CN105885358A - Halogen-free high temperature resistant resin - Google Patents
Halogen-free high temperature resistant resin Download PDFInfo
- Publication number
- CN105885358A CN105885358A CN201610496827.5A CN201610496827A CN105885358A CN 105885358 A CN105885358 A CN 105885358A CN 201610496827 A CN201610496827 A CN 201610496827A CN 105885358 A CN105885358 A CN 105885358A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- resin
- halogen
- free
- type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
-
- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses halogen-free high temperature resistant resin. The halogen-free high temperature resistant resin is prepared from the following raw materials in parts by weight: 5-45 parts of halogen-free flame retardant resin, 100 parts of thermosetting epoxy resin, 99-115 parts of curing agent and 1-5 parts of accelerators, wherein the halogen-free flame retardant resin is one or more of phosphorus containing halogen-free flame retardant epoxy resin, halogen-free flame retardant benzoxazine resin and silicon containing halogen-free flame retardant epoxy resin; the thermosetting epoxy resin is trifunctional epoxy resin and/or tetrafunctional epoxy resin or a mixture of one or more of trifunctional epoxy resin and tetrafunctional epoxy resin and bifunctional epoxy resin. The halogen-free high temperature resistant resin has the advantages that the halogen-free high temperature resistant resin has the effect of improving the flame retardance and thermal stability of epoxy resin, not only avoids environmental pollution caused by brominated epoxy resin in the using and recovering processes but also can achieve lasting flame retardant effects, can maintain original thermal properties and mechanical properties of resin and is suitable for the winding technology of glass fibers and carbon fibers.
Description
Technical field
The invention belongs to resin material technical field, be specifically related to a kind of halogen-free refractory resin.
Background technology
Extra-high voltage direct current converter valve, as the nucleus equipment of extra-high voltage direct-current transmission, is to realize alterating and direct current
The core function unit converted, it is high that it has technical difficulty, and integrated level is big, and interdisciplinary fields are many, can
High technical characterstic is required by property.But in actual applications, due to the components and parts fault in valve tower,
The reasons such as shelf depreciation, cause converter valve fire incident, in order to protect converter valve properly functioning,
Need converter valve insulating part as insulation load-carrying construction part, play load-bearing, protective effect, add the resistance of halogen system
The shortcoming that the epoxy resins insulation part of combustion agent is maximum is to form a large amount of hydrogen halide when burning, this
After the water suction of kind of gas, hardware is had strong corrosivity, therefore a kind of brand-new, Halogen need to be developed
Fire resistant resin, in order to produce the extra-high voltage converter valve of strong mechanical performance, electrical property and heat resistance
Insulating part, to improve the safety and reliability of extra-high voltage direct current converter valve.
Summary of the invention
The technical problem to be solved is for above-mentioned the deficiencies in the prior art, it is provided that a kind of
Halogen-free refractory resin.This fire resistant resin has good resistance to elevated temperatures, mechanical performance and technique
Performance, the operation phase is long, it is adaptable to glass fibre and the winding process of carbon fiber, can be used for extra-high voltage and changes
The making of stream valve insulating part.
For solving above-mentioned technical problem, the technical solution used in the present invention is: a kind of halogen-free refractory tree
Fat, it is characterised in that be made up of the raw material of following weight portion: halogen-free flame-retardant resin 5～45 parts, heat
Thermoset epoxy resin 100 parts, firming agent 99～115 parts, accelerator 1～5 parts；Described Halogen hinders
Combustion resin is phosphor-containing halogen-free fire retarding epoxide resin, halogen-free flameproof benzoxazine resins and siliceous halogen-free flameproof
One or more in epoxy resin；Described thermosetting epoxy resin be trifunctional epoxy resin and/
Or four-functional group epoxy resin, or it is in trifunctional epoxy resin and four-functional group epoxy resin
One or more mixture with difunctional epoxy resin；Described firming agent is amine curing agent or acid
Anhydride firming agent；Described accelerator is dimethyl benzylamine or Imidizole accelerator；Described halogen-free refractory tree
The glass transition temperature of fat is not less than 180 DEG C.
Above-mentioned a kind of halogen-free refractory resin, it is characterised in that be made up of the raw material of following weight portion:
Halogen-free flame-retardant resin 10～35 parts, thermosetting epoxy resin 100 parts, firming agent 105～110 parts,
Accelerator 2～4 parts.
Above-mentioned a kind of halogen-free refractory resin, it is characterised in that be made up of the raw material of following weight portion:
Halogen-free flame-retardant resin 15 parts, thermosetting epoxy resin 100 parts, 108 parts of firming agent, accelerator 2
Part.
Above-mentioned a kind of halogen-free refractory resin, it is characterised in that described phosphor-containing halogen-free flame retardant epoxy tree
Fat is phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, resorcinol four
Phenyl bisphosphate, DOPO type phosphorus-containing flame-retardant epoxy resin and ODOPB type phosphor-containing flame-proof asphalt mixtures modified by epoxy resin
One or more in fat.
Above-mentioned a kind of halogen-free refractory resin, it is characterised in that described siliceous halogen-free flameproof asphalt mixtures modified by epoxy resin
Fat is O, O, O-tri-glycidyl benzene siliconic acid ester, 2-glycidyl epoxide dimethylsilane, [2-(3,4-
Epoxycyclohexyl) ethyl] one or more in diphenyl silane and methyl phenyl silicone resin.
Above-mentioned a kind of halogen-free refractory resin, it is characterised in that described halogen-free flameproof benzimidazole dihydrochloride tree
Fat is bisphenol A-type benzoxazine resins, bisphenol-f type benzoxazine resins, MDA type benzimidazole dihydrochloride
One or several in resin, phenolphthalein type benzoxazine resins and dicyclopentadiene type benzoxazine resins
Kind.
Above-mentioned a kind of halogen-free refractory resin, it is characterised in that described trifunctional epoxy resin is
AFG-90 epoxy resin, TDE-85 epoxy resin, trisphenyl glycidyl ether methylmethane or three are shunk
Glyceryl para-aminophenol, described four-functional group epoxy resin be AG-80 epoxy resin, four shrink sweet
Oil ether tetraphenyl ethane or four glycidyl group-4,4'-MDA, described difunctional ring
Epoxy resins is CYD-128 epoxy resin, bisphenol A epoxide resin or novolac epoxy resin.
Above-mentioned a kind of halogen-free refractory resin, it is characterised in that described trifunctional epoxy resin and
One or more in four-functional group epoxy resin are double officials with the mixture of difunctional epoxy resin
The weight/mass percentage composition that can roll into a ball epoxy resin is not more than 35%.
Above-mentioned a kind of halogen-free refractory resin, it is characterised in that described amine curing agent is firming agent
DDM, firming agent DDS and firming agent DADMT are according to (15～20): (10～15): (65～
90) mixed curing agent of mass ratio mixing, described acid anhydride type curing agent is methyl tetrahydro phthalic anhydride, first
Base HHPA or methylnadic anhydride.
Above-mentioned a kind of halogen-free refractory resin, it is characterised in that described Imidizole accelerator is 2-methyl
One or more in imidazoles, undecyl imidazole and 2-ethyl-4-methylimidazole.
Described weight portion can be gram, two, jin, the weight metering unit such as kilogram, ton.
The present invention compared with prior art has the advantage that
1, the halogen-free refractory resin of the present invention improves anti-flammability and the heat stability of epoxy resin,
Not only avoid brominated epoxy resin using and in removal process to environment, moreover it is possible to reach
Persistently flame retardant effect, and the original thermal property of resin and mechanical property can be kept.The vitrification of resin
Transition temperature is not less than 180 DEG C, and hot strength reaches more than 50MPa, it is adaptable to glass fibre and carbon are fine
The winding process of dimension.
2, the halogen-free refractory resin of the present invention not only has excellent mechanical property, anti-flammability, viscous
The features such as conjunction property, electrical insulating property and cure shrinkage are low, can be used for the system of extra-high voltage converter valve insulating part
Make, moreover it is possible to be widely used in the electric necks such as semiconductor packages, insulant and printed circuit plate substrate
Territory.
Below by embodiment, technical scheme is described in further detail.
Detailed description of the invention
Embodiment 1
The halogen-free refractory resin of the present embodiment, is made up of following raw material at room temperature mix homogeneously: nothing
Halogen flame-retarded resin 45g, thermosetting epoxy resin 100g, firming agent 115g, accelerator 1g；Described
The glass transition temperature of halogen-free refractory resin is not less than 180 DEG C；Between described halogen-free flame-retardant resin is
Tetraphenyl, thermosetting epoxy resin is AFG-90 epoxy resin, and firming agent is
Methyl hexahydrophthalic anhydride, accelerator is dimethyl benzylamine.
Embodiment 2
The present embodiment is same as in Example 1, and wherein difference is: described halogen-free refractory resin
Phosphorous for phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, DOPO type
Fire retarding epoxide resin, ODOPB type phosphorus-containing flame-retardant epoxy resin, O, O, O-tri-glycidyl phenyl silicon
Acid esters, 2-glycidyl epoxide dimethylsilane, [2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane,
Methyl phenyl silicone resin, bisphenol A-type benzoxazine resins, bisphenol-f type benzoxazine resins,
MDA type benzoxazine resins, phenolphthalein type benzoxazine resins or dicyclopentadiene type benzimidazole dihydrochloride tree
Fat, or be phosphorus containing hydroquinone epoxy resin, resorcinol tetraphenyldiphosphate, two (3-contractings
Water glycerol) base benzenephosphonic acid fat, DOPO type phosphorus-containing flame-retardant epoxy resin, ODOPB type phosphor-containing flame-proof
Epoxy resin, O, O, O-tri-glycidyl benzene siliconic acid ester, 2-glycidyl epoxide dimethylsilane,
[2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane, methyl phenyl silicone resin, bisphenol A-type
Benzoxazine resins, bisphenol-f type benzoxazine resins, MDA type benzoxazine resins, phenolphthalein type
At least two in benzoxazine resins and dicyclopentadiene type benzoxazine resins；Described thermosetting ring
Epoxy resins is TDE-85 epoxy resin, trisphenyl glycidyl ether methylmethane or triglycidyl group pair
Amino-phenol, or be four-functional group epoxy resin, or be trifunctional epoxy resin and four senses
Group's epoxy resin, or be the one in trifunctional epoxy resin and four-functional group epoxy resin or several
Plant the mixture with difunctional epoxy resin, the percent mass of difunctional epoxy resin in mixture
Content is not more than 35%, and wherein trifunctional epoxy resin is AFG-90 epoxy resin, TDE-85
Epoxy resin, trisphenyl glycidyl ether methylmethane or triglycidyl group para-aminophenol, four senses
Group's epoxy resin is AG-80 epoxy resin, four glycidyl ether tetraphenyl ethane or four (+)-2,3-Epoxy-1-propanols
Base-4,4'-MDA, difunctional epoxy resin is CYD-128 epoxy resin, bis-phenol
A epoxy resin or novolac epoxy resin；Described firming agent be amine curing agent, methyl tetrahydro phthalic anhydride or
Methylnadic anhydride, wherein amine curing agent be firming agent DDM, firming agent DDS and firming agent
DADMT is according to (15～20): (10～15): the mixing of the mass ratio mixing of (65～90) is solid
Agent；Described accelerator is in 2-methylimidazole, undecyl imidazole and 2-ethyl-4-methylimidazole
One or more.
Embodiment 3
The halogen-free refractory resin of the present embodiment, is made up of following raw material at room temperature mix homogeneously: nothing
Halogen flame-retarded resin 5kg, thermosetting epoxy resin 100kg, firming agent 99kg, accelerator 5kg；Institute
Stating halogen-free flame-retardant resin is O, and O, O-tri-glycidyl benzene siliconic acid ester, thermosetting epoxy resin is 30kg
TDE-85 epoxy resin and 70kg AG-80 epoxy resin, firming agent is firming agent DDM, solidification
The mixed curing agent that agent DDS and firming agent DADMT mixes according to the mass ratio of 20:15:65, promotees
Entering agent is undecyl imidazole.
Embodiment 4
The present embodiment is same as in Example 3, and wherein difference is: described halogen-free flame-retardant resin is
Phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, the phosphorous resistance of DOPO type
Combustion epoxy resin, ODOPB type phosphorus-containing flame-retardant epoxy resin, resorcinol tetraphenyldiphosphate,
2-glycidyl epoxide dimethylsilane, [2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane, methyl
Phenyl polysiloxane resin, bisphenol A-type benzoxazine resins, bisphenol-f type benzoxazine resins,
MDA type benzoxazine resins, phenolphthalein type benzoxazine resins or dicyclopentadiene type benzimidazole dihydrochloride tree
Fat, or be phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, DOPO
Type phosphorus-containing flame-retardant epoxy resin, ODOPB type phosphorus-containing flame-retardant epoxy resin, O, O, O-tri-glycidyl
Benzene siliconic acid ester, resorcinol tetraphenyldiphosphate, 2-glycidyl epoxide dimethylsilane,
[2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane, methyl phenyl silicone resin, bisphenol A-type
Benzoxazine resins, bisphenol-f type benzoxazine resins, MDA type benzoxazine resins, phenolphthalein type
At least two in benzoxazine resins and dicyclopentadiene type benzoxazine resins；Described thermosetting ring
Epoxy resins is trifunctional epoxy resin or four-functional group epoxy resin, or is trifunctional asphalt mixtures modified by epoxy resin
One or more in fat and four-functional group epoxy resin and the mixture of difunctional epoxy resin, mix
In compound, the weight/mass percentage composition of difunctional epoxy resin is not more than 35%, or is AFG-90 ring
One in epoxy resins, trisphenyl glycidyl ether methylmethane and triglycidyl group para-aminophenol with
The mixture of four-functional group epoxy resin, or be TDE-85 epoxy resin and four glycidyl ethers
Tetraphenyl ethane, or be TDE-85 epoxy resin and four glycidyl group-4,4'-diaminourea hexichol first
Alkane, wherein trifunctional epoxy resin is AFG-90 epoxy resin, TDE-85 epoxy resin, triphen
Base glycidyl ether methylmethane or triglycidyl group para-aminophenol, four-functional group epoxy resin is
AG-80 epoxy resin, four glycidyl ether tetraphenyl ethane or four glycidyl group-4,4'-diaminourea
Diphenyl-methane, difunctional epoxy resin be CYD-128 epoxy resin, bisphenol A epoxide resin or
Novolac epoxy resin；Described firming agent is methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride or methyl Na Dike
Anhydride；Described accelerator is dimethyl benzylamine, 2-methylimidazole or 2-ethyl-4-methylimidazole, or
For two or three in 2-methylimidazole, undecyl imidazole and 2-ethyl-4-methylimidazole.
Embodiment 5
The halogen-free refractory resin of the present embodiment, is made up of following raw material at room temperature mix homogeneously: nothing
Halogen flame-retarded resin 10kg, thermosetting epoxy resin 100kg, firming agent 105kg, accelerator 3kg；
Described halogen-free flame-retardant resin is bisphenol A-type benzoxazine resins, and thermosetting epoxy resin is 70kg tri-
Phenyl glycidyl ether methylmethane and 30kg bisphenol A epoxide resin, firming agent be firming agent DDM,
The mixed curing agent that firming agent DDS and firming agent DADMT mixes according to the mass ratio of 18:12:80,
Accelerator is 2-ethyl-4-methylimidazole.
Embodiment 6
The present embodiment is same as in Example 5, and wherein difference is: described halogen-free flame-retardant resin is
Phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, the phosphorous resistance of DOPO type
Combustion epoxy resin, ODOPB type phosphorus-containing flame-retardant epoxy resin, O, O, O-tri-glycidyl benzene siliconic acid
Ester, resorcinol tetraphenyldiphosphate, 2-glycidyl epoxide dimethylsilane, [2-(3,4-epoxy
Cyclohexyl) ethyl] diphenyl silane, methyl phenyl silicone resin, bisphenol-f type benzimidazole dihydrochloride tree
Fat, MDA type benzoxazine resins, phenolphthalein type benzoxazine resins or dicyclopentadiene type benzo
Piperazine resin, or be phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat,
DOPO type phosphorus-containing flame-retardant epoxy resin, ODOPB type phosphorus-containing flame-retardant epoxy resin, O, O, O-tri-ring
Oxygen propyl group phenyl esters of silicon acis, resorcinol tetraphenyldiphosphate, 2-glycidyl epoxide dimethyl-silicon
Alkane, [2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane, methyl phenyl silicone resin, bis-phenol
A type benzoxazine resins, bisphenol-f type benzoxazine resins, MDA type benzoxazine resins, phenol
At least two in phthalein type benzoxazine resins and dicyclopentadiene type benzoxazine resins；Described thermosetting
Property epoxy resin is trifunctional epoxy resin and/or four-functional group epoxy resin, or is four-functional group
Epoxy resin and the mixture of difunctional epoxy resin, or be trifunctional epoxy resin and four officials
Can roll into a ball the mixture of epoxy resin and difunctional epoxy resin, or be AFG-90 epoxy resin,
One in TDE-85 epoxy resin and triglycidyl group para-aminophenol and difunctional asphalt mixtures modified by epoxy resin
The mixture of fat, in mixture, the weight/mass percentage composition of difunctional epoxy resin is not more than 35%, or
Person is trisphenyl glycidyl ether methylmethane and CYD-128 epoxy resin (wherein CYD-128 epoxy
The weight/mass percentage composition of resin is not more than 35%), or be trisphenyl glycidyl ether methylmethane and phenol
Formaldehyde epoxy resin (wherein the weight/mass percentage composition of novolac epoxy resin is not more than 35%), wherein three official
Can roll into a ball epoxy resin is AFG-90 epoxy resin, TDE-85 epoxy resin, trisphenyl glycidyl ether
Methylmethane or triglycidyl group para-aminophenol, four-functional group epoxy resin is AG-80 asphalt mixtures modified by epoxy resin
Fat, four glycidyl ether tetraphenyl ethane or four glycidyl group-4,4'-MDA, double
Functional group epoxy resin is CYD-128 epoxy resin, bisphenol A epoxide resin or novolac epoxy resin；
Described firming agent is methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride or methylnadic anhydride；Described promotion
Agent is dimethyl benzylamine, 2-methylimidazole or undecyl imidazole, or be 2-methylimidazole, 11
In alkyl imidazole and 2-ethyl-4-methylimidazole two or three.
Embodiment 7
The halogen-free refractory resin of the present embodiment, is made up of following raw material at room temperature mix homogeneously: nothing
Halogen flame-retarded resin 15kg, thermosetting epoxy resin 100kg, firming agent 108kg, accelerator 2kg；
Described halogen-free flame-retardant resin is that 3kg DOPO type phosphorus-containing flame-retardant epoxy resin, 2kg ODOPB type are phosphorous
Fire retarding epoxide resin, 5kg methyl phenyl silicone resin and 5kg MDA type benzoxazine resins,
Thermosetting epoxy resin is 20kg triglycidyl group para-aminophenol, 45kg tetra-glycidyl ether
Tetraphenyl ethane and 35kg CYD-128 epoxy resin, firming agent is methylnadic anhydride, promotes
Agent is 1kg 2-methylimidazole and 1kg 2-ethyl-4-methylimidazole.
Embodiment 8
The present embodiment is same as in Example 7, and wherein difference is: described halogen-free flame-retardant resin is
Phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, the phosphorous resistance of DOPO type
Combustion epoxy resin, ODOPB type phosphorus-containing flame-retardant epoxy resin, O, O, O-tri-glycidyl benzene siliconic acid
Ester, resorcinol tetraphenyldiphosphate, 2-glycidyl epoxide dimethylsilane, [2-(3,4-epoxy
Cyclohexyl) ethyl] diphenyl silane, methyl phenyl silicone resin, bisphenol A-type benzimidazole dihydrochloride tree
Fat, bisphenol-f type benzoxazine resins, MDA type benzoxazine resins, phenolphthalein type benzimidazole dihydrochloride tree
One, two kinds, three kinds or more than five kinds in fat and dicyclopentadiene type benzoxazine resins, or
Contain for phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, ODOPB type
Phosphorus fire retarding epoxide resin, O, O, O-tri-glycidyl benzene siliconic acid ester, resorcinol tetraphenyl diphosphonic acid
Ester, 2-glycidyl epoxide dimethylsilane, [2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane,
Methyl phenyl silicone resin, bisphenol A-type benzoxazine resins, bisphenol-f type benzoxazine resins,
MDA type benzoxazine resins, phenolphthalein type benzoxazine resins and dicyclopentadiene type benzimidazole dihydrochloride tree
In fat four kinds, or be phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid
Fat, O, O, O-tri-glycidyl benzene siliconic acid ester, resorcinol tetraphenyldiphosphate, two shrink sweet
Oil epoxide dimethylsilane, [2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane, the poly-silicon of aminomethyl phenyl
Oxygen alkane resin, bisphenol A-type benzoxazine resins, bisphenol-f type benzoxazine resins, MDA type benzene
And three kinds in piperazine resin, phenolphthalein type benzoxazine resins and dicyclopentadiene type benzoxazine resins
With the mixture of DOPO type phosphorus-containing flame-retardant epoxy resin, or be phosphorus containing hydroquinone epoxy resin,
Two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, O, O, O-tri-glycidyl benzene siliconic acid ester, resorcinol
Tetraphenyldiphosphate, 2-glycidyl epoxide dimethylsilane, [2-(3,4-epoxycyclohexyl) ethyl]
Diphenyl silane, bisphenol A-type benzoxazine resins, bisphenol-f type benzoxazine resins, MDA type
In benzoxazine resins, phenolphthalein type benzoxazine resins and dicyclopentadiene type benzoxazine resins two
Plant and DOPO type phosphorus-containing flame-retardant epoxy resin and the mixing of ODOPB type phosphorus-containing flame-retardant epoxy resin
Thing, or be phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, O, O, O-
Three glycidyl benzene siliconic acid esters, resorcinol tetraphenyldiphosphate, 2-glycidyl epoxide diformazan
Base silane, [2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane, bisphenol A-type benzoxazine resins,
Bisphenol-f type benzoxazine resins, phenolphthalein type benzoxazine resins and dicyclopentadiene type benzimidazole dihydrochloride tree
One in fat and DOPO type phosphorus-containing flame-retardant epoxy resin, ODOPB type phosphorus-containing flame-retardant epoxy resin
Mixture with methyl phenyl silicone resin；Described thermosetting epoxy resin is trifunctional epoxy
Resin and/or four-functional group epoxy resin, or be trifunctional epoxy resin and difunctional asphalt mixtures modified by epoxy resin
The mixture of fat, or be the mixture of four-functional group epoxy resin and difunctional epoxy resin, mixed
In compound, the weight/mass percentage composition of difunctional epoxy resin is no more than 35%, wherein trifunctional ring
Epoxy resins is AFG-90 epoxy resin, TDE-85 epoxy resin, trisphenyl glycidyl ether methylmethane
Or triglycidyl group para-aminophenol, four-functional group epoxy resin is AG-80 epoxy resin, four contractings
Water glycerol ether tetraphenyl ethane or four glycidyl group-4,4'-MDA, difunctional ring
Epoxy resins is CYD-128 epoxy resin, bisphenol A epoxide resin or novolac epoxy resin；Described solid
Agent is firming agent DDM, firming agent DDS and firming agent DADMT is according to (15～20): (10～
: the mixed curing agent of the mass ratio of (65～90) mixing, or be methyl tetrahydro phthalic anhydride or methyl 15)
HHPA；Described accelerator is dimethyl benzylamine, 2-methylimidazole, undecyl imidazole or 2-second
Base-4-methylimidazole, or be 2-methylimidazole and undecyl imidazole, or be undecyl imidazole
And 2-ethyl-4-methylimidazole, or it is 2-methylimidazole, undecyl imidazole and 2-ethyl-4-first
Base imidazoles.
Embodiment 9
The halogen-free refractory resin of the present embodiment, is made up of following raw material at room temperature mix homogeneously: nothing
Halogen flame-retarded resin 35kg, thermosetting epoxy resin 100kg, firming agent 110kg, accelerator 4kg；
Described halogen-free flame-retardant resin is that 10kg [2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane, 10kg are double
Phenol F type benzoxazine resins and 15kg phenolphthalein type benzoxazine resins, described thermosetting resin is 80kg
Four glycidyl group-4,4'-MDA and 20kg novolac epoxy resin, described firming agent is
Firming agent DDM, firming agent DDS and firming agent DADMT mix according to the mass ratio of 15:10:90
Mixed curing agent, accelerator is 1kg 2-methylimidazole, 1kg undecyl imidazole and 2kg 2-second
Base-4-methylimidazole.
Embodiment 10
The present embodiment is the same as in Example 9, and wherein difference is: described halogen-free flame-retardant resin is
Phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, resorcinol tetraphenyl
Bisphosphate, DOPO type phosphorus-containing flame-retardant epoxy resin, ODOPB type phosphorus-containing flame-retardant epoxy resin,
O, O, O-tri-glycidyl benzene siliconic acid ester, 2-glycidyl epoxide dimethylsilane, [2-(3,4-epoxy
Cyclohexyl) ethyl] diphenyl silane, methyl phenyl silicone resin, bisphenol A-type benzimidazole dihydrochloride tree
Fat, bisphenol-f type benzoxazine resins, MDA type benzoxazine resins, phenolphthalein type benzimidazole dihydrochloride tree
One, two kinds or more than four kinds in fat and dicyclopentadiene type benzoxazine resins, or be phosphorous
Hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, resorcinol tetraphenyl two phosphorus
Acid esters, DOPO type phosphorus-containing flame-retardant epoxy resin, ODOPB type phosphorus-containing flame-retardant epoxy resin, O, O, O-
Three glycidyl benzene siliconic acid esters, 2-glycidyl epoxide dimethylsilane, methyl phenyl silicone
Resin, bisphenol A-type benzoxazine resins, bisphenol-f type benzoxazine resins, MDA type benzo
In piperazine resin, phenolphthalein type benzoxazine resins and dicyclopentadiene type benzoxazine resins three kinds, or
Person is phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, resorcinol four
Phenyl bisphosphate, DOPO type phosphorus-containing flame-retardant epoxy resin, ODOPB type phosphor-containing flame-proof asphalt mixtures modified by epoxy resin
Fat, O, O, O-tri-glycidyl benzene siliconic acid ester, 2-glycidyl epoxide dimethylsilane, methylbenzene
Organopolysiloxane resin, bisphenol A-type benzoxazine resins, MDA type benzoxazine resins, phenolphthalein
In type benzoxazine resins and dicyclopentadiene type benzoxazine resins two kinds and [2-(3,4-epoxide ring
Hexyl) ethyl] mixture of diphenyl silane, or be phosphorus containing hydroquinone epoxy resin, two (3-
(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, resorcinol tetraphenyldiphosphate, DOPO type phosphor-containing flame-proof ring
Epoxy resins, ODOPB type phosphorus-containing flame-retardant epoxy resin, O, O, O-tri-glycidyl benzene siliconic acid ester,
2-glycidyl epoxide dimethylsilane, methyl phenyl silicone resin, bisphenol A-type benzimidazole dihydrochloride
One in resin, MDA type benzoxazine resins and dicyclopentadiene type benzoxazine resins with
[2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane and the mixture of bisphenol-f type benzoxazine resins；
Described thermosetting epoxy resin is trifunctional epoxy resin and/or four-functional group epoxy resin, or is
Trifunctional epoxy resin and the mixture of difunctional epoxy resin, or be trifunctional asphalt mixtures modified by epoxy resin
The mixture of fat and four-functional group epoxy resin and difunctional epoxy resin, or be AG-80 epoxy
The mixing of a kind of and difunctional epoxy resin in resin and four glycidyl ether tetraphenyl ethane
Thing, in mixture, the weight/mass percentage composition of difunctional epoxy resin is no more than 35%, wherein three officials
Can roll into a ball epoxy resin is AFG-90 epoxy resin, TDE-85 epoxy resin, trisphenyl glycidyl ether
Methylmethane or triglycidyl group para-aminophenol, four-functional group epoxy resin is AG-80 asphalt mixtures modified by epoxy resin
Fat, four glycidyl ether tetraphenyl ethane or four glycidyl group-4,4'-MDA, double
Functional group epoxy resin is CYD-128 epoxy resin, bisphenol A epoxide resin or novolac epoxy resin；
Described firming agent is methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride or methylnadic anhydride；Described promotion
Agent is dimethyl benzylamine, or is 2-methylimidazole, undecyl imidazole and 2-ethyl-4-methyl miaow
One or both in azoles.
Embodiment 11
The halogen-free refractory resin of the present embodiment, is made up of following raw material at room temperature mix homogeneously: nothing
Halogen flame-retarded resin 20kg, thermosetting epoxy resin 100kg, firming agent 106kg, accelerator 3kg；
Described halogen-free flame-retardant resin is 10kg resorcinol tetraphenyldiphosphate, 5kg 2-glycidyl epoxide
Dimethylsilane and 5kg methyl phenyl silicone resin, described thermosetting resin is four (+)-2,3-Epoxy-1-propanols
Ether tetraphenyl ethane, described firming agent is firming agent DDM, firming agent DDS and firming agent
The mixed curing agent that DADMT mixes according to the mass ratio of 15:15:65, accelerator is dimethyl benzylamine.
Embodiment 12
The present embodiment is identical with embodiment 11, and wherein difference is: described halogen-free flame-retardant resin
For phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, resorcinol four benzene
Base bisphosphate, DOPO type phosphorus-containing flame-retardant epoxy resin, ODOPB type phosphorus-containing flame-retardant epoxy resin,
O, O, O-tri-glycidyl benzene siliconic acid ester, 2-glycidyl epoxide dimethylsilane, [2-(3,4-epoxy
Cyclohexyl) ethyl] diphenyl silane, methyl phenyl silicone resin, bisphenol A-type benzimidazole dihydrochloride tree
Fat, bisphenol-f type benzoxazine resins, MDA type benzoxazine resins, phenolphthalein type benzimidazole dihydrochloride tree
One, two kinds or more than four kinds in fat and dicyclopentadiene type benzoxazine resins, or be phosphorous
Hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, DOPO type phosphor-containing flame-proof ring
Epoxy resins, ODOPB type phosphorus-containing flame-retardant epoxy resin, O, O, O-tri-glycidyl benzene siliconic acid ester,
2-glycidyl epoxide dimethylsilane, [2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane, methyl
Phenyl polysiloxane resin, bisphenol A-type benzoxazine resins, bisphenol-f type benzoxazine resins,
MDA type benzoxazine resins, phenolphthalein type benzoxazine resins and dicyclopentadiene type benzimidazole dihydrochloride tree
In fat three kinds, or be phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid
Fat, DOPO type phosphorus-containing flame-retardant epoxy resin, ODOPB type phosphorus-containing flame-retardant epoxy resin, O, O, O-
Three glycidyl benzene siliconic acid esters, [2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane, aminomethyl phenyl
Polyorganosiloxane resin, bisphenol A-type benzoxazine resins, bisphenol-f type benzoxazine resins, MDA
In type benzoxazine resins, phenolphthalein type benzoxazine resins and dicyclopentadiene type benzoxazine resins
Two kinds with the mixture of resorcinol tetraphenyldiphosphate, or be phosphorus containing hydroquinone asphalt mixtures modified by epoxy resin
Fat, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, DOPO type phosphorus-containing flame-retardant epoxy resin, ODOPB
Type phosphorus-containing flame-retardant epoxy resin, O, O, O-tri-glycidyl benzene siliconic acid ester, [2-(3,4-epoxycyclohexyl)
Ethyl] diphenyl silane, bisphenol A-type benzoxazine resins, bisphenol-f type benzoxazine resins, MDA
In type benzoxazine resins, phenolphthalein type benzoxazine resins and dicyclopentadiene type benzoxazine resins
A kind of with resorcinol tetraphenyldiphosphate and the mixture of 2-glycidyl epoxide dimethylsilane；
Described thermosetting epoxy resin is trifunctional epoxy resin, or is AG-80 epoxy resin or four contractings
Water glyceryl-4,4'-MDA, or be trifunctional epoxy resin and four-functional group epoxy
Resin, or be that one or more in trifunctional epoxy resin and four-functional group epoxy resin are with double
The mixture of functional group epoxy resin, in mixture, the weight/mass percentage composition of difunctional epoxy resin is equal
Being not more than 35%, wherein trifunctional epoxy resin is AFG-90 epoxy resin, TDE-85 epoxy
Resin, trisphenyl glycidyl ether methylmethane or triglycidyl group para-aminophenol, four-functional group ring
Epoxy resins is AG-80 epoxy resin, four glycidyl ether tetraphenyl ethane or four glycidyl groups
-4,4'-MDA, difunctional epoxy resin is CYD-128 epoxy resin, bisphenol-A
Epoxy resin or novolac epoxy resin；Described firming agent be methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride or
Methylnadic anhydride；Described accelerator is 2-methylimidazole, undecyl imidazole and 2-ethyl-4-
One in Methylimidazole., two or three.
Embodiment 13
The halogen-free refractory resin of the present embodiment, is made up of following raw material at room temperature mix homogeneously: nothing
Halogen flame-retarded resin 30kg, thermosetting epoxy resin 100kg, firming agent 110kg, accelerator 4kg；
Described halogen-free flame-retardant resin is 10kg phosphorus containing hydroquinone epoxy resin, 5kgDOPO type phosphor-containing flame-proof
Epoxy resin, 10kg bisphenol-f type benzoxazine resins and 5kg dicyclopentadiene type benzoxazine resins,
Described thermosetting resin is 50kg trisphenyl glycidyl ether methylmethane, 40kg four glycidyl group
-4,4'-MDA and 10kg novolac epoxy resin, described firming agent be firming agent DDM,
The mixed curing agent that firming agent DDS and firming agent DADMT mixes according to the mass ratio of 20:10:90,
Accelerator is dimethyl benzylamine.
Embodiment 14
The present embodiment is identical with embodiment 13, and wherein difference is: described halogen-free flame-retardant resin
For phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, resorcinol four benzene
Base bisphosphate, DOPO type phosphorus-containing flame-retardant epoxy resin, ODOPB type phosphorus-containing flame-retardant epoxy resin,
O, O, O-tri-glycidyl benzene siliconic acid ester, 2-glycidyl epoxide dimethylsilane, [2-(3,4-epoxy
Cyclohexyl) ethyl] diphenyl silane, methyl phenyl silicone resin, bisphenol A-type benzimidazole dihydrochloride tree
Fat, bisphenol-f type benzoxazine resins, MDA type benzoxazine resins, phenolphthalein type benzimidazole dihydrochloride tree
One, two kinds, three kinds or more than five kinds in fat and dicyclopentadiene type benzoxazine resins, or
It is that two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, resorcinol tetraphenyldiphosphate, DOPO type contain
Phosphorus fire retarding epoxide resin, ODOPB type phosphorus-containing flame-retardant epoxy resin, O, O, O-tri-glycidyl phenyl
Esters of silicon acis, 2-glycidyl epoxide dimethylsilane, [2-(3,4-epoxycyclohexyl) ethyl] diphenyl silicon
Alkane, methyl phenyl silicone resin, bisphenol A-type benzoxazine resins, bisphenol-f type benzimidazole dihydrochloride
Resin, MDA type benzoxazine resins, phenolphthalein type benzoxazine resins and dicyclopentadiene type benzo
In piperazine resin four kinds, or be two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, resorcinol four benzene
Base bisphosphate, ODOPB type phosphorus-containing flame-retardant epoxy resin, O, O, O-tri-glycidyl benzene siliconic acid
Ester, 2-glycidyl epoxide dimethylsilane, [2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane,
Methyl phenyl silicone resin, bisphenol A-type benzoxazine resins, bisphenol-f type benzoxazine resins,
MDA type benzoxazine resins, phenolphthalein type benzoxazine resins and dicyclopentadiene type benzimidazole dihydrochloride tree
The mixture of three kinds in fat and phosphorus containing hydroquinone epoxy resin, or be two (3-(+)-2,3-Epoxy-1-propanols)
Base benzenephosphonic acid fat, resorcinol tetraphenyldiphosphate, ODOPB type phosphorus-containing flame-retardant epoxy resin,
O, O, O-tri-glycidyl benzene siliconic acid ester, 2-glycidyl epoxide dimethylsilane, [2-(3,4-epoxy
Cyclohexyl) ethyl] diphenyl silane, methyl phenyl silicone resin, bisphenol A-type benzimidazole dihydrochloride tree
Fat, MDA type benzoxazine resins, phenolphthalein type benzoxazine resins and dicyclopentadiene type benzo
In piperazine resin two kinds and phosphorus containing hydroquinone epoxy resin and DOPO type phosphorus-containing flame-retardant epoxy resin
Mixture, or be two (3-(+)-2,3-Epoxy-1-propanol) base benzenephosphonic acid fat, resorcinol tetraphenyl diphosphonic acid
Ester, ODOPB type phosphorus-containing flame-retardant epoxy resin, O, O, O-tri-glycidyl benzene siliconic acid ester, two contractings
Water glycerol epoxide dimethylsilane, [2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane, aminomethyl phenyl
Polyorganosiloxane resin, bisphenol A-type benzoxazine resins, MDA type benzoxazine resins and phenolphthalein type
One in benzoxazine resins and phosphorus containing hydroquinone epoxy resin, DOPO type phosphor-containing flame-proof epoxy
Resin and the mixture of bisphenol-f type benzoxazine resins；Described thermosetting epoxy resin is trifunctional
Epoxy resin and/or four-functional group epoxy resin, or be trifunctional epoxy resin and difunctional ring
The mixture of epoxy resins, or be the mixing of four-functional group epoxy resin and difunctional epoxy resin
Thing, in mixture, the weight/mass percentage composition of difunctional epoxy resin is no more than 35%, wherein three officials
Can roll into a ball epoxy resin is AFG-90 epoxy resin, TDE-85 epoxy resin, trisphenyl glycidyl ether
Methylmethane or triglycidyl group para-aminophenol, four-functional group epoxy resin is AG-80 asphalt mixtures modified by epoxy resin
Fat, four glycidyl ether tetraphenyl ethane or four glycidyl group-4,4'-MDA, double
Functional group epoxy resin is CYD-128 epoxy resin, bisphenol A epoxide resin or novolac epoxy resin；
Described firming agent is methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride or methylnadic anhydride；Described promotion
Agent be the one in 2-methylimidazole, undecyl imidazole and 2-ethyl-4-methylimidazole, two kinds or
Three kinds.
The performance parameter of the halogen-free refractory resin of table 1 embodiment 1 to embodiment 14
It can be seen that the halogen-free refractory resin of the present invention has the fire-retardant of excellence from the data of table 1
Performance, heat stability and mechanical property, the glass transition temperature of halogen-free refractory resin is not less than
180 DEG C, hot strength reaches more than 50MPa, it is adaptable to glass fibre and the winding process of carbon fiber.
The above, be only presently preferred embodiments of the present invention, and the present invention not does any restriction, all
It is any simple modification, change and equivalence knot above example made according to inventive technique essence
Structure changes, and all still falls within the protection domain of technical solution of the present invention.
Claims (10)
1. a halogen-free refractory resin, it is characterised in that be made up of the raw material of following weight portion:
Halogen-free flame-retardant resin 5～45 parts, thermosetting epoxy resin 100 parts, firming agent 99～115 parts, promote
Enter agent 1～5 parts；Described halogen-free flame-retardant resin is phosphor-containing halogen-free fire retarding epoxide resin, halogen-free flameproof benzene
And one or more in piperazine resin and siliceous Halogenless fire retarded epoxy resin；Described thermoset epoxy tree
Fat is trifunctional epoxy resin and/or four-functional group epoxy resin, or is trifunctional epoxy resin
Mixture with one or more in four-functional group epoxy resin Yu difunctional epoxy resin；Described
Firming agent is amine curing agent or acid anhydride type curing agent；Described accelerator is dimethyl benzylamine or imidazoles rush
Enter agent；The glass transition temperature of described halogen-free refractory resin is not less than 180 DEG C.
A kind of halogen-free refractory resin the most according to claim 1, it is characterised in that by with
The raw material of lower weight portion is made: halogen-free flame-retardant resin 10～35 parts, thermosetting epoxy resin 100 parts,
Firming agent 105～110 parts, accelerator 2～4 parts.
A kind of halogen-free refractory resin the most according to claim 2, it is characterised in that by with
The raw material of lower weight portion is made: halogen-free flame-retardant resin 15 parts, thermosetting epoxy resin 100 parts, Gu
Agent 108 parts, accelerator 2 parts.
4. according to a kind of halogen-free refractory resin described in claim 1,2 or 3, it is characterised in that
Described phosphor-containing halogen-free fire retarding epoxide resin is phosphorus containing hydroquinone epoxy resin, two (3-(+)-2,3-Epoxy-1-propanols)
Base benzenephosphonic acid fat, resorcinol tetraphenyldiphosphate, DOPO type phosphorus-containing flame-retardant epoxy resin and
One or more in ODOPB type phosphorus-containing flame-retardant epoxy resin.
5. according to a kind of halogen-free refractory resin described in claim 1,2 or 3, it is characterised in that
Described siliceous Halogenless fire retarded epoxy resin is O, O, O-tri-glycidyl benzene siliconic acid ester, 2-glycidyl
Epoxide dimethylsilane, [2-(3,4-epoxycyclohexyl) ethyl] diphenyl silane and the poly-silica of aminomethyl phenyl
One or more in alkane resin.
6. according to a kind of halogen-free refractory resin described in claim 1,2 or 3, it is characterised in that
Described halogen-free flameproof benzoxazine resins is bisphenol A-type benzoxazine resins, bisphenol-f type benzimidazole dihydrochloride
Resin, MDA type benzoxazine resins, phenolphthalein type benzoxazine resins and dicyclopentadiene type benzo
One or more in piperazine resin.
7. according to a kind of halogen-free refractory resin described in claim 1,2 or 3, it is characterised in that
Described trifunctional epoxy resin is AFG-90 epoxy resin, TDE-85 epoxy resin, triphenyl contracting
Water glycerin ether methylmethane or triglycidyl group para-aminophenol, described four-functional group epoxy resin is
AG-80 epoxy resin, four glycidyl ether tetraphenyl ethane or four glycidyl group-4,4'-diaminourea
Diphenyl-methane, described difunctional epoxy resin is CYD-128 epoxy resin, bisphenol-A epoxy tree
Fat or novolac epoxy resin.
8. according to a kind of halogen-free refractory resin described in claim 1,2 or 3, it is characterised in that
One or more in described trifunctional epoxy resin and four-functional group epoxy resin and difunctional
In the mixture of epoxy resin, the weight/mass percentage composition of difunctional epoxy resin is not more than 35%.
9. according to a kind of halogen-free refractory resin described in claim 1,2 or 3, it is characterised in that
Described amine curing agent is firming agent DDM, firming agent DDS and firming agent DADMT according to (15～
20): (10～15): the mixed curing agent of the mass ratio mixing of (65～90), described anhydrides is solid
Agent is methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride or methylnadic anhydride.
10., according to a kind of halogen-free refractory resin described in claim 1,2 or 3, its feature exists
In, described Imidizole accelerator is 2-methylimidazole, undecyl imidazole and 2-ethyl-4-methylimidazole
In one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610496827.5A CN105885358A (en) | 2016-06-29 | 2016-06-29 | Halogen-free high temperature resistant resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610496827.5A CN105885358A (en) | 2016-06-29 | 2016-06-29 | Halogen-free high temperature resistant resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105885358A true CN105885358A (en) | 2016-08-24 |
Family
ID=56719424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610496827.5A Pending CN105885358A (en) | 2016-06-29 | 2016-06-29 | Halogen-free high temperature resistant resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105885358A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106854342A (en) * | 2016-12-22 | 2017-06-16 | 芜湖天道绿色新材料有限公司 | Low halogen, fire-retardant epoxy resin carbon fiber composite and preparation method thereof |
| CN108929519A (en) * | 2017-05-24 | 2018-12-04 | 洛阳尖端技术研究院 | A kind of basalt fiber composite material and preparation method thereof |
| CN110283300A (en) * | 2019-07-15 | 2019-09-27 | 上海华谊树脂有限公司 | One kind being suitable for molding epoxy composite of composite liquid and preparation method thereof |
| CN110330635A (en) * | 2019-06-26 | 2019-10-15 | 四川东材科技集团股份有限公司 | A kind of halogen-free flameproof heat-resistant water-soluble epoxy resin, composition and its preparation method and application |
| TWI734911B (en) * | 2017-05-10 | 2021-08-01 | 日商東麗股份有限公司 | Epoxy resin composition, prepreg, fiber reinforced composite material and manufacturing method thereof |
| CN113956750A (en) * | 2021-11-12 | 2022-01-21 | 中国林业科学研究院林产化学工业研究所 | Benzoxazine/epoxy resin composite flame-retardant anticorrosive coating and preparation method thereof |
| CN114103306A (en) * | 2021-11-05 | 2022-03-01 | 江苏耀鸿电子有限公司 | Halogen-free lead-free high-Tg copper-clad plate and processing technology thereof |
| CN114163780A (en) * | 2021-12-15 | 2022-03-11 | 广东电网有限责任公司 | Epoxy resin composition and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698739A (en) * | 2009-11-03 | 2010-04-28 | 西安唯实输配电技术有限公司 | Carbon fiber composite core composition and method for preparing carbon fiber composite core |
| CN103333467A (en) * | 2013-06-20 | 2013-10-02 | 湖北三江航天江北机械工程有限公司 | Epoxy resin composition for filament winding and preparation method thereof |
| CN104277418A (en) * | 2013-07-09 | 2015-01-14 | 上海杰事杰新材料(集团)股份有限公司 | Carbon fiber reinforced toughened epoxy resin composite material and preparation method thereof |
| CN104672431A (en) * | 2015-02-10 | 2015-06-03 | 北京化工大学 | Novel tetra-functionality epoxy resin as well as preparation method and application thereof |
-
2016
- 2016-06-29 CN CN201610496827.5A patent/CN105885358A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698739A (en) * | 2009-11-03 | 2010-04-28 | 西安唯实输配电技术有限公司 | Carbon fiber composite core composition and method for preparing carbon fiber composite core |
| CN103333467A (en) * | 2013-06-20 | 2013-10-02 | 湖北三江航天江北机械工程有限公司 | Epoxy resin composition for filament winding and preparation method thereof |
| CN104277418A (en) * | 2013-07-09 | 2015-01-14 | 上海杰事杰新材料(集团)股份有限公司 | Carbon fiber reinforced toughened epoxy resin composite material and preparation method thereof |
| CN104672431A (en) * | 2015-02-10 | 2015-06-03 | 北京化工大学 | Novel tetra-functionality epoxy resin as well as preparation method and application thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106854342A (en) * | 2016-12-22 | 2017-06-16 | 芜湖天道绿色新材料有限公司 | Low halogen, fire-retardant epoxy resin carbon fiber composite and preparation method thereof |
| TWI734911B (en) * | 2017-05-10 | 2021-08-01 | 日商東麗股份有限公司 | Epoxy resin composition, prepreg, fiber reinforced composite material and manufacturing method thereof |
| CN108929519A (en) * | 2017-05-24 | 2018-12-04 | 洛阳尖端技术研究院 | A kind of basalt fiber composite material and preparation method thereof |
| CN110330635A (en) * | 2019-06-26 | 2019-10-15 | 四川东材科技集团股份有限公司 | A kind of halogen-free flameproof heat-resistant water-soluble epoxy resin, composition and its preparation method and application |
| CN110330635B (en) * | 2019-06-26 | 2021-12-28 | 四川东材科技集团股份有限公司 | Halogen-free flame-retardant heat-resistant water-soluble epoxy resin, composition, preparation method and application thereof |
| CN110283300A (en) * | 2019-07-15 | 2019-09-27 | 上海华谊树脂有限公司 | One kind being suitable for molding epoxy composite of composite liquid and preparation method thereof |
| CN114103306A (en) * | 2021-11-05 | 2022-03-01 | 江苏耀鸿电子有限公司 | Halogen-free lead-free high-Tg copper-clad plate and processing technology thereof |
| CN113956750A (en) * | 2021-11-12 | 2022-01-21 | 中国林业科学研究院林产化学工业研究所 | Benzoxazine/epoxy resin composite flame-retardant anticorrosive coating and preparation method thereof |
| CN114163780A (en) * | 2021-12-15 | 2022-03-11 | 广东电网有限责任公司 | Epoxy resin composition and preparation method and application thereof |
| CN114163780B (en) * | 2021-12-15 | 2024-02-13 | 广东电网有限责任公司 | Epoxy resin composition and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105885358A (en) | Halogen-free high temperature resistant resin | |
| CN107011499B (en) | The composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla and its application | |
| US8399577B2 (en) | Curable epoxy resin composition | |
| Liu et al. | Preparation of silicon‐/phosphorous‐containing epoxy resins from the fusion process to bring a synergistic effect on improving the resins' thermal stability and flame retardancy | |
| TWI639646B (en) | Flame-retardant resin composition, thermosetting resin composition, composite metal substrate and flame-retardant electronic material | |
| CN105778413B (en) | A kind of halogen-free epoxy resin composition and prepreg and laminate using it | |
| CN103289326B (en) | For the halogen-free flame retardant epoxy resin composition of potting compound | |
| CN104559890B (en) | A kind of environmental protection flame retardant heat-conducting glue and preparation method thereof | |
| US20120025151A1 (en) | Curable epoxy resin composition | |
| CN106103532B (en) | Novolac hardeners and preparation method thereof containing alkoxysilyl, the composition containing curing agent, hardening product and its application | |
| CN105348742B (en) | Compositions of thermosetting resin, prepreg and the laminate of the benzoxazine colophony containing melamine-type | |
| JP6731907B2 (en) | Epoxy resin composition | |
| CN109535657A (en) | A kind of phosphorus silicon systems shock resistance Halogenless fire retarded epoxy resin material and preparation method thereof | |
| CN105733194A (en) | Epoxy resin with silicon-phosphorus-titanium three-element synergistic flame retardancy and preparation method thereof | |
| Luo et al. | Synthesis of a novel DPPA‐containing benzoxazine to flame‐retard epoxy resin with maintained thermal properties | |
| Ribera et al. | Flame retardant epoxy resins based on diglycidyl ether of isobutyl bis (hydroxypropyl) phosphine oxide | |
| CN107815277A (en) | A kind of flame-resistant electronic material | |
| CN106564240A (en) | Manufacturing method of glass fiber mat laminated plate high in proof tracking index | |
| CN106243629B (en) | A kind of preparation method and application of fire-retardant modified epoxy resin | |
| JP6101122B2 (en) | Epoxy resin composition for mold transformer, mold transformer, and method for producing mold transformer | |
| WO2001060913A1 (en) | Thermosetting resin composition | |
| CN104893243B (en) | The curing agent and epoxy composite of the phosphorus-nitrogen compound of base containing bisphenol S | |
| CN104098757B (en) | A kind of organic silicon-phosphorus hydridization extinguishing waterborn self-emulsifying epoxy resin firming agent and its production and use | |
| WO2014206487A1 (en) | A halogen free flame retardant epoxy resin composition | |
| CN104892906B (en) | The curing agent and epoxy composite of the phosphorus-nitrogen compound of phenolic group containing single aromatic ring |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160824 |