、无析出等特性。
具体实施方式
以下对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
以下实施例所用原料说明如下：
双酚A环氧树脂、DCPD苯酚酚醛环氧树脂，济南圣泉；聚苯醚S202A，旭化成；六苯氧基环三膦腈(HPCTP)，东营道一生物医药科技有限公司；三羟乙基异氰尿酸酯(THEIC),新乡市伟业化工有限公司；电子纤维布(7628玻璃纤维布)购自南亚塑胶；固化剂双氰胺、4,4’二氨基二苯砜(DDS)、2-甲基咪唑,山鑫葵高分子新材料有限公司；溶剂丙酮等常规助剂市售；二氧化硅，山东东岳有机硅新材料有限公司；二乙基次磷酸铝(ADP)，青岛欧普瑞新材料有限公司；DOPO衍生物阻燃剂HTP-6123，贵州源翼新材料有限公司；
Figure PCTCN2019123835-appb-000006
具有结构式(3)的DPO衍生物阻燃剂EDPO，
Figure PCTCN2019123835-appb-000007
具有结构式(4)的DPO衍生物阻燃剂PDPO，聚苯基膦酸二苯砜酯(PSPPP)均由青岛富斯林化工科技有限公司生产提供。
性能评价方式及实行标准：
垂直燃烧测试按照GB/T2408-2008方法测试，试样尺寸(mm)(125±5)×(13.0±0.5)×(1.6/1±0.25)；氧指数(LOI)测试按照GB/T2406.1-2008：试样尺寸(mm)(80±5)×(6.5±0.5)×(3±0.25)；玻璃转化温度(Tg)，DMA仪器量测；介电常数(Dk)、介电损耗(Df)，(10GHz)AET微波诱电分析仪量测；透光度按照GB/T2410-2008标准进行检验，试样尺寸(mm)(50)×(50)的方片厚度为3mm。具体测试结果如表一表二所示。
对比例1
称取100质量份的双酚A环氧树脂，按配方加入30份固化剂DDS、0.2份2-甲基咪唑在150℃再搅拌5min搅拌均匀置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃透明环氧树脂材料。
对比例2
称取100质量份的双酚A环氧树脂，然后按配方加入13份阻燃剂HPCTP，在150℃混合3-5min，呈透明状态后，趁热按配方加入30份固化剂DDS、0.2份2-甲基咪唑在150℃再搅拌5min搅拌均匀置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃环氧树脂材料。
对比例3
称取100质量份的双酚A环氧树脂，然后按配方加入19份阻燃剂HTP-6123，30份固化剂DDS、0.2份2-甲基咪唑在150℃再搅拌5min搅拌均匀置于真空干燥箱中除去气泡透明后， 趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃环氧树脂材料。
对比例4
称取100质量份的双酚A环氧树脂，然后按配方加入12份阻燃剂ADP，在150℃混合10min，混合均匀后趁热按配方加入30份固化剂DDS、0.2份2-甲基咪唑在150℃再搅拌5min搅拌均匀置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃半透明环氧树脂材料。
实施例1
称取100质量份的双酚A环氧树脂，然后按配方加入10份阻燃剂EDPO，在150℃混合3-5min，呈透明状态后，趁热加入30份固化剂DDS、0.2份2-甲基咪唑在150℃再搅拌5min置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃透明环氧树脂材料。
实施例2
称取100质量份的DCPD酚醛环氧树脂，然后按配方加入10份阻燃剂EDPO，在150℃混合3-5min，呈透明状态后，趁热加入30份固化剂DDS、0.2份2-甲基咪唑，在150℃再搅拌5min置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃透明环氧树脂材料。
实施例3
称取100质量份的双酚A环氧树脂，然后按配方加入10份阻燃剂PDPO升温混合3-5min，呈透明状态后，趁热加入30份固化剂DDS、0.2份2-甲基咪唑，在150℃再搅拌5min置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃透明环氧树脂材料。
实施例4
称取100质量份的DCPD酚醛环氧树脂配，然后按配方加入6份阻燃剂EDPO，4份阻燃剂HTP-6123,在150℃混合3-5min，呈透明状态后，趁热加入固化剂DDS，2-甲基咪唑，在150℃再搅拌5min置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃透明环氧树脂材料。
实施例5
称取100质量份的双酚A环氧树脂，然后按配方加入8份阻燃剂EDPO，2份THEIC在150℃混合3-5min，呈透明状态后，趁热加入30份固化剂DDS、0.2份2-甲基咪唑，在150℃再搅拌5min置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃ 固化2h，脱模后得到浅黄色阻燃透明环氧树脂材料。
实施例6
称取100质量份的双酚A环氧树脂，然后按配方加入11份阻燃剂EDPO，在150℃混合3-5min，呈透明状态后，趁热加入固化剂双氰胺，2-甲基咪唑，在150℃再搅拌5min置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃透明环氧树脂材料。
实施例7
称取100质量份的双酚A环氧树脂配，然后按配方加入5份阻燃剂EDPO，5份HPCTP在150℃混合3-5min，呈透明状态后，趁热加入30份固化剂DDS、0.2份2-甲基咪唑，在150℃再搅拌5min置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃透明环氧树脂材料。
实施例8
称取100质量份的双酚A环氧树脂配，然后按配方加入4份阻燃剂EDPO，4份HPCTP,2份THEIC在150℃混合3-5min，呈透明状态后，趁热加入30份固化剂DDS、0.2份2-甲基咪唑，在150℃再搅拌5min置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃透明环氧树脂材料。
实施例9
称取100质量份的DCPD酚醛环氧树脂，然后按配方加入4份阻燃剂PDPO，4份HPCTP，2份THEIC在150℃混合3-5min，呈透明状态后，趁热加入30份固化剂DDS、0.2份2-甲基咪唑，在150℃再搅拌5min置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃透明环氧树脂材料。
实施例10
称取100质量份的DCPD酚醛环氧树脂，然后按配方加入5份阻燃剂EDPO，4份HPCTP，2份THEIC在150℃混合3-5min，呈透明状态后，趁热加入8份固化剂双氰胺，0.2份2-甲基咪唑，在150℃再搅拌5min置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃透明环氧树脂材料。
实施例11
称取100质量份的DCPD酚醛环氧树脂，然后按配方加入3份阻燃剂PDPO，2份HTP-6123，3份HPCTP，2份THEIC在150℃混合3-5min，呈透明状态后，趁热加入30份固化剂DDS、0.2份2-甲基咪唑，在150℃再搅拌5min置于真空干燥箱中除去气泡透明后，趁热倒入标准模具中后于130℃固化2h，160℃固化2h，脱模后得到浅黄色阻燃透明环氧树脂材料。
表一
Figure PCTCN2019123835-appb-000008
根据表一具体的实施例，我们直接对制备的浇注料进行性能测试，纯环氧树脂在未加阻燃剂时，氧指数只有23.4％垂直燃烧无等级，透明度85％，对比我们常用的HPCTP,HTP-6123,ADP阻燃剂需要添加较大添加量才可以达到V0级，Tg降幅较大，尤其是ADP对透明度影响最大。而只需加入EDPO或者PDPO约10份时就可以达到V-0级，并且氧指数达到31.8％以上，明显优于常用的阻燃体系,透明度也与纯环氧体系保持一致；更换不同类型的环氧树脂以及固化剂时也可以有相似的阻燃效果。进一步我们DPO系列阻燃剂与HTP-6123,HPCTP以及THEIC进行两种、三种以及四种在一定比例复配时可以充分发挥协效作用，具有更高的阻燃效率，更好的阻燃效果和Tg点，达到了较满意的阻燃效果。
进一步，阻燃环氧树脂溶液的制备、树脂组合物的固化及基板的制备，如下所述：
对比例5
将双酚A环氧树脂配成固含量为50-70％的丙酮溶液，然后按配方加入二氧化硅，固化剂双氰胺，2-甲基咪唑混合5-10min,得到环氧树脂组合物的丙酮溶液即树脂清漆，浓度50-60％，以含浸或涂覆等方式使树脂组合物附着于玻璃纤维布，再进行155℃，2min加热烘烤成半固化态而得半固化片。取四张上述制得的半固化片及两张铜箔，依铜箔、四片半固化片、铜箔的顺序进行迭合，再于真空条件下经由150℃，2h和180℃，2h压合形成铜箔基板，分别将上述含铜箔基板及铜箔蚀刻后不含铜箔的基板做物性测定。
实施例12
将双酚A环氧树脂配成固含量为50-70％的丙酮溶液，然后按配方加入二氧化硅，阻燃剂EDPO，固化剂双氰胺，2-甲基咪唑混合5-10min,得到环氧树脂组合物的丙酮溶液即树脂清漆，浓度50-60％，以含浸或涂覆等方式使树脂组合物附着于玻璃纤维布，再进行155℃，2min加 热烘烤成半固化态而得半固化片。取四张上述制得的半固化片及两张铜箔，依铜箔、四片半固化片、铜箔的顺序进行迭合，再于真空条件下经由150℃，2h和180℃，2h压合形成铜箔基板，分别将上述含铜箔基板及铜箔蚀刻后不含铜箔的基板做物性测定。
实施例13
将双酚A环氧树脂配成固含量为50-70％的甲苯溶液，然后按配方加入二氧化硅，阻燃剂PDPO，固化剂双氰胺，三苯基膦混合5-10min,得到环氧树脂组合物的丙酮溶液即树脂清漆，浓度50-60％，以含浸或涂覆等方式使树脂组合物附着于玻璃纤维布，再进行155℃，2min加热烘烤成半固化态而得半固化片。取四张上述制得的半固化片及两张铜箔，依铜箔、四片半固化片、铜箔的顺序进行迭合，再于真空条件下经由150℃，2h和180℃，2h压合形成铜箔基板，分别将上述含铜箔基板及铜箔蚀刻后不含铜箔的基板做物性测定。
实施例14
将DCPD酚醛环氧树脂配成固含量为50-70％的甲苯溶液，然后按配方加入二氧化硅，阻燃剂PDPO，HTP-6123，固化剂双氰胺，2-甲基咪唑混合5-10min,得到环氧树脂组合物的丙酮溶液即树脂清漆，浓度50-60％，以含浸或涂覆等方式使树脂组合物附着于玻璃纤维布，再进行155℃，2min加热烘烤成半固化态而得半固化片。取四张上述制得的半固化片及两张铜箔，依铜箔、四片半固化片、铜箔的顺序进行迭合，再于真空条件下经由150℃，2h和180℃，2h压合形成铜箔基板，分别将上述含铜箔基板及铜箔蚀刻后不含铜箔的基板做物性测定。
实施例15
将双酚A型环氧树脂配成含量为50-70％的丙酮溶液，然后按配方加入二氧化硅，阻燃剂EDPO，THEIC，HTCTP,固化剂双氰胺，2-甲基咪唑混合5-10min,得到环氧聚苯醚树脂组合物的甲苯溶液即树脂清漆，浓度50-60％，以含浸或涂覆等方式使树脂组合物附着于玻璃纤维布，再进行155℃，2min加热烘烤成半固化态而得半固化片。取四张上述制得的半固化片及两张铜箔，依铜箔、四片半固化片、铜箔的顺序进行迭合，再于真空条件下经由150℃，2h和180℃，2h压合形成铜箔基板，分别将上述含铜箔基板及铜箔蚀刻后不含铜箔的基板做物性测定。
实施例16
将DCPD酚醛环氧树脂配成含量为50-70％的丙酮溶液，然后按配方加入二氧化硅，二氧化硅，阻燃剂EDPO，THEIC，HTP-6123，HPCTP,固化剂双氰胺，2-甲基咪唑混合5-10min,得到环氧聚苯醚树脂组合物的甲苯溶液即树脂清漆，浓度50-60％，以含浸或涂覆等方式使树脂组合物附着于玻璃纤维布，再进行155℃，2min加热烘烤成半固化态而得半固化片。取四张上述制得的半固化片及两张铜箔，依铜箔、四片半固化片、铜箔的顺序进行迭合，再于真空条件下经由150℃，2h和180℃，2h压合形成铜箔基板，分别将上述含铜箔基板及铜箔蚀 刻后不含铜箔的基板做物性测定。
实施例17
将DCPD酚醛环氧树脂按比例与聚苯醚树脂配成含量为50-70％的甲苯溶液，然后按配方加入二氧化硅，阻燃剂EDPO，PSPPP，固化剂双氰胺，2-甲基咪唑混合5-10min,得到环氧聚苯醚树脂组合物的甲苯溶液即树脂清漆，浓度50-60％，以含浸或涂覆等方式使树脂组合物附着于玻璃纤维布，再进行155℃，2min加热烘烤成半固化态而得半固化片。取四张上述制得的半固化片及两张铜箔，依铜箔、四片半固化片、铜箔的顺序进行迭合，再于真空条件下经由150℃，2h和180℃，2h压合形成铜箔基板，分别将上述含铜箔基板及铜箔蚀刻后不含铜箔的基板做物性测定。
实施例18
将双酚A环氧与DCPD酚醛环氧树脂及聚苯醚树脂按比例配成含量为50-70％的丙酮甲苯混合溶液，然后按配方加入二氧化硅，阻燃剂PDPO，THEIC，HTP-6123，HPCTP，固化剂双氰胺，2-甲基咪唑混合5-10min,得到环氧聚苯醚树脂组合物的甲苯溶液即树脂清漆，浓度50-60％，以含浸或涂覆等方式使树脂组合物附着于玻璃纤维布，再进行155℃，2min加热烘烤成半固化态而得半固化片。取四张上述制得的半固化片及两张铜箔，依铜箔、四片半固化片、铜箔的顺序进行迭合，再于真空条件下经由150℃，2h和180℃，2h压合形成铜箔基板，分别将上述含铜箔基板及铜箔蚀刻后不含铜箔的基板做物性测定。
具体数据见下表二。
表二
Figure PCTCN2019123835-appb-000009
将该阻燃树脂组合物体系应用到基板中，在环氧体系或者环氧复合树脂体系中都具有良好的综合性能。发现添加12份阻燃剂时环氧树脂基板可以达到V-0级，同时对介电性能无不良影响。二苯基氧化膦衍生物阻燃剂与DOPO衍生物或者PSPPP复配，以及与HPCTP和THEIC复配之后阻燃性能进一步提高，尤其是加入到DCPD酚醛环氧或环氧聚苯醚复合体系中时具有更优的介电性能。
以上所述仅为本发明的较佳实施例，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改和等同替换，均应包含在本发明的保护范围之内。

Claims (11)

  1. 一种无卤阻燃环氧树脂组合物，其特征在于：该组合物含有环氧树脂以及具有二苯基氧膦阻燃基团的复合阻燃剂。
  2. 一种无卤阻燃环氧树脂组合物，其特征在于：该组合物含有环氧树脂100份，具有二苯基氧膦阻燃基团的主阻燃剂5～15份，还含有协效阻燃剂0～10份，固化剂2～30份，固化促进交联剂0～1份。
  3. 权利要求1所述的一种无卤阻燃环氧树脂组合物，其特征在于：所述环氧树脂为分子链中含有两个或者两个以上活泼的环氧基团，选自双酚A型环氧树脂、双酚F型环氧树脂、酚醛环氧树脂、双环戊二烯环氧树脂、缩水甘油酯/醚型环氧树脂、苯并噁嗪改性环氧树脂、马来酰亚胺改性环氧树脂、含磷环氧树脂以及聚苯醚改性环氧基树脂中的一种或多种共混而成的树脂材料。
  4. 权利要求1、2、3任一项所述的一种无卤阻燃环氧树脂组合物，其特征在于：所述主阻燃剂为含有二苯基氧化膦结构基团的无卤阻燃剂，具有如下式(Ⅰ)所示的化学结构式：
    Figure PCTCN2019123835-appb-100001
    其中式(Ⅰ)中R任选自C1-C18的烷基、带有芳香环或者杂环结构取代基的烷基。
  5. 权利要求4所述的一种无卤阻燃环氧树脂组合物，其特征在于：式(Ⅰ)中R任选自C1-C6的烷基、带有芳香环或者杂环结构取代基的烷基。
  6. 权利要求4所述的一种无卤阻燃环氧树脂组合物，其特征在于：式(Ⅰ)中R优选自——CH 2——、——CH 2——CH 2——、——CH 2——CH 2——CH 2——、——CH 2——CH 2——CH 2——CH 2——、
    Figure PCTCN2019123835-appb-100002
    Figure PCTCN2019123835-appb-100003
    中的任一种。
  7. 权利要求2所述的一种无卤阻燃环氧树脂组合物，其特征在于：所述协效阻燃剂为 聚苯基膦酸二苯砜酯、六苯氧基环三磷腈、1,2-双(9,10-二氢-9-氧-10-磷杂菲-10-氧化物)乙烷、1-苯-1,2-双(9,10-二氢-9-氧-10-磷杂菲-10-氧化物)乙烷、对苯二亚甲基双(9,10-二氢-9-氧-10-磷杂菲-10-氧化物)、三羟乙基异氰尿酸酯中的至少一种的混合物。
  8. 根据权利要求2所述的一种无卤阻燃环氧树脂组合物，其特征在于：所述主阻燃剂：协效阻燃剂按质量比3～10：3～1组成。
  9. 根据权利要求2所述一种无卤阻燃环氧树脂组合物，其特征在于：所述固化剂为脂肪胺、芳香胺、聚酰胺、改性胺、双氰胺、酸酐、低熔点活性聚酯中的一种及以上的混合物；所述组合物进一步包含增强纤维、增韧剂、填料、硅烷偶联剂、溶剂中的至少两种的混合物。
  10. 根据权利要求9所述一种无卤阻燃环氧树脂组合物，其特征在于：所述增强纤维优选自电子纤维布、玻璃纤维、玄武岩纤维中的一种；所述溶剂优选自丙酮、丁酮、甲苯中的一种或两种以上的混合物；所述增韧剂优选自含有丁二烯结构聚合物中的一种或两种以上的混合物；所述填料优选自二氧化硅；所述固化促进剂优选自三苯基膦、咪唑、2-甲基咪唑、2-苯基咪唑中的一种或两种以上的混合物。
  11. 根据权利要求1-3，5-10任一项所述的一种无卤阻燃环氧树脂组合物在对阻燃、介电性能有较高要求的半固化片、电子胶黏剂、层压板、涂覆膜、覆铜板或灌封材料中的应用。
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