CN111363339A - Phosphorus-silicon-containing flame retardant, preparation method thereof, flame-retardant resin composition, prepreg and metal-foil-clad laminate - Google Patents

Phosphorus-silicon-containing flame retardant, preparation method thereof, flame-retardant resin composition, prepreg and metal-foil-clad laminate Download PDF

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CN111363339A
CN111363339A CN201811600045.7A CN201811600045A CN111363339A CN 111363339 A CN111363339 A CN 111363339A CN 201811600045 A CN201811600045 A CN 201811600045A CN 111363339 A CN111363339 A CN 111363339A
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flame retardant
phosphorus
silicon
resin
butyl
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范华勇
黄增彪
林伟
佘乃东
许永静
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • 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
    • C07F9/50—Organo-phosphines
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    • 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
    • C07F9/657163—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 the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657172—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 the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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    • 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
    • C07F9/657163—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 the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657181—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 the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/00—Properties of the layers or laminate
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    • B32B2307/7265—Non-permeable
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    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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Abstract

The invention provides a phosphorus-silicon-containing flame retardant, a preparation method thereof, a flame-retardant resin composition, a prepreg and a metal foil-clad laminate. The phosphorus-silicon-containing flame retardant has the structure shown in the formula (I), can simultaneously play the roles of a curing agent and a halogen-free flame retardant, and can achieve the flame retardant effect of UL94V-0 at lower phosphorus content.

Description

Phosphorus-silicon-containing flame retardant, preparation method thereof, flame-retardant resin composition, prepreg and metal-foil-clad laminate
Technical Field
The invention relates to the technical field of flame retardants, and particularly relates to a reactive phosphorus-silicon-containing flame retardant, and a preparation method and application thereof.
Background
With the development of synthetic material industry and the continuous expansion of application fields, the flame retardant has wide market prospect in various fields of chemical building materials, electronic and electric appliances, transportation, aerospace, daily furniture, interior decoration, clothes, food and housing, and the like.
The organic phosphorus flame retardant is a flame retardant with better flame retardant performance, can replace halogenated flame retardants, and is an environment-friendly flame retardant. Among them, phosphorus-containing flame retardants represented by 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 1, 8-dinaphthyl-1, 3, 2-dioxaphosphorinane (NDPO), 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DPPO), 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) and diphenylanthraquinone phosphine oxide (DPPQ) are widely used as epoxy resin flame retardants because of their good flame retardancy. The organic silicon flame retardant is a novel halogen-free flame retardant with high efficiency, low toxicity, anti-dripping and environmental protection, and is also a char-forming smoke suppressant. The organic silicon flame retardant not only endows the base material with excellent flame retardant performance, but also can improve the processing performance, the heat resistance and the like of the base material. Therefore, the development of the flame retardant was rapidly started from the 80 th of the 20 th century.
Disclosure of Invention
In the technical field of copper-clad plates, the currently adopted flame retardants are mainly a bromine-containing system and a halogen-free phosphorus-containing system, the bromine content in the general bromine-containing system formula needs to reach more than 15 percent to reach the V-0 level in the flame retardant property, and the high bromine content reduces the heat resistance of the system and generates hydrogen bromide gas. In addition, in recent years, carcinogens such as dioxin and dibenzofuran have been detected in combustion products of electronic and electrical equipment waste containing halogen such as bromine and chlorine, and thus the use of brominated epoxy resins has been limited. In order to reduce the bromine content in the system, special structural resin with flame retardant effect can be added, but the cost is greatly increased. For halogen-free phosphorus-containing systems, the phosphorus content should be at least 2.5% flame retardant to achieve V-0. Because of adding a large amount of phosphorus-containing resin, the brittleness of the material is large, the processability is poor, the price of the phosphorus-containing resin is high, and the product cost is high.
The inventor finds that the reaction type phosphorus-containing silicon flame retardant obtained by constructing special organic phosphorus and organic silicon on the main chain of the same molecule through a phenyl (di) silyl ether structure (or a naphthalene (di) silyl ether structure) can overcome the defects of a single flame retardant and can obtain the technical effect far superior to the simple compounding of two flame retardants, thereby completing the invention.
Specifically, the present invention can be implemented by the following means.
One aspect of the present invention provides a phosphorus-silicon-containing flame retardant having a structure represented by formula (I):
Figure BDA0001922242920000021
wherein the content of the first and second substances,
R1、R2、R3、R4each independently is a C6-C18 aryl group, a C1-C6 aliphatic group, or a C2-C6 alkenyl group;
a is
Figure BDA0001922242920000022
(DOPO structure),
Figure BDA0001922242920000023
(DPO structure),
Figure BDA0001922242920000024
(DPPO structure),
Figure BDA0001922242920000025
Any one of (NDPO structure);
b is
Figure BDA0001922242920000026
Any one of the above.
In certain embodiments, R1、R2、R3、R4Each independently is 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:
reacting an organophosphorus compound with a monohalosilane,
wherein the organophosphorus compound has any one of the following structures:
Figure BDA0001922242920000031
wherein Q is p-dihydroxyphenyl (HQ) or p-dihydroxynaphthyl (NQ), preferably
Figure BDA0001922242920000032
Any one of the above-mentioned (B) and (C),
the monohalosilane has a structure represented by formula (II):
Figure BDA0001922242920000033
wherein X is halogen, preferably chlorine, bromine or iodine, most preferably chlorine; r5, R6, R7 are each independently a C6-C18 aryl group, a C1-C6 aliphatic group or a C2-C6 alkenyl group, with the proviso that at least one of R5, R6, R7 contains a vinyl group,
the reaction of the organophosphorus compound with the monohalosilane is preferably carried out in the presence of a catalyst.
In certain embodiments, the mole ratio of the monohalosilane to the organophosphorus compound is greater than or equal to 2;
in certain embodiments, 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;
in certain embodiments, the amount of the catalyst is 2 to 4 times, more preferably 2.2 to 3 times, the number of moles of the organophosphorus compound;
in certain embodiments, the reaction of the monohalosilane with the organophosphorus compound is carried out in a solvent system selected from the group consisting of Dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP); preferably, when DMAc is used as a solvent, the concentration of a reaction system is 15-30%; when DMAc is used as a solvent, the concentration of a reaction system is 18-25%;
in certain embodiments, the reaction temperature is from 0 ℃ to 60 ℃, more preferably from ambient temperature to 60 ℃;
in certain embodiments, the reaction time is 5 to 24 hours, more preferably 10 to 15 hours;
in certain embodiments, the reaction is carried out in the presence of a protective gas, preferably nitrogen.
In certain embodiments, the process further comprises a post-treatment step after the reaction, which comprises filtration and optionally evaporation of low boilers, and further comprises subsequent washing and drying;
preferably, the washing reagent is selected from the group consisting of alcohol solvents, ester solvents, and deionized water, more preferably deionized water.
Another aspect of the present invention provides a flame retardant resin composition comprising a thermosetting resin, a phosphorus-containing silicon flame retardant as described above, and optionally an initiator and optionally a filler.
In certain embodiments, the phosphorus-containing silicon flame retardant comprises 1 to 30%, preferably 5 to 20% by weight of the total flame retardant resin composition.
In certain embodiments, the phosphorus content of the flame retardant resin composition is less than 2.5% by weight, more preferably less than 1% by weight.
In certain embodiments, the thermosetting resin is a double-bond-bearing resin.
In certain embodiments, the double bond-bearing resin may be selected from a polyolefin resin, a double bond-bearing silicone resin, a double bond-bearing polyphenylene ether resin, or a bismaleimide resin.
In certain embodiments, 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 Caoda's polybutadiene B-1000, or Samtomer's styrene-butadiene-divinylbenzene copolymer R250.
In certain embodiments, the polyphenylene ether resin with double bonds may be selected from the group consisting of polyphenylene ethers with methyl methacrylate end groups (e.g., SA9000 by Sabic), and polyphenylene ethers with vinylbenzyl end groups.
In certain embodiments, the silicone resin with double bonds may be selected from silicones with vinyl groups, such as vinyl-terminated silicones and vinyl resins of special structure and having a vinyl content of 0.5% or more, the vinyl-terminated silicones being selected from Runz chemical RH-Vi1323, RH-Vi1324, RH-Vi1325, RH-Vi321, RH-Vi 322; the vinyl silicone resin with special structure is selected from RH-Vi306, RH-Vi306B, RH-Vi306B and RH-Vi 315.
In certain embodiments, the bismaleimide resin may be selected from one or more of 4,4 '-diphenylmethane bismaleimide, 4' -diphenyl ether bismaleimide, 4 '-diphenylisopropyl bismaleimide, and 4, 4' -diphenylsulfone bismaleimide.
In certain embodiments, the thermosetting resin may be present in an amount of 30 to 99 parts by weight, preferably 30 to 70 parts by weight, based on 100 parts by weight of the total organic solids in the flame retardant resin composition.
In certain embodiments, the initiator is a free radical initiator. Preferably, the free radical initiator may be selected from organic peroxide initiators; more preferably, the organic peroxide initiator may be selected from di-t-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-amyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, 1-di-t-butylperoxy-3, 5, 5-trimethylcyclohexane, 1-di-t-butylperoxycyclohexane, 2-di (t-butylperoxy) butane, bis (4-t-butylcyclohexyl) peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, dipentyl hexylperoxide, dicumyl peroxide, di-n-butyl peroxyl, di-butyl-3, 5, 5-t-butyl peroxybutyrate, di, Any one of bis (t-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexyne, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-amyl hydroperoxide, t-butyl cumyl peroxide, diisopropylbenzene hydroperoxide, tert-butyl peroxycarbonate-2-ethylhexanoate, t-butyl peroxycarbonate-2-ethylhexyl, n-butyl-4, 4-di (t-butylperoxy) valerate, methyl ethyl ketone peroxide, or cyclohexane peroxide.
In certain embodiments, the filler is an inorganic filler. The inorganic filler may be selected from any one or a mixture of at least two of aluminum hydroxide, boehmite, silica, talc, mica, barium sulfate, lithopone, calcium carbonate, wollastonite, kaolin, brucite, diatomaceous earth, bentonite, aluminum oxide, boron nitride, or pumice powder.
In certain embodiments, the filler may be contained in an amount of 0 to 50 parts by weight, preferably 0 to 30 parts by weight, based on 100 parts by weight of the total amount of the flame retardant resin composition.
In certain embodiments, the flame retardant resin composition may also contain a co-curing agent, i.e., a reactive monomer or polymer that is used as a curing agent with the phosphorus-containing silicon flame retardant of the present invention. In one embodiment, such reactive monomers or polymers can be co-reacted 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, Triallylisocyanurate (TAIC), diallyl phthalate, and multifunctional acrylate monomers, all of which are commercially available.
Another aspect of the present invention provides a prepreg comprising a substrate and a flame retardant resin composition as described above attached to the substrate by impregnation or coating.
In certain embodiments, the substrate is a fibrous cloth, preferably a glass fiber cloth. The material of the glass cloth may be inorganic fibers (e.g., glass fibers such as E glass, D glass, L glass, M glass, S glass, T glass, NE glass, quartz, etc.) or organic fibers (e.g., polyimide, polyamide, polyester, polyphenylene ether, liquid crystal polymer, etc.).
In certain embodiments, the prepreg is formed from a resin composition in a semi-cured state and a substrate. The prepreg forming process may be: the resin composition in a varnish state infiltrates the base material, and is heated to volatilize the solvent and turn into a semi-cured state.
Another aspect of the present invention also provides a metal-clad laminate including at least one prepreg as described above and a metal foil clad on one or both sides of the prepreg.
In certain embodiments, the metal foil comprises copper foil.
The invention has at least one of the following technical effects:
(1) the DOPO, DPO, DPPO and NDPO structures and the silane structures containing vinyl are constructed on the main chain of the same molecule through the symmetrical structure of the phenyl (di) silyl ether or the naphthalene (di) silyl ether, UL94V-0 can be realized under lower phosphorus content, the defects of brittleness, poor humidity resistance and the like of phosphorus-containing compounds are overcome, and the main chain structure of the flame retardant contains an organic silicon chain segment, so that the flame retardant has good process processability.
(2) The flame retardant is a reactive flame retardant, has reactive vinyl groups, and can be used as a curing agent of a resin system containing unsaturated reactive groups. After being cured with the resin containing unsaturated reactive groups, the Tg of the system is not reduced, the dielectric property is excellent, and the use performance is not influenced by migration and precipitation in the later use process.
(3) When the phosphorus-silicon-containing flame retardant is used, a phosphorus compound can form polyphosphoric acid at high temperature, the polyphosphoric acid is a strong dehydrating agent and catalyzes and promotes the formation of carbon, and silicon elements migrate to the surface due to low surface energy and form SiC ceramic layers with carbide layers, so that the thermal stability of the carbon layers is further improved, and the phosphorus/silicon synergistic flame retardant effect is exerted.
(4) Compared with the flame retardant with a phosphate ester structure, the main chain of the flame retardant contains a phenyl silyl ether structure or a naphthyl silyl ether structure, so that the flame retardant has better flame retardant efficiency, and the resin composition and the copper-clad plate prepared from the resin composition have excellent heat resistance, low water absorption and flame retardance.
Drawings
FIG. 1 shows the reaction curve of the phosphorus-silicon-containing flame retardant of the present invention with an initiator.
FIG. 2 shows the reaction curve of polyphenylene ether resin with phosphorus-containing silicon flame retardant and initiator.
Detailed Description
The present invention is further described below by way of specific examples, but the embodiments of the present invention are not limited to these examples.
Preparation example 1
Stirring 100g of DOPO-HQ and 400g of dimethylacetamide (DMAc) in a four-neck flask provided with a stirrer, a condensation reflux pipe and a thermometer for 20-30 min, introducing nitrogen, adding 75g of dimethylvinylchlorosilane once after the DOPO and the DMAc are fully dissolved, slowly dropwise adding a triethylamine catalyst, controlling 80g of triethylamine to completely drip in about 1h at normal temperature, heating to 50 ℃ for reacting for about 12h, filtering, washing with water, and drying to obtain 150g of a product, wherein Mn is 495 according to GPC test, and P content in the flame retardant is: 6.3%, Si content: 11.4 percent. Denoted as PSi 1.
FIG. 1 shows the DSC reaction curve of the prepared phosphorus-silicon-containing flame retardant with an initiator dicumyl peroxide (DCP), and FIG. 2 shows the DSC reaction curve of the polyphenylene ether resin SA9000 with the phosphorus-silicon-containing flame retardant and the initiator DCP. As can be seen from the DSC reaction curve of fig. 1: the phosphorus-silicon-containing flame retardant starts to react at about 155 ℃ and reaches a reaction peak value at 203 ℃, which shows that the phosphorus-silicon-containing flame retardant has strong reactivity. When the phosphorus-silicon-containing flame retardant is matched with SA9000, as shown in a DSC reaction curve of fig. 2, the reaction peak is strong, which indicates that the phosphorus-silicon-containing flame retardant and other double-bond-containing resins can form a cross-linked network and prevent the risk of precipitation in the product application process.
Preparation example 2
Stirring 100g of DPO-NQ and 420g of DMAc in a four-neck flask provided with a stirrer, a condensation reflux pipe and a thermometer for 20-30 min, introducing nitrogen, after the DPO-NQ and the DMAc are fully dissolved, adding 84g of diphenylvinyl chlorosilane at one time, slowly dropwise adding a triethylamine catalyst, controlling 80g of triethylamine to be completely dripped in about 1h at normal temperature, heating to 50 ℃ to react for about 12h, filtering, washing and drying to obtain 162g of a product, testing the Mn of the product to be 561 through GPC, and testing the P content of the flame retardant: 6.4%, Si content: 12.7 percent. Denoted as PSi 2.
Example 1
Dissolving 5 parts by weight of phosphorus-silicon-containing flame retardant PSi1, 59.8 parts by weight of methacrylate-based polyphenylene ether resin SA9000 and 32.2 parts by weight of triallyl isocyanurate (TAIC) in a toluene solvent, adjusting the viscosity to a proper value, adding 3 parts by weight of Benzoyl Peroxide (BPO), uniformly stirring, gluing by using 2116 cloth of Shanghai macrosum, baking the bonding sheets at 150 ℃ for 3min for later use, overlapping 6 bonding sheets, covering copper foils on two sides, curing at 200 ℃ for 120min, flattening the plate, and P in a cured substance contains phosphorus: 0.315%, Si contains phosphorus: 0.57 percent, and the plate performance test results are shown in Table 1.
Example 2
Dissolving 10 parts by weight of phosphorus-silicon-containing flame retardant PSi1 and 87 parts by weight of methacrylate-based polyphenylene ether resin SA9000 in a toluene solvent, adjusting the viscosity to a proper value, adding 3 parts by weight of dicumyl peroxide (DCP), uniformly stirring, gluing by adopting Shanghai Honghe 2116 cloth, baking at 150 ℃ for 3min to obtain adhesive sheets for later use, overlapping 6 adhesive sheets, covering copper foils on two surfaces of the adhesive sheets, curing at 200 ℃ for 120min, flattening the plate, and forming P in a cured substance, wherein the P in the cured substance contains phosphorus: 0.63%, Si contains phosphorus: 1.14%, the results of the performance tests are shown in Table 1.
Example 3
Dissolving 15 parts by weight of phosphorus-silicon-containing flame retardant PSi1, 53.3 parts by weight of Japanese Caoda polybutadiene B-1000 and 28.7 parts by weight of triallyl isocyanurate (TAIC) in a toluene solvent, adjusting the viscosity to a proper value, adding 3 parts by weight of dicumyl peroxide (DCP), uniformly stirring, gluing by using a Shanghai macro and 2116 cloth, baking the bonding sheets at 150 ℃ for 3min for later use, overlapping 6 bonding sheets, covering the two sides with copper foils, curing at 200 ℃ for 120min, flattening the plate, and containing P in a cured substance: 0.95%, Si contains phosphorus: 1.71%, the results of the performance tests are shown in Table 1.
Example 4
Dissolving 5 parts by weight of phosphorus-silicon-containing flame retardant PSi2, 59.8 parts by weight of methacrylate-based polyphenylene ether resin SA9000 and 32.2 parts by weight of triallyl isocyanurate (TAIC) in a toluene solvent, adjusting the viscosity to a proper value, adding 3 parts by weight of Benzoyl Peroxide (BPO), uniformly stirring, gluing by using 2116 cloth of Shanghai macrosum, baking the bonding sheets at 150 ℃ for 3min for later use, overlapping 6 bonding sheets, covering copper foils on two sides, curing at 200 ℃ for 120min, flattening the plate, and P in a cured substance contains phosphorus: 0.315%, Si contains phosphorus: 0.57 percent, and the plate performance test results are shown in Table 1.
Example 5
Dissolving 10 parts by weight of phosphorus-silicon-containing flame retardant PSi2 and 87 parts by weight of Japanese Caoda polybutadiene B-1000 in a toluene solvent, adjusting the viscosity to a proper value, adding 3 parts by weight of dicumyl peroxide (DCP), uniformly stirring, gluing by adopting Shanghai Honghe 'h' 2116 cloth, baking the adhesive sheets at 150 ℃ for 3min for later use, overlapping 6 adhesive sheets, covering copper foils on two surfaces of the adhesive sheets, curing at 200 ℃ for 120min, flattening the plate, and forming P in a cured substance, wherein the P is phosphorus: 0.63%, Si contains phosphorus: 1.14%, the results of the performance tests are shown in Table 1.
Comparative example 1
60 parts by weight of methacrylate-based polyphenylene ether resin SA9000 and 37 parts by weight of triallyl isocyanurate acid (TAIC) are dissolved in toluene solvent, the solution is adjusted to a proper viscosity, 3 parts by weight of Benzoyl Peroxide (BPO) are added, after uniform stirring, the solution is glued by adopting Shanghai macrohe 2116 cloth, adhesive sheets are prepared after baking for 3min at 150 ℃, 6 adhesive sheets are superposed, copper foils are coated on two sides of the adhesive sheets, the adhesive sheets are cured for 120min at 200 ℃, the plate is flat, and P in a cured substance contains phosphorus: 0%, Si contains phosphorus: 0%, the results of the plate property test are shown in Table 1.
Comparative example 2
Dissolving 5 parts by weight of phosphazene flame retardant SPB-100 of Mitsubishi chemical and 92 parts by weight of methacrylate-based polyphenylene ether resin SA9000 in toluene solvent, adjusting to proper viscosity, adding 3 parts by weight of dicumyl peroxide (DCP), uniformly stirring, gluing by adopting 2116 cloth of Shanghai Honghe, baking the bonding sheets at 150 ℃ for 3min for later use, superposing 6 bonding sheets, covering copper foils on two sides, curing at 200 ℃ for 120min, flattening the plate, wherein P in a cured substance contains phosphorus: 0.67%, Si contains phosphorus: 0%, the results of the performance tests are shown in Table 1.
Comparative example 3
Dissolving 15 parts by weight of phosphazene flame retardant SPB-100 of Mitsubishi chemical, 53.3 parts by weight of methacrylate-based polyphenylene ether resin SA9000 and 28.7 parts by weight of triallyl isocyanurate (TAIC) in a toluene solvent, adjusting to a proper viscosity, adding 3 parts by weight of dicumyl peroxide (DCP), uniformly stirring, gluing by using 2116 cloth of Shanghai hong Kong, baking for 3min at 150 ℃, preparing adhesive sheets for later use, overlapping 6 adhesive sheets, covering copper foils on two surfaces, curing for 120min at 200 ℃, flattening the plate, and containing P in a cured substance: 2.01%, Si contains phosphorus: 0%, the results of the performance tests are shown in Table 1.
Comparative example 4
In order to further explain the flame retardant effect, a compounding experiment is adopted, Si element is introduced into the comparative example by adopting the double-end vinyl silicone resin RH-Vi1325 in the grain-moistening chemical industry, and phosphorus element is introduced into the comparative example by adopting the SPB-100; dissolving 4.7 parts by weight of phosphazene flame retardant SPB-100 of Mitsubishi chemical, 2.73 parts by weight of silicone resin, 58.2 parts by weight of methacrylate-based polyphenylene ether resin SA9000 and 31.3 parts by weight of triallyl isocyanurate (TAIC) in a toluene solvent, adjusting the viscosity to a proper value, adding 3 parts by weight of dicumyl peroxide (DCP), uniformly stirring, sizing by adopting 2116 cloth of Shanghai macro and the Shanghai macro, baking for 3min at 150 ℃, then preparing an adhesive sheet, superposing 6 adhesive sheets, covering copper foils on two sides, curing for 120min at 200 ℃, flattening the plate, wherein P in a cured product contains phosphorus: 0.63%, Si contains phosphorus: 1.14%, the results of the performance tests are shown in Table 1.
Comparative example 5
Dissolving 20 parts by weight of American jaba fire retardant BT-93W, 53.3 parts by weight of methacrylate-based polyphenylene ether resin SA9000 and 28.7 parts by weight of triallyl isocyanurate (TAIC) in a toluene solvent, adjusting the viscosity to a proper value, adding 3 parts by weight of dicumyl peroxide (DCP), uniformly stirring, gluing by adopting Shanghai macro-harmony 2116 cloth, baking the bonding sheets for 3min at 150 ℃, overlapping 6 bonding sheets, covering copper foils on two surfaces, curing for 120min at 200 ℃, flattening the plate, wherein P in a cured substance contains phosphorus: 0%, Si contains phosphorus: 0%, Br content: 13.2%, the results of the performance tests are shown in Table 1.
TABLE 1
Example 1 Example 2 Example 3 Example 4 Example 5
PSi1 5 10 15
PSi2 5 10
Polybutadiene 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
The content of P in the composition 0.315 0.63 0.95 0.329 0.67
The composition Si contains phosphorus% 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
Water absorption/% 0.09 0.08 0.07 0.075 0.081
PCT/2h OXO OOO OOO OOO OOO
T288/min ＞60 ＞60 ＞60 ＞60 ＞60
Total time of combustion/s 95 44 24 76 43
UL grade V-1 V-0 V-0 V-1 V-0
TABLE 1 (continuation)
Figure BDA0001922242920000111
All the raw materials in the examples and comparative examples are specified below:
SA 9000: sabic, methacrylate-based polyphenylene ether resin;
TAIC: welengi technologies ltd, triallyl isocyanurate acid;
DCP: avastin, dicumyl peroxide;
BPO: avastin, benzoyl peroxide;
RH-Vi 1325: a grain-moistening chemical, double-end vinyl silicone resin;
BT-93W: yabao, ethylene bistetrabromophthalimide, with a bromine content of 66%;
SPB 100: mitsubishi chemical, phosphazene flame retardant, phosphorus content 13.4%;
polybutadiene B-1000: polybutadiene, Japan Caoda.
The composition characteristics in table 1 were tested as follows:
(1) glass transition temperature (Tg): the DMA test was used and the measurement was carried out according to the DMA test method specified in IPC-TM-6502.4.24.
(2) Dielectric constant (Dk) and dielectric loss factor (Df): testing according to the SPDR method.
(3) Wet heat resistance (PCT) evaluation, the copper foil on the surface of the copper clad laminate was etched, the laminate was evaluated, the laminate was placed in a pressure cooker, treated at 120 ℃ and 105KPa for 2 hours, and then immersed in a tin furnace at 288 ℃, and the time was recorded when the laminate was exploded, and the evaluation was completed when the laminate did not blister or laminate after 5 minutes in the tin furnace, × represents laminate explosion, O represents no laminate explosion, 3 samples were prepared simultaneously from one sheet, and the test was passed when both samples did not delaminate and explode.
(4) T288: the measurement was carried out by using a TMA meter according to the T288 test method specified in IPC-TM-6502.4.24.1.
(5) Water absorption: the measurement was carried out according to the water absorption test method specified in IPC-TM-6502.6.2.1.
(6) Flame retardancy: the method is carried out according to the UL94 standard method.
As shown in the table, in examples 1 to 3, the flame retardancy becomes excellent with the increase of the phosphorus content and the silicon content in the plate material after adding different parts of the phosphorus-containing silicon flame retardant PSi 1. The PSi2 flame retardant behaves in accordance with PSi1, and in particular when 10 parts are added V-0 is achieved, whereas the phosphorus content is only 0.63% and the silicon content is 1.14%.
In addition, the phosphorus-silicon-containing flame retardant has good comprehensive performance. Because the silicon vinyl group of the phosphorus-containing silicon flame retardant has reactivity and forms a three-dimensional whole with the main resin after being added (as can be seen from an obvious exothermic peak of a DSC reaction curve chart), the Tg of the system is not reduced, the dielectric property is excellent, and the moisture and heat resistance performance (after being subjected to high-pressure steaming and tin immersion at 288 ℃ for 5min) is very good.
Comparative example 1 is a panel without flame retardant, and burning to a jig, it was seen that the flame retardancy was poor; while the most used of the prior resin systems containing unsaturated reactive groups are phosphorus-or bromine-containing additive flame retardants, such as comparative example 2 and comparative example 3, in the case of using phosphazene flame retardant SPB-100 of Mitsubishi chemistry, the flame retardancy is too poor in the case of adding a small amount of the comparative example 2, and in the case of adding 15 amounts of the comparative example 3, the flame retardancy reaches substantially V-0 when the phosphorus content reaches 2.0%, but the Tg of the sheet material is deteriorated since the small-molecular inorganic substance SPB-100 does not react into the three-dimensional structure of the cured product, and in PCT, the sheet material partially fails the 2h test. Comparative example 5, in which the American jaba bromine-containing flame retardant BT-93W was used, only approached a V-0 level in the case of addition to 20 parts, although it had no effect on Tg. Comparative example 4 is to introduce silicon element through the silicon resin with vinyl and phosphorus element through SPB-100, and compound investigation is carried out, and the phosphorus content in comparative example 4 and example 2 is the same as the silicon content, the total burning time of example 2 is 44 seconds and is V-0 grade, the total burning time of comparative example 4 is 86 seconds and is V-1 grade, and it is known that the compound flame retardant effect is obviously worse compared with the phosphorus-containing silicon flame retardant of the invention.
Therefore, the comprehensive performance of the phosphorus-silicon-containing flame retardant is superior to that of a phosphorus and silicon compound system, and also superior to that of a system which singly uses phosphorus flame retardant or bromine flame retardant, and particularly, the phosphorus-silicon-containing flame retardant has the best performance in the aspects of flame retardance and heat resistance. The phosphorus-silicon-containing flame retardant can exert the phosphorus/silicon synergistic flame-retardant effect, and the mechanism of the phosphorus/silicon-containing flame retardant is as follows: at high temperature, the surface tension of the silicon-containing compound is small, and the silicon-containing compound tends to migrate to the surface of the material and undergo oxidative decomposition and the like to form SiO2Meanwhile, the phosphorus compound promotes dehydration and carbonization, and the silicon and the carbonized layer can form a ceramic (SiC) -like structure to reinforce and protect the carbon layer, so that the synergistic flame retardant effect is achieved. In addition, the flame retardant with reactive vinyl groups of the present invention can also prevent the risk of precipitation during long-term use.
The above are only some embodiments of the present invention, and it is obvious to those skilled in the art that other various changes and modifications can be made according to the technical solution and technical idea of the present invention, and all such changes and modifications should fall within the scope of the claims of the present invention.

Claims (10)

1. A phosphorus-silicon-containing flame retardant, characterized in that the phosphorus-silicon-containing flame retardant has a structure represented by formula (I):
Figure FDA0001922242910000011
wherein the content of the first and second substances,
R1、R2、R3、R4each independently is a C6-C18 aryl group, a C1-C6 aliphatic group, or a C2-C6 alkenyl group;
a is
Figure FDA0001922242910000012
Any one of (a);
b is
Figure FDA0001922242910000013
Any one of the above.
2. The phosphorus-silicon-containing flame retardant of claim 1, wherein R is1、R2、R3、R4Each independently is phenyl, C1-C5 alkyl, or vinyl.
3. A method of preparing the phosphorus-silicon-containing flame retardant of claim 1, comprising:
reacting an organophosphorus compound with a monohalosilane,
wherein the organophosphorus compound has any one of the following structures:
Figure FDA0001922242910000021
wherein Q is p-dihydroxyphenyl or p-dihydroxynaphthyl, preferably
Figure FDA0001922242910000022
Any one of the above-mentioned (B) and (C),
the monohalosilane has a structure represented by formula (II):
Figure FDA0001922242910000023
wherein X is halogen, preferably chlorine, bromine or iodine, most preferably chlorine; r5, R6, R7 are each independently a C6-C18 aryl group, a C1-C6 aliphatic group or a C2-C6 alkenyl group, with the proviso that at least one of R5, R6, R7 contains a vinyl group,
the reaction of the organophosphorus compound with the monohalosilane is preferably carried out in the presence of a catalyst.
4. The method of claim 3, wherein the mole ratio of monohalosilane to organophosphorus compound is 2 or more;
preferably, 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;
preferably, the amount of the catalyst is 2 to 4 times, more preferably 2.2 to 3 times of the mole number of the organophosphorus compound;
preferably, the reaction of the monohalosilane with the organophosphorus compound is carried out in a solvent system selected from the group consisting of Dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP); preferably, when DMAc is used as a solvent, the concentration of a reaction system is 15-30%; when DMAc is used as a solvent, the concentration of a reaction system is 18-25%;
preferably, the reaction temperature is 0-60 ℃, and more preferably normal temperature to 60 ℃;
preferably, the reaction time is 5 to 24 hours, more preferably 10 to 15 hours;
preferably, the reaction is carried out in the presence of a protective gas, the preferred protective gas being nitrogen.
5. The process according to claim 3 or 4, further comprising a post-treatment step after the reaction, said post-treatment comprising filtration and optionally evaporation of low boilers, further comprising subsequent washing and drying;
preferably, the washing reagent is selected from the group consisting of alcohol solvents, ester solvents, and deionized water, more preferably deionized water.
6. A flame retardant resin composition comprising a thermosetting resin, the phosphorus-containing silicon flame retardant of claim 1 or 2, and optionally an initiator and optionally a filler.
7. The flame retardant resin composition according to claim 6, wherein the phosphorus-silicon containing flame retardant comprises 1 to 35%, preferably 5 to 20% by weight of the total flame retardant resin composition;
preferably, the phosphorus content of the flame retardant resin composition is less than 2.5% by weight, more preferably less than 1% by weight.
8. The flame-retardant resin composition according to claim 6 or 7,
the thermosetting resin is a resin with double bonds, preferably selected from polyolefin resin, organic silicon resin with double bonds, polyphenyl ether resin with double bonds or bismaleimide resin; more preferably, the polyolefin resin is selected from one or more of styrene-butadiene copolymer, polybutadiene or styrene-butadiene-divinylbenzene copolymer; the polyphenylene ether resin with double bonds is selected from polyphenylene ether with methyl methacrylate as a terminal group and polyphenylene ether with vinyl benzyl as a terminal group; the silicone resin with double bonds is selected from silicone resins with vinyl groups; the bismaleimide resin is selected from one or more of 4,4 '-diphenylmethane bismaleimide, 4' -diphenyl ether bismaleimide, 4 '-diphenyl isopropyl bismaleimide and 4, 4' -diphenyl sulfone bismaleimide.
The initiator is a free radical initiator, preferably the free radical initiator is selected from organic peroxide initiators; more preferably, the organic peroxide initiator is selected from the group consisting of di-t-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-amyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, 1-di-t-butylperoxy-3, 5, 5-trimethylcyclohexane, 1-di-t-butylperoxycyclohexane, 2-di (t-butylperoxy) butane, bis (4-t-butylcyclohexyl) peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, dipentyl hydroperoxide, dicumyl peroxide, and mixtures thereof, Any one of bis (t-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexyne, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-amyl hydroperoxide, t-butyl cumyl peroxide, diisopropylbenzene hydroperoxide, tert-butyl peroxycarbonate-2-ethyl hexanoate, t-butyl peroxycarbonate-2-ethylhexyl, n-butyl-4, 4-di (t-butylperoxy) valerate, methyl ethyl ketone peroxide or cyclohexane peroxide;
the filler is an inorganic filler, preferably selected from any one or a mixture of at least two of aluminum hydroxide, boehmite, silica, talcum powder, mica, barium sulfate, lithopone, calcium carbonate, wollastonite, kaolin, brucite, diatomite, bentonite, aluminum oxide, boron nitride or pumice powder.
9. A prepreg comprising a substrate and the flame retardant resin composition of any one of claims 6 to 8 attached thereto by impregnation or coating.
10. A metal-clad laminate comprising at least one prepreg according to claim 9 and a metal foil on one or both sides of the prepreg.
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