CN102276959A - Halogen-free non-phosphorization flame-retardant epoxy resin composition and preparation method thereof - Google Patents
Halogen-free non-phosphorization flame-retardant epoxy resin composition and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/926—Flow or feed rate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92828—Raw material handling or dosing, e.g. active hopper or feeding device
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention provides a halogen-free non-phosphorization flame-retardant epoxy resin composition and a preparation method thereof. The preparation method comprises the following steps of: premixing the common epoxy resin, flame-retardant epoxy resin, a curing agent, a curing accelerator, a flame-retardant synergistic agent and an inorganic filler; melting, mixing and extruding; and crushing and sieving to prepare the halogen-free non-phosphorization flame-retardant epoxy resin composition. The flame-retardant epoxy resin composition does not contain harmful substances such as halogen, diantimony trioxide, phosphorus and the like, has excellent fire resistance which can reach UL94V-O grade flame-retardant standard and high electrical property, can be applied in the fields of electronic packaging and copper-clad laminate.
Description
Technical field
The invention belongs to polymeric material field, relate to composition epoxy resin, especially a kind of non-halogen non-phosphorus fire-retardant epoxy resin composition and method of making the same.
Background technology
Resins, epoxy is to carry out polycondensation and the product that makes by the compound with epoxy group(ing) and multi-hydroxy or polyol compound, it is one of most widely used matrix resin in the polymer matrix composite, cohesiveness, chemical resistance, electrical insulation properties, mechanical property with high strength, excellence, and be easy to processing, shrinking percentage is low, coefficient of linear expansion is little and advantage such as with low cost, is widely used in the encapsulation of electronic devices and components such as voltage dependent resistor, ceramic condenser, diode, triode.
But because the limiting oxygen index(LOI) (LOI) of Resins, epoxy is lower, have only 19.5, belong to combustible material, therefore need carry out fire-retardant finish it.Usually, the method for improving ethoxyline resin antiflaming is to introduce halogen-containing fire retardant in Resins, epoxy, and cooperates the flame retardant as the antimonous oxide class, thereby gives Resins, epoxy with flame retardancy and self-extinguishing.But nowadays, the flame retardant of antimonous oxide class has been listed in carcinogenic substance, and halogen flame can produce dioxin toxic smoke and corrosive gasess such as (Dioxin) when burning, has had a strong impact on human beings'health and human environment of depending on for existence.For human health and requirement on environmental protection, developing fire retardant harmless, free from environmental pollution and that flame retarding efficiency is high has become the research focus.
In fire retardant, the fire retardant that phosphorus series compound has the environmental protection notion as a new generation by extensive studies and application, becomes the main flow of fire retardant now, and has entered the volume production operational phase.As No. 5376453, United States Patent (USP), use the phosphoric acid ester of band epoxy group(ing) to cooperate nitrogenous solidifying agent to make veneer sheet, thereby make its flame retardant resistance reach the requirement of UL94V-0.But in fact, optimal environment-friendly materials still can not be thought by phosphorus system, because phosphorus flame retardant can cause the oxidations such as lake, rivers and creeks and then the another kind of environment problem of deriving because of hydrolysis; Another aspect, phosphorus flame retardant can cause electronic product reliability to descend or inefficacy, and it may produce toxic gas (as methylphosphine) in combustion processes because its high-hydroscopicity reaches thereby dissociated characteristic.Therefore, phosphorus flame retardant will also probably all be banned use of future.In order to prevent trouble before it happens, exploitation non-halogen non-phosphorus type fire retardant will become a problem that is with historically new significance.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, the non-halogen non-phosphorus fire-retardant epoxy resin composition and method of making the same of a kind of good flame retardant resistance and good electric property is provided.
The present invention realizes that the technical scheme of its purpose is:
A kind of non-halogen non-phosphorus fire-retardant epoxy resin composition, it constitutes component and mass fraction is respectively:
Wherein, fire retarding epoxide resin makes like this:
(1) in the four-hole boiling flask that heating jacket, agitator, thermometer, distillation column and prolong are housed, add a certain amount of liquid-state epoxy resin, be warming up to more than 120 ℃, open vacuum pump, vacuum tightness＜-0.08MPa, stir 0.5h, extract the cut in the liquid epoxies out;
(2) the many rings diphenol that adds in removing the liquid-state epoxy resin of cut/encircle the catalyzer of dicarboxylic acid and catalyzer total amount 85% slowly is warming up to 130～140 ℃, logical simultaneously nitrogen protection more, after treating its thorough mixing, slowly be warming up to 150～180 ℃, reaction 2～4h is cooled to 130～140 ℃;
(3) catalyzer of adding organic boronic and catalyzer total amount 10% simultaneously, transfers to 160～190 ℃ and nitrogen protections with temperature, and reaction 2～4h is cooled to 130～140 ℃;
(4) catalyzer of adding nitrogen-containing heterocycle compound and catalyzer total amount 5% simultaneously, transfers between 140～170 ℃ temperature and nitrogen protection, reaction 1～3h; Color becomes light yellow transparent liquid, stopped reaction;
(5) cooling discharge behind the cooling compressing tablet, can obtain light yellow transparent solid-state fire retarding epoxide resin;
The raw material of described fire retarding epoxide resin constitutes and mass fraction is:
60～80 parts of liquid-state epoxy resins;
0～35 part of dicarboxylic acid of many ring diphenol/encircle more;
0～25 part of organic boronic;
2～23 parts of nitrogen-containing heterocycle compounds;
0.02～0.1 part of catalyzer;
If encircle diphenol/encircle dicarboxylic acid is 0 part more more, omit step (2).
And described liquid-state epoxy resin is a bis-epoxy base fluid attitude Resins, epoxy, and oxirane value is not less than 0.5eq/100g, comprises one or more the mixture in Racemic glycidol ether type epoxy, glycidyl ester type epoxy resin, the glycidyl amine type epoxy resin.
Many ring diphenol/encircle dicarboxylic acid comprise naphthalenediol, R-dinaphthalene diphenol, S-dinaphthalene diphenol, '-biphenyl diphenol, biphenyl dicarboxylic acid more;
Organic boronic comprises one or more the mixture in phenylo boric acid, 2-hydroxybenzene boric acid, 3-hydroxybenzene boric acid, 4-hydroxybenzene boric acid, 2-carboxyl phenylo boric acid, 3-carboxyl phenylo boric acid, the 4-carboxyl phenylo boric acid;
Nitrogen-containing heterocycle compound comprises 5,5-dimethyl hydantion, 5-methyl-5-ethylhydantoin, 5, the mixture of one or more in the 5-diethyl glycolylurea;
Catalyzer comprises one or more the mixture in tetramethyl ammonium chloride, benzyl trimethyl ammonium chloride, triphenyl phosphorus, methyltriphenylphospbromide bromide phosphorus, the Ethyltriphenylphosphonium brimide.
And described ordinary epoxy resin is bisphenol A type epoxy resin, and requiring softening temperature is that 60～120 ℃, oxirane value are 0.105～0.225eq/100g.
And described solidifying agent comprises one or more the mixture in organic acid or anhydrides, the phenols curing agent.
And described curing catalyst comprises any one in imidazoles, imidazolines, trialkyl phosphorus, quaternary ammonium salt, quaternary phosphine salt, the organic ureas.
And described fire retarding synergist comprises one or more the mixture in aluminium hydroxide, magnesium hydroxide, zinc borate, boric acid titanium, lime borate, Zinc aluminate, oxalic acid aluminium, the melamine cyanurate.
And described mineral filler comprises one or more the mixture in silica flour, talcum powder, lime carbonate, barium sulfate, the mica powder, and median size is 1～50 μ m.
A kind of preparation non-halogen non-phosphorus fire-retardant epoxy resin method for compositions, step is:
Described Resins, epoxy, fire retarding epoxide resin, solidifying agent, curing catalyst, fire retarding synergist and mineral filler are carried out pre-mixing by the quality proportioning, and the premixed time is 5～20min, rotating speed 500～1000r/min; After the mixing, melting mixing is extruded, and wherein, 70～150 ℃ of extrusion temperatures, forcing machine rotating speed 1500～3000r/min, rate of feeding 900～2400r/min pulverize again, rotating speed 1500～2600r/min, rate of feeding 600～2400r/min.
Advantage of the present invention and positively effect are:
1, objectionable impuritiess such as not halogen-containing, the antimonous oxide of fire retarded epoxy resin composition of the present invention, phosphorus, and cooperate the synergistic effect of fire retarding synergist, environmental protection; Flame retardant resistance can reach the flame-retardant standard of UL94V-0 level, has good flame retardant resistance and good electric property.
2, the self-control fire retarding epoxide resin synthesis technique of the present invention's employing is simple, produces and stablizes, and no fugitive constituent generates in building-up process, and the feature of environmental protection is strong.Its special component constitutes and the requirement of each component has determined it to can be used for the electronic package material field as sealing material, potting compound, plastic cement and being used for the copper-clad plate field.
3, the present invention further improves flame retardant resistance, the water tolerance of Resins, epoxy in conjunction with the flame retardant resistance of flame resistivity, nitrogen heterocyclic ring and organic boron of condensed ring or biphenyl, thereby satisfies the non-halogen non-phosphorusization of electronic devices and components packaged material and copper-clad plate.
Embodiment
The invention will be further described below in conjunction with specific embodiment, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
Described liquid-state epoxy resin is a bis-epoxy base fluid attitude Resins, epoxy, and oxirane value is not less than 0.5eq/100g, comprises one or more the mixture in Racemic glycidol ether type epoxy, glycidyl ester type epoxy resin, the glycidyl amine type epoxy resin.
Liquid-state epoxy resin comprises one or more in the following Resins, epoxy:
The Racemic glycidol ether type epoxy comprises E51, E54, CYD127, CYD127E, CYD128, NPEL127, NPEL128 Resins, epoxy, YDE-162, YDE-165, YDE-170, YDE-175;
Glycidyl ester type epoxy resin comprises o-phthalic acid diglycidyl ester, interior methyne tetrahydrophthalic acid glycidyl ester;
Glycidyl amine type epoxy resin comprises 5,5-dimethyl hydantion Resins, epoxy;
Above-mentioned model is producer's model, distinguishes to be the oxirane value difference.
Described Resins, epoxy also comprises the non-above loop-like epoxy resins kind that limits except that comprising the above Resins, epoxy.
Embodiment 1:
A kind of non-halogen non-phosphorus fire-retardant epoxy resin composition consists of: the composition of Resins, epoxy, fire retarding epoxide resin A, solidifying agent, curing catalyst, fire retarding synergist sees Table 1.
Its preparation method is: Resins, epoxy, fire retarding epoxide resin A, solidifying agent, curing catalyst, fire retarding synergist and other components are carried out pre-mixing by the quality proportioning, and the premixed time is 5～20min, rotating speed 500～1000r/min; Then, melting mixing is extruded melting mixing and is extruded, 70～150 ℃ of extrusion temperatures, forcing machine rotating speed 1500～3000r/min, rate of feeding 900～2400r/min, pulverize again that (rotating speed 1500～2600r/min, rate of feeding 600～2400r/min) can described fire-retardant epoxy resin compositions.
Wherein, the synthetic method of fire retarding epoxide resin A is:
In the 1L four-hole boiling flask of heating jacket, agitator, thermometer, distillation column and prolong is housed, add 560g NPEL127E (South Asia, Taiwan, bisphenol A type epoxy resin, oxirane value 0.5435～0.5682eq/100g) is warming up to 120 ℃, opens vacuum pump, stir 0.5h, close vacuum pump;
Add 139.3g5,5-dimethyl hydantion and 0.7g Ethyltriphenylphosphonium brimide transfer between 140～170 ℃ temperature and nitrogen protection, reaction 1～3h; Color becomes light yellow transparent liquid, stopped reaction.
Cooling discharge behind the cooling compressing tablet, can obtain light yellow transparent solid-state fire retarding epoxide resin.
After tested, the oxirane value of this fire retarding epoxide resin is 0.133eq/100g, and softening temperature is 85 ℃, and nitrogen content is 4.36wt%, boron-containing quantity 0wt%.
Embodiment 2:
A kind of non-halogen non-phosphorus fire-retardant epoxy resin composition consists of: the composition of Resins, epoxy, fire retarding epoxide resin B, solidifying agent, curing catalyst, fire retarding synergist sees Table 1.
Its preparation method is: Resins, epoxy, fire retarding epoxide resin B, solidifying agent, curing catalyst, fire retarding synergist and other components are carried out pre-mixing by the quality proportioning, and the premixed time is 5～20min, rotating speed 500～1000r/min; Then, melting mixing is extruded, and wherein 70～150 ℃ of extrusion temperatures, forcing machine rotating speed 1500～3000r/min, rate of feeding 900～2400r/min pulverize again, rotating speed 1500～2600r/min, rate of feeding 600～2400r/min can described fire-retardant epoxy resin compositions.
Wherein, the synthetic method of fire retarding epoxide resin B is:
In the 1L four-hole boiling flask of heating jacket, agitator, thermometer, distillation column and prolong is housed, add 520g NPEL127E (South Asia, Taiwan, bisphenol A type epoxy resin, oxirane value 0.5435～0.5682eq/100g),, be warming up to 120 ℃, open vacuum pump, stir 0.5h, close vacuum pump;
Add 79gS-dinaphthalene diphenol and 1.2g Ethyltriphenylphosphonium brimide, be warming up to 130～140 ℃, after logical nitrogen mixes, be warming up to 150～180 ℃, reaction 2～4h is cooled to 130～140 ℃;
Add 96g 5,5-dimethyl hydantion and 0.1g Ethyltriphenylphosphonium brimide transfer between 140～170 ℃ temperature and nitrogen protection, reaction 1～3h; Color becomes light yellow transparent liquid, stopped reaction;
Cooling discharge behind the cooling compressing tablet, can obtain light yellow transparent solid-state fire retarding epoxide resin.
After tested, the oxirane value of this Resins, epoxy is 0.12eq/100g, and softening temperature is 83 ℃, and nitrogen content is 3wt%, boron-containing quantity 0wt%.
Embodiment 3:
A kind of non-halogen non-phosphorus fire-retardant epoxy resin composition consists of: the composition of Resins, epoxy, fire retarding epoxide resin C, solidifying agent, curing catalyst, fire retarding synergist sees Table 1.
Its preparation method is: Resins, epoxy, fire retarding epoxide resin C, solidifying agent, curing catalyst, fire retarding synergist and other components are carried out pre-mixing by the quality proportioning, and the premixed time is 5～20min, rotating speed 500～1000r/min; Then, melting mixing is extruded, and wherein 70～150 ℃ of extrusion temperatures, forcing machine rotating speed 1500～3000r/min, rate of feeding 900～2400r/min pulverize again, rotating speed 1500～2600r/min, rate of feeding 600～2400r/min can described fire-retardant epoxy resin compositions.
Wherein, the synthetic method of fire retarding epoxide resin C is:
In the 1L four-hole boiling flask of heating jacket, agitator, thermometer, distillation column and prolong is housed, add 522g NPEL127E (South Asia, Taiwan, bisphenol A type epoxy resin, oxirane value 0.5435～0.5682eq/100g),, be warming up to 120 ℃, open vacuum pump, stir 0.5h, close vacuum pump;
Add 43.5gS-dinaphthalene diphenol and 1.13g Ethyltriphenylphosphonium brimide, be warming up to 130～140 ℃, after logical nitrogen mixes, be warming up to 150～180 ℃, reaction 2～4h is cooled to 130～140 ℃;
Adding 66g4-carboxyl phenylo boric acid and 0.2g Ethyltriphenylphosphonium brimide, temperature is transferred to 160～190 ℃, reaction 2～4h reduces to 130～140 ℃;
Adding 65g5,5-diethyl glycolylurea and 0.07g Ethyltriphenylphosphonium brimide transfer between 140～170 ℃ temperature and nitrogen protection, reaction 1～3h; Color becomes light yellow transparent liquid, stopped reaction.
Cooling discharge behind the cooling compressing tablet, can obtain light yellow transparent solid-state fire retarding epoxide resin;
After tested, the oxirane value of this Resins, epoxy is 0.112eq/100g, and softening temperature is 92 ℃, and nitrogen content is 2wt%, boron-containing quantity 0.6wt%.
The proportioning of three example composition components and coating curing rerum natura can be as shown in table 1.
The flame retardant resistance of table 1 epoxy composite set of dispense ratio and coating curing thing
It is as follows that it constitutes components description:
Ordinary epoxy resin is bisphenol A type epoxy resin; Requiring the Resins, epoxy softening temperature is 60～120 ℃, and oxirane value is 0.105～0.225eq/100g, accounts for 10～30 mass parts of total composition.
Make fire retarding epoxide resin by oneself, account for 20～40 mass parts of total composition.
Solidifying agent comprises at least a in organic acid or anhydrides, the phenols curing agent, accounts for 1.5～15 mass parts of total composition.
Curing catalyst comprises any in imidazoles, imidazolines, trialkyl phosphorus, quaternary ammonium salt, quaternary phosphine salt, the organic ureas, accounts for 0.1～0.3 mass parts of total composition.
Fire retarding synergist comprises at least a in aluminium hydroxide, magnesium hydroxide, zinc borate, boric acid titanium, lime borate, Zinc aluminate, oxalic acid aluminium, the melamine cyanurate, accounts for 5～20 mass parts of total composition.
Mineral filler comprises silica flour, zinc borate, aluminium hydroxide, magnesium hydroxide etc.The median size of these mineral fillers because median size hour, causes resin combination viscosity to rise easily, causes its packaging process variation between 1～50 micron; And when median size is big, can causes resin and filler distribution inhomogeneous again, thereby have influence on its physical and mechanical properties.The addition of this mineral filler accounts for 30～50 mass parts of total composition.
Using method of the present invention:
With powder (fire-retardant epoxy resin composition provided by the invention) on electronic devices and components such as the voltage dependent resistor of preheating 20～50min, ceramic condenser immerse in the previously prepared powder in 140～160 ℃ of baking ovens, be put in again and solidify 1～3h in 140～170 ℃ of baking ovens and get final product.
Testing performance index method involved in the present invention is as follows:
(1) melt viscosity: use the Brookfield cone-and-plate viscometer under different temperature, to measure the melt viscosity of phosphorous-containing polyester solidifying agent;
(2) softening temperature: measure according to the method described in the GB12007.6-89 " Resins, epoxy softening point measurement method ring and ball method ";
(3) flame retardant resistance is measured: according to the testing vertical flammability method among the UL94 " the flammable performance test of equipment and device component material ", determine the flame retardant rating of matrix material.Batten size: long 125 ± 5mm, wide 13.0 ± 0.5mm, thickness 1.5 ± 0.2mm;
(4) water-intake rate: test according to GB 1034 described methods.
(5) oxirane value is measured: measure according to the method described in the GB1677-1981 (hydrochloric acid acetone method).
Claims (8)
1. non-halogen non-phosphorus fire-retardant epoxy resin composition is characterized in that: it constitutes component and mass fraction is respectively:
Wherein, fire retarding epoxide resin makes like this:
(1) in the four-hole boiling flask that heating jacket, agitator, thermometer, distillation column and prolong are housed, add a certain amount of liquid-state epoxy resin, be warming up to more than 120 ℃, open vacuum pump, vacuum tightness＜-0.08MPa, stir 0.5h, extract the cut in the liquid epoxies out;
(2) the many rings diphenol that adds in removing the liquid-state epoxy resin of cut/encircle the catalyzer of dicarboxylic acid and catalyzer total amount 85% slowly is warming up to 130～140 ℃, logical simultaneously nitrogen protection more, after treating its thorough mixing, slowly be warming up to 150～180 ℃, reaction 2～4h is cooled to 130～140 ℃;
(3) catalyzer of adding organic boronic and catalyzer total amount 10% simultaneously, transfers to 160～190 ℃ and nitrogen protections with temperature, and reaction 2～4h is cooled to 130～140 ℃;
(4) catalyzer of adding nitrogen-containing heterocycle compound and catalyzer total amount 5% simultaneously, transfers between 140～170 ℃ temperature and nitrogen protection, reaction 1～3h; Color becomes light yellow transparent liquid, stopped reaction;
(5) cooling discharge behind the cooling compressing tablet, can obtain light yellow transparent solid-state fire retarding epoxide resin;
The raw material of described fire retarding epoxide resin constitutes and mass fraction is:
60～80 parts of liquid-state epoxy resins;
0～35 part of dicarboxylic acid of many ring diphenol/encircle more;
0～25 part of organic boronic;
2～23 parts of nitrogen-containing heterocycle compounds;
0.02～0.1 part of catalyzer;
If encircle diphenol/encircle dicarboxylic acid is 0 part more more, omit step (2).
2. non-halogen non-phosphorus fire-retardant epoxy resin composition according to claim 1 is characterized in that: the components description book that relates in the described fire retarding epoxide resin is as follows:
Described liquid-state epoxy resin is a bis-epoxy base fluid attitude Resins, epoxy, and oxirane value is not less than 0.5eq/1OOg, comprises one or more the mixture in Racemic glycidol ether type epoxy, glycidyl ester type epoxy resin, the glycidyl amine type epoxy resin.
Many ring diphenol/encircle dicarboxylic acid comprise naphthalenediol, R-dinaphthalene diphenol, S-dinaphthalene diphenol, '-biphenyl diphenol, biphenyl dicarboxylic acid more;
Organic boronic comprises one or more the mixture in phenylo boric acid, 2-hydroxybenzene boric acid, 3-hydroxybenzene boric acid, 4-hydroxybenzene boric acid, 2-carboxyl phenylo boric acid, 3-carboxyl phenylo boric acid, the 4-carboxyl phenylo boric acid;
Nitrogen-containing heterocycle compound comprises 5,5-dimethyl hydantion, 5-methyl-5-ethylhydantoin, 5, the mixture of one or more in the 5-diethyl glycolylurea;
Catalyzer comprises one or more the mixture in tetramethyl ammonium chloride, benzyl trimethyl ammonium chloride, methyltriphenylphospbromide bromide phosphorus, the Ethyltriphenylphosphonium brimide.
3. non-halogen non-phosphorus fire-retardant epoxy resin composition according to claim 1 is characterized in that: described ordinary epoxy resin, be bisphenol A type epoxy resin, and requiring softening temperature is that 60～120 ℃, oxirane value are 0.105～0.225eq/100g.
4. non-halogen non-phosphorus fire-retardant epoxy resin composition according to claim 1 is characterized in that: described solidifying agent comprises one or more the mixture in organic acid or anhydrides, the phenols curing agent.
5. non-halogen non-phosphorus fire-retardant epoxy resin composition according to claim 1 is characterized in that: described curing catalyst comprises any one in imidazoles, imidazolines, trialkyl phosphorus, quaternary ammonium salt, quaternary phosphine salt, the organic ureas.
6. non-halogen non-phosphorus fire-retardant epoxy resin composition according to claim 1 is characterized in that: described fire retarding synergist comprises one or more the mixture in aluminium hydroxide, magnesium hydroxide, zinc borate, boric acid titanium, lime borate, Zinc aluminate, oxalic acid aluminium, the melamine cyanurate.
7. non-halogen non-phosphorus fire-retardant epoxy resin composition according to claim 1 is characterized in that: described mineral filler comprises one or more the mixture in silica flour, talcum powder, lime carbonate, barium sulfate, the mica powder, and median size is 1～50 μ m.
8. one kind prepares non-halogen non-phosphorus fire-retardant epoxy resin method for compositions as claimed in claim 1, and it is characterized in that: step is:
Described Resins, epoxy, fire retarding epoxide resin, solidifying agent, curing catalyst, fire retarding synergist and mineral filler are carried out pre-mixing by the quality proportioning, and the premixed time is 5～20min, rotating speed 500～1000r/min; After the mixing, melting mixing is extruded, and wherein, 70～150 ℃ of extrusion temperatures, forcing machine rotating speed 1500～3000r/min, rate of feeding 900～2400r/min pulverize again, rotating speed 1500～2600r/min, rate of feeding 600～2400r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101690763A CN102276959B (en) | 2011-06-22 | 2011-06-22 | Halogen-free non-phosphorization flame-retardant epoxy resin composition and preparation method thereof |
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|---|---|---|---|
| CN2011101690763A CN102276959B (en) | 2011-06-22 | 2011-06-22 | Halogen-free non-phosphorization flame-retardant epoxy resin composition and preparation method thereof |
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Cited By (10)
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| CN103435973A (en) * | 2013-09-06 | 2013-12-11 | 苏州生益科技有限公司 | Halogen-free epoxy resin composition as well as prepreg and laminate made from same |
| CN105316936A (en) * | 2014-06-06 | 2016-02-10 | 泉州红瑞兴纺织有限公司 | Flame-retardant finishing agent and use thereof |
| CN105593261A (en) * | 2013-09-30 | 2016-05-18 | 东丽株式会社 | Two-pack epoxy resin composition for fiber-reinforced composite material, and the fiber-reinforced composite material |
| CN107033547A (en) * | 2017-05-12 | 2017-08-11 | 广东博汇新材料科技股份有限公司 | Environmental protection flame retardant composition epoxy resin and its preparation method and application |
| CN108424513A (en) * | 2018-03-30 | 2018-08-21 | 吴天航 | A kind of N-B synergistics high-fire-resistance curing agent and its synthetic method |
| CN108485191A (en) * | 2018-03-30 | 2018-09-04 | 吴先锋 | A kind of composition epoxy resin and preparation method thereof with excellent flame retardancy and durability of fire-retardant |
| CN112409809A (en) * | 2019-08-23 | 2021-02-26 | B/E航空公司 | Flame retardant potting compound for backlight device |
| CN113698737A (en) * | 2021-10-15 | 2021-11-26 | 湖南美莱珀科技发展有限公司 | Flame-retardant material, master batch containing flame-retardant material and preparation method of master batch |
| US11319406B2 (en) * | 2017-11-14 | 2022-05-03 | Eneos Corporation | Prepreg, fiber-reinforced composite material, and molded article |
| CN116789936A (en) * | 2023-07-24 | 2023-09-22 | 大连齐化新材料有限公司 | Production method of 5, 5-dimethyl hydantoin modified bisphenol A type epoxy resin |
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| CN103435973B (en) * | 2013-09-06 | 2016-03-23 | 苏州生益科技有限公司 | A kind of halogen-free epoxy resin composition and the prepreg using it to make and veneer sheet |
| CN103435973A (en) * | 2013-09-06 | 2013-12-11 | 苏州生益科技有限公司 | Halogen-free epoxy resin composition as well as prepreg and laminate made from same |
| CN105593261A (en) * | 2013-09-30 | 2016-05-18 | 东丽株式会社 | Two-pack epoxy resin composition for fiber-reinforced composite material, and the fiber-reinforced composite material |
| CN105316936A (en) * | 2014-06-06 | 2016-02-10 | 泉州红瑞兴纺织有限公司 | Flame-retardant finishing agent and use thereof |
| CN107033547B (en) * | 2017-05-12 | 2019-03-01 | 广东博汇新材料科技股份有限公司 | Environmental protection flame retardant composition epoxy resin and its preparation method and application |
| CN107033547A (en) * | 2017-05-12 | 2017-08-11 | 广东博汇新材料科技股份有限公司 | Environmental protection flame retardant composition epoxy resin and its preparation method and application |
| US11319406B2 (en) * | 2017-11-14 | 2022-05-03 | Eneos Corporation | Prepreg, fiber-reinforced composite material, and molded article |
| CN108485191A (en) * | 2018-03-30 | 2018-09-04 | 吴先锋 | A kind of composition epoxy resin and preparation method thereof with excellent flame retardancy and durability of fire-retardant |
| CN108485191B (en) * | 2018-03-30 | 2020-06-12 | 吴先锋 | Epoxy resin composition with excellent flame retardance and flame retardance durability and preparation method thereof |
| CN108424513A (en) * | 2018-03-30 | 2018-08-21 | 吴天航 | A kind of N-B synergistics high-fire-resistance curing agent and its synthetic method |
| CN112409809A (en) * | 2019-08-23 | 2021-02-26 | B/E航空公司 | Flame retardant potting compound for backlight device |
| CN112409809B (en) * | 2019-08-23 | 2023-06-20 | B/E航空公司 | Flame retardant potting compound for backlight devices |
| CN113698737A (en) * | 2021-10-15 | 2021-11-26 | 湖南美莱珀科技发展有限公司 | Flame-retardant material, master batch containing flame-retardant material and preparation method of master batch |
| CN116789936A (en) * | 2023-07-24 | 2023-09-22 | 大连齐化新材料有限公司 | Production method of 5, 5-dimethyl hydantoin modified bisphenol A type epoxy resin |
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