CN101597308B - Preparation method of hexaaniline cyclotriphosphazene and non-halogen flame retardant epoxy resin composition - Google Patents
Preparation method of hexaaniline cyclotriphosphazene and non-halogen flame retardant epoxy resin composition Download PDFInfo
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- CN101597308B CN101597308B CN2009100867881A CN200910086788A CN101597308B CN 101597308 B CN101597308 B CN 101597308B CN 2009100867881 A CN2009100867881 A CN 2009100867881A CN 200910086788 A CN200910086788 A CN 200910086788A CN 101597308 B CN101597308 B CN 101597308B
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Abstract
The invention discloses a preparation method of hexaaniline cyclotriphosphazene and non-halogen flame retardant epoxy resin composition. The preparation method of hexaaniline cyclotriphosphazene comprises the following steps: adding solvent, hexachlorocyclotriphosphazene, aniline and acid-binding agent into a reaction device, stirring and introducing nitrogen for protection, heating the mixture to 50-120 DEG C, adding catalyst into the reaction device, reacting for 5-16h and cooling to room temperature, filtering, carrying out reduced pressure distillation on the filtrate, carrying out evaporation to remove solvent to obtain brown thick product, placing the product in a drying oven, drying for 8h in vacuum at 40-70 DEG C, crushing to obtain powder product, namely the hexaaniline cyclotriphosphazene. The non-halogen flame retardant epoxy resin composition applied to large-scale and very-large-scale integrated circuits encapsulation is prepared by mixing the prepared hexaaniline cyclotriphosphazene with o-cresol formaldehyde epoxy resin, microsilica, curing catalyst, silane coupling agent, lubricant, flexibilizer and stearic acid, milling, crashing and demagnetizing.
Description
Technical field
The present invention relates to the polymer composite preparation field, particularly relate to the preparation method of a kind of hexaaniline cyclotriphosphazene and halogen-free flame retardant epoxy resin composition.
Background technology
Resins, epoxy has excellent physical and mechanical properties and electric property, has the good ratio of performance to price simultaneously, therefore is widely used as coating, tackiness agent, composite resin matrix, electronic package material etc.Especially Resins, epoxy has been brought into play great effect in electronic component and unicircuit (IC) encapsulation.The present electronic component and the encapsulation of unicircuit more than 95% is to adopt epoxy resin composite material (EMC).Wherein employed matrix resin mainly is an o-cresol formaldehyde epoxy resin, and employed filler is mainly silicon powder.
Development of Packaging Technology trend is at present: encapsulation develops to little, thin, light, high-density direction, and encapsulating structure is developed to the multicore sheet by single-chip, and is developed to the three-dimensional assembling by bidimensional; Packaged material is developed to plastics and matrix material thereof by pottery.Packing forms is developed to QFP (encapsulation of needle-like planar array) and BGA (BGA Package) direction by traditional DIP (dual inline type), and each pin of chip number is more and more, and pin-pitch is more and more littler, and encapsulation process is to the unleaded development of green.Just along with Development of Packaging Technology, epoxy resin encapsulating material has been proposed harsh more requirement, satisfy following a few method and require: high heat-resisting good, high workability, low suction (moisture absorption) property, low line (heat) swelling property, high thermal conductivity and environmental protectionization.
Traditional epoxy resin composite material (EMC) is that interpolation brominated epoxy resin and antimonous oxide realize that it is fire-retardant.Yet brominated epoxy resin can produce toxic gas during burning, and antimonous oxide powder poison is toxic, has caused negative impact for HUMAN HEALTH and environment.So the RoHS of European Union instructs and the WEEE instruction all requires not contain electronic component and unicircuit does not contain bromide.Think the requirement of satisfying the RoHS of European Union instruction and WEEE instruction, developing green halogen-free flameproof is the task of top priority.
Fire-retardant for the halogen-free environmentalization that realizes EMC, many investigators study, mainly are to replace brominated epoxy resin and antimonous oxide by oxyhydroxide (as aluminium hydroxide, magnesium hydroxide) or phosphonium flame retardant (as red phosphorus and phosphoric acid salt etc.).But the flame retardant effect of oxyhydroxide is poor, needs addition big, brings the viscosity of epoxy resin composite material (EMC) to increase and demoulding difficulty thereupon, causes the encapsulation defective.When using red phosphorus or phosphoric acid salt, when packaging component was exposed to hygrothermal environment, the phosphoric acid that is produced can cause the corrosion of plain conductor, reduced its reliability.
Summary of the invention
Embodiment of the present invention provides the preparation method of a kind of hexaaniline cyclotriphosphazene and halogen-free flame retardant epoxy resin composition, makes the composition epoxy resin that hexaaniline cyclotriphosphazene can be used for preparing good flame resistance and modest viscosity.
The present invention is achieved through the following technical solutions:
The embodiment of the invention provides a kind of preparation method of hexaaniline cyclotriphosphazene, comprising:
Organic solvent, hexachlorocyclotriphosphazene, aniline, acid binding agent are added in the reaction unit; stir; feed nitrogen protection; be heated to 50～120 ℃; in reaction unit, add tetrabutyl phosphonium bromide amine catalyzer again; react 5～16 hours postcooling to room temperature; suction filtration; filtrate is carried out underpressure distillation; described organic solvent is removed in evaporation, obtains brown thick product, places in the loft drier; vacuum tightness less than under-0.09MPa the condition after under 40～70 ℃ of temperature dry 8 hours, pulverize and obtain powdered product and be hexaaniline cyclotriphosphazene.
The embodiment of the invention also provides a kind of preparation method of halogen-free flame retardant epoxy resin composition, comprising:
Earlier ball-shaped silicon micro powder is added in the high-speed mixer, add silane coupling agent, after mixing 1 minute under 500～1500 rev/mins the high-speed stirring state, placed 5～10 minutes, under 500～1500 rev/mins high-speed stirring state, mix 1min again, placed 5～10 minutes;
Add other each feed composition, mixed 1～5 minute under 500～1500 rev/mins high-speed stirring state, then mixture is joined melting mixing in the twin screw extruder, melting temperature is 95～100 ℃, mixing time is 3～5 minutes, obtains mixing product after mixing;
Utilize cylinder that the above-mentioned mixing product compacting that makes is cooled to laminar solid, pulverize, sieve, promptly obtain halogen-free flame retardant epoxy resin composition after the demagnetization.
The technical scheme that provides by the invention described above embodiment as can be seen, embodiment of the present invention cooperates by solvent, hexachlorocyclotriphosphazene, aniline, acid binding agent, under nitrogen protection, reaction makes a kind of hexaaniline cyclotriphosphazene.This hexaaniline cyclotriphosphazene mixes with components such as Resins, epoxy and solidifying agent, can prepare the high performance EMC material of environmental protectionization, and flame retardant properties improves greatly, can be used for the encapsulation of large-scale integrated circuit.
Description of drawings
Preparation technology's schema of the composition epoxy resin that Fig. 1 provides for the embodiment of the invention.
Embodiment
For ease of understanding, the invention will be further described below in conjunction with specific embodiment.
Embodiment one
The embodiment of the invention provides a kind of preparation method of hexaaniline cyclotriphosphazene, and this method comprises:
Organic solvent, hexachlorocyclotriphosphazene, aniline, acid binding agent are added in the reaction unit; stir; feed nitrogen (employing purity is not less than 99.9% nitrogen) protection; be heated to 50～120 ℃; in reaction unit, add tetrabutyl phosphonium bromide amine catalyzer again; react 5～16 hours postcooling to room temperature; suction filtration; filtrate is carried out underpressure distillation; described solvent is removed in evaporation, obtains brown thick product, places in the loft drier; after under 40～70 ℃ of temperature dry 8 hours, pulverizing obtains powdered product and is hexaaniline cyclotriphosphazene under vacuum.
The structural formula of the hexaaniline cyclotriphosphazene that makes is:
The above-mentioned mixture for preparing the solvent that uses in the method for hexaaniline cyclotriphosphazene as any or both in tetrahydrofuran (THF), the benzene; The hexachlorocyclotriphosphazene that uses and the mol ratio of aniline are 1: 6, and hexachlorocyclotriphosphazene and aniline can only be that a kind of employing dropping mode adds, and another kind then will adopt direct adding.
The acid binding agent that uses in the aforesaid method is triethylamine, and the add-on of acid binding agent is and the equimolar amount of aniline.
The add-on of the tetrabutyl phosphonium bromide amine catalyzer that uses in the aforesaid method is to account for 0.1%～1% of hexachlorocyclotriphosphazene molar weight, is preferably and accounts for 0.3%～0.6% of hexachlorocyclotriphosphazene molar weight.
The hexaaniline cyclotriphosphazene of present embodiment preparation is a kind of nitrogen flame retardant, can replace present brominated Resins, epoxy, be used for the preparation of composition epoxy resin (EMC) as flame-retardant system, prepared composition epoxy resin (EMC) flame retardant properties improves greatly.This hexaaniline cyclotriphosphazene as the nitrogen flame retardant has the following advantages: (1) toxicity is less, shows by Bioexperiment, and the poison exponent that uses halogenated flame retardant is 5 times of nitrogen flame retardant; (2) flame retarding efficiency height; (3) corrodibility is very little, can discharge HX gas during the halogenide burning, and its corrodibility is very strong, but its corrodibility of gas that nitrogenous compound produces when burning is very little, can not produce big corrosive nature to electric product; (4) heat decomposition temperature is higher, so cause the decomposition of fire retardant at materials processing or the Shi Buhui that is heated; (5) be a kind of environmentally friendly fire retardant material.
Embodiment two
Present embodiment provides a kind of and prepares the method for composition epoxy resin with hexaaniline cyclotriphosphazene, mainly is that the hexaaniline cyclotriphosphazene that utilizes embodiment one to make prepares a kind of halogen-free flame retardant epoxy resin composition, and this method specifically comprises:
The hexaaniline cyclotriphosphazene that the preparation method who utilizes in the foregoing description one is made is with after o-cresol formaldehyde epoxy resin, ball-shaped silicon micro powder, imidazoles curing catalyst, silane coupling agent, toughner and stearic acid or each raw material of wax series lubricant agent mix, through mixing, pulverize, demagnetization promptly makes halogen-free flame retardant epoxy resin composition after handling.Wherein, hexaaniline cyclotriphosphazene and Resins, epoxy, solidifying agent, curing catalyst, silicon powder, lubricant, toughner and stearic quality proportioning are:
O-cresol formaldehyde epoxy resin 10～30 mass parts
Hexaaniline cyclotriphosphazene 1～10 mass parts
Cyanurotriamide modified linear phenolic resin 5～25 mass parts
Ball-shaped silicon micro powder 100～150 mass parts
Silane coupling agent 1～2 mass parts
Imidazoles curing catalyst 0.1～2 mass parts
Toughner 2～10 mass parts
Stearic acid (stearic acid lubricant) 1～5 mass parts.
The imidazoles curing catalyst that uses among the above-mentioned preparation method is glyoxal ethyline, 4-methylimidazole, any in the 2-phenylimidazole; The toughner that uses is in carboxyl end of the liquid acrylonitrile-butadiene rubber (CTBN), terminal hydroxy liquid polybutadiene, the liquid silastic any.
Above-mentioned preparation method's concrete steps are:
Earlier ball-shaped silicon micro powder is added in the high-speed mixer, add silane coupling agent, after mixing 1 minute under 500～1500 rev/mins the high-speed stirring state, placed 5～10 minutes, under 500～1500 rev/mins high-speed stirring state, mix 1min again, placed 5～10 minutes;
Add other each feed composition, mixed 1～5 minute under 500～1500 rev/mins high-speed stirring state, then mixture is joined melting mixing in the twin screw extruder, melting temperature is 95～100 ℃, mixing time is 3～5 minutes, obtains mixing product after mixing;
Utilize cylinder that the above-mentioned mixing product that makes is cooled to laminar solid, pulverize, sieve, promptly obtain halogen-free flame retardant epoxy resin composition after the demagnetization.Concrete technical process can be referring to Fig. 1.
The hexaaniline cyclotriphosphazene that utilizes the embodiment of the invention to make is raw material, can make a kind of composition epoxy resin of halogen-free flameproof, this composition epoxy resin can be used for the large-scale integrated circuit encapsulation, has good flame resistance, flame retarding efficiency height and the good advantage of the feature of environmental protection.
Embodiment three
Present embodiment provides a kind of preparation method of hexaaniline cyclotriphosphazene, specifically comprises the steps:
Get hexachlorocyclotriphosphazene 5g, tetrahydrofuran (THF) 80mL puts into the there-necked flask of 250mL, add triethylamine 12mL, fully stir, reflux, bath temperature is controlled at 75 ℃, slowly drip 8mL aniline and 0.02g four butyl bromation amine mixing solutions, behind the reaction 13h, be cooled to room temperature, obtain pale yellow solution, pale yellow solution is carried out air distillation with the vacuum pump suction filtration, remove and desolvate, obtain brown dope, this material is placed in the vacuum drying oven (vacuum tightness less than-0.09MPa), in 60 ℃ down behind the dry 8h, pulverizing makes the brown ceramic powder product and is hexaaniline cyclotriphosphazene, yield 80.2%.
Embodiment four
Present embodiment provides a kind of and prepares the method for composition epoxy resin with hexaaniline cyclotriphosphazene, specifically comprises the steps:
Get 8mL aniline, tetrahydrofuran (THF) 80mL puts into the there-necked flask of 250mL, add triethylamine 12mL, and adding 0.02g four butyl bromation amine, fully stir, reflux, bath temperature is controlled at 75 ℃, gets hexachlorocyclotriphosphazene 5g and is dissolved in the 20ml tetrahydrofuran (THF), slowly is added drop-wise in the reactor, behind the reaction 8h, be cooled to room temperature, obtain pale yellow solution, pale yellow solution is carried out air distillation with the vacuum pump suction filtration, remove and desolvate, obtain brown dope, this material is placed in the vacuum drying oven (vacuum tightness less than-0.09MPa), in 60 ℃ down behind the dry 8h, pulverizing makes the brown ceramic powder product and is hexaaniline cyclotriphosphazene, yield 88.5%.
Embodiment five～six and comparative example
Present embodiment the five, the 6th, the hexaaniline cyclotriphosphazene that utilizes the foregoing description to make prepares halogen-free flame retardant epoxy resin composition, and the comparative example be with brominated epoxy resin preparation the halogen fire retarded epoxy resin composition arranged, specifically get the raw material of each embodiment by the prescription of following table 1:
Table 1 embodiment five-six and comparative example's composition epoxy resin (EMC) prescription
The preparation method of composition epoxy resin: carry out successively surface treatment, the component of ball-shaped silicon micro powder mixing, melting mixing, cooling, pulverize, be pressed into material cake, packing, cryopreservation operation.
Wherein the surface treatment of ball-shaped silicon micro powder adopts the silane coupling agent of dilution to be sprayed on the silicon powder, simultaneously in high-speed mixer, carry out high-speed mixing, left standstill then 2～5 minutes, carry out said process again, carry out so repeatedly 3～5 times, improve the surface treatment effect of silicon powder so greatly.Adopt the twin screw extruder melting mixing, also can adopt two roller mill melting mixing, Fig. 1 is seen in concrete technical process, and performance sees Table 2.
Adopt following method that the composition epoxy resin performance that the embodiment of the invention makes is tested:
Volume specific resistance: test by GB/T 1410-2006.
Gelation time: carry out according to electron trade standard SJ/P11197-1999 standard.
Bending property: carry out according to GB/T 9341-2000 standard.
Impact property: carry out according to the GB/T1043-1993 standard.
Heat-drawn wire: carry out according to the GB/T1634-1979 standard.
Water-intake rate: place 100 ℃ of deionization boiling water to boil 24h disk, the weight after the test suction can calculate the water-intake rate of moulding compound.
Thermal conductivity: at first use dsc measurement material specific heat, measure thermal diffusivity, calculation of thermal conductivity then with the anti-company's laser heat conducting instrument of speeding;
Thermal expansivity: heat machinery (TMA) method, probe temperature: 25～300 ℃, temperature rise rate: 5 ℃/min.
Flame retardant resistance: the vertical combustion performance, test the thick batten of 3.2mm by UL-94 vertical combustion standard.
Oxygen index test: undertaken by the GB/T2406 standard.
The performance of the halogen-free flame retardant epoxy resin composition of table 2 large-scale integrated circuit encapsulation usefulness
As can be seen from Table 2, adopt hexaaniline cyclotriphosphazene (HPACTPZ) to carry out fire-retardant to EMC, its oxygen index of composition epoxy resin EMC after the curing reaches 35.8, be higher than traditional bromine and be flame-retardant system (oxygen index 28.0) (composition epoxy resin that makes referring to the comparative example), this shows that hexaaniline cyclotriphosphazene (HPACTPZ) has flame retardant resistance preferably to formed matrix material behind the epoxy resin cure, its fire retardant mechanism is P, the N synergy, system can be because the thermolysis effect makes the incombustible volatile matter (CO2 of material production after catching fire, oxynitrides etc.), the stable foam layer of very fast formation on the incendiary surface.Simultaneously, because hexaaniline cyclotriphosphazene (HPACTPZ) contains a large amount of phenyl ring, the charring rate that therefore burns is higher, excellent in flame retardance.It can also be seen that from table 2, has short gelation time through fire-retardant composition epoxy resin (EMC) material of hexaaniline cyclotriphosphazene (HPACTPZ), higher heat-drawn wire, Tg, flexural strength, modulus in flexure and volume specific resistance, show that hexaaniline cyclotriphosphazene (HPACTPZ) has promoted the curing reaction of Resins, epoxy, curing speed is accelerated, and degree of crosslinking is bigger.This mainly is because HPACTPZ contains more-NH group, promoted the curing reaction of Resins, epoxy greatly, this is for the preparation fast setting and without male offspring solidified composition epoxy resin (EMC) material is extremely beneficial, and this based epoxy resin composition (EMC) the novel large-scale technique of integrated circuit packaging is desired just.
In sum, the epoxy compounds of embodiment of the invention preparation has high glass transition, has improved thermotolerance.Hexaaniline cyclotriphosphazene (HPACTPZ) has the excellent fire retardant effect to Resins, epoxy, prepared composition epoxy resin (EMC) can reach UL-94V0 level flame retardant properties, its oxygen index reaches 35.8, flame retardant properties is better than traditional brominated flame-retardant system greatly, hexaaniline cyclotriphosphazene (HPACTPZ) has been accelerated the curing reaction of Resins, epoxy simultaneously, can be used for preparing the encapsulation of fast setting and solidified large-scale integrated circuit without issue and use EMC, be particularly suitable for halogen-free flame retardant epoxy resin composition extensive and super large-scale integration encapsulation usefulness.
The above; only be the preferable embodiment of the present invention; but protection scope of the present invention is not limited thereto; the present invention is not caused any restriction because of the precedence of each embodiment yet; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (7)
1. the preparation method of a hexaaniline cyclotriphosphazene is characterized in that, comprising:
Organic solvent, hexachlorocyclotriphosphazene, aniline, acid binding agent are added in the reaction unit; stir; feed nitrogen protection; be heated to 50～120 ℃; in reaction unit, add the Tetrabutyl amonium bromide catalyzer again; react 5～16 hours postcooling to room temperature; suction filtration; filtrate is carried out underpressure distillation; described organic solvent is removed in evaporation, obtains brown thick product, places in the loft drier; vacuum tightness less than under-0.09MPa the condition after under 40～70 ℃ of temperature dry 8 hours, pulverize and obtain powdered product and be hexaaniline cyclotriphosphazene.
2. the preparation method of hexaaniline cyclotriphosphazene according to claim 1 is characterized in that, the organic solvent that adopts in the described method is the mixture of any or both in tetrahydrofuran (THF), the benzene.
3. the preparation method of hexaaniline cyclotriphosphazene according to claim 1 is characterized in that, the hexachlorocyclotriphosphazene that uses in the described method and the mol ratio of aniline are 1: 6.
4. the preparation method of hexaaniline cyclotriphosphazene according to claim 1 is characterized in that, a kind of employing dropping mode in hexachlorocyclotriphosphazene that uses in the described method and the aniline adds, and another kind directly adds.
5. the preparation method of hexaaniline cyclotriphosphazene according to claim 1 is characterized in that, the acid binding agent that uses in the described method is triethylamine, and the add-on of acid binding agent is and the equimolar amount of aniline.
6. the preparation method of hexaaniline cyclotriphosphazene according to claim 1 is characterized in that, the add-on of the Tetrabutyl amonium bromide catalyzer that uses in the described method is 0.1%～1% of the molar weight of hexachlorocyclotriphosphazene.
7. the preparation method of hexaaniline cyclotriphosphazene according to claim 1 is characterized in that, the add-on of the Tetrabutyl amonium bromide catalyzer that uses in the described method is 0.3%～0.6% of the molar weight of hexachlorocyclotriphosphazene.
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Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130103307A (en) | 2010-04-30 | 2013-09-23 | 다우 글로벌 테크놀로지스 엘엘씨 | Phosphazene blocked azole compounds as latent catalysts for epoxy resins |
| CN102134376B (en) * | 2010-12-29 | 2012-12-05 | 四川东材科技集团股份有限公司 | Halogen-free flame-retardant resin composition and preparation method of prepreg and laminated plate |
| CN102746615B (en) * | 2011-04-21 | 2016-10-05 | 咸阳天华电子科技有限公司 | High heat resistant type height insulating heat-conductive aluminum-based copper-clad plate glue composition and preparation technology |
| CN102250147B (en) * | 2011-05-17 | 2014-04-30 | 北京理工大学 | Preparation method and application of cyclotriphosphazene containing silicon functional groups |
| CN103554657B (en) * | 2013-10-18 | 2016-01-20 | 浙江工业大学之江学院工业研究院 | A kind of Halogen-free flame-retardant polypropylene composite cable material and preparation method thereof |
| CN104650147B (en) * | 2014-07-30 | 2016-06-22 | 青岛科技大学 | A kind of synthetic method of hexaaniline cyclotriphosphazene |
| CN104926882B (en) * | 2015-05-15 | 2018-06-05 | 湘潭大学 | A kind of fire retardant based on three phosphonitrile of naphthylamines basic ring and preparation method thereof |
| CN104927308A (en) * | 2015-06-30 | 2015-09-23 | 江南大学 | Epoxy resin toughening agent based on cyclotriphosphazene six-arm star polymer and preparation method for epoxy resin toughening agent |
| CN107344951B (en) * | 2016-05-04 | 2019-02-19 | 青岛科技大学 | Phenyl modified poly- three phosphonitrile of amino ring and preparation method thereof |
| CN106398109B (en) * | 2016-10-07 | 2018-08-10 | 河南工业大学 | A kind of preparation method that three phosphonitrile of ring is phenolic resin cured |
| CN109734749A (en) * | 2018-12-10 | 2019-05-10 | 苏州科技大学 | Five phenoxy group cyclotrinitrile phosphide of reactive flame retardant allyloxy and preparation method thereof |
| CN109575082A (en) * | 2018-12-10 | 2019-04-05 | 苏州科技大学 | Reactive flame retardant allyl amido pentaphene amido cyclotrinitrile phosphide and preparation method thereof |
| CN109438755A (en) * | 2018-12-10 | 2019-03-08 | 苏州科技大学 | Five anilino- cyclotrinitrile phosphide of reactive flame retardant allyloxy and preparation method thereof |
| CN109651439A (en) * | 2018-12-10 | 2019-04-19 | 苏州科技大学 | Five alkoxycyclotriphosphderivative compound of reactive flame retardant allyl amido and preparation method thereof |
| CN109651441A (en) * | 2018-12-10 | 2019-04-19 | 苏州科技大学 | Five alkoxycyclotriphosphderivative compound of reactive flame retardant allyloxy and preparation method thereof |
| CN109734748A (en) * | 2018-12-10 | 2019-05-10 | 苏州科技大学 | Reactive flame retardant allyl amido pentaphene oxygroup cyclotrinitrile phosphide and preparation method thereof |
| CN109666183A (en) * | 2018-12-14 | 2019-04-23 | 航天科工武汉磁电有限责任公司 | Siliceous three phosphonitrile of ring, preparation method and application |
| CN111349310A (en) * | 2018-12-22 | 2020-06-30 | 浙江林境环保包装有限公司 | Powdery halogen-free flame-retardant epoxy resin composition, preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012243A (en) * | 2007-01-26 | 2007-08-08 | 华中科技大学 | Cyclophosphaxene compound as photosensitivity flame-proof material and synthetic method thereof |
| CN101029165A (en) * | 2006-03-01 | 2007-09-05 | 广东榕泰实业股份有限公司 | Epoxy-resin mould plastic for packing IC circuit and its production |
-
2009
- 2009-06-30 CN CN2009100867881A patent/CN101597308B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029165A (en) * | 2006-03-01 | 2007-09-05 | 广东榕泰实业股份有限公司 | Epoxy-resin mould plastic for packing IC circuit and its production |
| CN101012243A (en) * | 2007-01-26 | 2007-08-08 | 华中科技大学 | Cyclophosphaxene compound as photosensitivity flame-proof material and synthetic method thereof |
Non-Patent Citations (3)
| Title |
|---|
| J.F.Bickley et al..Supramolecular variations on a molecular theme: the structural diversity of phosphazenes (RNH)6P3N3 in the solid state.《Dalton Trans.》.2003,1235-1244. * |
| 孙德等.新型无卤阻燃剂六苯胺基环三磷腈的合成.《中国氯碱》.2007,(第12期),9-10和42. * |
| 杨明山等.集成电路封装用环氧树脂模塑料性能影响因素研究.《塑料工业》.2007,第35卷(第2期),5-9和16. * |
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