WO2016141707A1 - 含磷阻燃组合物以及使用它的含磷聚苯醚树脂组合物、预浸料和层压板 - Google Patents

含磷阻燃组合物以及使用它的含磷聚苯醚树脂组合物、预浸料和层压板 Download PDF

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WO2016141707A1
WO2016141707A1 PCT/CN2015/090079 CN2015090079W WO2016141707A1 WO 2016141707 A1 WO2016141707 A1 WO 2016141707A1 CN 2015090079 W CN2015090079 W CN 2015090079W WO 2016141707 A1 WO2016141707 A1 WO 2016141707A1
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carbon atoms
polyphenylene ether
ether resin
weight
parts
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PCT/CN2015/090079
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English (en)
French (fr)
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曾宪平
陈广兵
关迟记
杨文华
何烈相
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广东生益科技股份有限公司
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Publication of WO2016141707A1 publication Critical patent/WO2016141707A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • C08K5/49—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the invention belongs to the technical field of copper clad laminates, and relates to a phosphorus-containing composition and a phosphorus-containing polyphenylene ether resin composition, a prepreg and a laminate using the same.
  • the epoxy resin circuit board generally has a high dielectric constant and dielectric loss tangent (dielectric constant greater than 4, dielectric loss tangent is about 0.02), and high frequency characteristics are insufficient, which cannot meet the requirements of high frequency signal. Therefore, it is necessary to develop a resin excellent in dielectric properties, that is, a resin having a low dielectric constant and a dielectric loss tangent.
  • Heat resistance has also been studied by many technicians as high-frequency high-speed materials. However, due to its high melting point and poor fluidity, it is subject to many restrictions. The melt viscosity of prepregs is large and cannot meet multi-layer printing. The manufacturing requirements of the circuit board. By lowering the molecular weight of the polyphenylene ether resin, it is possible to effectively lower the melting temperature and improve the fluidity, but this also sacrifices the heat resistance of the polyphenylene ether resin.
  • CN1745142A uses a polyphenylene ether resin containing a vinyl phenyl group and a methylene phenyl group as a host resin, and uses a trialenyl isocyanurate as a crosslinking curing agent, and if necessary, an inorganic filler or a flame retardant.
  • an olefin resin can be used as a compatibilizer, but the performance of the cured product is not mentioned. research.
  • US2009/0247032 uses a vinyl bifunctional polyphenylene ether resin as the main body, and a cyanate ester having a naphthalene ring structure, a bisphenol A type cyanate, a brominated flame retardant and an inorganic filler to obtain a It has good fluidity and can obtain good peel strength, heat and humidity resistance and flame retardancy under the premise of ensuring good dielectric properties.
  • WO2006/023371A1 provides a combination of a difunctionalized polyphenylene ether resin and an unsaturated olefin monomer, which can improve the fluidity and post-curing properties of the polyphenylene ether resin, but does not indicate a bifunctional polyphenylene ether resin.
  • the performance advantage in the field of laminates, and the use of unsaturated olefin monomers are low molecular weight compounds, which are also easily volatilized at high temperatures and have poor processability.
  • some materials containing phosphorus epoxy resin and phosphorus-containing phenolic resin can achieve good flame retardant effect, but in terms of dielectric properties. Poor performance and too much
  • the introduction of ground phosphorus brings about deterioration of moisture and heat resistance, and cannot meet the reliability requirements of high-layer PCBs; the added type of phosphinate alone has poor flame retardant effect, especially in resin systems with lower carbon formation; Since the phosphazene compound has a relatively low melting point and strong plasticity, a large amount of addition causes a large decrease in heat resistance such as a decrease in the glass transition temperature, and at the same time, even when used alone, it is difficult to achieve flame retardancy V- even when added in a large amount. The level of 0. Similar problems exist with other phosphate compounds.
  • the object of the present invention is a phosphorus-containing flame retardant composition which can achieve halogen-free flame retardant at a lower added amount, achieving UL 94V-0.
  • Another object of the present invention is to provide a phosphorus-containing polyphenylene ether resin composition which can maintain good dielectric properties and heat resistance of a polyphenylene ether resin, and achieve halogen-free flame retardant, and the flame retardant reaches UL 94V- 0.
  • Another object of the present invention is to provide a prepreg and a copper-clad laminate produced by using the above phosphorus-containing polyphenylene ether resin composition, which has good dielectric properties and heat resistance, and realizes halogen-free flame retardant. The flame retardant reaches UL 94V-0.
  • a phosphorus-containing flame retardant composition comprising:
  • R 1 is one of a C2 to C20 alkylene or an aromatic hydrocarbon.
  • the content of the hypophosphite compound is, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight or 45 parts by weight.
  • the content of the polyphosphazene compound is, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight or 45 parts by weight.
  • the above phosphorus-containing composition as a flame retardant, a synergistic effect between the three phosphorus-containing compounds can be exerted, and a halogen-free flame retardant can be achieved with a small addition amount to a V-0 level.
  • the component (A) DOPO derivative can be obtained by the following method, specifically: the reaction temperature of the compound DOPO and the diol under the action of a catalyst is 50-300 ° C, and the reaction time is 0.5. ⁇ 48 hours, the reaction is obtained, the specific reaction formula is as follows:
  • n is an integer of 2 to 20.
  • the above-mentioned reaction is obtained by dehydration condensation reaction with a glycol compound under the action of a catalyst through an active hydrogen atom of DOPO; wherein the molar charge ratio of DOPO and glycol is controlled 0.5 to 100, preferably 0.5 to 10, and still more preferably 0.5 to 5. If the molar ratio is too low, the DOPO conversion rate is low, and if the molar ratio is too high, the subsequent recovery of the diol is difficult.
  • the catalyst is not particularly limited, and any catalyst which can promote the dehydration reaction and the Arbuzov reaction can be used.
  • the optional catalysts are alkyl halides, alkali metals, alkaline earth metal halides, transition metals and their halogenated acids, acids, Arbuzov.
  • the derivative of DOPO can be of the following structural formula:
  • the component (B) hypophosphite compound has the following structure:
  • M is a metal atom selected from the group consisting of sodium, calcium, magnesium, aluminum, arsenic, and zinc. Or any of the irons.
  • M is preferably aluminum or sodium from the viewpoint of lowering its water absorption rate and increasing its phosphorus content, but M is more preferably further if it is further considered to minimize the influence of the phosphorus-containing composition addition on the dielectric properties after curing of the resin composition. aluminum.
  • hypophosphite compound in the present invention is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • the component (C) described in the present invention is a polyphosphazene compound.
  • Polyphosphazene compound is a kind of all-phosphorus nitrogen heterocyclic non-conjugated compound with excellent light stability and thermal stability, high limiting oxygen index, low smoke emission and good chemical resistance, water resistance and resistance. Solvent.
  • the polyphosphazene compound in the present invention has the following structural formula:
  • n is an integer from 3 to 100, such as 5, 10, 20, 30, 40, 50, 60, 70, 80 or 90.
  • R is any one of a phenoxy group, an alkyl group having 1 to 10 carbon atoms, a vinylphenoxy group or an allylphenoxy group;
  • q is an integer from 3 to 25, such as 4, 6, 7, 10, 13, 16, 19 or 22; and R is a phenoxy group, an alkyl group having 1 to 10 carbon atoms, a vinylphenoxy group or an alkene group; Any one of propylphenoxy groups.
  • the present invention also provides a phosphorus-containing polyphenylene ether resin composition comprising the phosphorus-containing composition as described above and a terminally functionalized polyphenylene ether resin.
  • the terminal functionalized polyphenylene ether resin is any one of a hydroxylated polyphenylene ether resin, an epoxidized polyphenylene ether resin, a vinylated polyphenylene ether resin or a cyanated polyphenylene ether resin.
  • a and b are independently an integer of 1 to 30, for example, 2, 5, 8, 11, 14, 17, 20, 23, 26 or 29, and Z is a formula (3) or (4)
  • Z is a formula (3) or (4)
  • -(-OY-)- is a structure represented by the formula (5)
  • -(-OXO-)- is a structure represented by the formula (6):
  • A is an arylene group, a carbonyl group or an alkylene group having 1 to 10 (for example, 2, 3, 4, 5, 6, 7, 8, or 9) carbon atoms, and m is 0 to 10 ( An integer of, for example, 1 , 2 , 3 , 4, 5, 6, 7, 8, or 9), wherein R 1 , R 2 and R 3 are the same or different and are independently hydrogen or an alkyl group having 10 or less carbon atoms;
  • R 4 is the same as or different from R 6 and independently represents a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms, and R 5 and R 7 are the same or different. And independently a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms;
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are the same or different and independently represent a hydrogen atom, a halogen atom or a carbon atom of 8 or less.
  • R 16 is a hydrogen atom or an alkyl group having 1 to 10 (e.g., 2, 3, 4, 5, 6, 7, 8, or 9) carbon atoms.
  • terminally functionalized polyphenylene ether resin is of the formula (7) or (8):
  • R 1 to R 3 are the same or different and independently represent hydrogen or an alkyl group having 10 or less carbon atoms; and R 4 is the same as or different from R 6 and independently represents a hydrogen atom, a halogen atom, and a carbon atom; 8 or less alkyl or phenyl; R 5 and R 7 are the same or different and independently represent a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms; R 8 , R 9 and R 10 ; R 11 , R 12 , R 13 , R 14 and R 15 are the same or different and independently represent a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms; b is independently an integer of 1 to 30, for example, 2, 5, 8, 11, 14, 17, 20, 23, 26 or 29, and B is an alkylene group having 20 or less carbon atoms,
  • R 4 is the same as or different from R 6 and independently represents a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; and R 5 is the same as or different from R 7 and is a halogen atom or a carbon.
  • An alkyl group having 8 or less atoms or a phenyl group; and R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are the same or different and are a hydrogen atom, a halogen atom or a carbon atom.
  • 8 or less alkyl or phenyl; a and b are independently an integer of 1 to 30;
  • B is an alkylene group having 20 or less carbon atoms, and n is 0 or 1.
  • terminal functionalized polyphenylene ether resin may also be a structure represented by the formulas (9) to (13):
  • R 1 to R 3 are the same or different and are hydrogen or an alkyl group having 10 or less carbon atoms; and R 4 is the same as or different from R 6 and is a hydrogen atom, a halogen atom or an alkyl group having 8 or less carbon atoms; Or a phenyl group; R 5 and R 7 are the same or different and are a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 And R 15 are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; and a and b are independently an integer of 1 to 30.
  • R 1 to R 3 are the same or different and are hydrogen or an alkyl group having 10 or less carbon atoms; and R 4 is the same as or different from R 6 and is a hydrogen atom, a halogen atom or an alkyl group having 8 or less carbon atoms; Or a phenyl group; R 5 and R 7 are the same or different and are a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 And R 15 are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; and a and b are independently an integer of 1 to 30.
  • R 1 to R 3 are the same or different and are hydrogen or an alkyl group having 10 or less carbon atoms; and R 4 is the same as or different from R 6 and is a hydrogen atom, a halogen atom or an alkyl group having 8 or less carbon atoms; Or a phenyl group; R 5 and R 7 are the same or different and are a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 And R 15 are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; and a and b are independently an integer of 1 to 30.
  • R 4 is the same as or different from R 6 and is a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; and R 5 is the same as or different from R 7 and is a halogen atom or a carbon atom; 8 or less alkyl or phenyl; R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are the same or different and are a hydrogen atom, a halogen atom or a carbon atom of 8 or less.
  • Alkyl or phenyl; a and b are independently an integer from 1 to 30.
  • R 4 is the same as or different from R 6 and is a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; and R 5 is the same as or different from R 7 and is a halogen atom or a carbon atom; 8 or less alkyl or phenyl; R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are the same or different and are a hydrogen atom, a halogen atom or a carbon atom of 8 or less.
  • Alkyl or phenyl; a and b are independently an integer from 1 to 30.
  • the phosphorus-containing flame-retardant composition is added in an amount of 15 to 60 parts by weight, for example, 25 parts by weight based on 100 parts by weight of the terminal-functionalized polyphenylene ether resin.
  • the amount of the flame retardant composition added is less than 15 parts by weight, the flame retardancy of the system is less than V-0, and when the amount is more than 60 parts, the cured polyphenylene ether resin composition can be sufficiently ensured. Good flame retardancy, but due to the large water absorption of the phosphorus-containing flame retardant composition, the heat resistance and dielectric properties of the system are greatly deteriorated.
  • the phosphorus-containing polyphenylene ether resin composition further includes a crosslinking agent which is a polyolefin resin having an unsaturated double bond
  • a crosslinking agent which is a polyolefin resin having an unsaturated double bond
  • the polyolefin resin having an unsaturated double bond is Polybutadiene and its graft modified polymer such as maleic anhydride grafted polybutadiene polymer, acrylic modified butadiene polymer, butadiene-styrene copolymer, butadiene-benzene Ethylene-divinylbenzene copolymer or cyclic olefin copolymer Any one or a mixture of at least two.
  • the polyolefin resin having an unsaturated double bond is added in an amount of 10 to 100 parts by weight, for example, 15 parts by weight, 20 parts by weight, 25 parts by weight, based on 100 parts by weight of the terminal functionalized polyphenylene ether resin. 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight Parts or 95 parts by weight.
  • the addition of an appropriate ratio of the olefin resin can further improve the dielectric properties of the fixed-line system such as Dk/Df, and further, the unsaturated double bond carried in the olefin resin can be further combined with the polyphenylene ether resin. Crosslinking and curing can further improve heat resistance.
  • the amount added is less than 10 parts, the amount of unsaturated double bonds introduced into the olefin resin is too small to effectively crosslink, failing to improve heat resistance and dielectric properties; if the amount of olefin resin exceeds 100 In part, the rigidity of the olefin resin itself is too poor, and the coefficient of expansion is large, which causes a large decrease in heat resistance of the cured product.
  • the terminal functionalized polyphenylene ether resin has a number average molecular weight of 500 to 5,000, preferably a number average molecular weight of 500 to 3,000, and more preferably a number average molecular weight of 800 to 2,500.
  • a terminal functionalized polyphenylene ether resin having a number average molecular weight of more than 5,000 is used, solubility is deteriorated during processing, and it is impossible to perform sizing using a conventional laminate process, and heating is required to make a process in the process of copper clad laminate processing.
  • the resin composition and the laminate material also have lower dielectric properties.
  • the functionalized polyphenylene ether resin having a smaller number average molecular weight can better improve the compatibility with the crosslinking agent, that is, the molecular weight The smaller the mixing, the better the compatibility between the mixed components and the better the storage stability.
  • the lower molecular weight provides better flow and facilitates better fillability during multilayer board processing.
  • the phosphorus-containing polyphenylene ether resin composition further includes a co-crosslinking agent, and the co-crosslinking agent is
  • the bismaleimide resin or/and the polyfunctional acrylate compound are preferably maleimide resins.
  • the co-crosslinking agent is added in an amount of 5 to 50 parts by weight, for example, 7 parts by weight, 10 parts by weight, 13 parts by weight, 16 parts by weight, and 19 parts by weight based on 100 parts by weight of the terminal-functionalized polyphenylene ether resin. Parts, 22 parts by weight, 25 parts by weight, 28 parts by weight, 31 parts by weight, 35 parts by weight, 38 parts by weight, 41 parts by weight, 44 parts by weight or 47 parts by weight.
  • the main purpose of the introduction of the co-crosslinking agent is to further improve the heat resistance of the cured product of the polyphenylene ether, since the maleimide resin can be functionalized with the terminal functionalized polyphenylene ether resin and the olefin resin.
  • the saturated double bond undergoes a curing cross-linking reaction to form a cross-linked network structure composed of three, and the system has better heat resistance stability; if the amount of maleimide resin added is too small, the crosslink density is not improved. For the purpose of improving heat resistance, if the amount is too large, the crosslinking density of the system can be effectively increased, but the polarity of the structure of the maleimide itself is large, which causes a significant decrease in dielectric properties.
  • the phosphorus-containing polyphenylene ether resin composition further includes an initiator.
  • the initiator has a half-life temperature t 1/2 of not less than 100 ° C and is a peroxide radical initiator selected from the group consisting of dicumyl peroxide, tert-butyl peroxybenzoate, 2,5-di(2- Ethylhexanoyl peroxy)-2,5-dimethylhexane, di-(tert-butylperoxyisopropyl)benzene, peroxy(2,4-dichlorobenzoyl), 2,5- Dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butyl peroxy-2-ethylhexyl carbonate, 2,5-dimethyl-2,5-bis(tert-butyl Oxy)-3-hexyne, butyl 4,4-di(tert-butylperoxy)pentanoate, 1,1-
  • the initiator in the polyphenylene ether resin composition of the present invention aims to improve the crosslinking curing effect.
  • the terminal functionalized polyphenylene ether resin and the crosslinking agent can also be cured under heating and high temperature conditions, but laminated When the board is applied, the process conditions are difficult to meet the high temperature requirements, which makes the processing difficulty increase, and on the other hand, it is not conducive to the process efficiency and increase the production cost, so it is more advantageous to add the initiator.
  • the initiator is added in an amount of 0.5 to 7 parts by weight, for example, 1.3 parts by weight, 1.6 parts by weight, 1.9 parts by weight, 2.2 parts by weight, 2.5 parts by weight, based on 100 parts by weight of the terminal functionalized polyphenylene ether resin. 3.1 parts by weight, 3.5 parts by weight, 3.9 parts by weight, 4.3 parts by weight, 4.7 parts by weight, 5 parts by weight, 5.4 parts by weight, 5.8 parts by weight, 6.2 parts by weight or 6.6 parts by weight.
  • the phosphorus-containing polyphenylene ether resin composition further comprises a silane coupling agent, and the silane coupling agent is added in an amount of 0.1 to 10 by weight based on 100 parts by weight of the terminal-functionalized polyphenylene ether resin.
  • a silane coupling agent for example, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, and 6 parts by weight 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight or 9.5 parts by weight.
  • the kind of the coupling agent is not particularly limited.
  • the coupling agent can further reduce the surface tension of the cured resin, further reduce the viscosity, and improve the fluidity of the resin composition.
  • the addition of a coupling agent can effectively improve the bonding force between the resin and the filler, eliminate the interface between the two, and further reduce the water absorption rate of the cured product.
  • the coupling agent may be a silane, a silane prepolymer or a titanate, and the silane coupling agent may be an epoxy silane coupling agent, an amino silane coupling agent, a phenylamino silane coupling agent, or a vinyl group.
  • Silane coupling agent isocyanate-based silane coupling agent, acryl-based silane coupling agent, isobutylene silane coupling agent, styryl silane coupling agent, urea-based silane coupling agent, chloropropyl silane coupling agent, sulfur a silane coupling agent or a sulfurized silane coupling agent or the like.
  • the phosphorus-containing polyphenylene ether resin composition further comprises a filler, the filler is an organic or inorganic filler, and the inorganic filler is selected from the group consisting of crystalline silica, fused silica, spherical silica, and hollow dioxide.
  • the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder.
  • the shape, particle diameter and the like of the inorganic filler are also not particularly limited, and usually have a particle diameter of 0.01 to 50 ⁇ m, preferably 0.01 to 20 ⁇ m, more preferably 0.01 to 10 ⁇ m, and the inorganic filler having such a particle diameter range is more easily dispersed in the resin liquid. .
  • the filler is added in an amount of 10 to 300 parts by weight, for example, 30 parts by weight, 60 parts by weight, 90 parts by weight, 120 parts by weight, 150 parts by weight, and 180 parts by weight based on 100 parts by weight of the terminal functionalized polyphenylene ether resin. Parts by weight, 210 parts by weight, 240 parts by weight or 270 parts by weight.
  • the phosphorus-containing polyphenylene ether resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, or a lubricant. . These various additives may be used singly or in combination of two or more kinds.
  • the present invention provides a prepreg prepared using the above-described phosphorus-containing polyphenylene ether resin composition, comprising a substrate and a phosphorus-containing polyphenylene ether resin composition as described above adhered to the substrate by impregnation and drying .
  • the end group functionalized polyphenylene ether resin, the phosphorus containing composition, the optional crosslinking agent, optionally the co-crosslinking agent, the optional initiator, the optional coupling agent, and optionally the filler are first dissolved.
  • a uniform glue is prepared in one or more organic solvents.
  • the organic solvent is not particularly limited as long as it can dissolve the above components without affecting its reactivity; suitable solvents include: ketones such as methyl ethyl ketone, acetone, etc., ethers such as propylene glycol monomethyl ether, dibutyl ether, etc., esters Such as ethyl acetate, aromatics such as toluene, xylene, etc., halogenated hydrocarbons such as trichloroethane and the like. Each solvent may be used singly or in combination.
  • Resin in glue The concentration of the solid matter can be appropriately changed depending on the kind and process in which the glue is impregnated into the substrate, for example, a suitable concentration thereof is 30 to 80%.
  • the prepreg is obtained by impregnating the substrate with the glue prepared above, followed by heating and drying to remove the organic solvent and partially curing the resin composition in the substrate.
  • the substrate is a woven or non-woven fabric made of organic fibers, carbon fibers or glass fibers; for a woven or non-woven fabric made of glass fibers, the main component comprises 50 to 80% by weight of SiO 2 . And a weight ratio of 0 to 30% of CaO, a weight ratio of 0 to 20% of Al 2 O 3 , a weight ratio of 5 to 25% of B 2 O 3 , and a weight ratio of 0 to 5% of MgO.
  • the reinforcing material is preferably a braided fiber cloth, optionally E-Glass, T-Glass, NE-Glass, L-Glass, Q-Glass.
  • the content of the resin used to impregnate the above substrate is preferably such that the content of the resin in the prepreg is 30% by mass or more. Since the dielectric constant of the substrate tends to be higher than that of the resin composition, in order to lower the dielectric constant of the laminate prepared from these prepregs, the content of the resin composition component in the prepreg is preferably higher than the above content.
  • the present invention also provides a laminate comprising at least one laminated prepreg as described above.
  • the present invention provides a copper-clad laminate produced using the above phosphorus-containing polyphenylene ether resin composition, comprising a plurality of laminated prepregs and copper laminated on one or both sides of the laminated prepreg. Foil.
  • a multilayer printed wiring board can also be prepared by the following methods and steps: using a printed wiring board as an inner printed circuit board, surface-treating the copper foil thereon, and pressing according to requirements
  • the prepreg of the present invention and the above-mentioned surface-treated printed wiring board stack are hot-pressed in a certain order, and the hot pressing conditions may be determined according to the composition ratio of the polyphenylene ether resin composition of the present invention, and there is no particular limited.
  • the hot pressing conditions are preferably hot pressed for a period of time in a temperature range of 150 to 250 ° C and a pressure range of 1.0 MPa to 10.0 MPa.
  • the laminate and the printed wiring board obtained by this method and the step have good high-frequency characteristics such as dielectric properties and the like, and also have good workability, heat resistance and moisture resistance.
  • the copper foil used may be selected from an electrolytic copper foil or a rolled copper foil, and the surface roughness thereof is less than 5 ⁇ m. It can improve and improve the signal loss of laminate materials used in high frequency and high speed printed circuit boards.
  • the copper foil used above can also be chemically treated with a silane coupling agent, and the coupling agent used is an epoxy silane coupling agent and a vinyl silane coupling.
  • the present invention also provides a printed circuit board comprising at least one laminated prepreg as described above.
  • the present invention has the following beneficial effects:
  • the polyphenylene ether resin composition of the present invention is a low molecular weight functionalized polyphenylene ether resin composition, has good processability, maintains good dielectric properties and heat resistance of the polyphenylene ether resin, and adds a specific structure.
  • the phosphorus-containing flame retardant component not only maintains the heat resistance, dielectric properties, and low water absorption of the original polyphenylene ether resin system, but also achieves halogen-free flame retardant, and the flame retardant reaches UL 94V-0 level.
  • Synthetic method Referring to Synthesis Example 1, dichloromethane was replaced with dichloro-p-xylene to obtain DOPO derivative 2 of the formula (1) wherein R 1 was a phenyl group.
  • the hypophosphite compound is:
  • the polyphosphazene compound has the following structure:
  • R is a methyl group, wherein n is an integer from 3 to 100.
  • the hypophosphite compound is:
  • the polyphosphazene compound has the following structure:
  • R is an ethyl group, wherein n is an integer of from 3 to 100.
  • the hypophosphite compound is:
  • the polyphosphazene compound has the following structure:
  • the hypophosphite compound is:
  • the polyphosphazene compound has a mixture of both of the following structures:
  • R is a methyl group, wherein n is an integer of 80;
  • the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
  • a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
  • B-1000 as a crosslinking agent, 2.0 g of dicumyl peroxide as an initiator, 30 g of the phosphorus-containing composition of the mixing example 2 as a flame retardant, 0.8 g of a vinyl silane coupling agent and 80 g of silica (SC) -2050SQ)
  • SC silica
  • the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
  • a copper foil having a thickness of 35 ⁇ m was attached to both sides of the eight prepregs prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
  • Crosslinking agent 15 g of bismaleimide resin as co-curing agent, 3.0 g of dicumyl peroxide as initiator, 35 g of phosphorus-containing composition of mixing example 2 as flame retardant, 2 g of vinyl silane A coupling agent and 150 g of silica were used as a filler, and the above mixture was mixed in toluene and stirred to dissolve to obtain a uniform resin composition, that is, a gum solution.
  • the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
  • a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
  • the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
  • a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
  • styrene-terminated polyphenylene ether resin OPE-2000 and 100 g of toluene as a solvent were mixed and dissolved to obtain a terminal-functionalized polyphenylene ether resin solution, and then 20 g of styrene-butadiene copolymer R100 was added as a crosslinking agent.
  • the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
  • a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
  • a crosslinking agent 45 g of bismaleimide resin as a co-curing agent, 3.0 g of dicumyl peroxide as an initiator, and 35 g of the phosphorus-containing composition of the mixing example 4 as a flame retardant, treated with 200 g of vinylsilane Silica SC-2300SVJ as a filler, the above mixture is mixed in toluene, The mixture was stirred and dissolved to obtain a uniform resin composition, that is, a gum solution.
  • the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
  • a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
  • a diene polymer Ricon 156MA17 as a crosslinking agent
  • 25 g of a maleimide resin as a co-crosslinking agent
  • 2.5 g of dicumyl peroxide as an initiator
  • 35 g of a phosphorus-containing composition of the mixing example 3 as a flame retardant 300 g of vinylsilane-treated silica SC-2300SVJ was used as a filler, and the above mixture was mixed in toluene and stirred to dissolve to obtain a uniform resin composition, that is, a gum solution.
  • the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
  • a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
  • the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg. 8 rise prepregs prepared above the overlap are attached to each side
  • a copper foil having a thickness of 35 ⁇ m was heat-pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
  • the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
  • a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
  • a coupling agent adding 2 g of dicumyl peroxide as an initiator, 45 g of ethyl-bis(tetrabromophthalimide) BT-93W, 0.8 g of an epoxy silane coupling agent and 80 g of silica as A filler, the above mixture was mixed in toluene, and stirred to dissolve to obtain a uniform resin composition, that is, a gum solution.
  • the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
  • a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
  • the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
  • a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
  • thermosetting composition composed of a polyphenylene ether resin, an olefin resin, and a bismaleimide resin can be cured to have excellent heat resistance and dielectric properties while satisfying the flame retardancy requirement of UL 94V-0.

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Abstract

本发明提供了一种含磷阻燃组合物，包括：次磷酸盐化合物、DOPO衍生物及聚磷腈化合物，使用该组合物作为阻燃，可以发挥几种含磷化合物之间的协同效果，在较少的添加量下，实现无卤阻燃，达到V-0级别。本发明还提供了一种包含上述含磷阻燃组合物的聚苯醚树脂组合物及使用其制作的预浸料与覆铜箔层压板。该聚苯醚树脂组合物固化后，在不适用卤素阻燃剂的条件下实现阻燃V-0级别，且保持了聚苯醚树脂良好的介电特性及耐热性，由其制作的预浸料与覆铜箔层压板，具有良好的介电特性和耐热性，在保证优良耐热性和介电性能的同时实现无卤阻燃，阻燃达到UL 94-V0级别；适合高频高速印制线路板领域使用，符合未来的绿色环保要求。

Description

含磷阻燃组合物以及使用它的含磷聚苯醚树脂组合物、预浸料和层压板 技术领域
本发明属于覆铜板技术领域，涉及一种含磷组合物以及使用它的含磷聚苯醚树脂组合物、预浸料和层压板。
背景技术
近年来，随着计算机和信息通讯设备高性能化、高功能化以及网络化的发展，为了高速传输及处理大容量信息，操作信号趋向于高频化，因而对电路基板的材料提出了要求，尤其是在那些使用宽带的电子设备如移动通信装置上有迅速的发展。
现有的用于印制电路基板的材料中，广泛使用粘接特性优异的环氧树脂。然而，环氧树脂电路基板一般介电常数和介质损耗角正切较高(介电常数大于4，介质损耗角正切在0.02左右)，高频特性不充分，不能适应信号高频化的要求。因此必须研制介电特性优异的树脂，即介电常数和介质损耗角正切低的树脂。长期以来本领域的技术人员对介电性能很好的热固性的氰酸酯、双马来酰亚胺树脂、碳氢树脂等进行了研究；另外，聚苯醚树脂由于具有良好的介电性能、耐热性，也被广大技术人员作为高频高速材料进行了大量的研究，但由于其熔点高、流动性差而在应用上受到很多限制，预浸料的熔融粘度大，无法满足多层印制线路板的工艺制作要求。通过降低聚苯醚树脂的分子量，可以有效的降低其熔融温度、改善流动性，但是这也牺牲了聚苯醚树脂的耐热性。
CN1745142A使用了一种端基含有乙烯苯基和间乙烯苯基的聚苯醚树脂作为主体树脂，利用异氰脲酸三烯酯作为交联固化剂，必要时还可以加入无机填料、阻燃剂得到一种聚苯醚树脂组合物，然后浸渍NE型玻璃纤维织物，得到 具有优良介电特性，具有较高玻璃化转变温度的预浸料和层压板，但是由于该组合物中使用异氰脲酸三烯酯作为交联固化剂，其分子量较低，在预浸料制作过程中极容易挥发，从而不利于稳定的制作预浸料和层压板材。虽然该专利中有提到为改善耐热性，粘结性和尺寸稳定性，除PPE以外，如果需要，可以使用烯烃树脂作为相容剂，但是并未对提其对固化物的各项性能进行研究。
US2009/0247032采用了一种乙烯基双官能度的聚苯醚树脂作为主体，以及带有萘环结构的氰酸酯、双酚A型氰酸酯、溴化阻燃剂和无机填料，得到一种具有很好流动性、并可以在保证良好介电性能的前提下得到很好剥离强度，耐湿热性和阻燃性。
WO2006/023371A1提供了一种双官能化的聚苯醚树脂和不饱和烯烃单体的组合物，可以改进聚苯醚树脂的流动性及固化后性能，但并未指出双官能化聚苯醚树脂用于层压板领域时的性能优势，且使用的为不饱和烯烃单体为低分子量化合物，在高温下也容易挥发，工艺性差。
由上所述可知，通过对低分子量的官能化是解决聚苯醚分子量降低带来的耐热性下降的问题，但对于在层压板领域的具体应用时，如何选择合适的固化交联及体现官能化聚苯醚树脂的性能优势，还需作进一步研究。
另外，随着社会对环保意识的加强，电子产品的环保问题也日益突出，于是如何实现基板材料的无卤化，也是今年来本技术领域人员研究的重点，目前实现无卤阻燃的技术手段主要引入磷元素进行阻燃，常见的物质有含磷环氧树脂、含磷酚醛树脂、磷酸酯类化合物及聚磷酸酯化合物、磷腈化合物、次磷酸盐类化合物，但是由于这些材料本身特性的限制，单独使用都无法满足高速材料领域对耐热性和介电性能的要求，如含磷环氧树脂、含磷酚醛树脂部分材料虽然可以达到很好的阻燃效果，但是由于在介电性能方面表现不佳，同时过多 地磷引入带来耐湿热性能的恶化，无法满足高多层PCB的可靠性要求；添加型的次膦酸盐单独使用的阻燃效果不佳，特别是在成炭较低的树脂体系；聚磷腈化合物由于本省的熔点比较低，增塑性强，大量的添加带来耐热性大幅下降如玻璃化转变温度降低，同时单独使用时，即使大量的添加，也很难做到阻燃V-0的级别。其他的磷酸酯类化合物也同样存在类似问题。
综合来看，如何实现同时满足高速基板材料要求的优异介电性能，如低的介电常数和介质损耗正切值，又能实现无卤阻燃的新技术是未来本领域研究的一个重点方向之一。
发明内容
针对已有技术的问题，本发明的目的在于一种含磷阻燃组合物，其可以在较低的添加量下达到无卤阻燃，达到UL 94V-0。本发明的目的还在于提供一种含磷聚苯醚树脂组合物，其既能保持聚苯醚树脂良好的介电特性及耐热性，且实现无卤阻燃，阻燃剂达到UL 94V-0。本发明的另一目的还在于提供一种使用上述含磷聚苯醚树脂组合物制作的预浸料及覆铜箔层压板，具有良好的介电特性和耐热性，且实现无卤阻燃，阻燃剂达到UL 94V-0。
为了实现上述目的，本发明采用了如下技术方案：
一种含磷阻燃组合物，所述阻燃组合物包括：
(A)式(1)所示的DOPO衍生物，100重量份；
(B)次磷酸盐化合物，5～50重量份；
(C)聚磷腈化合物，10～50重量份
Figure PCTCN2015090079-appb-000001
R1为C2～C20的亚烷烃或亚芳香烃中的一种。
所述次磷酸盐化合物的含量例如为10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份或45重量份。
所述聚磷腈化合物的含量例如为10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份或45重量份。
在本发明中，使用上述含磷组合物作为阻燃剂，可以发挥三种含磷化合物之间的协同效果，在较少的添加量下，实现无卤阻燃，达到V-0级别。
本发明中，所述组分(A)DOPO衍生物可以由如下方法合成而得到，具体为：由化合物DOPO和二元醇在催化剂的作用下，反应温度为50～300℃，反应时间为0.5～48小时，反应得到，具体反应式如下：
Figure PCTCN2015090079-appb-000002
式中n为2～20的整数。
上述所述的反应通过DOPO的活泼氢原子，在催化剂作用下与二元醇化合物发生脱水缩合反应的得到；其中DOPO和二元醇的摩尔投料比控制在 0.5～100，优选0.5～10，更进一步优选为0.5～5，如果摩尔比太低，将会导致DOPO转化率低，如果摩尔比太高，又会带来二元醇后续的回收困难。
所述的催化剂没有特别限制，任何可以促进脱水反应和Arbuzov反应的催化剂都可以使用，可选的催化剂有烷基卤化物，碱金属，碱土金属卤化物，过渡金属及其卤代物，酸，Arbuzov催化剂，其中优选为Arbuzov催化剂。
举例来讲，所述的DOPO的衍生物可以为如下结构式：
Figure PCTCN2015090079-appb-000003
优选地，所述组分(B)次磷酸盐化合物具有如下结构：
Figure PCTCN2015090079-appb-000004
其中m为2或3；R3和R4独立地为碳原子数为1～6的烷烃基或芳烃基，M为金属原子，该金属原子选自钠、钙、镁、铝、砷、锌或铁中的任意一种。从降低其吸水率和提高其磷含量的角度考虑，M优选为铝或钠，但如果进一步考虑尽可能降低含磷组合物加入对树脂组合物固化后的介电性能的影响，M更优选为铝。
更具体地来讲，本发明中所述次磷酸盐化合物为
Figure PCTCN2015090079-appb-000005
本发明中所述的组份(C)为聚磷腈化合物。聚磷腈化合物为一种全磷氮杂环非共轭化合物，具有优异的光稳定性和热稳定性，高极限氧指数，低排烟量且有很好的耐化学特性，耐水性及耐溶剂性。
本发明中的聚磷腈化合物具有如下结构式：
Figure PCTCN2015090079-appb-000006
其中n为3～100的整数，例如5、10、20、30、40、50、60、70、80或90。
其中R为苯氧基、碳原子数为1～10的烷基、乙烯基苯氧基或烯丙基苯氧基中的任意一种；
或，
Figure PCTCN2015090079-appb-000007
其中q为3～25的整数，例如4、6、7、10、13、16、19或22；R为苯氧基、碳原子数为1～10的烷基、乙烯基苯氧基或烯丙基苯氧基中的任意一种。
本发明还提供了一种含磷聚苯醚树脂组合物，其包含如上所述的含磷组合物和端基官能化聚苯醚树脂。
本发明中，所述端基官能化聚苯醚树脂为端羟基化聚苯醚树脂、环氧化聚苯醚树脂、乙烯基化聚苯醚树脂或氰基化聚苯醚树脂中的任意一种或者至少两种的混合物，优选为乙烯基化聚苯醚树脂或/和氰基化聚苯醚树脂，进一步优选为乙烯基化聚苯醚树脂。
本发明中，所述端基官能化聚苯醚树脂结构式如式(2)所示：
Figure PCTCN2015090079-appb-000008
式(2)中，a和b独立地为1～30的整数，例如2、5、8、11、14、17、20、23、26或29，Z为式(3)或(4)所示的结构，-(-O-Y-)-为式(5)所示的结构，-(-O-X-O-)-为式(6)所示的结构：
Figure PCTCN2015090079-appb-000009
式(4)中，A为亚芳香基、羰基或碳原子数为1～10(例如2、3、4、5、6、7、8或9)的亚烷基，m为0～10(例如1、2、3、4、5、6、7、8或9)的整数，R1、R2和R3相同或不同，独立地为氢或碳原子数10以下的烷基；
Figure PCTCN2015090079-appb-000010
式(5)中，R4与R6相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基，R5与R7相同或不同，独立地为卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基；
Figure PCTCN2015090079-appb-000011
式(6)中，R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基，B为碳原子数20以下的亚烃基、
Figure PCTCN2015090079-appb-000012
或
Figure PCTCN2015090079-appb-000013
n为0或1；R16为氢原子或碳原子数为1～10(例如2、3、4、5、6、7、8或9)的烷基。
更具体来讲，所述端基官能化聚苯醚树脂为式(7)或(8)所示的结构：
Figure PCTCN2015090079-appb-000014
式(7)中，R1～R3相同或不同，独立地为氢或碳原子数10以下的烷基；R4与R6相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7相同或不同，独立地为卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基；a和b独立地为1～30的整数，例如2、5、8、11、14、17、20、23、26或29，B 为碳原子数20以下的亚烃基、
Figure PCTCN2015090079-appb-000015
Figure PCTCN2015090079-appb-000016
n为0或者1，R16为氢原子或碳原子数为1～10的烷基；
Figure PCTCN2015090079-appb-000017
式(8)中，R4与R6相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7相同或不同，为卤素原子、碳原子数8以下的烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；a和b独立地为1～30的整数；B为碳原子数20以下的亚烃基，n为0或者1。
更进一步，所述端基官能化聚苯醚树脂还可以为式(9)至(13)所示的结构：
Figure PCTCN2015090079-appb-000018
式(9)中，R1～R3相同或不同，为氢或碳原子数10以下的烷基；R4与R6相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7相同或不同，为卤素原子、碳原子数8以下的烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；a和b独立地为1～30的整数。
Figure PCTCN2015090079-appb-000019
式(10)中，R1～R3相同或不同，为氢或碳原子数10以下的烷基；R4与R6相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7相同或不同，为卤素原子、碳原子数8以下的烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；a和b独立地为1～30的整数。
Figure PCTCN2015090079-appb-000020
式(11)中，R1～R3相同或不同，为氢或碳原子数10以下的烷基；R4与R6相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7相同或不同，为卤素原子、碳原子数8以下的烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；a和b独立地为1～30的整数。
Figure PCTCN2015090079-appb-000021
式(12)中，R4与R6相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7相同或不同，为卤素原子、碳原子数8以下的烷基或苯 基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；a和b独立地为1～30的整数。
Figure PCTCN2015090079-appb-000022
式(13)中，R4与R6相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7相同或不同，为卤素原子、碳原子数8以下的烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；a和b独立地为1～30的整数。
优选地，在含磷聚苯醚树脂组合物中，以所述端基官能化聚苯醚树脂为100重量份计，含磷阻燃组合物的添加量为15～60重量份，例如25重量份、30重量份、35重量份、40重量份、45重量份、50重量份或55重量份，优选为20～50重量份，进一步优选为25～40重量份。通过添加含磷阻燃组合物，发挥含磷组合物之间的协同效果，使固化后的聚苯醚树脂组合物可以达到良好的阻燃。但含量阻燃组合物的添加量小于15重量份时，体系的阻燃达不到V-0级别，到添加量超过60份时，虽然可以充分的保证固化后的聚苯醚树脂组合物达到良好的阻燃，但是由于含磷阻燃组合物本身吸水偏大，导致体系的耐热性、介电性能会大幅恶化。
本发明中，所述含磷聚苯醚树脂组合物还包括交联剂，所述交联剂为带有不饱和双键的聚烯烃树脂，所述带有不饱和双键的聚烯烃树脂为聚丁二烯及其接枝改性聚合物如马来酸酐接枝该性聚丁二烯聚合物、丙烯酸改性丁二烯聚合物、丁二烯-苯乙烯共聚物、丁二烯-苯乙烯-二乙烯基苯共聚物或环烯烃共聚物 中的任意一种或者至少两种的混合物。
以端基官能化聚苯醚树脂为100重量份计，所述带有不饱和双键的聚烯烃树脂的添加量为10～100重量份，例如15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重量份或95重量份。由于烯烃树脂的介电性能优异，所以添加合适比例的烯烃树脂可以进一步改善固话体系的介电性能如Dk/Df，同时由于烯烃树脂中带有的不饱和双键可以与聚苯醚树脂进一步交联固化，可以进一步提高耐热性。当添加量小于10份时，烯烃树脂中引入的不饱和双键量太少，无法起到有效交联的效果，达不到提高耐热性和介电性能的目的；如果烯烃树脂量超过100份，则由于烯烃树脂本身的刚性太差，膨胀系数大的原因也会导致固化物的耐热性巨大下降。
优选地，所述端基官能化聚苯醚树脂的数均分子量为500～5000，优选数均分子量为500～3000，更优选数均分子量为800～2500。当使用数均分子量超过5000的端基官能化聚苯醚树脂时，在加工过程中溶解性变差，无法使用常规的层压板工艺进行上胶，需要加温，使得在覆铜板加工过程中工艺困难，操作危险，且流动性也会随之下降，使得多层板加工困难；而当数均分子量小于500的时候，其耐热性、介电性能会下降，不利于制得高耐热性的树脂组合物和层压板材料，同时介电特性也会降低。当所述端基官能化聚苯醚树脂进一步和交联剂混合时，具有较小数均分子量的官能化聚苯醚树脂能够更好地改善与交联剂之间的相容性，即分子量越小，混合组分之间的相容性更好，储存稳定性更好。另外，较低的分子量可以提供更好的流动性，有利于在多层板加工过程中提供更良好的填胶性。
本发明中，所述含磷聚苯醚树脂组合物还包括共交联剂，所述共交联剂为 双马来酰亚胺树脂或/和多官能团丙烯酸酯化合物，优选为马来酰亚胺树脂。
以端基官能化聚苯醚树脂为100重量份计，所述共交联剂的添加量为5～50重量份，例如7重量份、10重量份、13重量份、16重量份、19重量份、22重量份、25重量份、28重量份、31重量份、35重量份、38重量份、41重量份、44重量份或47重量份。所述共交联剂的引入，主要目的是出于进一步提高聚苯醚固化产物的耐热性角度出发，由于马来酰亚胺树脂可以和端基官能化聚苯醚树脂及烯烃树脂的不饱和双键发生固化交联反应，形成一个由三者共同组成的交联网状结构，体系具有更好的耐热稳定性；马来酰亚胺树脂添加量太少起不到改善交联密度，提高耐热性的目的，如果量太多虽然可以有效提高体系的交联密度，但是由于马来酰亚胺本身结构的极性较大，会带来介电性能的明显下降。
在本发明中，所述含磷聚苯醚树脂组合物还包括引发剂。所述引发剂的半衰期温度t1/2不小于100℃，为过氧化物自由基引发剂，选自过氧化二异丙苯、过氧化苯甲酸叔丁酯、2，5-二(2-乙基己酰过氧)-2，5-二甲基己烷、二-(叔丁基过氧异丙基)苯、过氧化(2，4-二氯苯甲酰)、2，5-二甲基-2，5-双(叔丁基过氧)己烷、过氧化-2-乙基己基碳酸叔丁酯、2，5-二甲基-2，5-双(叔丁基过氧)-3-己炔、4，4-二(叔丁基过氧化)戊酸丁酯、1，1-双(叔丁基过氧化)-3，3，5-三甲基环己烷、3，3，5，7，7-五甲基-1，2，4-三氧杂环庚烷、二叔丁基过氧化物或叔丁基过氧化异丙苯中的任意一种或者至少两种的混合物，优选过氧化二异丙苯，因为该化合物具有较高的半衰期温度和反应起始温度，因此在不需要固化时，在半固化过程中，不会过度地引发固化反应，也不会降低聚苯醚树脂的储存稳定性。
本发明聚苯醚树脂组合物中的引发剂，目的在于提高交联固化效果。虽然端基官能化聚苯醚树脂和交联剂也可以在加热高温条件下进行固化，但是层压 板应用时，工艺条件很难以满足高温要求，使其加工难度增加，另外一方面也不利于工艺效率，增加生产成本，因此加入引发剂更加有利。以端基官能化聚苯醚树脂为100重量份计，所述引发剂的添加量为0.5～7重量份，例如1.3重量份、1.6重量份、1.9重量份、2.2重量份、2.5重量份、3.1重量份、3.5重量份、3.9重量份、4.3重量份、4.7重量份、5重量份、5.4重量份、5.8重量份、6.2重量份或6.6重量份。
本发明中，所述含磷聚苯醚树脂组合物还包括硅烷偶联剂，以端基官能化聚苯醚树脂为100重量份计，所述硅烷偶联剂的添加量为0.1～10重量份，例如0.5重量份、1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份、4.5重量份、5重量份、5.5重量份、6重量份、6.5重量份、7重量份、7.5重量份、8重量份、8.5重量份、9重量份或9.5重量份。
对偶联剂的种类没有特别的限定。偶联剂可以进一步降低树脂固化物的表面张力，使其粘度得到进一步的降低，提高树脂组合物的流动性。特别在添加填料的场合下，偶联剂的加入可以有效地提高树脂和填料之间的结合力，消除这两者之间的界面，进一步降低固化物的吸水率。所述的偶联剂可以为硅烷类、硅烷预聚体、钛酸酯类，硅烷偶联剂可以为环氧基硅烷偶联剂、氨基硅烷偶联剂、苯氨基硅烷偶联剂、乙烯基硅烷偶联剂、异氰酸酯基硅烷偶联剂、丙烯基硅烷偶联剂、异丁烯基硅烷偶联剂、苯乙烯基硅烷偶联剂、脲基硅烷偶联剂、氯丙基硅烷偶联剂、硫基硅烷偶联剂或硫化基硅烷偶联剂等。
本发明中，所述含磷聚苯醚树脂组合物还包括填料，所述填料为有机或无机填料，无机填料选自结晶型二氧化硅、熔融二氧化硅、球形二氧化硅、空心二氧化硅、玻璃粉、氮化铝、氮化硼、碳化硅、氢氧化铝、二氧化钛、钛酸锶、钛酸钡、氧化铝、硫酸钡、滑石粉、硅酸钙、碳酸钙或云母中的任意一种或者 至少两种的混合物；有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物。
另外，无机填料的形状、粒径等也无特别限定，通常粒径为0.01-50μm，优选为0.01-20μm，更优选为0.01-10μm，这种粒径范围的无机填料在树脂液中更易分散。
以端基官能化聚苯醚树脂为100重量份计，所述填料的添加量为10～300重量份，例如30重量份、60重量份、90重量份、120重量份、150重量份、180重量份、210重量份、240重量份或270重量份。
本发明所述的“包括”，意指其除所述组份外，还可以包括其他组份，这些其他组份赋予所述含磷聚苯醚树脂组合物不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由……组成”。
例如，所述含磷聚苯醚树脂组合物还可以含有各种添加剂，作为具体例，可以举出抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
进一步地，本发明提供一种使用上述含磷聚苯醚树脂组合物制作的预浸料，包括基材及通过含浸干燥后附着于基材上的如上所述的含磷聚苯醚树脂组合物。
制作时，首先将端基官能化聚苯醚树脂、含磷组合物、任选交联剂、任选地共交联剂、任选引发剂、任选的偶联剂以及任选地填料溶解到一种或多种有机溶剂中，制得均一的胶液。对有机溶剂没有特别的限定，只要可以溶解以上组分，且不会影响其反应性；适合的溶剂包括：酮类如甲乙酮、丙酮等，醚类如丙二醇单甲醚、二丁醚等，酯类如乙酸乙酯，芳香类如甲苯、二甲苯等，卤代烃类如三氯乙烷等。每种溶剂可以单独使用，也可以组合使用。胶液中树脂 固体物质的浓度可以根据胶液浸渍到基材的种类和工艺做适当地改变，例如其合适的浓度为30～80％。通过上述制得的胶液浸渍到基材，而后对其进行加热烘干以除去有机溶剂并部分固化基材内的树脂组合物，便得到预浸料。
所述基材为有机纤维、碳纤维或玻璃纤维制得的纺织物或无纺织物；对于玻璃纤维制得的纺织物或无纺织物，其主要成分中包含有重量比50～80％的SiO2、重量比0～30％的CaO、重量比0～20％的Al2O3、重量比5～25％的B2O3、及重量比0～5％的MgO。所述增强材料优选为编制纤维布，可选为E-Glass，T-Glass，NE-Glass，L-Glass，Q-Glass。
用来浸渍上述基材的树脂含量，优选为使得预浸料中的树脂含量为30质量％或更高。由于基材的介电常数往往要高于树脂组合物，为了降低由这些预浸料制得的层压板的介电常数，树脂组合物成分在预浸料中的含量优选高于上述含量。如使用树脂组分含量为40％的预浸料制得的层压板，其介电常数为3.5，而使用树脂含量为50％或更高的预浸料制得的层压板，其介电常数为3.2或更低。此外，以上所述的预浸料是在条件为80～170℃下烘烤2～15分钟，但并不局限于此。
另外，本发明还提供一种层压板，其包括至少一张叠合的如上所述的预浸料。
另外，本发明还提供一种使用上述含磷聚苯醚树脂组合物制作的覆铜箔层压板，包括数张叠合的预浸料及压覆于叠合后预浸料的一面或两面的铜箔。
具体为通过堆叠一张或多张本发明的预浸料，在其一面或两面附上铜箔等，而后进行热压而制得，在层压板表面的铜箔上进行蚀刻形成需要的线路图而得到印制线路板。此外，还可以通过以下方法和步骤制备多层印制线路板：使用印制线路板作为内层印制线路板，对其上面的铜箔进行表面处理，按照需求按 一定顺序将本发明的预浸料和上述做好表面处理的印制线路板堆叠进行热压，热压条件可根据本发明的聚苯醚树脂组合物的组成比例而定，对此没有特别的限定。热压条件优选为150～250℃的温度范围和1.0MPa～10.0MPa的压力范围下热压一段时间。用这种方法和步骤获得的层压板和印制线路板具有良好的高频特性如介电性能等同时还具有良好的工艺加工性、耐热性及耐湿性。
此外，为了进一步提高材料在高频高速领域的应用，在本发明中的覆铜箔层压板生产中，使用的铜箔，可以选择电解铜箔或压延铜箔，其表面粗糙度小于5微米，可以改善及提高层压板材料在高频高速印制线路板使用的信号损失。同时，为了提高铜箔接触预浸料一面的结合力，上述所用的铜箔还可以使用硅烷偶联剂进行化学处理，所用的偶联剂为环氧基硅烷偶联剂、乙烯基硅烷偶联剂或丙烯酸酯基硅烷偶联剂中的一种或多种的混合物，目的是提高铜箔和基材的结合力，防止在印制线路板使用过程中发生掉新、掉焊盘等风险。
本发明还提供了一种印制电路板，其包括至少一张叠合的如上所述的预浸料。
与已有技术相比，本发明具有如下有益效果：
本发明的聚苯醚树脂组合物，为低分子量的官能化聚苯醚树脂组合物，具有良好的工艺加工性，保持了聚苯醚树脂良好的介电特性及耐热性，再添加特定结构含磷阻燃剂成分，既保持了原有聚苯醚树脂体系的耐热性、介电性能、低吸水性，同时实现无卤阻燃，阻燃达到UL 94V-0级别。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本发明的技术方案。
合成例1：DOPO衍生物的制备
往配有加料漏斗、热电偶、机械搅拌器和氮流的四颈反应器中加入叔丁醇 钾230g，溶剂无水DMSO1.5L。在室温下搅拌该混合物，直至其变成均匀溶液。将溶液冷却至10℃，以10小份加入DOPO 42.3g，以保持反应温度低于30℃。在1小时内将加料漏斗中的二氯乙烷92g缓慢加入到上述溶液中。加热至50度反应1小时。冷却至10℃反应并将加入3L水。过滤浆料，并用水、丙酮合乙酸乙酯洗涤湿滤饼，得到532g粗湿物质，将该物质在MeCN/乙醇/水5320ml中回流，并缓慢冷却到5℃。通过漏斗过滤白色固体，并在80℃真空烘箱中干燥8～10小时，得到干燥的白色粉末260g，即为式(1)的DOPO衍生物1，其中R1为-CH2-CH2-。
合成例2
合成方法参照合成例1，将其中的二氯甲烷替换成二氯对二甲苯，得到式(1)的DOPO衍生物2，其中R1为苯基。
混合例1：含磷阻燃组合物的制备(P15.4％)
将35重量份的次磷酸盐化合物、100重量份的合成例1的DOPO衍生物以及18重量份的聚磷腈化合物混合，得到含磷组合物；
所述次磷酸盐化合物为：
Figure PCTCN2015090079-appb-000023
所述聚磷腈化合物具有如下结构：
Figure PCTCN2015090079-appb-000024
其中R为甲基，其中n为3～100的整数。
混合例2：含磷组合物的制备(P16％)
将50重量份的次磷酸盐化合物、100重量份的合成例1的DOPO衍生物以 及25重量份的聚磷腈化合物混合，得到含磷组合物；
所述次磷酸盐化合物为：
Figure PCTCN2015090079-appb-000025
所述聚磷腈化合物具有如下结构：
Figure PCTCN2015090079-appb-000026
其中R为乙基，其中n为的3～100的整数。
混合例3：含磷组合物的制备(P13.8％)
将10重量份的次磷酸盐化合物、100重量份的合成例1的DOPO衍生物以及25重量份的聚磷腈化合物混合，得到含磷组合物；
所述次磷酸盐化合物为：
Figure PCTCN2015090079-appb-000027
所述聚磷腈化合物具有如下结构：
Figure PCTCN2015090079-appb-000028
其中q为3；其中R为苯氧基。
混合例4含磷组合物的制备(P15％)
将30重量份的次磷酸盐化合物、100重量份的合成例2的DOPO衍生物以及40重量份的聚磷腈化合物混合，得到含磷组合物；
所述次磷酸盐化合物为：
Figure PCTCN2015090079-appb-000029
所述聚磷腈化合物具有如下结构两者的混合物：
Figure PCTCN2015090079-appb-000030
其中R为甲基，其中n为80的整数；
Figure PCTCN2015090079-appb-000031
其中q为3；其中R为苯氧基。
实施例1
将100g甲基丙烯酸酸甲酯改性的聚苯醚SA9000和作为溶剂的甲苯混合，溶解完全得到端基官能化聚苯醚树脂溶液，然后加入45g苯乙烯-丁二烯共聚物R100作为交联剂，加入2g过氧化二异丙苯作为引发剂，45g混合例1的含磷组合物作为阻燃剂，0.8g环氧基硅烷偶联剂和80g二氧化硅(SC-2050SQ)作为填料，将上述混合物在甲苯中混合，并搅拌溶解得到均一的树脂组合物，即胶液。
将上述制备得到的胶液浸渗到E-玻纤布，在155℃下加热干燥3～10min，将溶剂挥发完全，得到预浸料。在重叠以上制备得到的8涨预浸料两面各附上厚度为35μm的铜箔，在200℃的温度和3.0MPa的压力下热压90分钟，得到双面覆铜的层压板。
实施例2
将100g甲基丙烯酸酸甲酯基改性的聚苯醚SA9000和作为溶剂的甲苯混合，溶解完全得到端基官能化聚苯醚树脂溶液，然后加入20g聚丁二烯聚物 B-1000作为交联剂，加入2.0g过氧化二异丙苯作为引发剂，30g混合例2的含磷组合物作为阻燃剂，0.8g乙烯基硅烷偶联剂和80g二氧化硅(SC-2050SQ)作为填料，将上述混合物在甲苯中混合，并搅拌溶解得到均一的树脂组合物，即胶液。
将上述制备得到的胶液浸渗到E-玻纤布，在155℃下加热干燥3～10min，将溶剂挥发完全，得到预浸料。在重叠以上制备得到的8张预浸料两面各附上厚度为35μm的铜箔，在200℃的温度和3.0MPa的压力下热压90分钟，得到双面覆铜的层压板。
实施例3
将100g甲基丙烯酸酸甲酯基改性的聚苯醚SA9000和作为溶剂的甲苯100g混合，溶解完全得到端基官能化聚苯醚树脂溶液，然后加入30g苯乙烯-丁二烯共聚物R100作为交联剂，15g双马来酰亚胺树脂作为共固化剂，再加入3.0g过氧化二异丙苯作为引发剂，35g混合例2的含磷组合物作为阻燃剂，2g乙烯基基硅烷偶联剂和150g二氧化硅作为填料，将上述混合物在甲苯中混合，并搅拌溶解得到均一的树脂组合物，即胶液。
将上述制备得到的胶液浸渗到E-玻纤布，在155℃下加热干燥3～10min，将溶剂挥发完全，得到预浸料。在重叠以上制备得到的8涨预浸料两面各附上厚度为35μm的铜箔，在200℃的温度和3.0MPa的压力下热压90分钟，得到双面覆铜的层压板。
实施例4
将100g苯乙烯基聚苯醚OPE-2000和作为溶剂的甲苯100g混合，溶解完全得到端基官能化聚苯醚树脂溶液，然后加入35g聚丁二烯聚合物B-2000作为交联剂，加入2.5g过氧化二异丙苯作为引发剂，50g混合例3的含磷组合物作 为阻燃剂，150g乙烯基处理的二氧化硅作为填料，将上述混合物在甲苯中混合，并搅拌溶解得到均一的树脂组合物，即胶液。
将上述制备得到的胶液浸渗到E-玻纤布，在155℃下加热干燥3～10min，将溶剂挥发完全，得到预浸料。在重叠以上制备得到的8涨预浸料两面各附上厚度为35μm的铜箔，在200℃的温度和3.0MPa的压力下热压90分钟，得到双面覆铜的层压板。
实施例5
将100g苯乙烯基封端的聚苯醚树脂OPE-2000和作为溶剂的甲苯100g混合溶解完全得到端基官能化聚苯醚树脂溶液，然后加入20g苯乙烯-丁二烯共聚物R100作为交联剂，10g双马来酰亚胺树脂作为共固化剂，再加入3.0g过氧化二异丙苯作为引发剂，45g混合例2的含磷组合物作为阻燃剂，200g乙烯基基硅烷偶联剂和150g二氧化硅作为填料，将上述混合物在甲苯中混合，并搅拌溶解得到均一的树脂组合物，即胶液。
将上述制备得到的胶液浸渗到E-玻纤布，在155℃下加热干燥3～10min，将溶剂挥发完全，得到预浸料。在重叠以上制备得到的8涨预浸料两面各附上厚度为35μm的铜箔，在200℃的温度和3.0MPa的压力下热压90分钟，得到双面覆铜的层压板。
实施例6
将100g甲基丙烯酸酸甲酯基改性的聚苯醚SA9000和作为溶剂的甲苯100g混合溶解完全得到端基官能化聚苯醚树脂溶液，然后加入75g苯乙烯-丁二烯共聚物R100作为交联剂，45g双马来酰亚胺树脂作为共固化剂，再加入3.0g过氧化二异丙苯作为引发剂，35g混合例4的含磷组合物作为阻燃剂，200g乙烯基基硅烷处理的二氧化硅SC-2300SVJ作为填料，将上述混合物在甲苯中混合， 并搅拌溶解得到均一的树脂组合物，即胶液。将上述制备得到的胶液浸渗到E-玻纤布，在155℃下加热干燥3～10min，将溶剂挥发完全，得到预浸料。在重叠以上制备得到的8涨预浸料两面各附上厚度为35μm的铜箔，在200℃的温度和3.0MPa的压力下热压90分钟，得到双面覆铜的层压板。
实施例7
将将100g甲基丙烯酸酸甲酯基改性的聚苯醚SA9000和作为溶剂的甲苯100g混合，溶解完全得到端基官能化聚苯醚树脂溶液，然后加入30马来酸酐接枝改性聚丁二烯聚合物Ricon156MA17作为交联剂，25g马来酰亚胺树脂作为共交联剂，加入2.5g过氧化二异丙苯作为引发剂，35g混合例3的含磷组合物作为阻燃剂，300g乙烯基基硅烷处理的二氧化硅SC-2300SVJ作为填料，将上述混合物在甲苯中混合，并搅拌溶解得到均一的树脂组合物，即胶液。
将上述制备得到的胶液浸渗到E-玻纤布，在155℃下加热干燥3～10min，将溶剂挥发完全，得到预浸料。在重叠以上制备得到的8涨预浸料两面各附上厚度为35μm的铜箔，在200℃的温度和3.0MPa的压力下热压90分钟，得到双面覆铜的层压板。
比较例1
将100g甲基丙烯酸酸甲酯基改性的聚苯醚SA9000和作为溶剂的甲苯混合，溶解完全得到端基官能化聚苯醚树脂溶液，然后加入45g苯乙烯-丁二烯共聚物R100作为交联剂，加入2g过氧化二异丙苯作为引发剂，54gDOPO衍生物XP-7866作为阻燃剂，0.8g环氧基硅烷偶联剂和80g二氧化硅作为填料，将上述混合物在甲苯中混合，并搅拌溶解得到均一的树脂组合物，即胶液。
将上述制备得到的胶液浸渗到E-玻纤布，在155℃下加热干燥3～10min，将溶剂挥发完全，得到预浸料。在重叠以上制备得到的8涨预浸料两面各附上 厚度为35μm的铜箔，在200℃的温度和3.0MPa的压力下热压90分钟，得到双面覆铜的层压板。
比较例2
将100g甲基丙烯酸酸甲酯基改性的聚苯醚SA9000和作为溶剂的甲苯混合，溶解完全得到端基官能化聚苯醚树脂溶液，然后加入45g苯乙烯-丁二烯共聚物R100作为交联剂，加入2g过氧化二异丙苯作为引发剂，100g聚磷腈SPB-100作为阻燃剂，0.8g环氧基硅烷偶联剂和80g二氧化硅作为填料，将上述混合物在甲苯中混合，并搅拌溶解得到均一的树脂组合物，即胶液。
将上述制备得到的胶液浸渗到E-玻纤布，在155℃下加热干燥3～10min，将溶剂挥发完全，得到预浸料。在重叠以上制备得到的8涨预浸料两面各附上厚度为35μm的铜箔，在200℃的温度和3.0MPa的压力下热压90分钟，得到双面覆铜的层压板。
比较例3
将100g甲基丙烯酸酸甲酯基改性的聚苯醚SA9000和作为溶剂的甲苯混合，溶解完全得到端基官能化聚苯醚树脂溶液，然后加入45g苯乙烯-丁二烯共聚物R100作为交联剂，加入2g过氧化二异丙苯作为引发剂，45g乙基-双(四溴苯邻二甲酰亚胺)BT-93W，0.8g环氧基硅烷偶联剂和80g二氧化硅作为填料，将上述混合物在甲苯中混合，并搅拌溶解得到均一的树脂组合物，即胶液。
将上述制备得到的胶液浸渗到E-玻纤布，在155℃下加热干燥3～10min，将溶剂挥发完全，得到预浸料。在重叠以上制备得到的8涨预浸料两面各附上厚度为35μm的铜箔，在200℃的温度和3.0MPa的压力下热压90分钟，得到双面覆铜的层压板。
比较例4
将100g甲基丙烯酸酸甲酯基改性的聚苯醚SA9000和作为溶剂的甲苯100g混合，溶解完全得到端基官能化聚苯醚树脂溶液，10g双马来酰亚胺树脂作为共固化剂，再加入3.0g过氧化二异丙苯作为引发剂，25g混合例2的含磷组合物作为阻燃剂，2g乙烯基基硅烷偶联剂和150g二氧化硅作为填料，将上述混合物在甲苯中混合，并搅拌溶解得到均一的树脂组合物，即胶液。
将上述制备得到的胶液浸渗到E-玻纤布，在155℃下加热干燥3～10min，将溶剂挥发完全，得到预浸料。在重叠以上制备得到的8涨预浸料两面各附上厚度为35μm的铜箔，在200℃的温度和3.0MPa的压力下热压90分钟，得到双面覆铜的层压板。
对实施例和比较例进行性能测试，结果如表1和表2所示：
表1
Figure PCTCN2015090079-appb-000032
表2
Figure PCTCN2015090079-appb-000033
从以上测试结果可以看出，实施例1～7种采用的含磷阻燃剂组合物，可以在较少的添加量下，达到良好的V-0阻燃剂级别，当其搭配官能化的聚苯醚树脂、烯烃树脂以及双马来酰亚胺树脂组成的热固性组合物固化后可以到到具有优良耐热性、介电性能同时又满足UL 94V-0的阻燃要求。
对比例1中，单独使用DOPO衍生物作为阻燃剂时，即使添加量增加，其阻燃效果也不充分；而单独使用聚磷腈化合物作为阻燃剂，即使添加量很大耶无法满足UL 94V-0的阻燃要求，且由于增塑性带来了固化产物的玻璃化转变温度急剧下降，耐热性极差；对比例4种使用单一的双马来酰亚胺作为交联剂时，固化产物的耐热性和阻燃性较好，但是会导致介电性能的恶化；对比例3使用了含溴的阻燃剂，可以达到很好的耐热性和阻燃性能，但无法满足无卤环保技术需求。
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范 围和公开范围之内。

Claims (10)

  1. 一种含磷阻燃组合物，其特征在于，所述阻燃组合物包括：
    (A)式(1)所示的DOPO衍生物，100重量份；
    (B)次磷酸盐化合物，5～50重量份；
    (C)聚磷腈化合物，10～50重量份；
    Figure PCTCN2015090079-appb-100001
    R1选自C2～C20的亚烷烃或亚芳香烃中的一种。
  2. 如权利要求1所述的阻燃组合物，其特征在于，所述组分(B)次磷酸盐化合物具有如下结构：
    Figure PCTCN2015090079-appb-100002
    其中m为2或3；R3和R4独立地为碳原子数为1～6的烷烃基或芳烃基，M为金属原子，该金属原子选自钠、钙、镁、铝、砷、锌或铁中的任意一种，优选为铝或钠，更优选为铝；
    优选地，所述组份(C)聚磷腈化合物具有如下结构式：
    Figure PCTCN2015090079-appb-100003
    其中R为苯氧基、碳原子数为1～10的烷基、乙烯基苯氧基或烯丙基苯氧基中的任意一种；
    n为3～100的整数；
    或，
    Figure PCTCN2015090079-appb-100004
    R为苯氧基、碳原子数为1～10的烷基、乙烯基苯氧基或烯丙基苯氧基中的任意一种；
    q为3～25的整数。
  3. 一种含磷聚苯醚树脂组合物，其特征在于，其包含如权利要求1或2所述的含磷阻燃组合物和端基官能化聚苯醚树脂。
  4. 如权利要求3所述的树脂组合物，其特征在于，以所述端基官能化聚苯醚树脂为100重量份计，含磷阻燃组合物的添加量为15～60重量份，优选为20～50重量份，进一步优选为25～40重量份；
    优选地，所述端基官能化聚苯醚树脂为端羟基化聚苯醚树脂、环氧化聚苯醚树脂、乙烯基化聚苯醚树脂或氰基化聚苯醚树脂中的任意一种或者至少两种的混合物，优选为乙烯基化聚苯醚树脂或/和氰基化聚苯醚树脂，进一步优选为乙烯基化聚苯醚树脂；
    优选地，所述端基官能化聚苯醚树脂结构式如式(2)所示：
    Figure PCTCN2015090079-appb-100005
    式(2)中，a和b独立地为1～30的整数，Z为式(3)或(4)所示的结构，-(-O-Y-)-为式(5)所示的结构，-(-O-X-O-)-为式(6)所示的结构：
    Figure PCTCN2015090079-appb-100006
    Figure PCTCN2015090079-appb-100007
    式(4)中，A为亚芳香基、羰基或碳原子数为1～10的亚烷基，m为0～10的整数，R1、R2和R3相同或不同，独立地为氢或碳原子数10以下的烷基；
    Figure PCTCN2015090079-appb-100008
    式(5)中，R4与R6相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基，R5与R7相同或不同，独立地为卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基；
    Figure PCTCN2015090079-appb-100009
    式(6)中，R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基，B为碳原子数20以下的亚烃基、
    Figure PCTCN2015090079-appb-100010
    Figure PCTCN2015090079-appb-100011
    n为0或1；R16为氢原子或碳原子数为1～10的烷基；
    优选地，所述端基官能化聚苯醚树脂为式(7)或(8)所示的结构：
    Figure PCTCN2015090079-appb-100012
    式(7)中，R1～R3相同或不同，独立地为氢或碳原子数10以下的烷基；R4与R6相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7相同或不同，独立地为卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基；a和b独立地为1～30的整数，B为碳原子数20以下的亚烃基、
    Figure PCTCN2015090079-appb-100013
    n为0或者1，R16为氢原子或碳原子数为1～10的烷基；
    Figure PCTCN2015090079-appb-100014
    式(8)中，R4与R6相同或不同，独立地为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7相同或不同，为卤素原子、碳原子数8以下的烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；a和b独立地为1～30的整数；B为碳原子数20以下的亚烃基，n为0或者1；
    优选地，所述端基官能化聚苯醚树脂为式(9)至(13)所示的结构：
    Figure PCTCN2015090079-appb-100015
    式(9)中，R1～R3相同或不同，为氢或碳原子数10以下的烷基；R4与R6相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7相同或不同，为卤素原子、碳原子数8以下的烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；a和b独立地为1～30的整数；或，
    Figure PCTCN2015090079-appb-100016
    式(10)中，R1～R3相同或不同，为氢或碳原子数10以下的烷基；R4与R6相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7相同或不同，为卤素原子、碳原子数8以下的烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；a和b独立地为1～30的整数；或，
    Figure PCTCN2015090079-appb-100017
    式(11)中，R1～R3相同或不同，为氢或碳原子数10以下的烷基；R4与R6相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7 相同或不同，为卤素原子、碳原子数8以下的烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；a和b独立地为1～30的整数；或，
    Figure PCTCN2015090079-appb-100018
    式(12)中，R4与R6相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7相同或不同，为卤素原子、碳原子数8以下的烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；a和b独立地为1～30的整数；或，
    Figure PCTCN2015090079-appb-100019
    式(13)中，R4与R6相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；R5与R7相同或不同，为卤素原子、碳原子数8以下的烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基；a和b独立地为1～30的整数。
  5. 如权利要求3-4之一所述的树脂组合物，其特征在于，所述含磷聚苯醚树脂组合物还包括交联剂；
    优选地，所述交联剂为带有不饱和双键的聚烯烃树脂，所述带有不饱和双键的聚烯烃树脂为聚丁二烯、马来酸酐改性聚丁二烯聚合物、丙烯酸改性聚丁 二烯聚合物、丁二烯-苯乙烯共聚物、丁二烯-苯乙烯-二乙烯基苯共聚物或环烯烃共聚物中的任意一种或者至少两种的混合物；
    优选地，以端基官能化聚苯醚树脂为100重量份计，所述带有不饱和双键的聚烯烃树脂的添加量为10～100重量份；
    优选地，所述端基官能化聚苯醚树脂的数均分子量为500～5000，优选数均分子量为500～3000，更优选数均分子量为800～2500；
    优选地，所述含磷聚苯醚树脂组合物还包括共交联剂；
    优选地，所述共交联剂为双马来酰亚胺树脂或/和多官能团丙烯酸酯化合物，优选为马来酰亚胺树脂；
    优选地，以端基官能化聚苯醚树脂为100重量份计，所述共交联剂的添加量为5～50重量份。
  6. 如权利要求3-5之一所述的树脂组合物，其特征在于，所述含磷聚苯醚树脂组合物还包括引发剂；
    优选地，所述引发剂的半衰期温度t1/2不小于100℃，为过氧化物自由基引发剂，选自过氧化二异丙苯、过氧化苯甲酸叔丁酯、2，5-二(2-乙基己酰过氧)-2，5-二甲基己烷、二-(叔丁基过氧异丙基)苯、过氧化(2，4-二氯苯甲酰)、2，5-二甲基-2，5-双(叔丁基过氧)己烷、过氧化-2-乙基己基碳酸叔丁酯、2，5-二甲基-2，5-双(叔丁基过氧)-3-己炔、4，4-二(叔丁基过氧化)戊酸丁酯、1，1-双(叔丁基过氧化)-3，3，5-三甲基环己烷、3，3，5，7，7-五甲基-1，2，4-三氧杂环庚烷、二叔丁基过氧化物或叔丁基过氧化异丙苯中的任意一种或者至少两种的混合物，优选过氧化二异丙苯；
    优选地，以端基官能化聚苯醚树脂为100重量份计，所述引发剂的添加量为0.5～7重量份；
    优选地，所述含磷聚苯醚树脂组合物还包括硅烷偶联剂，以端基官能化聚苯醚树脂为100重量份计，所述硅烷偶联剂的添加量为0.1～10重量份；
    优选地，所述含磷聚苯醚树脂组合物还包括填料，所述填料为有机或无机填料；
    优选地，所述无机填料选自结晶型二氧化硅、熔融二氧化硅、球形二氧化硅、空心二氧化硅、玻璃粉、氮化铝、氮化硼、碳化硅、氢氧化铝、二氧化钛、钛酸锶、钛酸钡、氧化铝、硫酸钡、滑石粉、硅酸钙、碳酸钙或云母中的任意一种或者至少两种的混合物；
    优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物；
    优选地，以端基官能化聚苯醚树脂为100重量份计，所述填料的添加量为10～300重量份。
  7. 一种预浸料，包括基材及通过含浸干燥后附着于基材上的如权利要求3-6之一所述的含磷聚苯醚树脂组合物。
  8. 一种层压板，包括至少一张叠合的如权利要求7所述的预浸料。
  9. 一种覆铜箔层压板，包括至少一张叠合的如权利要求7所述的预浸料及压覆于叠合后预浸料的一面或两面的铜箔；
    优选地，所述铜箔为电解铜箔或压延铜箔，所述铜箔为使用硅烷偶联剂进行化学处理，所用的偶联剂为环氧基硅烷偶联剂、乙烯基硅烷偶联剂或丙烯酸酯基硅烷偶联剂中的一种或至少两种的混合物，且其表面粗糙度小于5微米。
  10. 一种印制电路板，包括至少一张叠合的如权利要求7所述的预浸料。
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