CN110628179A - Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof - Google Patents
Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof Download PDFInfo
- Publication number
- CN110628179A CN110628179A CN201910820938.0A CN201910820938A CN110628179A CN 110628179 A CN110628179 A CN 110628179A CN 201910820938 A CN201910820938 A CN 201910820938A CN 110628179 A CN110628179 A CN 110628179A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- packaging material
- electronic packaging
- fluorine
- phosphorus
- 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.)
- Granted
Links
Classifications
-
- 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
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- 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
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
-
- 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
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a low dielectric constant flame-retardant electronic packaging material and a preparation method thereof, wherein the low dielectric constant flame-retardant electronic packaging material comprises 50-99 wt% of a high molecular matrix and 1-50 wt% of a phosphorus-fluorine-containing flame retardant. The low-dielectric-constant flame-retardant electronic packaging material contains two flame-retardant elements of phosphorus and fluorine, wherein the phosphorus element can play a role in gas-phase flame retardance and condensed-phase flame retardance so as to promote the system to be catalyzed into charcoal; the introduction of fluorine can improve the thermal stability of the material; the two elements are mutually cooperated, so that the thermal stability and the flame retardant property of the material can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of flame-retardant organic materials, and particularly relates to a low-dielectric-constant flame-retardant electronic packaging material and a preparation method thereof.
Background
High molecular materials such as epoxy resin, Polycarbonate (PC) and acrylonitrile-butadiene-styrene terpolymer (ABS) are widely used in the field of electronic packaging due to their advantages of high transparency, good dimensional stability, excellent dielectric properties, good electrical insulation, etc. However, with the rapid development of electronic products, the processing and transmission of digital information gradually progress to higher frequency and higher speed, and the dielectric properties of the electronic packaging material polymer material have been more demanding, and it is a necessary trend to meet the development of the electronic packaging material to further reduce the dielectric constant and dielectric loss of the material. The introduction of fluorine into the material is an important means for preparing the low dielectric constant material, the electron cloud density of fluorine atoms is high, the polarizability is low, the volume of the fluorine is large, the stacking density of the polymer can be reduced, the free volume of the polymer is increased, the dielectric constant of the polymer material is reduced, the carbon-fluorine bond has high binding energy, and the heat resistance of the polymer can be effectively improved by the introduction of the fluorine-containing compound. The high polymer material generally has the characteristic of flammability, and has fire hazard in application, so that the flame retardance of the material is also indispensable in the application of the electronic packaging field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a low-dielectric-constant flame-retardant electronic packaging material.
The invention also aims to provide a preparation method of the low-dielectric-constant flame-retardant electronic packaging material.
The technical scheme of the invention is as follows:
a low-dielectric-constant flame-retardant electronic packaging material comprises 50-99 wt% of a polymer matrix and 1-50 wt% of a phosphorus-fluorine-containing flame retardant, wherein the polymer matrix comprises epoxy resin, polycarbonate and acrylonitrile-butadiene-styrene terpolymer, and the structural formula of the phosphorus-fluorine-containing flame retardant is shown in the specification
In a preferred embodiment of the present invention, the phosphorus-fluorine containing flame retardant is synthesized by the following route:
further preferably, the preparation method of the phosphorus-fluorine-containing flame retardant comprises the following steps:
(1) sequentially adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3, 5-bis (trifluoromethyl) benzyl alcohol, a first solvent and a second solvent into a reaction container, slowly dripping triethylamine into the reaction container by using a constant-pressure dropping funnel under the stirring of an ice bath, and reacting at room temperature for 5-24 hours after dripping is finished; the first solvent is tetrahydrofuran, dichloromethane or toluene, the second solvent is carbon tetrachloride or chloroform, and the first solvent and the second solvent are different from each other;
(2) extracting the material obtained in the step (1) by using water, drying an organic layer by using anhydrous magnesium sulfate, and filtering to obtain a filtrate;
(3) and (3) carrying out rotary evaporation on the filtrate to remove the first solvent and the second solvent, and fully drying the obtained white solid in vacuum to obtain the phosphorus-fluorine-containing flame retardant.
Still more preferably, the first solvent is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3, 5-bis (trifluoromethyl) benzyl alcohol and triethylamine in a molar ratio of 1: 0.1-10.
Still more preferably, the mass ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the first solvent to the second solvent is 1: 1 to 200.
In one of the preparation methods of the low-dielectric constant flame-retardant electronic packaging material, the polymer matrix is epoxy resin, and the preparation method specifically comprises the following steps: weighing 50-99 wt% of epoxy resin prepolymer, 1-50 wt% of phosphorus-fluorine-containing flame retardant and 5-15 wt% of 4, 4' -diaminodiphenylmethane (DDM); heating the epoxy resin prepolymer to 60-140 ℃, adding a phosphorus-fluorine-containing flame retardant, stirring until the mixture is transparent, adding 4, 4' -diaminodiphenylmethane, stirring until the mixture is completely dissolved, pouring the mixture into a mold, and carrying out temperature programming for curing to obtain the low-dielectric-constant flame-retardant electronic packaging material; wherein the temperature programming comprises: 115-125 ℃ curing for 3-5h, 135-145 ℃ curing for 1-3h, and 170-185 ℃ curing for 1-3 h.
In a preferred embodiment of the present invention, the epoxy resin prepolymer is an E51 bisphenol a type epoxy resin.
In a preferred embodiment of the present invention, the mass ratio of the epoxy resin prepolymer to the 4, 4' -diaminodiphenylmethane is 8: 2.02.
In a preferred embodiment of the present invention, the temperature programming is: curing at 120 ℃ for 4h, at 140 ℃ for 2h and at 180 ℃ for 2 h.
In the second preparation method of the low-dielectric constant flame-retardant electronic packaging material, the polymer matrix is polycarbonate or acrylonitrile-butadiene-styrene terpolymer, and the method specifically comprises the following steps: and adding a phosphorus-fluorine-containing flame retardant into the dried master batch of the high polymer matrix, mixing and extruding by using a double-screw extruder, and further granulating and drying to obtain the low-dielectric-constant flame-retardant electronic packaging material.
The invention has the beneficial effects that:
1. the low-dielectric-constant flame-retardant electronic packaging material contains two flame-retardant elements of phosphorus and fluorine, wherein the phosphorus element can play a role in gas-phase flame retardance and condensed-phase flame retardance so as to promote the system to be catalyzed into charcoal; the introduction of fluorine can improve the thermal stability of the material; the two elements are mutually cooperated, so that the thermal stability and the flame retardant property of the material can be effectively improved.
2. The phosphorus-fluorine-containing flame retardant is a multi-benzene ring structure flame retardant, and compared with the similar fat-type phosphorus-fluorine-containing flame retardant, the phosphorus-fluorine-containing flame retardant has the advantages of better thermal stability, difficult decomposition, higher char formation rate and further synergy on the thermal stability and flame retardant property of a system.
3. One end of the molecular structure of the phosphorus-fluorine-containing flame retardant contains DOPO, and the DOPO has good solubility in a polymer matrix, so that the compatibility of the flame retardant and the polymer matrix can be improved, and the prepared flame-retardant electronic packaging material can keep good transparency and mechanical properties.
4. The low dielectric constant flame-retardant electronic packaging material of the invention introduces fluorine element in the system, fluorine is a special element, and the low dielectric constant flame-retardant electronic packaging material has the characteristics of low polarizability, large molecular volume and high binding energy of carbon-fluorine bonds, so that the fluorine element can reduce the dielectric constant and dielectric loss of the material, and expand and enhance the application and competitiveness of high molecular materials in the field of electronic packaging.
Drawings
FIG. 1 shows an infrared absorption spectrum of a low-k flame retardant electronic packaging material prepared in example 1 of the present invention.
FIG. 2 is an appearance diagram of a pure epoxy resin (left) and a low dielectric constant flame retardant electronic packaging material prepared in example 1.
FIG. 3 is a graph of carbon layers of pure epoxy resin (left) and the low dielectric constant flame retardant electronic packaging material prepared in example 5 after cone calorimeter testing.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
(1) Adding 2g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3.16g of 3, 5-bis (trifluoromethyl) benzyl alcohol, 15mL of dichloromethane and 15mL of carbon tetrachloride into a reaction bottle in sequence, slowly dripping triethylamine into the reaction bottle by using a constant-pressure dropping funnel under the stirring of an ice bath, reacting at room temperature for 12 hours after dripping is finished, extracting the obtained solution for 3 times by using water, drying and filtering an organic layer by using anhydrous magnesium sulfate, removing the solvent by rotary evaporation of the filtrate, placing the obtained white solid into a vacuum drying box, and drying at 60 ℃ for 24 hours to obtain the phosphorus and fluorine containing flame retardant.
(2) Weighing E51 bisphenol A epoxy resin prepolymer, heating to 90 ℃, adding 1 wt% of phosphorus-fluorine-containing flame retardant, stirring until the mixture is transparent, adding curing agent 4, 4 '-diaminodiphenylmethane (DDM) in proportion, stirring until the mixture is completely dissolved (the mass ratio of the E51 bisphenol A epoxy resin prepolymer to the 4, 4' -diaminodiphenylmethane is 8: 2.02), pouring the mixture into an aluminum mold, and heating by a program to cure the mixture to obtain the low-dielectric-constant flame-retardant electronic packaging material; the temperature programming is as follows: curing at 120 ℃ for 4h, at 140 ℃ for 2h and at 180 ℃ for 2 h.
FIG. 2 is an appearance of pure epoxy (left) and the low-k flame retardant electronic packaging material prepared in this example, wherein it can be seen that the epoxy resin still maintains better transparency after the flame retardant is added.
The oxygen index value of the low dielectric constant flame-retardant electronic packaging material measured by an oxygen index tester is 28.8% (26.0% of pure epoxy), and the dielectric constant of the low dielectric constant flame-retardant electronic packaging material measured by an LCR tester at 200MHz is 6.3 (6.6% of pure epoxy) and the dielectric loss is 0.0275 (0.0295% of pure epoxy).
Example 2
(1) Adding 3.36g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3.16g of 3, 5-bis (trifluoromethyl) benzyl alcohol, 15mL of dichloromethane and 15mL of carbon tetrachloride into a reaction bottle in sequence, slowly dripping triethylamine into the reaction bottle by using a constant-pressure dropping funnel under the stirring of an ice bath, reacting at room temperature for 12h after dripping is finished, extracting the obtained solution for 3 times by using water, taking an organic layer, drying and filtering the organic layer by using anhydrous magnesium sulfate, removing the solvent by rotary evaporation of the filtrate, placing the obtained white solid into a vacuum drying oven, and drying for 24h at 60 ℃ to obtain the phosphorus and fluorine containing flame retardant.
(2) Weighing the dried PC master batch, adding 1 wt% of phosphorus-fluorine-containing flame retardant, mixing and extruding by using a double-screw extruder, further granulating and drying, and preparing the standard sample strip of the low-dielectric-constant flame-retardant electronic packaging material by using an injection molding machine.
The oxygen index value of the standard bar was measured to be 28.4% (25.0% for pure polycarbonate) using an oxygen index tester, and the dielectric constant at 200MHz of the standard bar was 4.6 (4.8 for pure polycarbonate) and the dielectric loss was 0.0154 (0.0189 for pure polycarbonate) using an LCR tester.
Example 3
(1) Adding 2g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3.16g of 3, 5-bis (trifluoromethyl) benzyl alcohol, 15mL of dichloromethane and 15mL of carbon tetrachloride into a reaction bottle in sequence, slowly dripping triethylamine into the reaction bottle by using a constant-pressure dropping funnel under the stirring of an ice bath, reacting at room temperature for 18h after dripping is finished, extracting the obtained solution for 3 times by using water, drying and filtering an organic layer by using anhydrous magnesium sulfate, removing the solvent by rotary evaporation of the filtrate, placing the obtained white solid in a vacuum drying box, and drying at 60 ℃ for 24h to obtain the phosphorus and fluorine containing flame retardant.
(2) Weighing the dried ABS master batch, adding 1 wt% of phosphorus-fluorine-containing flame retardant, mixing and extruding by using a double-screw extruder, further granulating and drying, and preparing the standard sample strip of the low-dielectric-constant flame-retardant electronic packaging material by using an injection molding machine.
The oxygen index value of the standard specimen was 21.5% (18.0% for pure ABS) by using an oxygen index tester, the dielectric constant at 200MHz of the standard specimen was 2.6 (2.7 for pure ABS) by using an LCR tester, and the dielectric loss was 0.0115 (0.0121 for pure ABS).
Example 4
(1) Adding 2g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3.16g of 3, 5-bis (trifluoromethyl) benzyl alcohol, 15mL of dichloromethane and 15mL of carbon tetrachloride into a reaction bottle in sequence, slowly dripping triethylamine into the reaction bottle by using a constant-pressure dropping funnel under the stirring of an ice bath, reacting at room temperature for 12 hours after dripping is finished, extracting the obtained solution for 3 times by using water, drying and filtering an organic layer by using anhydrous magnesium sulfate, removing the solvent by rotary evaporation of the filtrate, placing the obtained white solid into a vacuum drying box, and drying at 60 ℃ for 24 hours to obtain the phosphorus and fluorine containing flame retardant.
(2) Weighing E51 bisphenol A epoxy resin prepolymer, heating to 90 ℃, adding 5 wt% of phosphorus-fluorine-containing flame retardant, stirring until the mixture is transparent, adding curing agent 4, 4 '-diaminodiphenylmethane (DDM) in proportion, stirring until the mixture is completely dissolved (the mass ratio of the E51 bisphenol A epoxy resin prepolymer to the 4, 4' -diaminodiphenylmethane is 8: 2.02), pouring the mixture into an aluminum mold, and heating by a program to cure the mixture to obtain the low-dielectric-constant flame-retardant electronic packaging material; the temperature programming is as follows: curing at 120 ℃ for 4h, at 140 ℃ for 2h and at 180 ℃ for 2 h.
The oxygen index value of the low dielectric constant flame-retardant electronic packaging material measured by an oxygen index tester is 35.1% (26.0% of pure epoxy), and the dielectric constant of the low dielectric constant flame-retardant electronic packaging material at 200MHz measured by an LCR tester is 5.8 (6.6% of pure epoxy) and the dielectric loss is 0.0253 (0.0295% of pure epoxy).
Example 5
(1) Adding 2g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3.16g of 3, 5-bis (trifluoromethyl) benzyl alcohol, 15mL of dichloromethane and 15mL of carbon tetrachloride into a reaction bottle in sequence, slowly dripping triethylamine into the reaction bottle by using a constant-pressure dropping funnel under the stirring of an ice bath, reacting at room temperature for 12 hours after dripping is finished, extracting the obtained solution for 3 times by using water, drying and filtering an organic layer by using anhydrous magnesium sulfate, removing the solvent by rotary evaporation of the filtrate, placing the obtained white solid into a vacuum drying box, and drying at 60 ℃ for 24 hours to obtain the phosphorus and fluorine containing flame retardant.
(2) Weighing E51 bisphenol A epoxy resin prepolymer, heating to 90 ℃, adding 10 wt% of phosphorus-fluorine-containing flame retardant, stirring until the mixture is transparent, adding curing agent 4, 4 '-diaminodiphenylmethane (DDM) in proportion, stirring until the mixture is completely dissolved (the mass ratio of the E51 bisphenol A epoxy resin prepolymer to the 4, 4' -diaminodiphenylmethane is 8: 2.02), pouring the mixture into an aluminum mold, and heating by a program to cure the mixture to obtain the low-dielectric-constant flame-retardant electronic packaging material; the temperature programming is as follows: curing at 120 ℃ for 4h, at 140 ℃ for 2h and at 180 ℃ for 2 h.
The oxygen index value of the low dielectric constant flame retardant electronic packaging material measured by an oxygen index tester is 35.1% (37.0% for pure epoxy), and the dielectric constant of the low dielectric constant flame retardant electronic packaging material at 200MHz measured by an LCR tester is 5.6 (6.6 for pure epoxy) and the dielectric loss is 0.0245 (0.0295 for pure epoxy).
Fig. 3 is an appearance diagram of a carbon layer of a pure epoxy (left) and a low-dielectric-constant flame-retardant electronic packaging material (right) prepared in this example after a cone calorimeter test, and it can be seen from the figure that the carbon layer of the low-dielectric-constant flame-retardant electronic packaging material prepared in this example has obvious expansion after combustion, because the design of the polyphenyl ring structure in the phosphorus and fluorine-containing flame retardant enables the material to form a compact carbon layer during combustion, and simultaneously, the intumescent carbon layer is formed under the combined action of gas-phase flame retardance and condensed-phase flame retardance of the phosphorus and fluorine-containing flame retardant.
Example 6
(1) Adding 2g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3.16g of 3, 5-bis (trifluoromethyl) benzyl alcohol, 15mL of toluene and 15mL of trichloromethane into a reaction bottle in sequence, slowly dripping triethylamine into the reaction bottle by using a constant-pressure dropping funnel under the stirring of an ice bath, reacting at room temperature for 12h after dripping is finished, extracting the obtained solution for 3 times by using water, taking an organic layer, drying and filtering the organic layer by using anhydrous magnesium sulfate, removing the solvent by rotary evaporation of the filtrate, placing the obtained white solid into a vacuum drying oven, and drying at 60 ℃ for 24h to obtain the phosphorus and fluorine containing flame retardant.
(2) Weighing E51 bisphenol A epoxy resin prepolymer, heating to 90 ℃, adding 1 wt% of phosphorus-fluorine-containing flame retardant, stirring until the mixture is transparent, adding curing agent 4, 4 '-diaminodiphenylmethane (DDM) in proportion, stirring until the mixture is completely dissolved (the mass ratio of the E51 bisphenol A epoxy resin prepolymer to the 4, 4' -diaminodiphenylmethane is 8: 2.02), pouring the mixture into an aluminum mold, and heating by a program to cure the mixture to obtain the low-dielectric-constant flame-retardant electronic packaging material; the temperature programming is as follows: curing at 120 ℃ for 4h, at 140 ℃ for 2h and at 180 ℃ for 2 h.
The oxygen index value of the low dielectric constant flame-retardant electronic packaging material measured by an oxygen index tester is 28.8% (26.0% of pure epoxy), and the dielectric constant of the low dielectric constant flame-retardant electronic packaging material measured by an LCR tester at 200MHz is 6.3 (6.6% of pure epoxy) and the dielectric loss is 0.0275 (0.0295% of pure epoxy).
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A low-dielectric-constant flame-retardant electronic packaging material is characterized in that: comprises 50-99 wt% of a polymer matrix and 1-50 wt% of a phosphorus-fluorine-containing flame retardant, wherein the polymer matrix comprises epoxy resin, polycarbonate and acrylonitrile-butadiene-styrene terpolymer, and the structural formula of the phosphorus-fluorine-containing flame retardant is shown in the specification
2. The low dielectric constant flame retardant electronic packaging material of claim 1, wherein: the synthetic route of the phosphorus-fluorine-containing flame retardant is as follows:
3. the low dielectric constant flame retardant electronic packaging material of claim 2, wherein: the preparation method of the phosphorus-fluorine-containing flame retardant comprises the following steps:
(1) sequentially adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3, 5-bis (trifluoromethyl) benzyl alcohol, a first solvent and a second solvent into a reaction container, slowly dripping triethylamine into the reaction container by using a constant-pressure dropping funnel under the stirring of an ice bath, and reacting at room temperature for 5-24 hours after dripping is finished; the first solvent is tetrahydrofuran, dichloromethane or toluene, the second solvent is carbon tetrachloride or chloroform, and the first solvent and the second solvent are different from each other;
(2) extracting the material obtained in the step (1) by using water, drying an organic layer by using anhydrous magnesium sulfate, and filtering to obtain a filtrate;
(3) and (3) carrying out rotary evaporation on the filtrate to remove the first solvent and the second solvent, and fully drying the obtained white solid in vacuum to obtain the phosphorus-fluorine-containing flame retardant.
4. The low dielectric constant flame retardant electronic packaging material of claim 3, wherein: the first solvent is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3, 5-bis (trifluoromethyl) benzyl alcohol and triethylamine with the molar ratio of 1: 0.1-10.
5. The low dielectric constant flame retardant electronic packaging material of claim 3, wherein: the mass ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the first solvent to the second solvent is 1: 1-200.
6. The method for preparing a low dielectric constant flame retardant electronic packaging material of any one of claims 1 to 5, wherein: the polymer matrix is epoxy resin, and specifically comprises: weighing 50-99 wt% of epoxy resin prepolymer, 1-50 wt% of phosphorus-fluorine-containing flame retardant and 5-15 wt% of 4, 4' -diaminodiphenylmethane (DDM); heating the epoxy resin prepolymer to 60-140 ℃, adding a phosphorus-fluorine-containing flame retardant, stirring until the mixture is transparent, adding 4, 4' -diaminodiphenylmethane, stirring until the mixture is completely dissolved, pouring the mixture into a mold, and carrying out temperature programming for curing to obtain the low-dielectric-constant flame-retardant electronic packaging material; wherein the temperature programming comprises: 115-125 ℃ curing for 3-5h, 135-145 ℃ curing for 1-3h, and 170-185 ℃ curing for 1-3 h.
7. The method of claim 6, wherein: the epoxy resin prepolymer is E51 bisphenol A epoxy resin.
8. The production method according to claim 6 or 7, characterized in that: the mass ratio of the epoxy resin prepolymer to the 4, 4' -diaminodiphenylmethane is 8: 2.02.
9. The production method according to claim 6 or 7, characterized in that: the temperature programming is as follows: curing at 120 ℃ for 4h, at 140 ℃ for 2h and at 180 ℃ for 2 h.
10. The method for preparing a low dielectric constant flame retardant electronic packaging material of any one of claims 1 to 5, wherein: the polymer matrix is polycarbonate or acrylonitrile-butadiene-styrene terpolymer, and specifically comprises the following components: and adding a phosphorus-fluorine-containing flame retardant into the dried master batch of the high polymer matrix, mixing and extruding by using a double-screw extruder, and further granulating and drying to obtain the low-dielectric-constant flame-retardant electronic packaging material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910820938.0A CN110628179B (en) | 2019-08-30 | 2019-08-30 | Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910820938.0A CN110628179B (en) | 2019-08-30 | 2019-08-30 | Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110628179A true CN110628179A (en) | 2019-12-31 |
| CN110628179B CN110628179B (en) | 2020-11-17 |
Family
ID=68969927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910820938.0A Active CN110628179B (en) | 2019-08-30 | 2019-08-30 | Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110628179B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115433146A (en) * | 2022-09-16 | 2022-12-06 | 西安思摩威新材料有限公司 | Compound for sealing film, composition and sealing film formed by using composition |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1455808A (en) * | 2001-03-21 | 2003-11-12 | 日华化学株式会社 | Flame retardant treating agent, flame retardant treating process and flame treatment fibers |
| CN102634174A (en) * | 2012-03-31 | 2012-08-15 | 四川东方绝缘材料股份有限公司 | Preparation method of flame-retardant copolyester film of phosphorus, silicon and fluorine |
| CN103772981A (en) * | 2013-12-30 | 2014-05-07 | 四川大学 | Low-dielectric-constant polymer/fluorinated graphene composite material and preparation method thereof |
| CN105732715A (en) * | 2016-01-27 | 2016-07-06 | 厦门大学 | Phosphorus-containing fluorine-containing synergic flame-retardant compound and preparation method thereof |
| CN106905561A (en) * | 2017-03-02 | 2017-06-30 | 张家港市山牧新材料技术开发有限公司 | A kind of fluorine-containing DOPO derivative flame retardants and preparation method thereof |
| CN106916186A (en) * | 2017-03-02 | 2017-07-04 | 张家港市山牧新材料技术开发有限公司 | A kind of fluorine-based DOPO derivative flame retardants and preparation method thereof |
| CN106928278A (en) * | 2017-03-02 | 2017-07-07 | 张家港市山牧新材料技术开发有限公司 | A kind of new DOPO based flameproofings and preparation method thereof |
| CN109265481A (en) * | 2018-08-06 | 2019-01-25 | 厦门大学 | A kind of fire retarding epoxide resin of richness fluorine fire retardant and preparation method thereof and richness fluorine fire retardant modification |
| CN109280218A (en) * | 2018-08-06 | 2019-01-29 | 厦门大学 | A kind of phosphor fluorine containing fire retardant and preparation method thereof and the modified fire retarding epoxide resin of the phosphor fluorine containing fire retardant |
| CN109721727A (en) * | 2018-12-29 | 2019-05-07 | 福建师范大学 | A kind of DOPO lateral group polyarylether ketone preparation method containing ternary fire proofing |
| CN109880078A (en) * | 2018-12-29 | 2019-06-14 | 福建师范大学泉港石化研究院 | A kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone and preparation method thereof |
-
2019
- 2019-08-30 CN CN201910820938.0A patent/CN110628179B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1455808A (en) * | 2001-03-21 | 2003-11-12 | 日华化学株式会社 | Flame retardant treating agent, flame retardant treating process and flame treatment fibers |
| CN102634174A (en) * | 2012-03-31 | 2012-08-15 | 四川东方绝缘材料股份有限公司 | Preparation method of flame-retardant copolyester film of phosphorus, silicon and fluorine |
| CN103772981A (en) * | 2013-12-30 | 2014-05-07 | 四川大学 | Low-dielectric-constant polymer/fluorinated graphene composite material and preparation method thereof |
| CN105732715A (en) * | 2016-01-27 | 2016-07-06 | 厦门大学 | Phosphorus-containing fluorine-containing synergic flame-retardant compound and preparation method thereof |
| CN106905561A (en) * | 2017-03-02 | 2017-06-30 | 张家港市山牧新材料技术开发有限公司 | A kind of fluorine-containing DOPO derivative flame retardants and preparation method thereof |
| CN106916186A (en) * | 2017-03-02 | 2017-07-04 | 张家港市山牧新材料技术开发有限公司 | A kind of fluorine-based DOPO derivative flame retardants and preparation method thereof |
| CN106928278A (en) * | 2017-03-02 | 2017-07-07 | 张家港市山牧新材料技术开发有限公司 | A kind of new DOPO based flameproofings and preparation method thereof |
| CN109265481A (en) * | 2018-08-06 | 2019-01-25 | 厦门大学 | A kind of fire retarding epoxide resin of richness fluorine fire retardant and preparation method thereof and richness fluorine fire retardant modification |
| CN109280218A (en) * | 2018-08-06 | 2019-01-29 | 厦门大学 | A kind of phosphor fluorine containing fire retardant and preparation method thereof and the modified fire retarding epoxide resin of the phosphor fluorine containing fire retardant |
| CN109721727A (en) * | 2018-12-29 | 2019-05-07 | 福建师范大学 | A kind of DOPO lateral group polyarylether ketone preparation method containing ternary fire proofing |
| CN109880078A (en) * | 2018-12-29 | 2019-06-14 | 福建师范大学泉港石化研究院 | A kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115433146A (en) * | 2022-09-16 | 2022-12-06 | 西安思摩威新材料有限公司 | Compound for sealing film, composition and sealing film formed by using composition |
| CN115433146B (en) * | 2022-09-16 | 2024-06-11 | 西安思摩威新材料有限公司 | Compound for packaging film, composition, and packaging film formed using the composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110628179B (en) | 2020-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Miao et al. | Biobased epoxy resin derived from eugenol with excellent integrated performance and high renewable carbon content | |
| CN102827409B (en) | Halogen-free flame-retardant organosilane cross-linked polyethylene, and preparation method and composition thereof | |
| CN102134304B (en) | Reactive type phosphoric epoxy resin flame retardant and preparation method thereof | |
| CN111234235B (en) | Oligomeric silicon-oxygen phosphate flame retardant and preparation method and application thereof | |
| CN101597308A (en) | The preparation method of hexaaniline cyclotriphosphazene and halogen-free flame retardant epoxy resin composition | |
| CN105061761A (en) | Nano zirconium phosphate-modified triazine macromolecular charring agent, and preparation method and application thereof | |
| DE10393198T5 (en) | Phosphazene composition | |
| CN110628179B (en) | Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof | |
| CN107011501A (en) | A kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material | |
| CN110256814B (en) | Preparation method of piperazine structure-containing DOPO derivative modified flame-retardant epoxy resin | |
| Bao et al. | Synthesis of a novel flame retardant with phosphaphenanthrene and phosphazene double functional groups and flame retardancy of poly (lactic acid) composites | |
| CN109721710A (en) | A kind of new compound DOPO-MA and its synthetic method | |
| CN108129825B (en) | high-CTI high-heat-resistance halogen-free flame-retardant PC/ABS composition and preparation method thereof | |
| CN113336993B (en) | Preparation method of anti-dripping nylon plate based on surface structured flame-retardant technology | |
| Shu et al. | Preparation and properties of bio-based flame retardant polyvinyl alcohol | |
| CN111100332B (en) | Preparation method and application of dumbbell type fluorine-containing polyphosphazene modified halloysite nanotube | |
| CN105859993A (en) | Flexible phosphorus-nitrogen flame retardant for epoxy resin, preparation method for flexible phosphorus-nitrogen flame retardant and application of flexible phosphorus-nitrogen flame retardant | |
| CN112143207A (en) | Low-dielectric-constant halogen-free flame-retardant PPE material and preparation method thereof | |
| CN118146516A (en) | Low-dielectric flame retardant and preparation method and application thereof | |
| CN116063353A (en) | Phosphorus-nitrogen reactive flame retardant, and preparation method and application thereof | |
| CN103509320B (en) | A kind of halogen-free flame-retardant polycarbonate composition and preparation method thereof | |
| CN113337177A (en) | Epoxy resin coating of porous organic polymer modified carbon nano tube and preparation method thereof | |
| CN114634654A (en) | Efficient halogen-free phosphorus and nitrogen intumescent flame retardant and preparation method thereof | |
| CN106750054A (en) | Graphene of chemical bonding polypropylene long-chain and preparation method thereof | |
| CN110643168A (en) | Black phosphorus nanosheet flame-retardant polyphenyl ether resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |