CN112480373A - Flame-retardant epoxy resin composition and preparation method and application thereof - Google Patents
Flame-retardant epoxy resin composition and preparation method and application thereof Download PDFInfo
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- CN112480373A CN112480373A CN201910858119.5A CN201910858119A CN112480373A CN 112480373 A CN112480373 A CN 112480373A CN 201910858119 A CN201910858119 A CN 201910858119A CN 112480373 A CN112480373 A CN 112480373A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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Abstract
The invention provides a flame-retardant epoxy resin composition and a preparation method and application thereof. Phenolic hydroxyl in the flame-retardant curing agent and epoxy resin are subjected to curing reaction, the curing efficiency is high, and the flame-retardant group finally exists in the flame-retardant epoxy resin composition in the form of molecular fragments, so that the phenomenon of micromolecule precipitation is avoided, the phenomenon that some additive flame retardants are easily dissolved in water to precipitate or hydrolyze is also avoided, and the efficient environment-friendly flame retardance is really realized. The flame-retardant epoxy resin composition provided by the invention has excellent flame retardant property and mechanical property, and the copper-clad plate prepared by using the flame retardant epoxy resin composition has high flame retardant property and dielectric property, and has the advantages of simple preparation process, easily obtained raw materials and wide industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a flame-retardant epoxy resin composition, and a preparation method and application thereof.
Background
Epoxy resin is a very important thermosetting resin, has excellent bonding property, electrical insulation property, wear resistance, chemical stability and mechanical property, has low shrinkage rate and is easy to process and form, and is widely applied to the fields of instruments, aerospace, adhesives, electronic and electrical insulating materials and the like, particularly in the field of processing and manufacturing of basic material copper-clad plates in the electronic industry, and epoxy resin is one of the most commonly used polymer matrixes. However, epoxy resins have a low Limiting Oxygen Index (LOI), are easily flammable, have poor flame retardancy, are easily ignited at high temperatures or in an electrostatic environment to cause fire, and must be subjected to flame retardant treatment for the safety of subsequent use.
At present, two methods are mainly used for improving the flame retardant property of epoxy resin, one is to directly add an additive flame retardant into the epoxy resin, and the other is to add bisphenol A containing a flame retardant group in the condensation polymerization reaction process of the epoxy resin and then react with epoxy chloropropane to generate the epoxy resin with the flame retardant group.
CN103087469A discloses a preparation method of an epoxy resin flame retardant, which comprises the following steps: mixing epoxy resin particles with organic clay MMT, adding aluminum hydroxide particles, melting the mixture, and cooling to obtain the flame-retardant epoxy resin; the organic clay and the aluminum hydroxide in the flame-retardant epoxy resin can effectively improve the flame-retardant property of the epoxy resin.
CN104017171B discloses a production method of brominated epoxy resin with high thermal stability, which comprises the following steps: reacting epoxy chloropropane and tetrabromobisphenol A in the presence of a catalyst to obtain brominated epoxy resin oligomer, and further reacting the brominated epoxy resin oligomer with tetrabromobisphenol A to obtain the brominated epoxy resin with high thermal stability. The brominated epoxy resin obtained by the method has high molecular weight, low TBBA residue and high flame retardant efficiency.
CN107033549A discloses a preparation method of a phosphorus-nitrogen flame-retardant epoxy resin, wherein in the preparation method, ammonium polyphosphate coated with melamine formaldehyde resin is obtained through the reaction of a melamine formaldehyde prepolymer and the ammonium polyphosphate, and then the ammonium polyphosphate coated with the melamine formaldehyde resin is mixed with nano calcium carbonate to obtain a flame retardant; and further blending and curing the flame retardant, epoxy resin and triethylamine curing agent to obtain the nitrogen-phosphorus flame-retardant epoxy resin.
In the field of the existing flame-retardant epoxy resin, the flame-retardant efficiency of the epoxy resin containing inorganic additive flame retardants such as aluminum hydroxide hydrate and magnesium hydroxide hydrate is low, and the addition of a large amount of inorganic flame retardants not only affects the flexibility of the epoxy resin and makes the resin hard and brittle, but also reduces the acid and alkali resistance of the epoxy resin. Although flame retardant epoxy resin containing halogen such as bromine has excellent flame retardant property, it generates products such as dioxin which are difficult to degrade when burned, causing serious environmental pollution and harming human health. Although the epoxy resin containing the nitrogen/phosphorus flame retardant avoids pollution caused by combustion products such as dioxin and the like, the epoxy resin still has environmental hidden dangers, and molecules, decomposition products or water-soluble substances of the nitrogen/phosphorus flame retardant enter the environment due to the migration and precipitation in the processes of production, storage, use and scrap treatment, and most of additive flame retardants are easy to hydrolyze, so that the environment is polluted, and the real environment-friendly flame retardance cannot be realized.
Therefore, the development of an epoxy resin material which can really achieve safety, environmental protection and flame retardance to meet the application requirements is a research focus in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a flame-retardant epoxy resin composition, a preparation method and an application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a flame retardant epoxy resin composition, which is prepared from the following raw materials:
50-100 parts by weight of epoxy resin
4-40 parts of flame-retardant curing agent
0.01-5 parts by weight of a curing accelerator.
The flame-retardant curing agent has a structure shown in a formula I:
wherein L is1、L2Each independently selected from groups containing a terminal phenolic hydroxyl group.
Z1、Z2Each independently selected from phosphorus-containing groups.
M1Selected from linear alkylene, branched alkylene or arylene.
M2Selected from any organic group that satisfies the chemical environment.
Y1、Y2Each independently selected from an inert group, a sulfur atom, an oxygen atom, or-H.
X1Selected from any organylene group that satisfies a chemical environment.
a. b, c, d, f, g, h are each independently selected from integers of 0 to 5, such as 0, 1, 2,3, 4 or 5; and a and b are not 0 at the same time, f and g are not 0 at the same time, g and h are not 0 at the same time, and b + c + h is less than or equal to 5 and a + d + g is less than or equal to 5.
e is an integer of 0 to 100, such as 0, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95, and specific values therebetween, which are not intended to be exhaustive for the sake of brevity and clarity.
In the flame-retardant epoxy resin composition provided by the invention, the raw materials for preparation comprise epoxy resin, a flame-retardant curing agent and a curing accelerator, wherein the flame-retardant curing agent is a reactive phosphorus-containing flame retardant with phenolic hydroxyl groups. In the preparation process of the flame-retardant epoxy resin, active epoxy groups in the epoxy resin and phenolic hydroxyl groups in the flame-retardant curing agent are subjected to ring opening under the action of a curing accelerator to obtain alcoholic hydroxyl groups, and then the alcoholic hydroxyl groups are cured and crosslinked to form a reticular macromolecule. Therefore, in the flame-retardant epoxy resin composition provided by the invention, the flame-retardant curing agent has the phenolic hydroxyl group as the curing group and the phosphorus-containing group as the flame-retardant curing agent, so that on one hand, the flame-retardant curing agent is used as the curing agent to enable the epoxy resin to be crosslinked to form a stable network structure, and the epoxy resin material with good mechanical property and high chemical stability is obtained; on the other hand, the flame-retardant group is introduced into the molecular fragment of the epoxy resin through a chemical bond, so that the flame-retardant group exists in the flame-retardant epoxy resin composition in the form of the molecular fragment finally, the phenomenon of micromolecule precipitation is avoided, and the phenomenon that an additive flame retardant is easily dissolved in water to precipitate or is hydrolyzed is also avoided.
In the present invention, the epoxy resin may be used in an amount of 50 parts by weight, 51 parts by weight, 53 parts by weight, 55 parts by weight, 58 parts by weight, 60 parts by weight, 63 parts by weight, 65 parts by weight, 68 parts by weight, 70 parts by weight, 73 parts by weight, 75 parts by weight, 78 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 93 parts by weight, 95 parts by weight, or 98 parts by weight, and specific point values therebetween are not limited to space and for brevity, and the present invention does not exhaust specific point values included in the range.
In the present invention, the flame retardant curing agent may be used in an amount of 4.5 parts by weight, 5 parts by weight, 7 parts by weight, 9 parts by weight, 10 parts by weight, 13 parts by weight, 15 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, 37 parts by weight, 39 parts by weight or 40 parts by weight, and specific points therebetween are not limited to space and for brevity, and the present invention does not exhaustively enumerate specific points included in the range.
In the present invention, the curing accelerator may be used in an amount of 0.02 parts by weight, 0.04 parts by weight, 0.05 parts by weight, 0.07 parts by weight, 0.09 parts by weight, 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 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, or 5 parts by weight, and specific point values therebetween, and the present invention is not exhaustive in the range of point values and for the sake of brevity.
Preferably, Z is1、Z2Each independently selected from
One of (1), R1Is selected from any one of saturated or unsaturated alkyl, aryl or heteroaryl, and is more preferably methyl, ethyl or phenyl.
Preferably, said M1One selected from the group consisting of C1-C30 linear or branched alkylene, C6-C30 arylene, and C5-C7 heteroarylene, more preferably C1-C5 linear alkylene, C3-C5 branched alkylene, or phenyl, and still more preferably C1-C3 linear alkylene, C3 branched alkylene, or phenyl.
The C1 to C30 include C2, C3, C5, C7, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C29, and the like.
The C6-C30 include C7, C9, C10, C12, C14, C15, C17, C20, C22, C24, C26, C28, C29 and the like.
The C5-C7 comprises C5, C6 or C7.
The C1-C5 linear alkylene comprises methylene, ethylene, propylene, butylene or pentylene.
The C3-C5 branched chain alkylene group comprises C3, C4 or C5 branched chain alkylene group.
Preferably, said M2Selected from N, S, C1-C30 straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl,
Wherein R is2-R9Each independently selected from one of C1-C10 straight chain or branched chain alkylene, L2、Y2、Z2Is connected to R2-R9Any connectable position of (a), n, m,i. k is each independently selected from an integer of 0 to 100, such as 0, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95, and specific point values therebetween, limited to space and for brevity, the invention is not intended to be exhaustive of the specific point values included in the ranges set forth.
The C1 to C30 include C2, C3, C5, C7, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C29, and the like.
The C6-C30 include C7, C9, C10, C12, C14, C15, C17, C20, C22, C24, C26, C28, C29 and the like.
The C5-C7 comprises C5, C6 or C7.
Preferably, said R is2-R9Each independently selected from one of C1-C6 linear or branched chain alkylene groups, such as C1, C2, C3, C4, C5 or C6 linear or branched chain alkylene groups.
Preferably, n, m, i, k are each independently selected from integers of 0 to 30, such as 0, 1, 5, 10, 15, 20, 25 or 29, and the specific values therebetween are limited by space and for brevity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, said Y is1、Y2Each independently selected from-H or ═ O.
Preferably, said X1One selected from N, S, substituted or unsubstituted C1 to C30 linear or branched alkylene groups, substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted C5 to C7 heteroarylene groups, substituted or unsubstituted C1 to C30 alkyleneamino groups, substituted or unsubstituted C1 to C30 alkyleneacyl groups, substituted or unsubstituted C1 to C30 alkyleneester groups, substituted or unsubstituted C6 to C30 arylamino groups, substituted or unsubstituted C6 to C30 aryloyl groups or C6 to C30 arylester groups, further preferably substituted or unsubstituted C1 to C5 linear or branched alkylene groups, substituted or unsubstituted C1 to C5 alkyleneamino groups, substituted or unsubstituted C1 to C5 alkyleneacyl groups, and substituted or unsubstituted C1 to C5 alkyleneester groups, further preferably-NH-R-, -R '-NH-, -R' -O-, -RV-C (O) -, substituted or unsubstituted C1-C5 linear orBranched alkylene groups, wherein, R, R ', R', RVEach independently selected from substituted or unsubstituted C1 to C10 straight or branched chain alkylene.
The term "substituted" as used herein means that any one or more hydrogen atoms on the designated atom is replaced with a substituent selected from the designated group, provided that the designated atom does not exceed a normal valence and that the result of the substitution is a stable compound. When the substituent is an oxo group or a keto group (i.e., ═ O), then 2 hydrogen atoms on the atom are substituted. The ketone substituent is absent on the aromatic ring. By "stable compound" is meant a compound that can be isolated from a reaction mixture sufficiently robustly to an effective purity and formulated to be effective.
The C1 to C30 include C2, C3, C5, C7, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C29, and the like.
The C6-C30 include C7, C9, C10, C12, C14, C15, C17, C20, C22, C24, C26, C28, C29 and the like.
The C5-C7 comprises C5, C6 or C7.
The C1-C5 comprise C1, C2, C3, C4 or C5.
Preferably, the flame retardant curing agent has a structure shown in formula II, formula III, formula IV, formula V or formula VI:
wherein L is1、L2Each independently selected from groups terminating in a phenolic hydroxyl group.
M1Is selected from one of C1-C3 (such as C1, C2 or C3) straight-chain alkylene, C3 branched-chain alkylene or phenyl.
M2Selected from N, -NH-RTC1-C6 (e.g., C1, C2, C3, C4, C5 or C6) straight-chain or branched-chain alkyl groups,
Wherein R isTIs C1-C6 (such as C1, C2, C3, C4, C5 or C6) straight chain or branched chain alkyl, R2-R9Each independently selected from C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) straight or branched chain alkylene, n, m, i, k each independently selected from integers of 0-30, e.g., 0, 1, 3,5, 8, 10, 15, 20, 25, or 29, and specific points therebetween, limited to space and for brevity, the invention is not intended to be exhaustive of the specific points encompassed by the scope.
R1Is methyl or ethyl.
R、R'、R”、RV、RPEach independently selected from substituted or unsubstituted C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight or branched chain alkylene.
Y1、Y2Each independently selected from-H or ═ O.
a. b, g and h are respectively and independently selected from 0, 1 or 2, a and b are not 0 at the same time, f and g are not 0 at the same time, and g and h are not 0 at the same time.
e is an integer from 0 to 20, such as 0, 1, 3,5, 8, 10, 13, 15, 18, or 19, and the specific values therebetween are not exhaustive for the invention and for brevity.
f is 0 or 1.
Preferably, the flame retardant curing agent is further preferably any one of or a combination of at least two of the compounds having the following structures:
wherein R isPAnd (b) one selected from substituted or unsubstituted C1-C5 (e.g., C1, C2, C3, C4, or C5) straight chain or branched chain alkylene.
e is an integer from 0 to 20, such as 0, 1, 3,5, 8, 10, 13, 15, 18, or 19, and the specific values therebetween are not exhaustive for the invention and for brevity.
Preferably, the epoxy resin is selected from any one of or a combination of at least two of bisphenol a type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol a type epoxy resin, biphenyl type epoxy resin, cyclopropedien type epoxy resin, and novolac epoxy resin, and more preferably bisphenol a type epoxy resin.
Preferably, the curing accelerator is any one selected from imidazole compounds, tertiary amine compounds, dicyandiamide, quaternary ammonium salts, organic phosphorus compounds, pyridine compounds and DBU.
Preferably, the imidazole compound is selected from any one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole or trimellitic acid 1-cyanoethyl-2-undecylimidazolium salt.
Preferably, the tertiary amine compound is selected from any one or a combination of at least two of triethanolamine, tetramethylguanidine, triethylenediamine, benzyldimethylamine or N, N-dimethylpiperazine.
Preferably, the organophosphorus compound is triphenylphosphine and derivatives thereof.
Preferably, the raw materials for preparing the flame-retardant epoxy resin composition also comprise a modifier.
Preferably, the mass of the modifier is 0.1-40% of the mass of the epoxy resin, such as 0.2%, 0.5%, 0.8%, 1%, 3%, 4%, 5%, 7%, 9%, 10%, 13%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 33%, 35%, 38%, or 40%, and specific values therebetween, are not exhaustive and for the sake of brevity.
Preferably, the modifier is selected from any one of polyamide resin, polyvinyl acetal, phenolic resin, vinyl resin, organic silicon, isocyanate, nitrile rubber, polyester resin or urea formaldehyde melamine resin or the combination of at least two of the above.
Preferably, the raw materials for preparing the flame-retardant epoxy resin composition also comprise a solid filler.
Preferably, the solid filler is selected from any one or a combination of at least two of white carbon black, titanium dioxide, aluminum hydroxide, carbon black, zinc stearate, talcum powder, calcium carbonate, barium sulfate, montmorillonite, diatomite, kaolin, gypsum, mica or magnesium hydroxide.
Preferably, the mass of the solid filler is 10-150% of the mass of the epoxy resin, such as 12%, 14%, 16%, 18%, 20%, 23%, 25%, 27%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 110%, 120%, 130%, 140%, 145% or 149%, and specific points therebetween, which are not intended to be space-wise and for brevity, the present invention is not exhaustive of the specific points included in the ranges.
Preferably, the preparation raw materials of the flame-retardant epoxy resin composition also comprise an auxiliary agent.
Preferably, the auxiliary agent is selected from any one or a combination of at least two of a defoaming agent, a coupling agent, an anti-aging agent, an anti-settling agent, a wetting dispersant or a toughening agent.
In another aspect, the present invention provides a method for preparing the flame retardant epoxy resin composition as described above, comprising the steps of:
adding epoxy resin, a flame-retardant curing agent, a curing accelerator and an organic solvent into a reaction device, and mixing and curing to obtain the flame-retardant epoxy resin composition.
Preferably, the organic solvent is selected from any one of ethanol, acetone, xylene, tetrahydrofuran, N-dimethylformamide or toluene or a combination of at least two thereof.
Preferably, the mixing is performed under stirring conditions.
Preferably, the mixing time is 5-60 min, such as 6min, 8min, 10min, 13min, 15min, 18min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 59min, and the specific points between the above points are limited by space and for simplicity, and the invention is not exhaustive.
Preferably, the curing temperature is 60 to 200 ℃, for example, 61 ℃, 63 ℃, 65 ℃, 68 ℃, 70 ℃, 75 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 195 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the scope.
Preferably, the curing time is 1 to 15 hours, such as 1.1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 14.5 hours or 15 hours, and specific point values therebetween, which are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the preparation method comprises the following steps:
(1) mixing epoxy resin and a flame-retardant curing agent in a reaction device, adding an organic solvent and a curing accelerator, and stirring and mixing for 5-60 min;
(2) and (2) injecting the mixture obtained in the step (1) into a mold, and curing for 1-15 h at the temperature of 60-200 ℃ to obtain the flame-retardant epoxy resin composition.
In another aspect, the present invention provides a use of the flame retardant epoxy resin composition as described above in a prepreg, a laminate, a metal foil-clad laminate or a printed wiring board.
Compared with the prior art, the invention has the following beneficial effects:
the preparation raw materials of the flame-retardant epoxy resin composition provided by the invention comprise epoxy resin, a flame-retardant curing agent and a curing accelerator. Phenolic hydroxyl in the flame-retardant curing agent and epoxy resin are subjected to curing reaction to obtain a stable network-structure macromolecule, and the curing effect is good; meanwhile, a phosphorus-containing flame-retardant group in the flame-retardant curing agent is introduced into the epoxy resin, so that the flame-retardant group exists in the flame-retardant epoxy resin composition in the form of molecular fragments, the phenomenon of micromolecule precipitation is avoided, the phenomenon of precipitation or hydrolysis of certain additive flame retardants due to water solubility is also avoided, and efficient environment-friendly flame retardance is really realized. The flame-retardant epoxy resin composition provided by the invention is used for preparing a copper-clad plate, the combustibility of the composition can reach V-0 level, the combustion performance after washing is V-0 level, and TgThe glass transition temperature can reach more than 180 ℃, the dielectric constant and the interlayer peeling strength are high, the interlayer peeling strength is 0.8-1.1N/mm, the bending strength is not lower than 550MPa, the dielectric constant (1MHz) is more than 4, the flame retardant stability, the mechanical property and the insulating property are excellent, the preparation process is simple, the raw materials are easy to obtain, and the industrial application prospect is wide.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
A flame-retardant curing agent has the following structure:
the preparation method comprises the following steps:
adding 1mol of 2, 3-dihydroxystyrene, 1mol of DOPO and 50mL of glacial acetic acid into a reaction kettle, heating to 50 ℃ under the condition of stirring, dropwise adding glacial acetic acid solution of 1mmol of Pb catalyst into the reaction system, and reacting for 16 h; separating and purifying to obtain the target product.
1H NMR(CDCl3400MHz, TMS). delta.9.35-9.51 (d,2H, -OH),7.21-7.94(m,8H, H of the phenyl ring), 6.41-6.65(m,3H, H of the phenyl ring), 2.71-2.84(m,1H, -CH-),1.47-1.61(t,3H, -CH-)3)。
Preparation example 2
A flame-retardant curing agent has the following structure:
the preparation method comprises the following steps:
adding 1mol of dimethyl phosphite, 1mol of trans-3, 5-dihydroxy stilbene and 50mL of glacial acetic acid into a reaction kettle, and heating to 55 ℃ under the condition of stirring; then adding 1mmol of glacial acetic acid solution of Pb catalyst into the reaction system dropwise under the stirring condition at 55 ℃ for reaction for 15 h; separating the product to obtain the target product.
1H NMR(CDCl3400MHz, TMS): Δ 9.31-9.52(s,2H, -OH),7.15-7.28(m,5H, H of the phenyl ring), 6.17-6.31(m,3H, H of the phenyl ring), 3.68-3.81(d,6H, -CH)3),3.13-3.24(m,1H,-CH-),2.98-3.07(m,2H,-CH2-)。
Preparation example 3
A flame-retardant curing agent has the following structure:
the preparation method comprises the following steps:
adding 1mol of dimethyl phosphite and 1mol of 2, 5-dihydroxybenzaldehyde into a reaction kettle, controlling the temperature in an ice bath to be 0-3 ℃, dropwise adding 1mol of triethylamine under stirring, gradually heating to 50 ℃, continuing to react for 2 hours, and carrying out reduced pressure distillation to obtain a target product.
1H NMR(CDCl3400MHz, TMS). delta.9.31-9.57 (d,2H, -OH),6.69-6.93(m,3H, H of the phenyl ring), 6.58-6.64(m,1H, -OH),4.78-4.86(d,6H, -CH-),3.46-3.62(d,6H, -CH-)3)。
Preparation example 4
A flame-retardant curing agent has the following structure:
the preparation method comprises the following steps:
adding 1mol of trans-3, 5-dihydroxystilbene, 1mol of DOPO and 50mL of glacial acetic acid into a reaction kettle, and heating to 50 ℃ under the stirring condition; then dropwise adding glacial acetic acid solution of 1mmol of Pb catalyst into the reaction system under the stirring condition at 50 ℃ for reacting for 16 h; separating and purifying to obtain the target product.
1H NMR(CDCl3400MHz, TMS): delta 9.38-9.54(s,2H, -OH),7.41-7.98(m,8H, H of the benzene ring of DOPO), 7.17-7.26(m,5H, H of the benzene ring), 6.23-6.41(m,3H, H of the benzene ring), 3.18-3.47(m,2H, -CH)2-),3.09-3.21(m,1H,-CH-)。
Preparation example 5
A flame-retardant curing agent has the following structure:
the preparation method comprises the following steps:
adding 1mol of 1, 4-benzoquinone, 1mL of toluene and 0.5mol of water into a reaction kettle, adding 1mol of diethyl phosphite under the protection of nitrogen, and reacting at 85 ℃ for 24 hours under the stirring condition; toluene was removed by rotary evaporation, and then the product was separated by a silica gel column to obtain the objective product as a pale yellow oil.
1H NMR(CDCl3400MHz, TMS): Δ 9.44-9.61(s,1H, -OH),7.33-7.49(br,1H, -OH),6.91-7.23(m,1H, H with the phenyl ring close to P), 6.59-6.81(m,2H, H with the phenyl ring), 3.91-4.18(m,4H, -CH)2-),1.18-1.31(t,6H,-CH3)。
Preparation example 6
A flame-retardant curing agent has the following structure:
the preparation method comprises the following steps:
adding 1mol of tert-butyl p-benzoquinone, 0.5mol of water and 1mL of toluene into a reaction kettle, adding 1mol of dimethyl phosphite under the protection of nitrogen, and reacting for 24 hours at 80 ℃ under the stirring condition; toluene was removed by rotary evaporation, and the product was isolated by silica gel column to give the desired product as a yellow oil.
1H NMR(CDCl3400MHz, TMS): delta 9.19-9.38(s,2H, -OH),6.73-6.91(m,2H, H of the phenyl ring), 3.57-3.72(d,6H, -O-CH)3),1.42-1.53(t,9H,-CH3)。
Preparation example 7
A flame-retardant curing agent has the following structure:
the preparation method comprises the following steps:
adding 1mol of 2, 4-dihydroxy-3-methylbenzaldehyde and 1mol of diethyl phosphite into a reaction kettle, controlling the temperature in an ice bath to be lower than 5 ℃, dropwise adding 1mol of triethylamine under stirring, gradually heating to 55 ℃, continuing to react for 1h, and carrying out reduced pressure distillation to obtain a target product.
1H NMR(CDCl3400MHz, TMS). delta.10.72-10.81 (s,1H, Ph-OH),7.79-7.84(s,1H, Ph-OH),6.90-6.96(s,1H, -OH),6.41-6.74(m,3H, H of the phenyl ring), 4.77-4.89(d,1H, -CH-),3.88-4.01(m,4H, -CH-)2-),1.33-1.45(t,6H,-CH3)。
Examples 1 to 7
The flame-retardant epoxy resin composition is prepared from the following raw materials:
80 parts by weight of epoxy resin
18 parts of flame-retardant curing agent
1.5 parts by weight of a curing accelerator;
the epoxy resin is bisphenol A epoxy resin E-44, the flame-retardant curing agent is the curing agent with phenolic hydroxyl groups and phosphorus-containing flame-retardant groups provided in preparation examples 1-7, and the curing accelerator is 2-methylimidazole.
The preparation method comprises the following steps:
(1) adding epoxy resin and a flame-retardant curing agent into a reaction kettle, adding a curing accelerator and an organic solvent N, N-dimethylformamide, and fully stirring for 30min to obtain a uniformly mixed mixture;
(2) and (2) injecting the mixture obtained in the step (1) into a mold, curing for 2h at the temperature of 90 ℃, then curing for 5h at the temperature of 130 ℃, and continuously heating to 180 ℃ for curing for 2h to obtain the flame-retardant epoxy resin composition.
Example 8
The embodiment provides a flame-retardant epoxy resin composition, which is prepared from the following raw materials:
50 parts by weight of epoxy resin
5 parts of flame-retardant curing agent
0.25 part by weight of a curing accelerator;
wherein the epoxy resin is bisphenol A epoxy resin E-44, the flame-retardant curing agent is the curing agent provided in preparation example 1 and having phenolic hydroxyl groups and phosphorus-containing flame-retardant groups, and the curing accelerator is 2-methylimidazole.
The preparation method comprises the following steps:
(1) adding epoxy resin and a flame-retardant curing agent into a reaction kettle, adding a curing accelerator and an organic solvent N, N-dimethylformamide, and fully stirring for 8min to obtain a uniformly mixed mixture;
(2) and (2) injecting the mixture obtained in the step (1) into a mold, curing for 2h at 70 ℃, then curing for 8h at 120 ℃, and continuously heating to 180 ℃ for curing for 1.5h to obtain the flame-retardant epoxy resin composition.
Example 9
The embodiment provides a flame-retardant epoxy resin composition, which is prepared from the following raw materials:
100 parts by weight of epoxy resin
37 parts of flame-retardant curing agent
3 parts of a curing accelerator;
wherein the epoxy resin is bisphenol A epoxy resin E-44, the flame-retardant curing agent is the curing agent provided in preparation example 1 and having phenolic hydroxyl groups and phosphorus-containing flame-retardant groups, and the curing accelerator is 2-methylimidazole.
The preparation method comprises the following steps:
(1) adding epoxy resin and a flame-retardant curing agent into a reaction kettle, adding a curing accelerator and an organic solvent N, N-dimethylformamide, and fully stirring for 50min to obtain a uniformly mixed mixture;
(2) and (2) injecting the mixture obtained in the step (1) into a mold, curing for 1.5h at the temperature of 95 ℃, then curing for 3h at the temperature of 140 ℃, and continuously heating to 190 ℃ to cure for 1h to obtain the flame-retardant epoxy resin composition.
Example 10
The embodiment provides a flame-retardant epoxy resin composition, which is prepared from the following raw materials:
wherein the epoxy resin is bisphenol A epoxy resin E-44, the flame-retardant curing agent is the curing agent with phenolic hydroxyl and phosphorus-containing flame-retardant groups provided in preparation example 1, the curing accelerator is 2-methylimidazole, the solid filler is silica micropowder (with an average particle size of 15 μm), and the auxiliary agent is a wetting dispersant.
The preparation method comprises the following steps:
(1) adding epoxy resin and a flame-retardant curing agent into a reaction kettle, adding a curing accelerator, an organic solvent N, N-dimethylformamide, a solid filler and an auxiliary agent, and fully stirring for 30min to obtain a uniformly mixed mixture;
(2) and (2) injecting the mixture obtained in the step (1) into a mold, curing for 2h at the temperature of 90 ℃, then curing for 5h at the temperature of 130 ℃, and continuously heating to 180 ℃ for curing for 2h to obtain the flame-retardant epoxy resin composition.
Comparative example 1
This comparative example is different from example 1 in that the flame retardant curing agent was replaced with 18 parts by weight of dicyandiamide curing agent.
Comparative example 2
This comparative example is different from example 1 in that 18 parts by weight of dicyandiamide curing agent was replaced with the flame retardant curing agent, and 18 parts by weight of triphenyl phosphate was added.
Comparative example 3
This comparative example differs from comparative example 2 in that triphenyl phosphate is replaced with an equal part by weight of aluminum tris (diethylphosphinate).
Comparative example 4
This comparative example is different from comparative example 2 in that the content of triphenyl phosphate is 50 parts by weight.
Comparative example 5
This comparative example is different from example 1 in that the reactive flame retardant is 2 parts by weight.
Comparative example 6
This comparative example is different from example 1 in that the reactive flame retardant was 43 parts by weight.
Performance testing
The epoxy resin-based copper clad laminate is prepared from the flame-retardant epoxy resin compositions provided in the embodiments 1-10 and the comparative examples 1-6 according to a known general method, and the following performance tests are carried out:
(1) glass transition temperature Tg: the testing instrument is a thermomechanical analyzer (TMA 2940, TA Instruments, Ventec), tests the thermal expansion curve of the copper-clad plate within the temperature range of 30-350 ℃, and calculates the glass transition temperature T from the inflection point in the thermal expansion curveg；
(2) Interlayer peel strength PS: the test was carried out according to the test conditions of "after thermal stress" in the IPC-4101 method, and the size of the test specimen was 75mm X50 mm;
(3) bending strength: according to a method specified by GB/T4722-92 standard, a simple beam is adopted for three-point loading, and the force from the sample bearing bending load to the sample breaking is measured to obtain the bending strength;
(4) dielectric constant Dk and dielectric loss factor Df: testing Dk and Df of a sample under the frequency of 1MHz and constant temperature and humidity according to a method specified by GB/T4722-92 standard, wherein the size of the sample is 50mm multiplied by 50 mm;
(5) combustibility: testing according to UL-94 vertical burning test standard;
(6) flame retardant stability: soaking the copper-clad plate in water for 1h, drying, and measuring the combustibility of the copper-clad plate according to the UL-94 vertical combustion test standard;
(7) mobility: and baking the copper-clad plate at 150 ℃ for 2h, and testing the weight difference percentage before and after baking.
The glass transition temperature, the interlayer peeling strength, the bending strength, the dielectric constant, the dielectric loss factor, the flammability, the flame retardant stability and the mobility of the flame-retardant epoxy resin-based copper-clad plates provided in the examples 1 to 10 and the comparative examples 1 to 6 are tested according to the method, wherein the test results of the glass transition temperature, the interlayer peeling strength and the bending strength are shown in table 1:
TABLE 1
The data in table 1 show that the epoxy resin-based copper clad laminate using the flame retardant curing agent in examples 1 to 10 has a glass transition temperature higher than that of the dicyandiamide-cured epoxy resin-based copper clad laminate in comparative examples 1 to 4, and has an increased interlayer peel strength and an increased bending strength, wherein the interlayer peel strength is 0.8 to 1.1N/mm, and the bending strength is 552 to 601MPa, which indicates that the flame retardant curing agent has a high curing efficiency, an enhanced and toughened effect on epoxy resin, and the obtained copper clad laminate has good mechanical properties. If the content of the flame-retardant curing agent in the flame-retardant epoxy resin composition is beyond the range defined by the present invention, curing cannot be effectively achieved if the content of the flame-retardant curing agent is too low (comparative example 5), and the epoxy resin can be excessively crosslinked if the content of the flame-retardant curing agent is too high (comparative example 6), so that the material is hard and brittle and the mechanical properties are affected.
The test results of the dielectric constant, dielectric loss factor, flammability, flame retardant stability and mobility of the flame retardant epoxy resin-based copper-clad plate provided in the embodiments 1 to 10 and the comparative examples 1 to 6 are shown in table 2:
TABLE 2
The data in table 2 show that the flame-retardant epoxy resin-based copper-clad plate using the flame-retardant curing agent in examples 1-10 has significantly excellent combustibility and flame-retardant stability, extremely low migration, improved dielectric properties and a dielectric constant (1MHz) of more than 4, compared with the dicyandiamide cured epoxy resin-based copper-clad plate in comparative example 1; the flame-retardant curing agent of the embodiment 1 is replaced by the combination of the equivalent additive flame retardant and the equivalent dicyandiamide curing agent (a comparative example 2 and a comparative example 3), the obtained copper-clad plate has obviously reduced combustibility and poor flame-retardant stability, the flame-retardant performance of the copper-clad plate is obviously reduced after washing, and the migration phenomenon is obvious; the combustibility of the material can be optimized by increasing the dosage of the additive flame retardant in the epoxy resin base (comparative example 4), but the flame retardant stability of the material is still poor, and the migration is obvious, which shows that the additive flame retardant has low flame retardant efficiency and obvious migration precipitation phenomenon compared with the flame retardant curing agent disclosed by the invention. If the content of the flame retardant curing agent in the flame retardant epoxy resin composition is out of the range defined in the present invention, curing and flame retardancy cannot be effectively achieved if the content of the flame retardant curing agent is too low (comparative example 5), and if the content of the flame retardant curing agent is too high (comparative example 6), the epoxy resin is excessively crosslinked, which affects mechanical properties and causes waste of resources.
In conclusion, the flame-retardant epoxy resin obtained by curing the preparation raw materials and the flame-retardant curing agent and the copper-clad plate prepared from the flame-retardant epoxy resin have excellent flame retardance, and the flame retardance of the material can reach V-0 level; the flame-retardant curing agent provided by the invention participates in the curing crosslinking reaction of epoxy resin, so that a flame-retardant group finally exists in the resin in a molecular fragment form, the flame-retardant performance of the material is stable, the phenomena of micromolecule precipitation, water solubility or hydrolysis are avoided, the material cannot cause the reduction of the flame-retardant performance due to the migration precipitation of a flame retardant caused by operations such as washing, and the flame-retardant performance of the material after washing can still reach V-0 level; in addition, the curing efficiency of the flame-retardant curing agent is high, and the glass transition temperature of the flame-retardant epoxy resin composition can be increased, so that the flame-retardant epoxy resin composition and the copper-clad plate prepared from the flame-retardant epoxy resin composition have good mechanical properties and dielectric properties.
The applicant states that the flame retardant epoxy resin composition, the preparation method and the application of the present invention are illustrated by the above examples, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention is implemented only by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The flame-retardant epoxy resin composition is characterized in that the flame-retardant epoxy resin composition is prepared from the following raw materials:
50-100 parts by weight of epoxy resin
4-40 parts of flame-retardant curing agent
0.01-5 parts by weight of curing accelerator
The flame-retardant curing agent has a structure shown in a formula I:
wherein L is1、L2Each independently selected from a group containing a terminal phenolic hydroxyl group;
Z1、Z2each independently selected from phosphorus-containing groups;
M1selected from linear alkylene, branched alkylene or arylene;
M2selected from any organic group that satisfies a chemical environment;
Y1、Y2each independently selected from an inert group, a sulfur atom, an oxygen atom, or-H;
X1selected from any organylene group that satisfies a chemical environment;
a. b, c, d, f, g and h are respectively and independently selected from integers of 0-5, a and b are not 0 at the same time, f and g are not 0 at the same time, g and h are not 0 at the same time, and meanwhile, b + c + h is less than or equal to 5 and a + d + g is less than or equal to 5;
e is an integer of 0 to 100.
2. The flame-retardant epoxy resin composition according to claim 1, wherein Z is1、Z2Each independently selected from
One of (1), R1Any one selected from saturated or unsaturated alkyl, aryl or heteroaryl, more preferably methyl, ethyl or phenyl;
preferably, said M1One selected from C1-C30 linear chain or branched chain alkylene, C6-C30 arylene or C5-C7 heteroarylene, more preferably C1-C5 linear chain alkylene, C3-C5 branched chain alkylene or phenyl, and more preferably C1-C3 linear chain alkylene, C3 branched chain alkylene or phenyl;
preferably, said M2Selected from N, S, C1-C30 straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl,
Wherein R is2-R9Each independently selected from one of C1-C10 straight chain or branched chain alkylene, L2、Y2、Z2Is connected to R2-R9N, m, i, k are each independently selected from integers of 0 to 100;
preferably, said R is2-R9Each independently selected from one of C1-C6 straight chain or branched chain alkylene;
preferably, n, m, i and k are respectively and independently selected from integers of 0-30;
preferably, said Y is1、Y2Each is independently selected from-H or ═ O;
preferably, said X1One selected from N, S, substituted or unsubstituted C1 to C30 linear or branched alkylene groups, substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted C5 to C7 heteroarylene groups, substituted or unsubstituted C1 to C30 alkyleneamino groups, substituted or unsubstituted C1 to C30 alkyleneacyl groups, substituted or unsubstituted C1 to C30 alkyleneester groups, substituted or unsubstituted C6 to C30 arylamino groups, substituted or unsubstituted C6 to C30 aryloyl groups or C6 to C30 arylester groups, further preferably substituted or unsubstituted C1 to C5 linear or branched alkylene groups, substituted or unsubstituted C1 to C5 alkyleneamino groups, substituted or unsubstituted C1 to C5 alkyleneacyl groups, and substituted or unsubstituted C1 to C5 alkyleneester groups, further preferably-NH-R-, -R '-NH-, -R' -O-, -RV-C (O) -, substituted or unsubstituted C1-C5 linear or branched alkylene, wherein, R, R', R ", R ″VEach independently selected from substituted or unsubstituted C1 to C10 straight or branched chain alkylene.
3. The flame retardant epoxy resin composition according to claim 1 or 2, wherein the flame retardant curing agent preferably has a structure represented by formula II, formula III, formula IV, formula V or formula VI:
wherein L is1、L2Each independently selected from a group terminating in a phenolic hydroxyl group;
M1one selected from C1-C3 straight chain alkylene, C3 branched chain alkylene or phenyl;
M2selected from N, -NH-RTStraight chain or branched chain alkyl of C1-C6,
Wherein R isTIs C1-C6 straight chain or branched chain alkyl, R2-R9Each independently selected from C1-C6 straight chain or branched chain alkylene, n, m, i and k are each independently selected from integers of 0-30;
R1is methyl or ethyl;
R、R'、R”、RV、RPeach independently selected from substituted or unsubstituted C1-C10 straight or branched chain alkylene;
Y1、Y2each is independently selected from-H or ═ O;
a. b, g and h are respectively and independently selected from 0, 1 or 2, a and b are not 0 at the same time, f and g are not 0 at the same time, and g and h are not 0 at the same time;
e is an integer of 0-20, f is 0 or 1;
preferably, the flame retardant curing agent is further preferably any one of or a combination of at least two of the compounds having the following structures:
wherein R isPOne selected from substituted or unsubstituted C1-C5 straight chain or branched chain alkylene, and e is an integer of 0-20.
4. The flame-retardant epoxy resin composition according to any one of claims 1 to 3, wherein the epoxy resin is selected from any one of bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenyl type epoxy resin, cyclopropenyl type epoxy resin, novolac epoxy resin, or a combination of at least two thereof, and is preferably bisphenol A type epoxy resin.
5. The flame-retardant epoxy resin composition according to any one of claims 1 to 4, wherein the curing accelerator is any one selected from the group consisting of imidazole compounds, tertiary amine compounds, dicyandiamide, quaternary ammonium salts, organic phosphorus compounds, pyridine compounds and DBU;
preferably, the imidazole compound is selected from any one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole or trimellitic acid 1-cyanoethyl-2-undecylimidazolium salt;
preferably, the tertiary amine compound is selected from any one or a combination of at least two of triethanolamine, tetramethylguanidine, triethylenediamine, benzyldimethylamine or N, N-dimethylpiperazine;
preferably, the organophosphorus compound is triphenylphosphine and derivatives thereof.
6. The flame-retardant epoxy resin composition according to any one of claims 1 to 5, wherein a modifier is further included in a raw material for preparing the flame-retardant epoxy resin composition;
preferably, the mass of the modifier is 0.1-40% of the mass of the epoxy resin;
preferably, the modifier is selected from any one of polyamide resin, polyvinyl acetal, phenolic resin, vinyl resin, organic silicon, isocyanate, nitrile rubber, polyester resin or urea formaldehyde melamine resin or the combination of at least two of the above.
7. The flame-retardant epoxy resin composition according to any one of claims 1 to 6, further comprising a solid filler;
preferably, the solid filler is selected from any one or a combination of at least two of white carbon black, titanium dioxide, aluminum hydroxide, carbon black, zinc stearate, talcum powder, calcium carbonate, barium sulfate, montmorillonite, diatomite, kaolin, gypsum, mica or magnesium hydroxide;
preferably, the mass of the solid filler is 10-150% of the mass of the epoxy resin;
preferably, the preparation raw materials of the flame-retardant epoxy resin composition also comprise an auxiliary agent;
preferably, the auxiliary agent is selected from any one or a combination of at least two of a defoaming agent, a coupling agent, an anti-aging agent, an anti-settling agent, a wetting dispersant or a toughening agent.
8. A method for preparing the flame-retardant epoxy resin composition according to any one of claims 1 to 7, comprising the steps of:
adding epoxy resin, a flame-retardant curing agent, a curing accelerator and an organic solvent into a reaction device, and mixing and curing to obtain the flame-retardant epoxy resin composition.
9. The method according to claim 8, wherein the organic solvent is selected from any one or a combination of at least two of ethanol, acetone, xylene, tetrahydrofuran, N-dimethylformamide, and toluene;
preferably, the mixing is performed under stirring conditions;
preferably, the mixing time is 5-60 min;
preferably, the curing temperature is 60-200 ℃;
preferably, the curing time is 1-15 h;
preferably, the preparation method comprises the following steps:
(1) mixing epoxy resin and a flame-retardant curing agent in a reaction device, adding an organic solvent and a curing accelerator, and stirring and mixing for 5-60 min;
(2) and (2) injecting the mixture obtained in the step (1) into a mold, and curing for 1-15 h at the temperature of 60-200 ℃ to obtain the flame-retardant epoxy resin composition.
10. Use of the flame retardant epoxy resin composition according to any one of claims 1 to 7 in a prepreg, a laminate, a metal foil-clad laminate or a printed wiring board.
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