WO2020132929A1 - 含磷硅阻燃剂、其制备方法、阻燃树脂组合物、预浸料和覆金属箔层压板 - Google Patents

含磷硅阻燃剂、其制备方法、阻燃树脂组合物、预浸料和覆金属箔层压板 Download PDF

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WO2020132929A1
WO2020132929A1 PCT/CN2018/123829 CN2018123829W WO2020132929A1 WO 2020132929 A1 WO2020132929 A1 WO 2020132929A1 CN 2018123829 W CN2018123829 W CN 2018123829W WO 2020132929 A1 WO2020132929 A1 WO 2020132929A1
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flame retardant
tert
peroxide
phosphorus
butyl
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PCT/CN2018/123829
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English (en)
French (fr)
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范华勇
黄增彪
林伟
佘乃东
许永静
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广东生益科技股份有限公司
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Priority to PCT/CN2018/123829 priority Critical patent/WO2020132929A1/zh
Publication of WO2020132929A1 publication Critical patent/WO2020132929A1/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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers

Definitions

  • the invention relates to the technical field of flame retardants, in particular to a reactive phosphorus-containing silicon flame retardant, its preparation method and application.
  • flame retardants have broad market prospects in various fields such as chemical building materials, electronic appliances, transportation, aerospace, daily furniture, interior decoration, clothing, food, housing and transportation.
  • Organophosphorus flame retardant is a kind of flame retardant with better flame retardant performance. It can replace halogenated flame retardant and is an environmentally friendly flame retardant.
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • NDPO 1,8-dinaphthyl-1,3,2-dioxan phosphating Hydrogen
  • DPPO 9,10-dihydro-9-oxa-10-phosphaanthracene-10-oxide
  • DPPO 9,10-dihydro-9-oxa-10-phosphaanthracene-10-oxide
  • Silicone flame retardant is a new type of halogen-free flame retardant with high efficiency, low toxicity, anti-melt dripping, and environmental friendliness. It is also a carbon-forming smoke suppressant. In addition to giving the substrate excellent flame retardant performance, the silicone flame retardant can also improve the processing performance and heat resistance of the substrate. Therefore, as a rising star of flame retardants, it has been rapidly developed since the 1980s.
  • the current flame retardants are mainly bromine-containing systems and halogen-free phosphorus-containing systems.
  • the bromine content of the bromine-containing system formulation needs to reach 15% or more flame retardant performance to achieve V-0 level, high
  • the bromine content reduces the heat resistance of the system and generates hydrogen bromide gas.
  • carcinogens such as dioxins and dibenzofurans have been detected in the combustion products of electronic and electrical equipment waste containing halogens such as bromine and chlorine, so the application of brominated epoxy resins has been restricted.
  • special structural resin with flame retardant effect can be added, but the cost is greatly increased.
  • the phosphorus content must be at least 2.5% flame retardant to achieve V-0. Due to the addition of a large amount of phosphorus-containing resin, the material has high brittleness and poor processability, and the price of phosphorus-containing resin is high, and the product cost remains high.
  • the inventors found through research that the special organophosphorus and the organosilicon are constructed on the main chain of the same molecule through the benzene (di) silicon ether structure (or naphthalene (di) silicon ether structure) to obtain the reactive phosphorus-containing silicon flame retardant
  • the agent can overcome the shortcomings of a single flame retardant, and can obtain a technical effect that is far superior to the simple compounding of two flame retardants, thus completing the present invention.
  • the present invention can be implemented by the following technical solutions.
  • An aspect of the present invention provides a phosphorus-containing silicon flame retardant, which has a structure represented by formula (I):
  • R 1 , R 2 , R 3 and R 4 are each independently a C6-C18 aryl group, a C1-C6 aliphatic group or a C2-C6 alkenyl group;
  • A is (DOPO structure), (DPO structure), (DPPO structure), (NDPO structure)
  • R 1 , R 2 , R 3 , and R 4 are each independently phenyl, C1-C5 alkyl, or vinyl.
  • Another aspect of the present invention provides a method for preparing the above phosphorus-containing silicon flame retardant, the method comprising:
  • organic phosphorus compound has any one of the following structures:
  • Q is p-dihydroxyphenyl (abbreviated as HQ) or p-dihydroxynaphthyl (abbreviated as NQ), preferably
  • the monohalosilane has a structure represented by formula (II):
  • R5, R6, R7 are each independently C6-C18 aryl, C1-C6 aliphatic or C2-C6 alkenyl, provided that R5, R6 , At least one of R7 contains vinyl,
  • the reaction of the organophosphorus compound with monohalosilane is preferably carried out in the presence of a catalyst.
  • the ratio of the number of moles of the monohalosilane to the organophosphorus compound is greater than or equal to 2;
  • the catalyst is selected from triethylamine, pyridine, sodium hydroxide, potassium hydroxide, anhydrous sodium carbonate, anhydrous potassium carbonate, sodium methoxide, more preferably, the catalyst is triethylamine ;
  • the amount of the catalyst is 2 to 4 times the mole number of the organic phosphorus compound, more preferably 2.2 to 3 times;
  • the reaction of the monohalosilane with the organophosphorus compound is performed in a solvent system selected from dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methyl Pyrrolidone (NMP); preferably, when DMAc is used as the solvent, the concentration of the reaction system is 15% to 30%; when DMAc is used as the solvent, the concentration of the reaction system is 18 to 25%;
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • NMP N-methyl Pyrrolidone
  • reaction temperature is 0-60°C, more preferably normal temperature to 60°C;
  • reaction time is 5-24 hours, more preferably 10-15 hours;
  • the reaction is carried out in the presence of a protective gas, and the preferred protective gas is nitrogen.
  • the method further includes a post-treatment post-reaction step, the post-treatment includes filtration and optional distillation of low boilers, and subsequent washing and drying;
  • the reagent used for washing is selected from alcohol solvents, ester solvents and deionized water, more preferably deionized water.
  • Another aspect of the present invention provides a flame retardant resin composition
  • a flame retardant resin composition comprising a thermosetting resin, a phosphorus-containing silicon flame retardant as described above, and an optional initiator and optional filler.
  • the phosphorus-containing silicon flame retardant accounts for 1-30%, preferably 5-20% of the total weight of the flame retardant resin composition.
  • the weight content of phosphorus in the flame retardant resin composition is less than 2.5%, more preferably less than 1%.
  • thermosetting resin is a resin with double bonds.
  • the resin with double bonds may be selected from polyolefin resins, silicone resins with double bonds, polyphenylene ether resins with double bonds, or bismaleimide resins.
  • the polyolefin resin may be selected from one or more of styrene-butadiene copolymers, polybutadiene, or styrene-butadiene-divinylbenzene copolymers, such as Samtomer’s Styrene-butadiene copolymer R-100, Japan's Caoda polybutadiene B-1000 or Samtomer's styrene-butadiene-divinylbenzene copolymer R250.
  • the polyphenylene ether resin with double bonds may be selected from polyphenylene ethers with methyl methacrylate end groups (eg, SA9000 from Sabic), and polyphenylene ethers with vinyl benzyl end groups.
  • the silicone resin with double bonds may be selected from silicone resins with vinyl groups, for example, double-ended vinyl silicone resins and special structure vinyl resins with a vinyl content of ⁇ 0.5%, double Vinyl-terminated silicone resin is selected from Runhe Chemicals RH-Vi1323, RH-Vi1324, RH-Vi1325, RH-Vi321, RH-Vi322; special structure vinyl silicone resin is selected from RH-Vi306, RH-Vi306B, RH-Vi306B, RH-Vi315.
  • silicone resins with vinyl groups for example, double-ended vinyl silicone resins and special structure vinyl resins with a vinyl content of ⁇ 0.5%
  • double Vinyl-terminated silicone resin is selected from Runhe Chemicals RH-Vi1323, RH-Vi1324, RH-Vi1325, RH-Vi321, RH-Vi322
  • special structure vinyl silicone resin is selected from RH-Vi306, RH-Vi306B, RH-Vi
  • the bismaleimide resin may be selected from 4,4'-diphenylmethane bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4 One or more of'-diphenylisopropylbismaleimide and 4,4'-diphenylsulfone bismaleimide.
  • the content of the thermosetting resin may be 30 to 99 parts by weight, preferably 30 to 70 parts by weight.
  • the initiator is a free radical initiator.
  • the free radical initiator can be selected from organic peroxide initiators; more preferably, the organic peroxide initiator can be selected from di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide , Cumene peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl Peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-tris Methylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, 2,
  • the filler is an inorganic filler.
  • the inorganic filler may be selected from aluminum hydroxide, boehmite, silica, talc, mica, barium sulfate, lithopone, calcium carbonate, wollastonite, kaolin, brucite, diatomaceous earth, bentonite, trioxide Any one or a mixture of at least two of aluminum, boron nitride or pumice powder.
  • the content of the filler may be 0-50 parts by weight, preferably 0-30 parts by weight, based on the total amount of the flame retardant resin composition being 100 parts by weight.
  • the flame retardant resin composition may also contain a co-curing agent, that is, a reactive monomer or polymer used as a curing agent together with the phosphorus-containing silicon flame retardant of the present invention.
  • a reactive monomer or polymer can co-react with the polymer or phosphorus-containing silicon flame retardant in the resin composition.
  • Exemplary monomers that may be suitable as co-curing agents include di-, tri-, or higher ethylenically unsaturated monomers, such as styrene, divinylbenzene, vinyltoluene, divinylbenzene, triallyl iso All of cyanurate (TAIC), diallyl phthalate and multifunctional acrylate monomers are commercially available.
  • TAIC cyanurate
  • diallyl phthalate and multifunctional acrylate monomers are commercially available.
  • Another aspect of the present invention provides a prepreg including a base material and the flame retardant resin composition as described above attached to the base material by dipping or coating.
  • the substrate is fiber cloth, preferably glass fiber cloth.
  • the material of the glass fiber cloth can be inorganic fibers (such as E glass, D glass, L glass, M glass, S glass, T glass, NE glass, quartz and other glass fibers) or organic fibers (such as polyimide, polyamide, Polyester, polyphenylene ether, liquid crystal polymer, etc.).
  • the prepreg is formed of the resin composition and the substrate in a semi-cured state.
  • the forming process of the prepreg may be: the resin composition in the state of varnish infiltrates the substrate, and after heating, the solvent is volatilized and converted into a semi-cured state.
  • Another aspect of the present invention also provides a metal foil-clad laminate including at least one prepreg as described above and metal foil coated on one side or both sides of the prepreg.
  • the metal foil includes copper foil.
  • the DOPO, DPO, DPPO, NDPO structure and the vinyl-containing silane structure are constructed on the main chain of the same molecule through the symmetric structure of benzene (di) silicon ether or naphthalene (di) silicon ether, which can
  • benzene (di) silicon ether or naphthalene (di) silicon ether which can The realization of UL94 V-0 at phosphorus content not only improves the disadvantages of phosphorus-containing compounds such as brittleness and poor heat and humidity resistance, but also contains silicone segments in the main chain structure of the flame retardant, which has good processability.
  • the flame retardant of the present invention is a reactive flame retardant, has a reactive vinyl group, and can be used as a curing agent for an unsaturated reactive group-containing resin system. After curing with the resin containing unsaturated reactive groups, it will not reduce the Tg of the system, the dielectric properties are also excellent, and will not migrate out during the later use process and affect the performance.
  • the phosphorus-containing silicon flame retardant of the present invention When the phosphorus-containing silicon flame retardant of the present invention is used, at high temperatures, the phosphorus compound will form polyphosphoric acid, which is a strong dehydrating agent, which catalyzes the formation of carbon, and the silicon element migrates to the surface due to the low surface energy.
  • the carbonized layer forms a SiC-based ceramic layer, which further increases the thermal stability of these carbon layers, thereby exerting a phosphorus/silicon synergistic flame retardant effect.
  • the main chain of the flame retardant of the present invention contains a phenyl silicon ether structure or a naphthalene silicon ether structure, which has better flame retardant efficiency, and thus the resin composition and its The produced copper clad laminate has excellent heat resistance, low water absorption rate and flame retardancy.
  • FIG. 1 shows the reaction curve of the phosphorus-containing silicon flame retardant of the present invention when matched with an initiator.
  • Figure 2 shows the reaction curve of polyphenylene ether resin with phosphorus-containing silicon flame retardant and initiator.
  • Figure 1 shows the DSC reaction curve of the prepared phosphorus-containing silicon flame retardant with initiator dicumyl peroxide (DCP)
  • Figure 2 shows the polyphenylene ether resin SA9000 with the phosphorus-containing silicon flame retardant and initiator DSC reaction curve when the agent is DCP.
  • the phosphorus-containing silicon flame retardant starts to react at about 155°C and reaches the reaction peak at 203°C, indicating that the phosphorus-containing silicon flame retardant has strong reactivity.
  • SA9000 shows the phosphorus-containing silicon flame retardant
  • there is a strong reaction peak indicating that the phosphorus-containing silicon flame retardant and other double bond-containing resins can form a cross-linked network during the product application process. Prevent the risk of precipitation.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 PSi1 5 10 15 A
  • a PSi2 A A A 5 10
  • Polybutadiene B-1000 A A 53.3
  • DCP 3 A 3 3
  • BPO A 3
  • Composition Si contains phosphorus% 0.57 1.14 1.71 0.59 1.21 Tg(DMA)/°C 225 224 225 227 218 Dk(10GHz) 3.52 3.54 3.51 3.53 3.52
  • Df(10GHz) 0.0061 0.0063 0.0062 0.0061 0.0063
  • OXO OOO OOO OOO OOO T288/min >60 >60 >60 >60 >60 >60 >60
  • SA9000 Sabic, methacrylate-based polyphenylene ether resin
  • TAIC Bailingwei Technology Co., Ltd., triallyl isocyanurate acid
  • DCP Aladdin, dicumyl peroxide
  • BPO Aladdin, benzoyl peroxide
  • RH-Vi1325 Runhe Chemical, double-ended vinyl silicone resin
  • BT-93W American Albemarle, ethylene bistetrabromophthalimide, bromine content 66%;
  • SPB100 Mitsubishi Chemical Japan, phosphazene flame retardant, phosphorus content 13.4%;
  • Polybutadiene B-1000 Japan Cao Da, polybutadiene.
  • Glass transition temperature (Tg) DMA test is used and measured according to the DMA test method specified in IPC-TM-650 2.4.24.
  • PCT heat and humidity resistance
  • T288 Use TMA instrument to measure according to the T288 test method specified in IPC-TM-650 2.4.24.1.
  • Examples 1 to 3 are after adding different parts of the phosphorus-containing silicon flame retardant PSi1, as the phosphorus content and silicon content in the plate increase, the flame retardancy becomes excellent.
  • the performance of PSi2 flame retardant is the same as that of PSi1, and V-0 can be achieved when it is added to 10 parts.
  • the phosphorus content is only 0.63% and the silicon content is 1.14%.
  • the phosphorus-containing silicon flame retardant of the present invention has good overall performance. Since the silicon vinyl group of the phosphorus-containing silicon flame retardant is reactive, it forms a three-dimensional whole with the host resin after addition (as can be seen from the obvious exothermic peak of the DSC reaction curve), so it will not reduce the Tg of the system, and The electrical performance is also very good, and the heat and humidity resistance (after high pressure cooking and then immersing tin at 288°C for 5min) is very good.
  • Comparative Example 1 is a plate without flame retardant. It is seen that the flame retardancy is poor when it is burned to the fixture; while for the current resin system containing unsaturated reactive groups, the most used is the additive flame retardant containing phosphorus or bromine. , Such as Comparative Example 2 and Comparative Example 3, in the case of using the phosphazene flame retardant SPB-100 of Mitsubishi Chemical in Japan, when the number of additions in Comparative Example 2 is small, the flame retardancy is too poor, while Comparative Example 3 is added In 15 cases, when the phosphorus content reaches 2.0%, the flame retardancy basically reaches V-0, but because the small molecule inorganic substance SPB-100 does not react into the three-dimensional structure of the cured product, it will deteriorate the Tg of the sheet, and In terms of PCT, some failed the 2h test.
  • Comparative Example 5 the American Yabao bromine-containing flame retardant BT-93W is used. Although it has no effect on Tg when added to 20 parts, it can only approach V-0 level.
  • Comparative Example 4 introduces silicon element through vinyl resin, and introduces phosphorus element through SPB-100 for compounding investigation, and the comparative example 4 has the same phosphorus content and silicon content as in Example 2, the total combustion of Example 2 The time is 44 seconds, which is the V-0 rating, and the total burning time of Comparative Example 4 is 86 seconds, which is the V-1 rating. It can be seen that the compounded flame retardant effect is significantly better than the phosphorus-containing silicon flame retardant of the present invention. difference.
  • the comprehensive performance of the phosphorus-containing silicon flame retardant of the present invention is superior to the phosphorus and silicon compound system, and is also superior to the system using phosphorus flame retardant or bromine flame retardant alone, especially in terms of flame retardancy and heat resistance
  • the phosphorus-containing silicon flame retardants of the present invention are the best performers.
  • the phosphorus-containing silicon flame retardant of the present invention can exert the phosphorus/silicon synergistic flame-retardant effect, and its mechanism may be as follows: at high temperatures, the surface tension of the silicon-containing compound is small, tending to migrate to the surface of the material, generating SiO 2 by oxidative decomposition, etc.
  • the phosphorus compound promotes dehydration and carbonization, while silicon can form a ceramic-like (SiC) structure with the carbonized layer to strengthen and protect the carbon layer, thereby playing a synergistic flame retardant role.
  • the flame retardant with reactive vinyl of the present invention can also prevent the risk of precipitation during long-term use.

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Abstract

提供一种含磷硅阻燃剂、其制备方法、阻燃树脂组合物、预浸料和覆金属箔层压板。含磷硅阻燃剂具有式(I)所示的结构，可以同时起到固化剂和无卤阻燃剂的功效，在较低的磷含量下可达到UL94 V-0的阻燃效果。(I)

Description

含磷硅阻燃剂、其制备方法、阻燃树脂组合物、预浸料和覆金属箔层压板 技术领域
本发明涉及阻燃剂技术领域，特别涉及一种具有反应性的含磷硅阻燃剂、其制备方法和应用。
背景技术
随着合成材料工业的发展和应用领域的不断拓展，阻燃剂在化学建材、电子电器、交通运输、航天航空、日用家具、室内装饰、衣食住行等各个领域中具有广阔的市场前景。
有机磷系阻燃剂是一种阻燃性能较好的阻燃剂，可代替卤化系阻燃剂，是一种对环境友好的阻燃剂。其中，以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(简称DOPO)、1,8-二萘基-1,3,2-二氧杂环磷化氢(简称NDPO)、9,10-二氢-9-氧杂-10-磷杂蒽-10-氧化物(简称DPPO)、10-(2,5-二羟基苯基)-10H-9-氧杂-10-磷杂菲-10-氧化物(简称DOPO-HQ)、二苯基蒽醌氧化瞵(简称DPPQ)为代表的含磷阻燃剂，因其良好的阻燃性能被广泛用作环氧树脂阻燃剂。有机硅阻燃剂是一种新型高效、低毒、防熔滴、环境友好的无卤阻燃剂，也是一种成炭型抑烟剂。有机硅阻燃剂在赋予基材优异的阻燃性能之外，还能改善基材的加工性能、耐热性能等。因此，作为阻燃剂的后起之秀，从20世纪80年代开始得到迅速发展。
发明内容
在覆铜板技术领域中，目前采用的阻燃剂主要是含溴体系和无卤含磷体系，一般含溴体系配方中溴含量需达到15％以上阻燃性能方能达到V-0水平，高的溴含量降低了体系的耐热性和产生溴化氢气体。此外，近年来在含溴、氯等卤素的电子电气设备废弃物的燃烧产物中已检测出二噁英、二苯并呋喃等致癌物质，因此溴化环氧树脂的应用受到限制。为降低体系中的溴含量，可加入具有阻燃效果的特殊结构树脂，但成本大幅度增加。对于无卤含磷体系而言，磷含量至少要达到2.5％阻燃才能达到V-0。由于添加大量的含磷树脂，材料的脆性大，加工性不良，并且含磷树脂的价格高，产品成本高居不下。
发明人经研究发现，将特殊的有机磷与有机硅通过苯(二)硅醚结构(或萘(二)硅醚结构)构筑在同一分子的主链上，获得的反应型含磷硅阻燃剂能够克服单一阻燃剂的缺点，且能获得远优于两种阻燃剂的简单复配的技术效果，从而完成了本发明。
具体而言，本发明可以通过以下技术方案实施。
本发明的一个方面提供一种含磷硅阻燃剂，其具有式(I)所示的结构：
Figure PCTCN2018123829-appb-000001
其中，
R 1、R 2、R 3、R 4各自独立地为C6-C18芳基、C1-C6脂族基团或C2-C6烯基；
A为
Figure PCTCN2018123829-appb-000002
(DOPO结构)、
Figure PCTCN2018123829-appb-000003
(DPO结构)、
Figure PCTCN2018123829-appb-000004
(DPPO结构)、
Figure PCTCN2018123829-appb-000005
(NDPO结构)中的任一种；
B为
Figure PCTCN2018123829-appb-000006
中的任一种。
在某些实施方案中，R 1、R 2、R 3、R 4各自独立地为苯基、C1-C5烷基或乙烯基。
本发明的另一方面提供一种制备上述含磷硅阻燃剂的方法，所述方法包括：
使有机磷化合物与单卤代硅烷反应，
其中，所述有机磷化合物具有以下结构中的任一种：
Figure PCTCN2018123829-appb-000007
其中Q为对二羟基苯基(简称HQ)或对二羟基萘基(简称NQ)，优选
Figure PCTCN2018123829-appb-000008
中的任一种，
所述单卤代硅烷具有式(II)所示的结构：
Figure PCTCN2018123829-appb-000009
其中X为卤素，优选氯，溴或碘，最优选氯；R5、R6、R7各自独立地为C6-C18芳基、C1-C6脂族基团或C2-C6烯基，条件是R5、R6、R7中至少一个含有乙烯基，
所述有机磷化合物与单卤代硅烷的反应优选在催化剂存在下进行。
在某些实施方案中，所述单卤代硅烷与所述有机磷化合物的摩尔数之比大于等于2；
在某些实施方案中，所述催化剂选自三乙胺、吡啶、氢氧化钠、氢氧化钾、无水碳酸钠、无水碳酸钾、甲醇钠，更优选地，所述催化剂为三乙胺；
在某些实施方案中，所述催化剂用量为有机磷化合物摩尔数的2～4倍，更优为2.2～3倍；
在某些实施方案中，单卤代硅烷与有机磷化合物的反应在溶剂体系中进行，所述溶剂体系选自二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)和N-甲基吡咯烷酮(NMP)；优选地，以DMAc作为溶剂时，反应体系浓度为15％～30％；以DMAc为溶剂时，反应体系浓度为18～25％；
在某些实施方案中，反应温度为0～60℃，更优选常温至60℃；
在某些实施方案中，反应时间为5～24小时，更优选10～15小时；
在某些实施方案中，反应在保护性气体存在下进行，优选的保护性气体为氮气。
在某些实施方案中，所述方法还包括反应后的后处理步骤，所述后处理包括过滤和任选的蒸除低沸物，还包括随后的洗涤和干燥；
优选地，所述洗涤所用的试剂选自醇类溶剂、酯类溶剂和去离子水，更优去离子水。
本发明的另一方面提供一种阻燃树脂组合物，所述阻燃树脂组合物包含热固性树脂、如上所述的含磷硅阻燃剂，以及任选的引发剂和任选的填料。
在某些实施方案中，所述含磷硅阻燃剂占所述阻燃树脂组合物总重量的1～30％，优选5～20％。
在某些实施方案中，所述阻燃树脂组合物中磷的重量含量小于2.5％，更优选小于1％。
在某些实施方案中，所述热固性树脂为带双键的树脂。
在某些实施方案中，带双键的树脂可以选自聚烯烃树脂、带有双键的有机硅树脂、带有双键的聚苯醚树脂或双马来酰亚胺树脂。
在某些实施方案中，聚烯烃树脂可以选自苯乙烯-丁二烯共聚物、聚丁二烯或苯乙烯-丁二烯-二乙烯苯共聚物中的一种或多种，例如Samtomer的苯乙烯-丁二烯共聚物R-100、日本曹达的聚丁二烯B-1000或Samtomer的苯乙烯-丁二烯-二乙烯基苯共聚物R250。
在某些实施方案中，带有双键的聚苯醚树脂可以选自端基为甲基丙烯酸甲酯的聚苯醚(例如Sabic的SA9000)、端基为乙烯基苄基的聚苯醚。
在某些实施方案中，带有双键的有机硅树脂可以选自带有乙烯基的硅树脂，例如，双端乙烯基硅树脂和特殊结构乙烯基树脂并且乙烯基含量需≥0.5％，双端乙烯基硅树脂选自润禾化工RH-Vi1323、RH-Vi1324、RH-Vi1325、RH-Vi321、RH-Vi322；特殊结构乙烯基硅树脂选自RH-Vi306、RH-Vi306B、RH-Vi306B、RH-Vi315。
在某些实施方案中，双马来酰亚胺树脂可以选自4,4’-二苯甲烷双马来酰亚胺、4,4’-二苯醚双马来酰亚胺、4,4’-二苯异丙基双马来酰亚胺、4,4’-二苯砜双马来酰亚胺中的一种或几种。
在某些实施方案中，以阻燃树脂组合物中有机固形物总量为100重量份计，热固性树脂的含量可以为30～99重量份，优选30～70重量份。
在某些实施方案中，引发剂为自由基引发剂。优选地，自由基引发剂可以选自有机过氧化物引发剂；更优选地，有机过氧化物引发剂可以选自二叔丁基过氧化物、过氧化二月桂酰、过氧化二苯甲酰、过氧化新癸酸异丙苯酯、过氧化新癸酸叔丁酯、过氧化特戊酸特戊酯、过氧化特戊酸叔丁酯、叔丁基过氧化异丁酸酯、叔丁基过氧化-3,5,5-三甲基己酸酯、过氧化乙酸叔丁酯、过氧化苯甲酸叔丁酯、1,1-二叔丁基过氧化-3,5,5-三甲基环己烷、1,1-二叔丁基过氧化环己烷、2,2-二(叔丁基过氧化)丁烷、双(4-叔丁基环己基)过氧化二碳酸酯、过氧化二碳酸酯十六酯、过氧化二碳酸酯十四酯、二特戊己过氧化物、二异丙苯过氧化物、双(叔丁基过氧化异丙基)苯、2,5-二甲基-2,5-二叔丁基过氧化己烷、2,5-二甲基-2,5-二叔丁基过氧化己炔、二异丙苯过氧化氢、异丙苯过氧化氢、特戊基过氧化氢、叔丁基过氧化氢、叔丁基过氧化异丙苯、二异丙苯过氧化氢、过氧化碳酸酯-2-乙基己酸叔丁酯、叔丁基过氧化碳酸-2-乙基己酯、4,4-二(叔丁基过氧化)戊酸正丁酯、过氧化甲乙酮或过氧化环己烷中的任意一种。
在某些实施方案中，填料为无机填料。无机填料可以选自氢氧化铝、勃姆石、二氧化硅、滑石粉、云母、硫酸钡、立德粉、碳酸钙、硅灰石、高岭土、水镁石、硅藻土、膨润土、三 氧化二铝、氮化硼或浮石粉中的任意一种或者至少两种的混合物。
在某些实施方案中，以阻燃树脂组合物总量为100重量份计，填料的含量可以为0-50重量份，优选0-30重量份。
在某些实施方案中，阻燃树脂组合物还可以含有共固化剂，即，与本发明的含磷硅阻燃剂一起用作固化剂的反应性单体或聚合物。在一个实施方案中，这样的反应性单体或聚合物能与树脂组合物中的聚合物或含磷硅阻燃剂共反应。可适合作为共固化剂的示例性单体包括二-、三-或更高级的烯属不饱和单体，如苯乙烯、二乙烯基苯、乙烯甲苯、二乙烯基苯、三烯丙基异氰脲酸酯(TAIC)、邻苯二甲酸二烯丙酯和多官能丙烯酸酯单体等，它们全都可由市场上购得。
本发明的另一方面提供一种预浸料，所述预浸料包括基材及通过浸渍或涂覆而附着于基材上的如上所述的阻燃树脂组合物。
在某些实施方案中，所述基材为纤维布，优选玻璃纤维布。玻璃纤维布的材料可以是无机纤维(例如E玻璃、D玻璃、L玻璃、M玻璃、S玻璃、T玻璃、NE玻璃、石英等玻璃纤维)或有机纤维(例如聚酰亚胺、聚酰胺、聚酯、聚苯醚、液晶聚合物等)。
在某些实施方案中，所述预浸料是由半固化状态的树脂组合物和基材形成。预浸料的形成过程可以为：清漆状态的树脂组合物浸润基材，经过加热使溶剂挥发并转变为半固化状态。
本发明的另一方面还提供一种覆金属箔层压板，所述覆金属箔层压板包括至少一张如上所述的预浸料及覆于预浸料一侧或两侧的金属箔。
在某些实施方案中，金属箔包括铜箔。
本发明具有以下技术效果中的至少一种：
(1)将DOPO、DPO、DPPO、NDPO结构与含乙烯基的硅烷结构通过苯(二)硅醚或萘(二)硅醚的对称结构构筑在同一分子的主链上，能在较低的磷含量下实现UL94 V-0，不仅改善了含磷化合物脆、耐湿热性差等缺点，而且阻燃剂主链结构中含有有机硅链段，具有良好的工艺加工性。
(2)本发明的阻燃剂为反应型阻燃剂，具有反应性的乙烯基基团，可以作为含不饱和反应基团的树脂体系的固化剂。与含不饱和反应基团的树脂固化后，不会降低体系的Tg，介电性能也优异，并且不会在后期使用过程中迁移析出而影响使用性能。
(3)本发明的含磷硅阻燃剂在使用时，在高温下，磷化合物会形成聚磷酸，是强脱水 剂，催化促成炭的形成，而硅元素由于表面能低而迁移到表面与碳化层形成SiC类陶瓷层，进一步增加这些炭层的热稳定性，从而发挥磷/硅协同阻燃效果。
(4)与具有磷酸酯结构的阻燃剂相比，本发明的阻燃剂的主链含有苯硅醚结构或萘硅醚结构，具有更优的阻燃效率，由此树脂组合物及其制作的覆铜板具有优异的耐热性、低的吸水率和阻燃性。
附图说明
图1显示了本发明的含磷硅阻燃剂搭配引发剂时的反应曲线。
图2显示了聚苯醚树脂搭配含磷硅阻燃剂和引发剂时的反应曲线。
具体实施方式
下面以具体实施例的方式进一步描述本发明，但本发明的实施方式不限于这些实施例。制备例1
将100g DOPO-HQ和400g二甲基乙酰胺(DMAc)于装有搅拌器、冷凝回流管、温度计的四口烧瓶中搅拌20～30min，同时通入氮气，待其充分溶解后，一次性加入二甲基乙烯基氯硅烷75g，并缓慢滴加三乙胺催化剂，在常温下控制80g三乙胺于1h左右滴完，然后升温至50℃反应12h左右，然后过滤、水洗、干燥，得到产物150g，通过GPC测试其Mn＝495，其阻燃剂中P含量：6.3％，Si含量：11.4％。记为PSi1。
图1显示了所制备的含磷硅阻燃剂搭配引发剂过氧化二异丙苯(DCP)时的DSC反应曲线，图2显示了聚苯醚树脂SA9000搭配该含磷硅阻燃剂和引发剂DCP时的DSC反应曲线。从图1的DSC反应曲线可以看出：含磷硅阻燃剂在155℃左右开始反应，在203℃时达到反应峰值，说明含磷硅阻燃剂具有很强的反应性。在含磷硅阻燃剂搭配SA9000时，如图2的DSC反应曲线所示，具有强烈反应峰，说明含磷硅阻燃剂与其他含双键的树脂能形成交联网络，在产品运用过程防止析出的风险。
制备例2
将100g DPO-NQ和420g DMAc于装有搅拌器、冷凝回流管、温度计的四口烧瓶中搅拌20～30min，同时通入氮气，待其充分溶解后，一次性加入二苯基乙烯基氯硅烷84g，并缓慢滴加三乙胺催化剂，在常温下控制80g三乙胺于1h左右滴完，然后升温至50℃反应12h左 右，然后过滤、水洗、干燥，得到产物162g，通过GPC测试其Mn＝561，其阻燃剂中P含量：6.4％，Si含量：12.7％。记为PSi2。
实施例1
将5重量份的含磷硅阻燃剂PSi1、59.8重量份的甲基丙烯酸酯基聚苯醚树脂SA9000和32.2重量份的三烯丙基异氰脲酸酯(TAIC)溶解于甲苯溶剂中，并调节至合适的粘度，再加入3重量份的过氧化苯甲酰(BPO)，搅拌均匀后采用上海宏和的2116布进行上胶，在150℃下烘烤3min后的粘接片备用，并6张粘接片叠置，两面覆上铜箔，在200℃下固化120min，板材平整，固化物中的P含磷：0.315％，Si含磷：0.57％，其板材性能测试结果示于表1。
实施例2
将10重量份的含磷硅阻燃剂PSi1、87重量份的甲基丙烯酸酯基聚苯醚树脂SA9000溶解于甲苯溶剂中，并调节至合适的粘度，再加入3重量份的过氧化二异丙苯(DCP)，搅拌均匀后采用上海宏和的2116布进行上胶，在150℃下烘烤3min后的粘接片备用，并6张粘接片叠置，两面覆上铜箔，在200℃下固化120min，板材平整，固化物中的P含磷：0.63％，Si含磷：1.14％，性能测试结果示于表1。
实施例3
将15重量份的含磷硅阻燃剂PSi1、53.3重量份的日本曹达聚丁二烯B-1000和28.7重量份的三烯丙基异氰脲酸酯(TAIC)溶解于甲苯溶剂中，并调节至合适的粘度，再加入3重量份的过氧化二异丙苯(DCP)，搅拌均匀后采用上海宏和的2116布进行上胶，在150℃下烘烤3min后的粘接片备用，并6张粘接片叠置，两面覆上铜箔，在200℃下固化120min，板材平整，固化物中的P含磷：0.95％，Si含磷：1.71％，性能测试结果示于表1。
实施例4
将5重量份的含磷硅阻燃剂PSi2、59.8重量份的甲基丙烯酸酯基聚苯醚树脂SA9000和32.2重量份的三烯丙基异氰脲酸酯(TAIC)溶解于甲苯溶剂中，并调节至合适的粘度，再加入3重量份的过氧化苯甲酰(BPO)，搅拌均匀后采用上海宏和的2116布进行上胶，在150℃下烘烤3min后的粘接片备用，并6张粘接片叠置，两面覆上铜箔，在200℃下固化120min，板材平整，固化物中的P含磷：0.315％，Si含磷：0.57％，其板材性能测试结果示于表1。
实施例5
将10重量份的含磷硅阻燃剂PSi2、87重量份的日本曹达聚丁二烯B-1000溶解于甲苯溶剂中，并调节至合适的粘度，再加入3重量份的过氧化二异丙苯(DCP)，搅拌均匀后采用上海宏和的2116布进行上胶，在150℃下烘烤3min后的粘接片备用，并6张粘接片叠置，两面覆上铜箔，在200℃下固化120min，板材平整，固化物中的P含磷：0.63％，Si含磷：1.14％，性能测试结果示于表1。
对比例1
60重量份的甲基丙烯酸酯基聚苯醚树脂SA9000和37重量份的三烯丙基异氰脲酸酯酸(TAIC)溶解于甲苯溶剂中，并调节至合适的粘度，再加入3重量份的过氧化苯甲酰(BPO)，搅拌均匀后采用上海宏和的2116布进行上胶，在150℃下烘烤3min后的粘接片备用，并6张粘接片叠置，两面覆上铜箔，在200℃下固化120min，板材平整，固化物中的P含磷：0％，Si含磷：0％，其板材性能测试结果示于表1。
对比例2
将5重量份日本三菱化学的磷腈阻燃剂SPB-100、92重量份的甲基丙烯酸酯基聚苯醚树脂SA9000溶解于甲苯溶剂中，并调节至合适的粘度，再加入3重量份的过氧化二异丙苯(DCP)，搅拌均匀后采用上海宏和的2116布进行上胶，在150℃下烘烤3min后的粘接片备用，并6张粘接片叠置，两面覆上铜箔，在200℃下固化120min，板材平整，固化物中的P含磷：0.67％，Si含磷：0％，性能测试结果示于表1。
对比例3
将15重量份日本三菱化学的磷腈阻燃剂SPB-100、53.3重量份的甲基丙烯酸酯基聚苯醚树脂SA9000和28.7重量份的三烯丙基异氰脲酸酯(TAIC)溶解于甲苯溶剂中，并调节至合适的粘度，再加入3重量份的过氧化二异丙苯(DCP)，搅拌均匀后采用上海宏和的2116布进行上胶，在150℃下烘烤3min后的粘接片备用，并6张粘接片叠置，两面覆上铜箔，在200℃下固化120min，板材平整，固化物中的P含磷：2.01％，Si含磷：0％，性能测试结果示于表1。
对比例4
为了进一步说明阻燃效果，采用复配实验，本对比例采用润禾化工双端乙烯基硅树脂RH-Vi1325引入Si元素，采用SPB-100引入磷元素；将4.7重量份日本三菱化学的磷腈阻燃剂SPB-100、2.73重量份的硅树脂、58.2重量份的甲基丙烯酸酯基聚苯醚树脂SA9000和31.3重量份的三烯丙基异氰脲酸酯(TAIC)溶解于甲苯溶剂中，并调节至合适的粘度，再加入3重量份的过氧化二异丙苯(DCP)，搅拌均匀后采用上海宏和的2116布进行上胶，在150℃下烘烤3min后的粘接片备用，并6张粘接片叠置，两面覆上铜箔，在200℃下固化120min，板材平整，固化物中的P含磷：0.63％，Si含磷：1.14％，性能测试结果示于表1。
对比例5
将20重量份美国雅宝阻含溴燃剂BT-93W、53.3重量份的甲基丙烯酸酯基聚苯醚树脂SA9000和28.7重量份的三烯丙基异氰脲酸酯(TAIC)溶解于甲苯溶剂中，并调节至合适的粘度，再加入3重量份的过氧化二异丙苯(DCP)，搅拌均匀后采用上海宏和的2116布进行上胶，在150℃下烘烤3min后的粘接片备用，并6张粘接片叠置，两面覆上铜箔，在200℃下固化120min，板材平整，固化物中的P含磷：0％，Si含磷：0％，Br含量：13.2％，性能测试结果示于表1。
表1
  实施例1 实施例2 实施例3 实施例4 实施例5
PSi1 5 10 15    
PSi2       5 10
聚丁二烯B-1000     53.3   87
SA9000 59.8 87 0 59.8 0
TAIC 32.2 0 28.7 32.2 0
DCP 3   3 3  
BPO   3     3
组合物P含量％ 0.315 0.63 0.95 0.329 0.67
组合物Si含磷％ 0.57 1.14 1.71 0.59 1.21
Tg(DMA)/℃ 225 224 225 227 218
Dk(10GHz) 3.52 3.54 3.51 3.53 3.52
Df(10GHz) 0.0061 0.0063 0.0062 0.0061 0.0063
吸水性/％ 0.09 0.08 0.07 0.075 0.081
PCT/2h OXO OOO OOO OOO OOO
T288/min ＞60 ＞60 ＞60 ＞60 ＞60
燃烧总时间/s 95 44 24 76 43
UL等级 V-1 V-0 V-0 V-1 V-0
表1(续)
Figure PCTCN2018123829-appb-000010
实施例和对比例中所有的原材料具体如下：
SA9000：Sabic，甲基丙烯酸酯基聚苯醚树脂；
TAIC：百灵威科技有限公司，三烯丙基异氰脲酸酯酸；
DCP：阿拉丁，过氧化二异丙苯；
BPO：阿拉丁，过氧化苯甲酰；
RH-Vi1325：润禾化工，双端乙烯基硅树脂；
BT-93W：美国雅宝，乙撑双四溴邻苯二甲酰亚胺，溴含量66％；
SPB100：日本三菱化学，磷腈类阻燃剂，磷含量13.4％；
聚丁二烯B-1000：日本曹达，聚丁二烯。
表1中组合物特性的测试方法如下：
(1)玻璃化转变温度(Tg)：使用DMA测试，按照IPC-TM-650 2.4.24所规定的DMA测试方法进行测定。
(2)介电常数(Dk)和介电损耗因子(Df)：按照SPDR方法测试。
(3)耐湿热性(PCT)评价：将覆铜板表面的铜箔蚀刻后，评价基板；将基板放置压力锅中，在120℃、105KPa条件下处理2小时后，浸渍在288℃的锡炉中，当基板分层爆板时记录相应时间；当基板在锡炉中超过5min还没出现起泡或分层时即可结束评价。×为分层爆板，O为不分层爆板。一块板材同时制备3个样品，两个样品不分层爆板时通过测试。
(4)T288：用TMA仪，按照IPC-TM-650 2.4.24.1所规定的T288测试方法进行测定。
(5)吸水性：按照IPC-TM-650 2.6.2.1所规定的吸水性测试方法进行测定。
(6)阻燃性：按照UL 94标准方法进行。
如上表所示，实施例1～3为添加不同份数的含磷硅阻燃剂PSi1后，随着板材中磷含量和硅含量的增加，阻燃性变得优异。PSi2阻燃剂的表现与PSi1一致，特别加到10份的情况下即可实现V-0，而此时的磷含量才0.63％，硅含量1.14％。
另外，本发明的含磷硅阻燃剂具有良好的综合性能。由于含磷硅阻燃剂的硅乙烯基具有反应性，加入后与主体树脂形成一个三维整体(可从DSC反应曲线图的明显放热峰看出)，所以不会降低体系的Tg，并且介电性能也非常优异，而且耐湿热性能(高压蒸煮后再288℃浸锡5min)非常好。
对比例1为不加阻燃剂的板材，燃烧至夹具，可见其阻燃性差；而对于目前的含不饱和反应基团的树脂体系使用最多的是含磷或者含溴的添加型阻燃剂，如对比例2和对比例3，采用日本三菱化学的磷腈阻燃剂SPB-100情况下，对比例2中添加份数少的情况下，阻燃性太差，而对比例3在添加15份情况下，磷含量达到2.0％时，阻燃性基本达到了V-0，但是由于SPB-100这种小分子无机物，没有反应到固化物三维结构中，所以会恶化板材Tg，并且PCT方面，有部分没有通过2h测试。对比例5中采用美国雅宝含溴阻燃剂BT-93W，在添加到20份的情况下虽然对Tg没有影响但只能只能接近V-0水平。对比例4通过带乙烯基的硅树脂引入硅元素，通过SPB-100引入磷元素，进行复配考察，并且对比例4与实施例2中的磷含量与硅含量相同，实施例2的总燃烧时间为44秒，为V-0等级，对比例4的总燃烧时间为86秒，为V-1等级，可知与本发明的含磷硅阻燃剂相比，复配的阻燃效果明显较差。
由此可见，本发明的含磷硅阻燃剂综合性能优于磷与硅复配体系，也优于单独使用磷阻燃或溴阻燃的体系，特别是在阻燃性和耐热性方面，本发明的含磷硅阻燃剂均是表现最好的。本发明的含磷硅阻燃剂可以发挥磷/硅协同阻燃效果，其机理可能如下：高温下，含硅化合物的表面张力较小，趋向于迁移到材料表面，发生氧化分解等生成SiO 2，同时磷化合物促进脱水碳化，而硅则能与碳化层形成类陶瓷(SiC)结构，加固及保护炭层，从而发挥协同阻燃 作用。另外，本发明的带有反应性乙烯基的阻燃剂还能防止长期使用过程析出的风险。
以上仅为本发明的部分实施例，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思做出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的范围。

Claims (10)

  1. 一种含磷硅阻燃剂，其特征在于，所述含磷硅阻燃剂具有式(I)所示的结构：
    Figure PCTCN2018123829-appb-100001
    其中，
    R 1、R 2、R 3、R 4各自独立地为C6-C18芳基、C1-C6脂族基团或C2-C6烯基；
    A为
    Figure PCTCN2018123829-appb-100002
    中的任一种；
    B为
    Figure PCTCN2018123829-appb-100003
    中的任一种。
  2. 如权利要求1所述的含磷硅阻燃剂，其特征在于，R 1、R 2、R 3、R 4各自独立地为苯基、C1-C5烷基或乙烯基。
  3. 一种制备如权利要求1所述的含磷硅阻燃剂的方法，其特征在于，所述方法包括：
    使有机磷化合物与单卤代硅烷反应，
    其中，所述有机磷化合物具有以下结构中的任一种：
    Figure PCTCN2018123829-appb-100004
    其中Q为对二羟基苯基或对二羟基萘基，优选
    Figure PCTCN2018123829-appb-100005
    中的任一种，
    所述单卤代硅烷具有式(II)所示的结构：
    Figure PCTCN2018123829-appb-100006
    其中X为卤素，优选氯，溴或碘，最优选氯；R5、R6、R7各自独立地为C6-C18芳基、C1-C6脂族基团或C2-C6烯基，条件是R5、R6、R7中至少一个含有乙烯基，
    所述有机磷化合物与单卤代硅烷的反应优选在催化剂存在下进行。
  4. 如权利要求3所述的方法，其特征在于，所述单卤代硅烷与所述有机磷化合物的摩尔数之比大于等于2；
    优选地，所述催化剂选自三乙胺、吡啶、氢氧化钠、氢氧化钾、无水碳酸钠、无水碳酸钾、甲醇钠，更优选地，所述催化剂为三乙胺；
    优选地，所述催化剂用量为有机磷化合物摩尔数的2～4倍，更优为2.2～3倍；
    优选地，单卤代硅烷与有机磷化合物的反应在溶剂体系中进行，所述溶剂体系选自二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)和N-甲基吡咯烷酮(NMP)；优选地，以DMAc作为溶剂时，反应体系浓度为15％～30％；以DMAc为溶剂时，反应体系浓度为18～25％；
    优选地，反应温度为0～60℃，更优选常温至60℃；
    优选地，反应时间为5～24小时，更优选10～15小时；
    优选地，反应在保护性气体存在下进行，优选的保护性气体为氮气。
  5. 如权利要求3或4所述的方法，其特征在于，所述方法还包括反应后的后处理步骤，所述后处理包括过滤和任选的蒸除低沸物，还包括随后的洗涤和干燥；
    优选地，所述洗涤所用的试剂选自醇类溶剂、酯类溶剂和去离子水，更优去离子水。
  6. 一种阻燃树脂组合物，其特征在于，所述阻燃树脂组合物包含热固性树脂、如权利要求1或2所述的含磷硅阻燃剂，以及任选的引发剂和任选的填料。
  7. 如权利要求6所述的阻燃树脂组合物，其特征在于，所述含磷硅阻燃剂占所述阻燃树脂组合物总重量的1～35％，优选5～20％；
    优选地，所述阻燃树脂组合物中磷的重量含量小于2.5％，更优选小于1％。
  8. 如权利要求6或7所述的阻燃树脂组合物，其特征在于，
    所述热固性树脂为带双键的树脂，优选选自聚烯烃树脂、带有双键的有机硅树脂、带有双键的聚苯醚树脂或双马来酰亚胺树脂；更优选地，聚烯烃树脂选自苯乙烯-丁二烯共聚物、聚丁二烯或苯乙烯-丁二烯-二乙烯苯共聚物中的一种或多种；带有双键的聚苯醚树脂选自端基为甲基丙烯酸甲酯的聚苯醚、端基为乙烯基苄基的聚苯醚；带有双键的有机硅树脂选自带有乙烯基的硅树脂；双马来酰亚胺树脂选自4,4’-二苯甲烷双马来酰亚胺、4,4’-二苯醚双马来酰亚胺、4,4’-二苯异丙基双马来酰亚胺、4,4’-二苯砜双马来酰亚胺中的一种或几种。
    所述引发剂为自由基引发剂，优选所述自由基引发剂选自有机过氧化物引发剂；更优选所述有机过氧化物引发剂选自二叔丁基过氧化物、过氧化二月桂酰、过氧化二苯甲酰、过氧化新癸酸异丙苯酯、过氧化新癸酸叔丁酯、过氧化特戊酸特戊酯、过氧化特戊酸叔丁酯、叔丁基过氧化异丁酸酯、叔丁基过氧化-3,5,5-三甲基己酸酯、过氧化乙酸叔丁酯、过氧化苯甲酸叔丁酯、1,1-二叔丁基过氧化-3,5,5-三甲基环己烷、1,1-二叔丁基过氧化环己烷、2,2-二(叔丁基过氧化)丁烷、双(4-叔丁基环己基)过氧化二碳酸酯、过氧化二碳酸酯十六酯、过氧化二碳酸酯十四酯、二特戊己过氧化物、二异丙苯过氧化物、双(叔丁基过氧化异丙基)苯、2,5-二甲基-2,5-二叔丁基过氧化己烷、2,5-二甲基-2,5-二叔丁基过氧化己炔、二异丙苯过氧化氢、异丙苯过氧化氢、特戊基过氧化氢、叔丁基过氧化氢、叔丁基过氧化异丙苯、二异丙苯过氧化氢、过氧化碳酸酯-2-乙基己酸叔丁酯、叔丁基过氧化碳酸-2-乙基己酯、4,4-二(叔丁基过氧化)戊酸正丁酯、过氧化甲乙酮或过氧化环己烷中的任意一种；
    所述填料为无机填料，优选选自氢氧化铝、勃姆石、二氧化硅、滑石粉、云母、硫酸钡、立德粉、碳酸钙、硅灰石、高岭土、水镁石、硅藻土、膨润土、三氧化二铝、氮化硼或浮石粉中的任意一种或者至少两种的混合物。
  9. 一种预浸料，其特征在于，所述预浸料包括基材及通过浸渍或涂覆而附着于基材上 的如权利要求6～8中任一项所述的阻燃树脂组合物。
  10. 一种覆金属箔层压板，其特征在于，所述覆金属箔层压板包括至少一张如权利要求9所述的预浸料及覆于预浸料一侧或两侧的金属箔。
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6534601B1 (en) * 2001-10-29 2003-03-18 Kukdo Chemical Co., Ltd. Flame retardant epoxy resin modified with phosphorus and silicon
CN102079758A (zh) * 2009-11-30 2011-06-01 中国中化股份有限公司 一种磷硅化合物的制备方法
CN102181058A (zh) * 2011-03-15 2011-09-14 赵争艳 一种应用于聚酯的新型磷硅协同阻燃剂的合成
CN102875817A (zh) * 2012-09-07 2013-01-16 四川东材绝缘技术有限公司 一种添加型含磷硅阻燃剂的制备方法
CN102964633A (zh) * 2012-11-23 2013-03-13 张家港顺昌化工有限公司 一种磷硅阻燃剂的制备方法
CN103897104A (zh) * 2014-03-04 2014-07-02 河北联合大学 一种含dopo侧基的聚合型磷-硅阻燃剂及其制备方法
CN103980430A (zh) * 2014-05-22 2014-08-13 西南科技大学 一种不饱和聚酯阻燃复合材料的制备方法
CN107266685A (zh) * 2017-05-08 2017-10-20 西南科技大学 一种含磷、硅聚合型阻燃剂及其制备方法
CN108341947A (zh) * 2018-02-09 2018-07-31 四川大学 一种本征阻燃半芳香族共聚芳醚酰胺及其制备方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6534601B1 (en) * 2001-10-29 2003-03-18 Kukdo Chemical Co., Ltd. Flame retardant epoxy resin modified with phosphorus and silicon
CN102079758A (zh) * 2009-11-30 2011-06-01 中国中化股份有限公司 一种磷硅化合物的制备方法
CN102181058A (zh) * 2011-03-15 2011-09-14 赵争艳 一种应用于聚酯的新型磷硅协同阻燃剂的合成
CN102875817A (zh) * 2012-09-07 2013-01-16 四川东材绝缘技术有限公司 一种添加型含磷硅阻燃剂的制备方法
CN102964633A (zh) * 2012-11-23 2013-03-13 张家港顺昌化工有限公司 一种磷硅阻燃剂的制备方法
CN103897104A (zh) * 2014-03-04 2014-07-02 河北联合大学 一种含dopo侧基的聚合型磷-硅阻燃剂及其制备方法
CN103980430A (zh) * 2014-05-22 2014-08-13 西南科技大学 一种不饱和聚酯阻燃复合材料的制备方法
CN107266685A (zh) * 2017-05-08 2017-10-20 西南科技大学 一种含磷、硅聚合型阻燃剂及其制备方法
CN108341947A (zh) * 2018-02-09 2018-07-31 四川大学 一种本征阻燃半芳香族共聚芳醚酰胺及其制备方法

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