CN102604372A - Polyamide composite material with flame retardance and heat conduction and preparation method thereof - Google Patents
Polyamide composite material with flame retardance and heat conduction and preparation method thereof Download PDFInfo
- Publication number
- CN102604372A CN102604372A CN2012100355781A CN201210035578A CN102604372A CN 102604372 A CN102604372 A CN 102604372A CN 2012100355781 A CN2012100355781 A CN 2012100355781A CN 201210035578 A CN201210035578 A CN 201210035578A CN 102604372 A CN102604372 A CN 102604372A
- Authority
- CN
- China
- Prior art keywords
- modification
- black lead
- graphite
- expanded graphite
- expansible black
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a polyamide composite material with flame retardance and heat conduction and a preparation method of the polyamide composite material. The polyamide composite material comprises the following components in percentage by weight: 30-70% of polyamide, 30-70% of modified compound graphite, 0.1-5% of a lubricant and 0.1-1% of an antioxidant; and the sum of the components is 100%. The preparation method of the polyamide composite material comprises the following steps of (1) adding the polyamide, the modified compound graphite, the lubricant and the antioxidant in a blending machine according to the proportion and blending for 5-10min; and (2) adding the mixed materials into a main feeding mouth of a double-screw extrusion machine, melting at a temperature of 230-260 DEG C and extruding for granulation. According to the polyamide composite material and the preparation method of the polyamide composite material, provided by the invention, magnesium hydroxide generated by an in-situ method is a good inorganic flame retardant, can act with expanded graphite together to endow the composite material with good flame retardant performance, can also play a role of coating, and improves the processing performance of graphite composite materials, and the composite material is good in flame retardance and heat conduction.
Description
Technical field
The present invention relates to a kind of polyamide-based matrix material and preparation method thereof, a kind of specifically polyamide compoiste material that has fire-retardant and heat conduction concurrently and preparation method thereof.
Background technology
Most polymers all is that inflammable material and thermal conductivity are lower, and polymkeric substance will reach fire-retardant purpose, and the most frequently used and easy method is to wherein adding fire retardant, such as halogenated flame retardant, and organic phosphorus flame retardant, inorganic combustion inhibitor etc.Expansible black lead is a kind of novel expansion type flame retardant, is heated when reaching certain temperature, because occlusion compound decomposition in the interlayer dot matrix, expansible black lead just begins to expand, and in the time of 1000 ℃, expands fully, reaches maximum volume.When expanding volume can reach initial more than 200 times.Graphite after the expansion is called expanded graphite or graphite worm, becomes the very low vermiform of density by former flakey, has formed an extraordinary thermal insulation layer, can be effectively heat insulation, and it is low in fire, to have a rate of heat release, and mass loss is little, the characteristics that the flue gas of generation is few.Be widely used in the polymer-based flame-proof composite material.Polymkeric substance will reach the purpose of heat conduction, and the most frequently used and easy approach is to wherein adding heat conductive filler, such as metal powder, graphite, carbon black, MOX, thomel, nitride, carbide etc.
Preparation has concurrently fire-retardant and polyamide compoiste material heat conduction; Normally in polymeric amide, add fire retardant and heat conductive filler; Because a large amount of fire retardants and the adding of thermal conducting agent cause the mechanical property of material sharply to descend, the cost of product is also very high simultaneously, so its application has received very big restriction.
Summary of the invention
Technical problem to be solved by this invention is: to the shortcoming that above prior art exists, propose a kind of polyamide compoiste material that has fire-retardant and heat conduction concurrently and preparation method thereof, matrix material is fire-retardant good with heat conductivility.
The technical scheme that the present invention solves above technical problem is:
A kind ofly have fire-retardant and polyamide compoiste material heat conduction concurrently, its weight percent component is: polymeric amide: 30～70%, and the composite graphite of modification: 30～70%, lubricant: 0.1～5%, oxidation inhibitor: 0.1～1%; More than each component sum be 100%; The composite graphite of modification is made up of modification expansible black lead and modified expanded graphite, and modification expansible black lead and modified expanded graphite weight proportion are: the modification expansible black lead: modified expanded graphite is 1:1～3:1;
Modification Preparation of Expansible Graphite technology is:
1. prepare magnesium chloride solution and alkaline solution: the solid content of magnesium chloride solution and alkaline solution is 10～60%;
2. coat to handle expansible black lead: expansible black lead is added in the magnesium chloride solution that 1. step prepare, and the back that stirs adds the alkaline solution that 1. step is prepared, treat that magnesium chloride solution and alkaline solution react completely after; Leave standstill, suction filtration is with deionized water wash 5-6 time; Suction filtration; Oven dry obtains coating the expansible black lead of processing, said magnesium chloride solution and alkaline solution weight sum be the polyamide compoiste material weight that will make 50～90%, said magnesium chloride solution and alkaline solution weight ratio are 1:1;
3. coupling processing expansible black lead: in the expansible black lead that the coating that 2. step is obtained is handled and the coupling agent adding blender; At 50-90 ℃ of following blend 5-10min; Obtain the modification expansible black lead, said coupling agent add-on is the 0.5-5% of the expansible black lead weight handled of the coating that 2. obtains of step;
The preparation technology of modified expanded graphite is:
⑴ preparation magnesium chloride solution and alkaline solution: the solid content of magnesium chloride solution and alkaline solution is 10～60%;
⑵ coat to handle expanded graphite: expanded graphite is added in the magnesium chloride solution of step ⑴ preparation, the back that stirs adds the alkaline solution of step ⑴ preparation, treat that magnesium chloride solution and alkaline solution react completely after; Leave standstill, suction filtration is with deionized water wash 5-6 time; Suction filtration; Oven dry obtains coating the expanded graphite of processing, said magnesium chloride solution and alkaline solution weight sum be the polyamide compoiste material weight that will make 10～50%, said magnesium chloride solution and alkaline solution weight ratio are 1:1;
⑶ coupling processing expanded graphite: in the expanded graphite that the coating that 2. step is obtained is handled and the coupling agent adding blender; At 50-90 ℃ of following blend 5-10min; Obtain modified expanded graphite, the 0.5-5% of the expanded graphite weight that the coating that said coupling agent add-on obtains for step ⑵ is handled;
The preparation technology of the composite graphite of modification is: modification expansible black lead and modified expanded graphite are added in the blender according to above proportioning, obtain the composite graphite of modification at 50-90 ℃ of following blend 5-10min.
The aforementioned preparation method who has the polyamide compoiste material of fire-retardant and heat conduction concurrently may further comprise the steps:
(1) adds polymeric amide, the composite graphite of modification, lubricant and oxidation inhibitor in the blender according to above proportioning, blend 5-10min;
(2) joins the main spout of twin screw extruder with the material that mixes, and under 230-260 ℃, melt extrudes granulation.
Expansible black lead is natural flake graphite (or the very high electrographite of degree of graphitization), and the intercalation compound after acidic oxidation agent (sulfuric acid, nitric acid and ydrogen peroxide 50, potassium permanganate) is handled is also claimed graphite oxide.The immersion of oxygenant also makes original graphite produce the small expansion behavior, and interlamellar spacing increases to 6-11A by original 3.35A.The graphite oxide key property is that unusual swelling property is arranged, and can at high temperature expand, so be expansible black lead.
Expanded graphite be graphite oxide at 960-980 ℃ of high temperature action, the decomposition of gasifying rapidly of the compound of graphite layers produces a certain amount of thrust; Destroy graphite layers bonded molecular force; Make the C-C bond rupture between the graphite lattice, aspect expands rapidly along the c direction of principal axis, and interlamellar spacing increases 50-500 doubly; By flaky graphite more closely, become fine cotton-shaped type quasiflake graphite.
What the present invention adopted is that a kind of " original position " reaction generates the method that Marinco H coats expansible black lead and expanded graphite; The expansible black lead and the expanded graphite that coat through Marinco H have higher tap density than expansible black lead and expanded graphite mixture before not coating; The density of two kinds of graphite is close, and consistency is better, pass through coupling processing again after; With polyamide substrate good consistency is arranged; During the preparation polyamide compoiste material, blanking is more easy with dispersion, has improved the processing characteristics of graphite composite material.Expansible black lead is a kind of expansion type flame retardant, is widely used in the flame-proof composite material; Marinco H is a kind of inorganic combustion inhibitor, it and expansible black lead acting in conjunction, performance good flame effect in matrix material.Expanded graphite verified with the polyamide preparation matrix material after; The capacity of heat transmission of polyamide compoiste material obviously improves, and just because the expanded graphite surface is fluffy, blanking is all compared difficulty with disperseing; Caused a very big processing difficult problem, so just be not widely used.The method of " original position " inorganic particulate coating graphite that the present invention adopts has solved this difficult problem well.
Characteristics of the present invention are that the expansible black lead of selecting for use is a fire retardant; It is again good thermal conducting agent; The total amount of filler of preparation flame-retarded heat-conducting polyamide compoiste material has just reduced like this, and the mechanical property of material can not reduce because of too much filler, has also reduced the cost of Composite Preparation simultaneously; The Marinco H that " original position " method generates is good inorganic combustion inhibitor; The matrix material excellent flame-retardant is given in ability and expansible black lead acting in conjunction; Can play the coating effect again, improve the processing characteristics of graphite composite material, also have certain thermal conductivity simultaneously; Add a small amount of expanded graphite and can obviously improve the heat conductivility of material.
The technical scheme that the present invention further limits is:
Aforesaidly have fire-retardant and polyamide compoiste material heat conduction concurrently, polymeric amide is a kind of among heat-resistant polyamide, PA6 or the PA66 or mixes.
Aforesaidly have fire-retardant and polyamide compoiste material heat conduction concurrently, the expansible black lead expansion multiplying power is 50-400 mL/g, and initial expansion temperature is greater than 300 ℃, and carbon content is more than 98%.
Aforesaidly have fire-retardant and polyamide compoiste material heat conduction concurrently, lubricant is stearate, stearic amide, low-molecular(weight)polymer or paraffin.
Aforesaidly have fire-retardant and polyamide compoiste material heat conduction concurrently, oxidation inhibitor is phenols or one or more mixtures of phosphorous acid esters.
Aforesaidly have fire-retardant and polyamide compoiste material heat conduction concurrently, coupling agent is silane coupling agent, titanate coupling agent or aluminate coupling agent.
Embodiment
Embodiment 1
A kind ofly have fire-retardant and polyamide compoiste material heat conduction concurrently, its weight percent component is:
PA6：69%，
The composite graphite 30% of modification, wherein the expansible black lead expansion multiplying power is 50 mL/g, and initial expansion temperature is greater than 300 ℃, and carbon content is 99%,
Paraffin: 1%;
Oxidation inhibitor: 1010 (0.1%), 168 (0.15%), add-on is 0.1% and 0.15% of PA6, the composite graphite of modification and a paraffin total amount.
Have the preparation method of the polyamide compoiste material of fire-retardant and heat conduction concurrently, may further comprise the steps:
The composite graphite of modification: 1. prepare magnesium chloride solution and sodium hydroxide solution: the magnesium chloride brine solid content is 16.4%, and the solid content of sodium hydroxide water is 13.8%; 2. coat to handle expansible black lead: stirring reaction was after for some time after the sodium hydroxide solution of the magnesium chloride solution and 75% of (polyamide compoiste material weight 75%) with 75% (polyamide compoiste material weight 75%) joined expansible black lead; Leave standstill; Suction filtration; Deionized water wash 5-6 time, suction filtration is dried the expansible black lead that obtains coating processing down for 100 ℃; 3. coat and handle expanded graphite: stirring reaction left standstill after for some time after magnesium chloride solution with 25% and 25% sodium hydroxide solution joined expanded graphite, suction filtration, and deionized water wash 5-6 time, suction filtration is dried the expanded graphite that obtains coating processing down for 100 ℃; 4. coupling processing expanded graphite: expanded graphite and 1% the titanate coupling agent that will coat after handling add in the high speed blender, at 80 ℃ of following blend 10min, obtain modified expanded graphite; Adopt identical method to obtain the modification expansible black lead; In modification expansible black lead and modified expanded graphite 3:1 adding by weight ratio high speed blender, blend 5min obtains the composite graphite of modification, and is subsequent use;
Material premix: polyamide substrate resin, the composite graphite of modification, paraffin and oxidation inhibitor are added blend 5min in the high speed blender by above proportioning;
Granulation: the main spout with the material adding twin screw extruder that mixes melt extrudes granulation at 250 ℃.
Embodiment 2
A kind ofly have fire-retardant and polyamide compoiste material heat conduction concurrently, its weight percent component is:
PA6：64%，
The composite graphite of modification: 35%, wherein the expansible black lead expansion multiplying power is 100 mL/g, and initial expansion temperature is greater than 300 ℃, and carbon content is 99%,
Paraffin: 1%;
Oxidation inhibitor: 1010 (0.15%), 168 (0.35%), add-on is 0.15% and 0.35% of PA6, the composite graphite of modification and a paraffin total amount.
Have the preparation method of the polyamide compoiste material of fire-retardant and heat conduction concurrently, may further comprise the steps:
The composite graphite of modification: 1. prepare magnesium chloride solution and sodium hydroxide solution: the magnesium chloride brine solid content is 16.4%, and the solid content of sodium hydroxide water is 13.8%; 2. coat to handle expansible black lead: stirring reaction was after for some time after the sodium hydroxide solution of the magnesium chloride solution and 60% of (polyamide compoiste material weight 60%) with 60% (polyamide compoiste material weight 60%) joined expansible black lead; Leave standstill; Suction filtration; Deionized water wash 5-6 time, suction filtration is dried the expansible black lead that obtains coating processing down for 100 ℃; 3. coat to handle expanded graphite: stirring reaction was after for some time after the magnesium chloride solution and 40% of (polyamide compoiste material weight 40%) with 40% (polyamide compoiste material weight 40%) sodium hydroxide solution joined expansible black lead; Leave standstill; Suction filtration; Deionized water wash 5-6 time, suction filtration is dried the expanded graphite that obtains coating processing down for 100 ℃; 4. coupling processing expanded graphite: expanded graphite and 1% the titanate coupling agent that will coat after handling add in the high speed blender, at 80 ℃ of following blend 10min, obtain modified expanded graphite; Adopt identical method to obtain the modification expansible black lead; Modification expansible black lead and modified expanded graphite are added in the high speed blender by weight 3:2, and blend 5min obtains the composite graphite of modification, and is subsequent use.
Material premix: polyamide substrate resin, the composite graphite of modification, paraffin and oxidation inhibitor are added blend 5min in the high speed blender by above proportioning.
Granulation: the main spout with the material adding twin screw extruder that mixes melt extrudes granulation at 250 ℃.
Embodiment 3
A kind ofly have fire-retardant and polyamide compoiste material heat conduction concurrently, its weight percent component is:
PA6：53.5%，
The composite graphite 45% of modification, wherein the expansible black lead expansion multiplying power is 200 mL/g, and initial expansion temperature is greater than 300 ℃, and carbon content is 99%,
Paraffin: 1.5%;
Oxidation inhibitor: 1010 (0.35%), 168 (0.55%), add-on is 0.35% and 0.55% of PA6, the composite graphite of modification and a paraffin total amount.
Have the preparation method of the polyamide compoiste material of fire-retardant and heat conduction concurrently, may further comprise the steps:
The composite graphite of modification: 1. prepare magnesium chloride solution and sodium hydroxide solution: the magnesium chloride brine solid content is 16.4%, and the solid content of sodium hydroxide water is 13.8%; 2. coat to handle expansible black lead: stirring reaction was after for some time after the magnesium chloride solution and 50% of (polyamide compoiste material weight 50%) with 50% (polyamide compoiste material weight 50%) sodium hydroxide solution joined expansible black lead; Leave standstill; Suction filtration; Deionized water wash 5-6 time, suction filtration is dried the expansible black lead that obtains coating processing down for 100 ℃; 3. coat to handle expanded graphite: stirring reaction was after for some time after the magnesium chloride solution and 50% of (polyamide compoiste material weight 50%) with 50% (polyamide compoiste material weight 50%) sodium hydroxide solution joined expansible black lead; Leave standstill; Suction filtration; Deionized water wash 5-6 time, suction filtration is dried the expanded graphite that obtains coating processing down for 100 ℃; 4. coupling processing expanded graphite: expanded graphite and 1% the titanate coupling agent that will coat after handling add in the high speed blender, at 80 ℃ of following blend 10min, obtain modified expanded graphite; The coupling processing expanded graphite: expansible black lead and 1.5% the titanate coupling agent that will coat after handling add in the high speed blender, at 80 ℃ of following blend 10min, obtain the modification expansible black lead; Modification expansible black lead and modification expansible black lead are added in the high speed blender by weight 5:2, obtain the composite graphite of modification at 80 ℃ of following blend 5min, subsequent use;
Material premix: polyamide substrate resin, the composite graphite of modification, paraffin and oxidation inhibitor are added blend 5min in the high speed blender by above proportioning;
Granulation: the main spout with the material adding twin screw extruder that mixes melt extrudes granulation under 250 ℃.
Embodiment 4
A kind ofly have fire-retardant and polyamide compoiste material heat conduction concurrently, its weight percent component is:
PA6：43%，
The composite graphite 55% of modification, wherein the expansible black lead expansion multiplying power is 300 mL/g, and initial expansion temperature is greater than 300 ℃, and carbon content is 99%,
Paraffin: 2%;
Oxidation inhibitor: 1010 (0.1%), 168 (0.15%), add-on is 0.1% and 0.15% of PA6, the composite graphite of modification and a paraffin total amount.
Have the preparation method of the polyamide compoiste material of fire-retardant and heat conduction concurrently, may further comprise the steps:
The composite graphite of modification: 1. prepare magnesium chloride solution and sodium hydroxide solution: the magnesium chloride brine solid content is 32.7%, and the solid content of sodium hydroxide water is 27.6%; 2. coat to handle expansible black lead: stirring reaction was after for some time after the magnesium chloride solution and 70% of (polyamide compoiste material weight 70%) with 70% (polyamide compoiste material weight 70%) sodium hydroxide solution joined expansible black lead; Leave standstill; Suction filtration; Deionized water wash 5-6 time, suction filtration is dried the expansible black lead that obtains coating processing down for 100 ℃; 3. coat to handle expanded graphite: stirring reaction was after for some time after the magnesium chloride solution and 30% of (polyamide compoiste material weight 30%) with 30% (polyamide compoiste material weight 30%) sodium hydroxide solution joined expansible black lead; Leave standstill; Suction filtration; Deionized water wash 5-6 time, suction filtration is dried the expanded graphite that obtains coating processing down for 100 ℃; 4. coupling processing expanded graphite: expanded graphite and 1% the titanate coupling agent that will coat after handling add in the high speed blender, at 80 ℃ of following blend 10min, obtain modified expanded graphite; Adopt identical method to obtain modification expansible black lead (2% titanate coupling agent); Modification expansible black lead and modified expanded graphite are added in the high speed blender by weight 5:2, obtain the composite graphite of modification at 80 ℃ of following blend 5min, subsequent use;
Material premix: the admixed graphite after polyamide substrate resin, the modification, paraffin and oxidation inhibitor are added blend 5min in the high speed blender by above proportioning;
Granulation: the main spout with the material adding twin screw extruder that mixes melt extrudes granulation under 250 ℃.
Embodiment 5
A kind ofly have fire-retardant and polyamide compoiste material heat conduction concurrently, its weight percent component is:
PA6：37%，
The composite graphite 60% of modification, wherein the expansible black lead expansion multiplying power is 350mL/g, and initial expansion temperature is greater than 300 ℃, and carbon content is 99%,
Paraffin: 3%;
Oxidation inhibitor: 1010 (0.1%), 168 (0.15%), add-on is 0.1% and 0.15% of PA6, the composite graphite of modification and a paraffin total amount.
Have the preparation method of the polyamide compoiste material of fire-retardant and heat conduction concurrently, may further comprise the steps:
The composite graphite of modification: 1. prepare magnesium chloride solution and sodium hydroxide solution: the magnesium chloride solution solid content is 32.7%, and the solid content of sodium hydroxide solution is 27.6%; 2. coat to handle expansible black lead: stirring reaction was after for some time after the sodium hydroxide solution of the magnesium chloride solution and 75% of (polyamide compoiste material weight 75%) with 75% (polyamide compoiste material weight 75%) joined expansible black lead; Leave standstill; Suction filtration; Deionized water wash 5-6 time, suction filtration is dried the expansible black lead that obtains coating processing down for 100 ℃; 3. coat to handle expanded graphite: stirring reaction was after for some time after magnesium chloride solution with 25% (polyamide compoiste material weight 25%) and 25% sodium hydroxide solution (polyamide compoiste material weight 25%) joined expansible black lead; Leave standstill; Suction filtration; Deionized water wash 5-6 time, suction filtration is dried the expanded graphite that obtains coating processing down for 100 ℃; 4. coupling processing expanded graphite: expanded graphite and 1% the titanate coupling agent that will coat after handling add in the high speed blender, at 80 ℃ of following blend 10min, obtain modified expanded graphite; Adopt identical method to obtain modification expansible black lead (2% titanate coupling agent); Modification expansible black lead and modified expanded graphite are added in the high speed blender by weight 3:1, obtain the composite graphite of modification at 80 ℃ of following blend 5min, subsequent use;
Material premix: polyamide substrate resin, the composite graphite of modification, paraffin and oxidation inhibitor are added blend 5min in the high speed blender by above proportioning;
Granulation: the main spout with the material adding twin screw extruder that mixes melt extrudes granulation under 250 ℃.
Embodiment 6
A kind ofly have fire-retardant and polyamide compoiste material heat conduction concurrently, its weight percent component is:
PA6：25%，
The composite graphite 70% of modification, wherein the expansible black lead expansion multiplying power is 400 mL/g, and initial expansion temperature is greater than 300 ℃, and carbon content is 99%,
Paraffin: 5%
Oxidation inhibitor: 1010 (0.1%), 168 (0.15%), add-on is 0.1% and 0.15% of PA6, the composite graphite of modification and a paraffin total amount.
Have the preparation method of the polyamide compoiste material of fire-retardant and heat conduction concurrently, may further comprise the steps:
The composite graphite of modification: 1. prepare magnesium chloride solution and sodium hydroxide solution: the magnesium chloride solution solid content is 49.2%, and the solid content of sodium hydroxide solution is 41.4%; 2. coat to handle expansible black lead: stirring reaction was after for some time after the sodium hydroxide solution of the magnesium chloride solution and 75% of (polyamide compoiste material weight 75%) with 75% (polyamide compoiste material weight 75%) joined expansible black lead; Leave standstill; Suction filtration; Deionized water wash 5-6 time, suction filtration is dried the expansible black lead that obtains coating processing down for 100 ℃; 3. coat to handle expanded graphite: stirring reaction was after for some time after the magnesium chloride solution and 25% of (polyamide compoiste material weight 25%) with 25% (polyamide compoiste material weight 25%) sodium hydroxide solution joined expansible black lead; Leave standstill; Suction filtration; Deionized water wash 5-6 time, suction filtration is dried the expanded graphite that obtains coating processing down for 100 ℃; 4. coupling processing expanded graphite: expanded graphite and 1% the titanate coupling agent that will coat after handling add in the high speed blender, at 80 ℃ of following blend 10min, obtain modified expanded graphite; Adopt identical method to obtain modification expansible black lead (2.5% titanate coupling agent); Modification expansible black lead and modified expanded graphite are added in the high speed blender by weight 3:1, obtain the composite graphite of modification at 80 ℃ of following blend 5min, subsequent use;
Material premix: polyamide substrate resin, the composite graphite of modification, paraffin and oxidation inhibitor are added blend 5min in the high speed blender by above proportioning;
Granulation: the main spout with the material adding twin screw extruder that mixes melt extrudes granulation at 250 ℃.
The parameter testing result of above embodiment sees table 1:
Table 1
The present invention can also have other embodiment, and the technical scheme that equal replacement of all employings or equivalent transformation form all drops within the scope of requirement protection of the present invention.
Claims (7)
1. one kind has concurrently fire-retardant and polyamide compoiste material heat conduction, and it is characterized in that: its weight percent component is: polymeric amide: 30～70%, and the composite graphite of modification: 30～70%, lubricant: 0.1～5%, oxidation inhibitor: 0.1～1%; More than each component sum be 100%; The composite graphite of said modification is made up of modification expansible black lead and modified expanded graphite, and said modification expansible black lead and modified expanded graphite weight proportion are: the modification expansible black lead: modified expanded graphite is 1:1～3:1;
Said modification Preparation of Expansible Graphite technology is:
1. prepare magnesium chloride solution and alkaline solution: the solid content of magnesium chloride solution and alkaline solution is 10～60%;
2. coat to handle expansible black lead: expansible black lead is added in the magnesium chloride solution that 1. step prepare, and the back that stirs adds the alkaline solution that 1. step is prepared, treat that magnesium chloride solution and alkaline solution react completely after; Leave standstill, suction filtration is with deionized water wash 5-6 time; Suction filtration; Oven dry obtains coating the expansible black lead of processing, said magnesium chloride solution and alkaline solution weight sum be the polyamide compoiste material weight that will make 50～90%, said magnesium chloride solution and alkaline solution weight ratio are 1:1;
3. coupling processing expansible black lead: in the expansible black lead that the coating that 2. step is obtained is handled and the coupling agent adding blender; At 50-90 ℃ of following blend 5-10min; Obtain the modification expansible black lead, said coupling agent add-on is the 0.5-5% of the expansible black lead weight handled of the coating that 2. obtains of step;
The preparation technology of said modified expanded graphite is:
⑴ preparation magnesium chloride solution and alkaline solution: the solid content of magnesium chloride solution and alkaline solution is 10～60%;
⑵ coat to handle expanded graphite: expanded graphite is added in the magnesium chloride solution of step ⑴ preparation, the back that stirs adds the alkaline solution of step ⑴ preparation, treat that magnesium chloride solution and alkaline solution react completely after; Leave standstill, suction filtration is with deionized water wash 5-6 time; Suction filtration; Oven dry obtains coating the expanded graphite of processing, said magnesium chloride solution and alkaline solution weight sum be the polyamide compoiste material weight that will make 10～50%, said magnesium chloride solution and alkaline solution weight ratio are 1:1;
⑶ coupling processing expanded graphite: in the expanded graphite that the coating that 2. step is obtained is handled and the coupling agent adding blender; At 50-90 ℃ of following blend 5-10min; Obtain modified expanded graphite, the 0.5-5% of the expanded graphite weight that the coating that said coupling agent add-on obtains for step ⑵ is handled;
The preparation technology of the composite graphite of said modification is: modification expansible black lead and modified expanded graphite are added in the blender according to above proportioning, obtain the composite graphite of modification at 50-90 ℃ of following blend 5-10min.
2. as claimed in claim 1ly have fire-retardant and polyamide compoiste material heat conduction concurrently, it is characterized in that: said polymeric amide is a kind of among heat-resistant polyamide, PA6 or the PA66 or mixes.
3. as claimed in claim 1ly have fire-retardant and polyamide compoiste material heat conduction concurrently, it is characterized in that: said expansible black lead expansion multiplying power is 50-400 mL/g, and initial expansion temperature is greater than 300 ℃, and carbon content is more than 98%.
4. as claimed in claim 1ly have fire-retardant and polyamide compoiste material heat conduction concurrently, it is characterized in that: said lubricant is stearate, stearic amide, low-molecular(weight)polymer or paraffin.
5. as claimed in claim 1ly have fire-retardant and polyamide compoiste material heat conduction concurrently, it is characterized in that: said oxidation inhibitor is phenols or one or more mixtures of phosphorous acid esters.
6. as claimed in claim 1ly have fire-retardant and polyamide compoiste material heat conduction concurrently, it is characterized in that: said coupling agent is silane coupling agent, titanate coupling agent or aluminate coupling agent.
7. the said preparation method who has the polyamide compoiste material of fire-retardant and heat conduction concurrently of claim 1 is characterized in that: may further comprise the steps:
(1) adds polymeric amide, the composite graphite of modification, lubricant and oxidation inhibitor in the blender according to the said proportioning of claim 1, blend 5-10min;
(2) joins the main spout of twin screw extruder with the material that mixes, and under 230-260 ℃, melt extrudes granulation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210035578 CN102604372B (en) | 2012-02-17 | 2012-02-17 | Polyamide composite material with flame retardance and heat conduction and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210035578 CN102604372B (en) | 2012-02-17 | 2012-02-17 | Polyamide composite material with flame retardance and heat conduction and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102604372A true CN102604372A (en) | 2012-07-25 |
| CN102604372B CN102604372B (en) | 2013-06-05 |
Family
ID=46522171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210035578 Active CN102604372B (en) | 2012-02-17 | 2012-02-17 | Polyamide composite material with flame retardance and heat conduction and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102604372B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911334A (en) * | 2012-11-14 | 2013-02-06 | 滕州市华海新型保温材料有限公司 | B1-grade high-fire-retardant low-smoke-generation rigid polyurethane foam |
| CN103333370A (en) * | 2013-07-25 | 2013-10-02 | 北京市建筑工程研究院有限责任公司 | Organic and inorganic microcapsule coating expansible graphite preparation method |
| CN104327497A (en) * | 2014-10-17 | 2015-02-04 | 苏州博云塑业有限公司 | Polyamide modified plastic and preparation method thereof |
| CN104371318A (en) * | 2014-11-19 | 2015-02-25 | 上海大学 | Polyamide composite material with high thermal conductivity and high heat resistance and preparation method thereof |
| CN105315668A (en) * | 2014-05-27 | 2016-02-10 | 大信科技有限公司 | Highly thermally conductive inorganic-polymer complex composition applied to lighting LED that contains expanded graphite and manufacturing method thereof |
| CN106280414A (en) * | 2016-08-04 | 2017-01-04 | 北京工商大学 | A kind of nylon base heat-conductive composite material and preparation method thereof |
| CN106543718A (en) * | 2016-11-25 | 2017-03-29 | 广东聚航新材料研究院有限公司 | A kind of high flame retardant high temperature resistant nylon composite material and preparation method thereof |
| CN108102142A (en) * | 2017-12-08 | 2018-06-01 | 中国科学院化学研究所 | The expansible graphite fire retardant and preparation method of a kind of surface encapsulated nanoparticles |
| CN109486179A (en) * | 2018-09-30 | 2019-03-19 | 张家港绿洲新材料科技有限公司 | A kind of nylon 6 composition and its application in the long runner product of thin-walled |
| CN113817314A (en) * | 2020-06-18 | 2021-12-21 | 中国石油化工股份有限公司 | Composition for flame-retardant floating cover, flame-retardant floating cover material and preparation method of flame-retardant floating cover material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1486606A1 (en) * | 2002-02-05 | 2004-12-15 | YKK Corporation | Flame-retardant molded article and fabric product |
| CN1900162A (en) * | 2006-07-12 | 2007-01-24 | 扬州大学 | Polyamide/graphite nano conductive composite material and its prepairng method |
| CN101081926A (en) * | 2007-06-26 | 2007-12-05 | 扬州大学 | High conductive polyamide/graphite nano conductive composite material and preparation method thereof |
| CN101121796A (en) * | 2006-06-23 | 2008-02-13 | 南京理工大学 | Polymer-base flame-proof composite material |
| CN101230192A (en) * | 2007-01-26 | 2008-07-30 | 南京聚隆化学实业有限责任公司 | High-fluidity glass fiber reinforced polyamide composite material and preparation method thereof |
| CN101608061A (en) * | 2008-06-17 | 2009-12-23 | 东丽纤维研究所（中国）有限公司 | A kind of polyamide/oxidized graphite composite material and preparation method thereof with high conduction performance |
| CN101875779A (en) * | 2009-12-21 | 2010-11-03 | 扬州大学 | Polyamide/nano expanded graphite/carbon fiber high-strength conducting composite material and preparation method thereof |
| CN102260406A (en) * | 2011-07-05 | 2011-11-30 | 南京理工大学 | Methyl cellulose (MC) nylon nano conductive composite material and preparation method thereof |
-
2012
- 2012-02-17 CN CN 201210035578 patent/CN102604372B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1486606A1 (en) * | 2002-02-05 | 2004-12-15 | YKK Corporation | Flame-retardant molded article and fabric product |
| CN101121796A (en) * | 2006-06-23 | 2008-02-13 | 南京理工大学 | Polymer-base flame-proof composite material |
| CN1900162A (en) * | 2006-07-12 | 2007-01-24 | 扬州大学 | Polyamide/graphite nano conductive composite material and its prepairng method |
| CN101230192A (en) * | 2007-01-26 | 2008-07-30 | 南京聚隆化学实业有限责任公司 | High-fluidity glass fiber reinforced polyamide composite material and preparation method thereof |
| CN101081926A (en) * | 2007-06-26 | 2007-12-05 | 扬州大学 | High conductive polyamide/graphite nano conductive composite material and preparation method thereof |
| CN101608061A (en) * | 2008-06-17 | 2009-12-23 | 东丽纤维研究所（中国）有限公司 | A kind of polyamide/oxidized graphite composite material and preparation method thereof with high conduction performance |
| CN101875779A (en) * | 2009-12-21 | 2010-11-03 | 扬州大学 | Polyamide/nano expanded graphite/carbon fiber high-strength conducting composite material and preparation method thereof |
| CN102260406A (en) * | 2011-07-05 | 2011-11-30 | 南京理工大学 | Methyl cellulose (MC) nylon nano conductive composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| DASARI, A，ET AL: "Roles of graphite oxide, clay and POSS during the combustion of polyamide 6", 《POLYMER》 * |
| 应宗荣，等: "表面处理膨胀石墨对聚酰胺6的改性研究", 《现代塑料加工应用》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911334A (en) * | 2012-11-14 | 2013-02-06 | 滕州市华海新型保温材料有限公司 | B1-grade high-fire-retardant low-smoke-generation rigid polyurethane foam |
| CN103333370A (en) * | 2013-07-25 | 2013-10-02 | 北京市建筑工程研究院有限责任公司 | Organic and inorganic microcapsule coating expansible graphite preparation method |
| CN103333370B (en) * | 2013-07-25 | 2015-05-13 | 北京市建筑工程研究院有限责任公司 | Organic and inorganic microcapsule coating expansible graphite preparation method |
| CN105315668A (en) * | 2014-05-27 | 2016-02-10 | 大信科技有限公司 | Highly thermally conductive inorganic-polymer complex composition applied to lighting LED that contains expanded graphite and manufacturing method thereof |
| CN104327497A (en) * | 2014-10-17 | 2015-02-04 | 苏州博云塑业有限公司 | Polyamide modified plastic and preparation method thereof |
| CN104371318A (en) * | 2014-11-19 | 2015-02-25 | 上海大学 | Polyamide composite material with high thermal conductivity and high heat resistance and preparation method thereof |
| CN106280414A (en) * | 2016-08-04 | 2017-01-04 | 北京工商大学 | A kind of nylon base heat-conductive composite material and preparation method thereof |
| CN106543718A (en) * | 2016-11-25 | 2017-03-29 | 广东聚航新材料研究院有限公司 | A kind of high flame retardant high temperature resistant nylon composite material and preparation method thereof |
| CN106543718B (en) * | 2016-11-25 | 2019-05-31 | 广东聚航新材料研究院有限公司 | A kind of high flame retardant high temperature resistant nylon composite material and preparation method thereof |
| CN108102142A (en) * | 2017-12-08 | 2018-06-01 | 中国科学院化学研究所 | The expansible graphite fire retardant and preparation method of a kind of surface encapsulated nanoparticles |
| CN109486179A (en) * | 2018-09-30 | 2019-03-19 | 张家港绿洲新材料科技有限公司 | A kind of nylon 6 composition and its application in the long runner product of thin-walled |
| CN109486179B (en) * | 2018-09-30 | 2021-03-30 | 张家港绿洲新材料科技有限公司 | Nylon 6 composition and application thereof in thin-wall long flow channel product |
| CN113817314A (en) * | 2020-06-18 | 2021-12-21 | 中国石油化工股份有限公司 | Composition for flame-retardant floating cover, flame-retardant floating cover material and preparation method of flame-retardant floating cover material |
| CN113817314B (en) * | 2020-06-18 | 2023-11-24 | 中国石油化工股份有限公司 | Composition for flame-retardant floating cover, flame-retardant floating cover material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102604372B (en) | 2013-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102604372B (en) | Polyamide composite material with flame retardance and heat conduction and preparation method thereof | |
| Xu et al. | Fabrication of green alginate-based and layered double hydroxides flame retardant for enhancing the fire retardancy properties of polypropylene | |
| Guan et al. | Enhanced thermal conductivity and satisfactory flame retardancy of epoxy/alumina composites by combination with graphene nanoplatelets and magnesium hydroxide | |
| Liu et al. | Synergistic flame retardant effects between hollow glass microspheres and magnesium hydroxide in ethylene-vinyl acetate composites | |
| CN102746560B (en) | Heat-conducting plastic and preparation method thereof | |
| CN102942728B (en) | Antistatic halogen-free fire retardation ultra-high molecule weight polyethylene material and preparation method thereof | |
| CN103522447B (en) | The preparation method of halogen-free composite flame retardant polypropylene/thermopolyurethane polyurethane elastomer composite material | |
| CN103554598B (en) | The preparation method of halogen-free flameproof high density polyethylene(HDPE)/ethylene-vinyl acetate copolymer | |
| CN103397443B (en) | Halogen-free flame-retardant polyethylene plastic woven cloth and method for manufacturing same | |
| CN106867076A (en) | A kind of mining Graphene enhancing dual anti-tubing preparation method of ultra-high molecular weight polyethylene | |
| CN104629187A (en) | Multifunctional polypropylene composite material and preparation method thereof | |
| CN104530694A (en) | Regenerated PA6 (polyamide 6)-base flame-retardant electric-insulating heat-conducting composite material, and preparation method and application thereof | |
| CN105175921B (en) | A kind of montmorillonite/polyaniline nano material flame retardant polystyrene composite | |
| CN112812435A (en) | Normal-temperature heat-conducting high-temperature flame-retardant polymer composite material and preparation method thereof | |
| CN108503895B (en) | Preparation method of lanthanum-loaded organic phosphorus-modified nitrogen-doped graphene and flame-retardant modified ABS thereof | |
| CN101759900B (en) | Halogen-free flame-retardant and anti-static polyethylene material, pipe and preparing method thereof | |
| CN102093688A (en) | High-performance halogen-free flame-retardant PC (polycarbonate)/ABS (acrylonitrile-butadiene-styrene) alloy and preparation method thereof | |
| Xie et al. | Ammonium polyphosphate/montmorillonite nanocomposite with a completely exfoliated structure and charring–foaming agent flame retardant thermoplastic polyurethane | |
| CN113583299A (en) | High-expansion fireproof low-smoke halogen-free flame retardant composition and thermoplastic resin composition | |
| Zhi-Guo et al. | Significantly enhanced thermal conductivity and flame retardance by silicon carbide nanowires/graphene oxide hybrid network | |
| Han et al. | One-step exfoliation and deprotonation of ANF/BNNS suspension for constructing 3D vertically aligned skeleton in epoxy-based thermal management composites | |
| CN101851408B (en) | Halogen-free flame-retardant polycarbonate composition and preparation method thereof | |
| CN113354868A (en) | Phosphorus-doped polypyrrole-loaded carbon nitride nanocomposite and preparation method and application thereof | |
| CN103613913B (en) | A kind of Halogen-free flame-retardant thermoplastic polyester elastomer material and preparation method thereof | |
| CN103642125B (en) | Nano clay and nitrogen phosphorus flame retardant cooperative flame retardant polypropylene material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |